CN112322334A - Multi-zone coupling control multistage catalytic cracking method and device based on raw material properties - Google Patents
Multi-zone coupling control multistage catalytic cracking method and device based on raw material properties Download PDFInfo
- Publication number
- CN112322334A CN112322334A CN202011130960.1A CN202011130960A CN112322334A CN 112322334 A CN112322334 A CN 112322334A CN 202011130960 A CN202011130960 A CN 202011130960A CN 112322334 A CN112322334 A CN 112322334A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- cracking
- regeneration
- zone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002994 raw material Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 85
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 65
- 230000008878 coupling Effects 0.000 title claims abstract description 16
- 238000010168 coupling process Methods 0.000 title claims abstract description 16
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 215
- 238000006243 chemical reaction Methods 0.000 claims abstract description 174
- 238000005336 cracking Methods 0.000 claims abstract description 137
- 238000011069 regeneration method Methods 0.000 claims abstract description 114
- 230000008929 regeneration Effects 0.000 claims abstract description 105
- 150000001336 alkenes Chemical class 0.000 claims abstract description 60
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 58
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 101
- 239000002808 molecular sieve Substances 0.000 claims description 97
- 239000007789 gas Substances 0.000 claims description 84
- 239000003921 oil Substances 0.000 claims description 54
- 238000005192 partition Methods 0.000 claims description 54
- 238000002485 combustion reaction Methods 0.000 claims description 49
- 239000002131 composite material Substances 0.000 claims description 49
- 238000011282 treatment Methods 0.000 claims description 49
- 230000008569 process Effects 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 229930195733 hydrocarbon Natural products 0.000 claims description 39
- 150000002430 hydrocarbons Chemical class 0.000 claims description 37
- 239000004215 Carbon black (E152) Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 24
- 230000004048 modification Effects 0.000 claims description 22
- 238000012986 modification Methods 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 21
- 229910052755 nonmetal Inorganic materials 0.000 claims description 19
- 239000000446 fuel Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 32
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 32
- 229910052799 carbon Inorganic materials 0.000 abstract description 27
- 239000000047 product Substances 0.000 description 86
- 235000019198 oils Nutrition 0.000 description 40
- 239000003502 gasoline Substances 0.000 description 21
- 239000000571 coke Substances 0.000 description 20
- 238000001035 drying Methods 0.000 description 19
- 239000012071 phase Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000002156 mixing Methods 0.000 description 17
- 238000005470 impregnation Methods 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 13
- 230000032683 aging Effects 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000002444 silanisation Methods 0.000 description 11
- 239000000295 fuel oil Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- -1 ethylene, propylene Chemical group 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000003776 cleavage reaction Methods 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008676 import Effects 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 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
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000010724 circulating oil Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000013072 incoming material Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910017677 NH4H2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/06—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/182—Regeneration
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/187—Controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a multi-zone coupling control multistage catalytic cracking method and a device based on raw material properties, wherein the catalytic cracking method comprises the following steps: enabling the alkane-rich raw material to enter a first riser to contact with an alkane cracking catalyst to generate a first cracking reaction, performing gas-solid separation on a product of the first cracking reaction, steam stripping the separated first catalyst to be regenerated, and then enabling at least part of the regenerated first catalyst to return to the first riser to form a first cycle; and enabling the olefin-rich raw material to enter a second riser to contact with an olefin cracking catalyst to generate a second cracking reaction, performing gas-solid separation on a product of the second cracking reaction, steam stripping the separated second spent catalyst, and then entering a second regeneration zone to regenerate, and enabling at least part of regenerated second catalyst to return to the second riser to form a second cycle. The method can obviously improve the yield of the low-carbon olefins such as propylene and the like.
Description
Technical Field
The invention relates to the field of catalytic cracking of hydrocarbon raw materials, in particular to a multi-zone coupling control multistage catalytic cracking method and device based on the properties of the raw materials.
Background
In recent years, with the improvement of technology and capacity, the surplus trend of oil refining and supply capacity has been shown, taking our country as an example, the oil refining capacity reaches 8.4 hundred million tons in 2018, 6.1 hundred million tons of crude oil are processed, 3.64 hundred million tons of produced gasoline and diesel oil are total, the average operating load is 72.4%, 1.1 hundred million tons are expected to be surplus in 2020, and with the further strictness of environmental requirements, the rapid development of new energy represented by electric power, hydrogen energy, biological fuel and the like and the improvement of the fuel efficiency of automobiles and other motor vehicles, the demand acceleration of gasoline will gradually decrease. Meanwhile, the demand of global chemicals is increased by 4% every year and is higher than the GDP acceleration of 3% in the world, so that the transformation of the traditional fuel type refineries into chemical type refineries is urgent, and particularly, how to transform the fuel type products such as gasoline and the like into the comprehensive production of high value-added chemicals is realized, and the social benefit and the economic benefit are improved.
Still taking our country as an example, in order to promote scientific development and continuous progress of petrochemical industry, the ministry of industry and informatization made and published "development plans of petrochemical and chemical industries (2016-: in 2015-2020, the ethylene consumption in China is increased from 4030 ten thousand tons to 4800 ten thousand tons, the annual average growth rate of demand is 3.6%, the propylene consumption is increased from 3180 ten thousand tons to 4000 ten thousand tons, the annual average growth rate is 4.7%, the ethylene yield in 2018 in China is 1841 ten thousand tons, the import is 258 ten thousand tons, the import dependence is 12.3%, the propylene yield is 3035 ten thousand tons, the import is 28.4 ten thousand tons, and the import dependence is 8.6%. Therefore, the domestic demand gap for several low-carbon olefins such as ethylene, propylene and the like is huge, the constraint of olefin import is eliminated, the overall development of the industry is promoted, and the method has important significance for the national overall strategic requirements. The gasoline or other light oil products are reasonably converted into low-carbon olefin products, and the urgent problems of excess oil refining and olefin product shortage in China can be solved at the same time.
At present, on the technical level, light olefins mainly come from a heavy oil fraction cracking process, and the overall yield of propylene is significantly lower than that of ethylene. In the future global low-carbon olefin market, the growth rate of propylene demand is greater than that of ethylene, so that process exploration on how to produce propylene at high yield is more and more concerned, and the catalytic cracking process is also a main direction of research.
The research and development of a deep catalytic cracking process (DCC process) is a technology for preparing gas olefin by taking heavy oil as a raw material and utilizing shape-selective catalytic reaction, is considered to realize the extension of an oil refining process to petrochemical industry, and creates a new way for directly preparing low-carbon olefin by taking heavy oil as a raw material. Aiming at the characteristics of heavy oil, in order to produce propylene in maximum quantity, the process adopts a riser plus bed reactor type, combines harsh operating conditions and catalyst selection, and has the advantages that the content of propylene in the cracking product can reach 21 percent, but the yield of byproduct dry gas and coke is also higher.
Chinese patent application CN101045667A discloses a combined catalytic conversion method for high yield of low carbon olefins, in which a heavy oil raw material is contacted with a regenerated catalyst and a selected carbon deposition catalyst in a down tube reactor for pre-cracking, a cracked product generated by the down tube is rapidly separated from a catalyst to be generated, then low carbon olefins in the cracked product are separated, the rest products (insufficient cracked product) are further subjected to deep cracking reaction in a riser under a harsher condition, then oil gas is separated from the carbon deposition catalyst, the carbon deposition catalyst enters one or more devices of a pre-lifting section of the down tube reactor, a stripper connected with the down tube reactor and a regenerator after being stripped, and the catalyst to be generated and an optional carbon deposition catalyst generated by the down tube are returned to the down tube reactor and the riser reactor after being coked and regenerated. The method adopts heavy oil raw materials to produce low-carbon olefins, designs a catalytic cracking process aiming at the heavy oil raw materials, and achieves the purpose of improving the yield of low-carbon hydrocarbons such as propylene and the like by quickly separating low-carbon hydrocarbon products and carrying out secondary deep cracking on insufficiently cracked products.
Chinese patent application CN101074392A discloses a method for producing propylene and high-quality gasoline and diesel oil by two-stage catalytic cracking, which aims at heavy hydrocarbons or various animal and vegetable oil raw materials rich in hydrocarbon and achieves the purpose of producing both propylene and high-quality light oil products by two-stage riser catalytic process. According to the method, heavy raw oil is in contact reaction with a regenerated catalyst in a first section riser, and diesel oil, gasoline with high olefin content, gaseous products and circulating oil with good properties are obtained after products are separated; then, the circulating oil obtained by the reaction of the first section of riser and the gasoline fraction with high olefin content enter the second section of riser to contact and react with the regenerated catalyst from the regenerator, so that more propylene is obtained and the quality of gasoline is greatly improved, thereby achieving the purpose of producing light oil products such as propylene and high-quality gasoline and diesel oil. The method still aims at the cracking of heavy oil raw materials, and also aims at the production of light oil products such as diesel oil and the like and improving the quality of the light oil products, the conversion rate of the raw materials to propane is reduced, and the yield of dry gas and coke is higher.
Chinese patent application CN102690682A discloses a catalytic cracking method and a device for producing propylene, in the method, heavy raw materials (including heavy hydrocarbons or various animal and vegetable oil raw materials rich in hydrocarbons) and a first catalytic cracking catalyst which takes Y-type zeolite as a main active component are subjected to contact reaction in a first lifting pipe, oil gas after the reaction is separated from the catalyst, and the oil gas is introduced into a product separation system; the light hydrocarbon (comprising gasoline and/or C4 hydrocarbon generated in the first riser or gasoline fraction produced by other devices such as one or more of catalytic cracking crude gasoline, catalytic cracking stable gasoline, coking gasoline and visbreaking gasoline) and a second catalytic cracking catalyst which takes shape selective zeolite with the pore diameter less than 0.7nm as a main active component are in contact reaction in a second riser reactor, oil gas and catalyst after reaction are introduced into a fluidized bed reactor connected with the second riser reactor in series for reaction, and the oil gas is introduced into a product separation system; the oil gas products in the first riser and the fluidized bed reactor are collected and fractionated by a common pipeline leading-out device. The method enables the heavy raw material and the light raw material to be separately reacted, and can achieve the aim of producing propylene, but the yield of the propylene is not ideal, and the yield of coke and dry gas is high.
At present, most of the catalytic cracking researches focus on the catalytic cracking of heavy raw materials or light hydrocarbon raw materials such as gasoline and the like, but the cracking products are complex, the propylene selectivity is low, and the yield of byproducts such as dry gas and coke is high in the process of pursuing relatively high propylene selectivity, which is still a common problem which is difficult to span. On the other hand, the design of these catalytic cracking processes and systems is around the property of heavy oil raw materials, and there are few studies and reports on the processes and systems mainly feeding light hydrocarbon processing products or byproducts (light hydrocarbon oil products such as C4+, etc.) from various processes or production lines and realizing high-efficiency catalytic cracking; in addition, as the heavy oil feedstock processing and oil refining technology and the capacity are improved, there may be many cases in which the byproduct fraction output downstream may be, for example, a certain hydrocarbon as a main raw material or an incoming material with a large number of hydrocarbons with a specific carbon number, and how to design a more feasible process according to the composition and properties of the incoming material, and at the same time, the yield of the target olefins can be improved, which is also one direction for realizing the improvement of the capacity of the low carbon olefins.
Disclosure of Invention
The invention aims to solve the technical problem of providing a multi-zone coupling control multistage catalytic cracking method based on the properties of raw materials, which can crack different light hydrocarbon raw materials in a zone in the same system according to the hydrocarbon types, effectively improve the yield of low-carbon olefins such as propylene and the like, and simultaneously reduce the generation of byproducts such as coke, dry gas and the like.
The invention also provides a multi-region coupling control multistage catalytic cracking device, which can realize catalytic cracking of the light hydrocarbon raw material, has the advantages of simple structure, small occupied area and the like, and is beneficial to practical industrial application.
In one aspect of the present invention, a multi-zone coupling control multistage catalytic cracking method based on raw material properties is provided, wherein a light hydrocarbon raw material is adopted as a cracking raw material, the light hydrocarbon raw material comprises an alkane-rich raw material and an olefin-rich raw material, a reaction device comprising a first riser and a second riser and a regenerator internally provided with a first regeneration zone and a second regeneration zone which are independent of each other are adopted, and the method comprises:
enabling the alkane-rich raw material to enter a first lifting pipe to contact with an alkane cracking catalyst to generate a first cracking reaction, and performing gas-solid separation on a product of the first cracking reaction to respectively obtain a first oil-gas product and a first catalyst to be generated; allowing the first catalyst to be regenerated to enter a first regeneration area for regeneration after steam stripping to obtain a first regenerated catalyst; returning at least a portion of the first regenerated catalyst to the first riser to form a first cycle;
enabling the olefin-rich raw material to enter a second lifting pipe to contact with an olefin cracking catalyst to generate a second cracking reaction, and performing gas-solid separation on a product of the second cracking reaction to respectively obtain a second oil gas product and a second spent catalyst; allowing the second spent catalyst to enter a second regeneration zone for regeneration after steam stripping to obtain a second regenerated catalyst; returning at least a portion of the second regenerated catalyst to the second riser to form a second cycle;
and collecting the separated first oil gas product and the second oil gas product to obtain a cracking product.
According to the catalytic cracking method provided by the invention, the alkane-rich raw material and the olefin-rich raw material are subjected to zone reaction (respectively and independently subjected to reaction) according to the process flow, and the catalytic cracking reaction of different hydrocarbon type raw materials can be enhanced according to the chemical properties of the raw materials and the targeted regulation and control reaction conditions of a cracking reaction mechanism, so that the conversion rate of the raw materials and the yield of low-carbon olefins such as propylene are improved, the generation of byproducts such as dry gas and coke is reduced, and the energy consumption can be reduced; in addition, the regeneration and utilization of the catalyst to be regenerated can not only reduce the preparation cost of low-carbon olefins such as propylene, but also realize the adjustment of reaction parameters inside the riser by flexibly controlling the amount of the regenerated catalyst returned to the riser, such as reaction temperature, solvent-oil ratio and the like, thereby being beneficial to the light-weight process.
In the invention, the obtained cracking product can be further subjected to treatments such as fractionation and the like to obtain products such as dry gas, liquefied gas, gasoline, diesel oil, oil slurry and the like, and can also be further refined to obtain low-carbon olefin products such as propylene and the like.
The polarity of the olefin is greater than that of the alkane, so that the olefin is easier to crack compared with the alkane, the alkane is not easy to crack due to higher activation energy, and the cracking reaction conditions are regulated, so that the alkane-rich raw material and the olefin-rich raw material can be cracked under respective proper conditions, the retention time of intermediate products is reduced, and the aims of improving the yield of target products, reducing the generation of byproducts, reducing energy consumption and the like are favorably fulfilled. Specifically, according to the studies of the inventors, the reaction conditions of the above-mentioned first riser (conditions of the first cracking reaction) may be: the reaction temperature is 500-700 ℃, for example 600-700 ℃, the reaction pressure is 0.1-0.35MPa, for example 0.1-0.3MPa or 0.1-0.2MPa, the catalyst-oil ratio is 5-40, for example 20-30, the residence time is 0.2-4s, for example 1-3 s; the reaction conditions of the second riser (conditions of the second cracking reaction) may be: the reaction temperature is 480-650 ℃, such as 500-600 ℃, the reaction pressure is 0.1-0.4MPa, such as 0.1-0.3MPa or 0.1-0.2MPa, the catalyst-oil ratio is 3-30, such as 15-25, and the retention time is 0.3-6s, such as 1-3 s. In specific implementation, the reaction temperature of the first cracking reaction is generally higher than that of the second cracking reaction, the solvent-oil ratio of the first cracking reaction is greater than that of the second cracking reaction, and the residence time of the first cracking reaction is greater than that of the second cracking reaction.
In the specific implementation process of the invention, the paraffin-rich raw material and/or olefin-rich raw material can be preheated and then enter the riser to carry out cracking reaction, which is more beneficial to the generation and the implementation of the reaction, wherein the preheating temperature of the paraffin-rich raw material can be generally 100-250 ℃, and the preheating temperature of the olefin-rich raw material can be 100-300 ℃; and/or, the paraffin-rich raw material and the olefin-rich raw material can be respectively mixed with the atomized steam and then enter the corresponding lifting pipe, the atomized steam not only can be used as lifting gas to lift the paraffin-rich raw material and the olefin-rich raw material, but also can play a partial pressure role, so that a more appropriate cracking atmosphere can be maintained in the first lifting pipe and the second lifting pipe, and specifically, the mass ratio of the paraffin-rich raw material to the atomized steam can be generally 1: (0.1-3), and further may be 1: (0.1-1), and further may be 1: (0.1-0.8) or 1: (0.2-0.6) or 1: (0.2-0.4), and/or the mass ratio of olefin-rich feedstock to atomizing vapor may be 1: (0.1-3), and further may be 1: (0.1-1), and further may be 1: (0.1-0.8) or 1: (0.2-0.7) or 1: (0.3-0.5); the atomizing steam may be water steam or the like commonly used in the art, and the present invention is not particularly limited thereto.
Specifically, in an embodiment of the present invention, the catalytic cracking method can be implemented by using a reaction apparatus including a first riser and a second riser, a stripping apparatus having a first zone and a second zone independent of each other inside, a settler disposed at the upper part of the stripping apparatus and communicating with the first zone and the second zone, and a regenerator having a first regeneration zone and a second regeneration zone independent of each other inside, wherein the first riser, the first zone, and the first regeneration zone form a reaction-stripping-regeneration route for an independent cracking reaction of an alkane-rich feedstock, and the second riser, the second zone, and the second regeneration zone form another reaction-stripping-regeneration route for an independent cracking reaction of an olefin-rich feedstock. Specifically, in the catalytic cracking process, a product of a first cracking reaction enters a first partition, in the first partition, a first oil gas product (namely, an oil gas phase in the first partition) in the product ascends to enter a settler, is output from the settler after gas-solid separation, and a first catalyst to be generated (namely, a solid phase in the first partition) descends and enters a first regeneration area after being subjected to steam stripping treatment (in countercurrent contact with a stripping gas to strip out the oil gas product adsorbed on the surface of the first catalyst to be generated); and the product of the second cracking reaction enters a second subarea, in the second subarea, a second oil gas product (namely, an oil gas phase in the second subarea) in the product ascends to enter a settler, is output from the settler after gas-solid separation, and a second spent catalyst (namely, a solid phase in the second subarea) descends and enters a second regeneration area after steam stripping treatment.
In specific implementation, for example, the stripping device may be divided into a first partition and a second partition by using a structure such as a partition (the structure such as the partition is disposed at the middle position of the stripping device along the axial direction of the stripping device), and the partitioned stripping device may be connected to the settler by using a conventional assembly method in the art, so that both the first partition and the second partition are communicated with the settler, thereby separating oil and gas products in the first partition and the second partition. The stripping device may be a conventional stripper in the art or a reactor with a stripping function, and may be selected according to the requirement, and the lower portion thereof may be provided with a stripping gas inlet communicated with the first partition and the second partition, for example, for introducing a stripping gas to strip the spent catalyst in the first partition and the second partition.
In an embodiment of the present invention, the reaction apparatus may further include a fluidized bed reactor having a first reaction zone and a second reaction zone provided therein, the first reaction zone and the second reaction zone being independent of each other, and the method further includes: enabling the product of the first cracking reaction to enter a first reaction zone to carry out a third cracking reaction, and carrying out gas-solid separation on the product of the third cracking reaction to respectively obtain a first oil-gas product and a first catalyst to be generated; and enabling the product of the second cracking reaction to enter a second reaction zone to carry out a fourth cracking reaction, and carrying out gas-solid separation on the product of the fourth cracking reaction to respectively obtain a second oil gas product and a second spent catalyst.
Specifically, the stripping device may be a fluidized bed reactor (the lower portion of the fluidized bed reactor is provided with a stripping gas inlet communicated with the first reaction zone and the second reaction zone, for introducing a stripping gas to strip the spent catalyst in the first reaction zone and the second reaction zone), in which the first reaction zone (i.e., the first partition) and the second reaction zone (i.e., the second partition) are independent from each other, and the catalytic cracking process is further described by taking an independent cracking reaction of the alkane-rich feedstock as an example: the product of the first cracking reaction enters a first reaction zone to carry out further cracking reaction (namely, a third cracking reaction), a first oil gas product in the product of the third cracking reaction ascends to enter a settler and is output from the settler after gas-solid separation, and a first catalyst to be generated descends and enters a first regeneration zone after steam stripping treatment.
The catalytic cracking process adopts a matching cracking mode of two parallel risers and fluidized bed partition reaction, can further strengthen the cracking depth of the light hydrocarbon raw material, is particularly suitable for cracking the light hydrocarbon raw material which is difficult to crack, and effectively improves the yield of the low-carbon olefins such as propylene.
In the practice of the present invention, the reaction conditions of the fluidized bed reactor can be generally controlled as follows: the mass space velocity is 5-25h-1For example, it can be 15-25h-1The bed linear velocity is 0.1-0.5m/s, and the reaction temperature is 600-650 ℃. In specific operation, the reaction conditions of the fluidized bed reactor can be properly adjusted according to the composition of the alkane-rich raw material, the olefin-rich raw material or the cracked products of each riser. The condition is favorable for further coordinating the matching of the material flow and the energy flow of the whole cracking system, the stability of the system is improved, the overall energy efficiency is improved, and the industrial feasibility is realized.
Further, a portion of the first regenerated catalyst may also be returned to the first reaction zone to form a third cycle; and/or, returning a portion of the second regenerated catalyst to the second reaction zone to form a fourth cycle. In practice, for example, a regenerated catalyst delivery pipe from the first regeneration zone to the first reaction zone may be added, and/or a regenerated catalyst delivery pipe from the second regeneration zone to the second reaction zone may be added. Through the third cycle and the fourth cycle, the first regenerated catalyst and the second regenerated catalyst can be respectively provided for the first reaction zone and the second reaction zone, which is beneficial to further improving the cracking reaction efficiency.
The stripping gas used in the above process may be, for example, high-temperature steam or the like which is commonly used in the art, and the present invention is not particularly limited thereto, and the linear velocity of the stripping gas may be generally 0.1 to 0.8m/s, and may further be 0.2 to 0.7m/s, or 0.2 to 0.6m/s, or 0.3 to 0.5 m/s.
In the invention, less spent catalyst is mixed in the oil gas product and enters the settler, so that the first spent catalyst and the second spent catalyst are basically not mixed in the settler, namely the independent cracking reaction of the alkane-rich raw material and the alkene-rich raw material is not influenced.
In the above process, the oil gas product enters the settler and then stays in the settler for a certain time, and the oil gas product has a higher temperature during the time, so that secondary reaction (mainly thermal cracking reaction) of a considerable degree is easy to occur, and the yield of by-products such as dry gas and coke is increased. Specifically, by using the gas-solid rapid separation device, the dilute phase space volume of the settler is properly reduced, the oil-gas product and the spent catalyst can be rapidly separated, and the side reaction is inhibited. The gas-solid rapid separation component can be a common semicircular cap-shaped component, a T-shaped component or a primary cyclone separator and the like in the field, for example, in a specific embodiment, the gas-solid rapid separation component can be the primary cyclone separator, the distance between the outlet of a riser of the primary cyclone separator and the inlet of the cyclone separator at the top of the settler is shortened, the secondary reaction can be obviously reduced, the yield of oil and gas products is favorably improved, and the generation rate of coke and dry gas is reduced.
The spent catalyst enters a regeneration zone of a regenerator and is in countercurrent contact with regenerated gas, and a scorching exothermic reaction is carried out at high temperature to burn off carbon deposition on the spent catalyst, so that regeneration is realized. In the present invention, the regeneration conditions in the regenerator can generally be controlled as follows: the temperature is 600-850 ℃, such as 650-750 ℃, and the linear velocity of the regeneration gas is 0.5-20m/s, such as 0.5-15m/s, 0.5-10m/s, 0.5-5m/s, 0.5-1m/s, 0.7-1m/s, or 0.7-0.8 m/s. Wherein the regeneration gas may be an oxygen-containing gas having an oxygen content of 10 to 35 wt%, and further may be an oxygen-containing gas having an oxygen content of 15 to 25 wt%, and may be, for example, air or the like.
Specifically, for example, the dense-phase zone of the regenerator may be divided into a first regeneration zone and a second regeneration zone which are independent of each other by a partition or other structure, and the dilute-phase zone may not be partitioned (the first regeneration zone and the second regeneration zone are controlled to be communicated with the dilute-phase zone during partitioning, and specifically, the partition or other structure may be disposed at the middle position of the dense-phase zone along the axial direction of the dense-phase zone), so as to implement the partitioned regeneration.
If the coking amount on the surface of the spent catalyst is large, the carbon deposit on the surface of the spent catalyst can be combusted to generate enough heat to meet the regeneration of the spent catalyst, because the invention aims at light hydrocarbon raw materials, less coke is generated on the surface of the spent catalyst during cracking, and the heat generated by the combustion of the coke is not enough to provide the heat required by the regeneration of the spent catalyst, in order to ensure the high-efficiency regeneration of the spent catalyst, the heat can be supplemented to the regeneration process of the spent catalyst in a mode of increasing the coke amount on the surface of the spent catalyst or other combustion promoters, for example, the spent catalyst can be contacted with fuel capable of forming coke and can be subjected to pre-combustion treatment to achieve the purpose of increasing the coke amount. Specifically, in one embodiment of the present invention, at least a portion of the first catalyst to be regenerated may be contacted with fuel and subjected to a pre-combustion process before entering the first regeneration zone; and/or, enabling at least part of the second spent catalyst to contact with fuel, pre-burning the second spent catalyst, and then entering a second regeneration zone; the pre-combustion treatment can be carried out by adopting an outer heat compensator arranged outside the regenerator, and the pre-combustion conditions in the outer heat compensator are as follows: the temperature is 400-800 deg.C, such as 500-600 deg.C, the absolute pressure is 0.05-0.4MPa, such as 0.06-0.3MPa or 0.07-0.2MPa or 0.08-0.15MPa, and the oxygen content is 0.005-7 wt%, such as 0.1-1 wt%. In the process, the spent catalyst (first spent catalyst/second spent catalyst) is contacted with the fuel and is subjected to pre-combustion (insufficient combustion/incomplete combustion) in a low-oxygen environment, so that combustion improver (such as coke and the like) formed by pre-combustion of the fuel is attached to the spent catalyst, and after the combustion improver attached to the spent catalyst enters a regeneration zone, the combustion improver is contacted with regeneration gas (such as air and the like) to be completely combusted (heat release), heat required by a regeneration reaction is supplied in a supplementing manner (namely heat is supplemented to the regeneration process), and the regeneration efficiency is improved; meanwhile, the processing can also make the combustion improver such as coke on the surface of the spent catalyst more uniform, and avoid the problems of catalyst structure damage, inactivation and the like caused by overhigh local temperature due to the aggregation of local combustion improver such as coke, thereby improving the heat balance and the production capacity of the whole device (system). The external heat compensator is matched with the regenerator, the catalyst to be regenerated is subjected to pre-combustion and regeneration treatment, the operation is continuous, and the catalyst to be regenerated is subjected to mild and stable combustion and regeneration, so that the structure and the physicochemical properties of the catalyst can be well maintained, the efficient regeneration is realized, and the catalytic cracking reaction of the alkane-rich raw material and the alkene-rich raw material is favorably carried out.
Specifically, the spent catalyst (first spent catalyst/second spent catalyst) enters an external heat compensator through a pipeline to be subjected to the pre-combustion treatment and then enters a regeneration zone to be regenerated; the fuel can be CO combustion improver commonly used in the field (for example, Al is adopted)2O3Or SiO2-Al2O3A CO combustion improver which is a carrier on which a noble metal such as platinum or palladium is supported as an active component); the low oxygen-containing gas can be introduced into the external heat compensator to maintain the low oxygen environment with the oxygen content of 0.005-7 wt%, and the pre-combustion medium is provided, specifically, the linear velocity of the low oxygen-containing gas can be generally 0.3-0.5 m/s; the two external heat compensators may be adopted, wherein one external heat compensator performs pre-combustion treatment on the first catalyst to be generated, and the other external heat compensator performs pre-combustion treatment on the second catalyst to be generated, or one external heat compensator may be divided into two independent pre-combustion areas by a partition plate or other structures, wherein one pre-combustion area is used for performing pre-combustion treatment on the first catalyst to be generated, and the other pre-combustion area performs pre-combustion treatment on the second catalyst to be generated.
Furthermore, fuel can enter the external heat compensator through a fuel distributor arranged at the upper part of a spent catalyst inlet (a first spent catalyst inlet/a second spent catalyst inlet) of the external heat compensator, so that the fuel is favorably and uniformly distributed on the surface of the spent catalyst, and after pre-combustion treatment, the surface of the spent catalyst is more uniformly attached with a combustion improver, so that the subsequent regeneration reaction is favorably realized. In addition, a fluidizing medium can be introduced from the lower part or the bottom of the external heat compensator to fluidize materials such as a combustion improver and a spent catalyst in the external heat compensator, so that the flowability of the materials is improved, and the uniform adhesion of the combustion improver to the surface of the spent catalyst is facilitated; the fluidizing medium may be conventional steam, and the like, and the present invention is not particularly limited thereto.
During specific operation, control valves can be arranged on the conveying pipelines of the spent catalyst and the regenerated catalyst, so that the catalyst amount and the operation temperature in the regenerator and the external heat compensator are kept stable, and independent operation can be performed when necessary; in addition, the amount of the regenerated catalyst to be fed to each reactor (the first riser, the second riser, and the fluidized bed reactor) may be adjusted as necessary, so that the reaction parameters (for example, the reaction temperature, the oil-to-oil ratio, and the like) of the reactors such as the first riser and the second riser may be adjusted.
In the invention, the raw material composition of the alkane cracking catalyst comprises 20-50 wt% of modified molecular sieve, 1-50 wt% of matrix, 3-35 wt% of binder and 3-15 wt% of composite auxiliary agent; the modified molecular sieve is obtained by alkali treatment of a molecular sieve, then non-metal element modification and metal element modification, and hydrothermal treatment can be carried out between the two modifications; the non-metallic elements are selected from at least two non-metallic elements in IIIA group, VA group, VIA group and VIIA group of the periodic table; the metal elements are at least three elements selected from IIA group, IVB group, VB group, VIB group, VIIB group, VIII group and lanthanide series of the periodic table, and at least comprise one transition metal element except lanthanide series; the composite auxiliary agent comprises inorganic acid and cellulose.
Further, the nonmetal can be at least two selected from B, P, S, Cl and Br, optionally, the nonmetal elements at least include S, such as P and S; the metal element is selected from at least three of Mn, V, Fe, Nb, Cr, Mo, W, Mg, Ca and La, optionally, the metal element comprises at least one group IIA metal (e.g. Mg) and at least one lanthanide metal, such as Nb, Mn, Mg, La.
Further, the molecular sieve may include at least one of ZSM-5, SAPO34, Y molecular sieve, beta molecular sieve. The particle size and the silica-alumina ratio of the molecular sieve are in proper ranges, which is more favorable for providing proper acid centers and alkali centers as a carrier, thereby being more favorable for loading metal and nonmetal elements. In one possible embodiment, it is advantageous to select nanoscale molecular sieve particles, for example, molecular sieves having a particle size of about 500-3000nm, such as 1500-2000nm, and a silica to alumina ratio of 90-110, such as about 100. The molecular sieve raw material can be purchased commercially according to design requirements, or entrusted to production, and can also be synthesized by self.
In the molecular sieve modification process, the molecular sieve is subjected to alkali treatment to realize desilication and pore expansion, so that coking of catalyst orifices is avoided, and ammonium exchange treatment can be carried out after pore expansion to recover the acidity of the molecular sieve, but ammonium exchange is not necessary. The alkali solution used for carrying out the alkali treatment may be an alkali solution conventionally used in the art for this purpose, and is selected from, for example, one or two of sodium hydroxide solution, potassium hydroxide solution, aqueous ammonia and the like; the ammonium ion exchange reagent used may be one or two conventionally used in the art for this purpose, and is selected from, for example, ammonium nitrate, ammonium chloride and the like.
Specifically, the following operations may be employed: firstly, mixing a molecular sieve and 0.2-1.0mol/L alkaline solution according to the mass ratio of 1:4-8, exchanging for 1-5h at the temperature of 70-90 ℃, then washing the molecular sieve to be neutral, drying for 3-12h at the temperature of 60-150 ℃ and roasting for 2-6h at the temperature of 400-; mixing the molecular sieve treated by the alkaline solution with 0.5-1.2mol/L ammonium ion-containing solution (such as 1mol/L ammonium nitrate solution) according to the mass ratio of 1:4-10, exchanging at the temperature of 70-90 ℃ for 1-5h, washing to be neutral, then drying at the temperature of 60-150 ℃ for 3-12h, and roasting at the temperature of 400-600 ℃ for 2-6h to obtain the molecular sieve treated by the alkaline solution.
Subsequently, the molecular sieve treated by the alkali can be modified by adopting an impregnation mode through various non-metal elements and metal elements. In specific implementation, although the loading sites of the nonmetal elements and the metal elements are different, and there is no adsorption competition relationship between the nonmetal elements and the metal elements, due to solubility and other reasons, separate impregnation is generally selected, for example, the nonmetal elements may be impregnated first and then the metal elements may be impregnated, and synchronous impregnation or stepwise impregnation may be generally selected among a plurality of metal elements and among a plurality of nonmetal elements according to solubility.
The metal modification can be generally achieved by impregnating the molecular sieve with a salt solution of a metal element, and in the metal element impregnation modification, for some metal salts which are difficult to dissolve, the corresponding salt of the metal can be dissolved in a dispersing agent to increase the solubility of the metal salt, for example, the corresponding salt of the metal can be dissolved by using a dispersing agent (such as a citric acid and/or oxalic acid solution) with a total concentration of about 0.1 to 4mol/L to prepare an impregnation solution, and then the molecular sieve is subjected to the metal element impregnation modification. The selection of the dispersant with the concentration is beneficial to both the dispersing effect and the impregnating effect (the dispersing effect can not be achieved when the concentration of the dispersant is too low, and the impregnating effect can be influenced when the concentration of the dispersant is too high), and the performance of the catalyst is beneficial. Wherein, the mass ratio of the impregnating solution to the molecular sieve can be set according to the expected metal element loading.
In one embodiment of the present invention, the alkane cracking catalyst is loaded with about 0.05 to about 5 wt%, such as 0.1 to about 1 wt%, of each nonmetal element and/or about 0.1 to about 10 wt%, such as 0.2 to about 2 wt%, of each metal element, based on the mass of the catalyst.
When the nonmetal modification and the metal modification are carried out, the hydrothermal treatment is needed between the two types of modification regardless of the sequence so as to dredge the molecular sieve channel and facilitate the loading of the next type of modification element. The conditions of the hydrothermal treatment are not particularly limited, and the treatment is generally carried out in an environment at a temperature of less than 550 ℃.
In general, each impregnation is followed by aging, drying and calcination. The aging temperature after each impregnation is 0-50 deg.C, such as 20-40 deg.C, and the aging time is 2-20h, such as 4-12 h; drying at 50-160 deg.C, such as 70-120 deg.C for 2-20h, such as 3-12 h; the roasting temperature is 300-800 ℃, such as 400-600 ℃, and the roasting time is 1-10h, such as 2-6 h.
Under the composition system of the alkane cracking catalyst, a proper amount of matrix material can provide a dispersion environment for a carrier and active ingredients, increase the mechanical strength and carbon capacity of the catalyst, facilitate the prevention of coking and inactivation of the catalyst and prolong the service life of the catalyst; meanwhile, the required catalyst is finally obtained by utilizing the bonding effect of the binder. Specifically, the binder includes at least one of alumina sol, silica sol, sesbania powder, and the like; the matrix may comprise at least one of pseudoboehmite, kaolin, a group IVB metal oxide, such as titania and/or zirconia, which may increase the pore structure of the matrix, thereby extending the reaction path of the alkane-rich feedstock in the catalyst and allowing the catalyst to perform better.
According to the research of the invention, if the content of the composite additive is too low, the loss amount of the catalyst can be increased, but if the content of the composite additive is too high, the viscosity of the raw material is too high, and the raw material is not easy to form. Therefore, the present invention limits the content of the composite assistant, and the mass content of the composite assistant is 3 to 30 wt% (if the composite assistant comprises a plurality of components, the sum of the mass contents of all the components is 3 to 30 wt%), for example, 3 to 12 wt%, or 5 to 12 wt%, or 8 to 12 wt%, or 10 to 12 wt%.
In order to further ensure that the acid property of the alkane cracking catalyst is not easily changed and be beneficial to ensuring the pore structure and the mechanical property of the alkane cracking catalyst, the types and the contents of the inorganic acid and the cellulose in the composite auxiliary agent can be properly adjusted and selected within the set range, the mass fraction of the inorganic acid is preferably not more than 2 wt% based on the mass of the catalyst, and the inorganic acid can comprise common inorganic acids such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid and the like, and can be selected from one of the nitric acid and the hydrochloric acid under comprehensive consideration; the cellulose may be selected from one of methyl cellulose and ethyl cellulose, but is not limited thereto.
After the selection and modification treatment of the raw material components are finished, the preparation of the alkane cracking catalyst can be finished according to the conventional operation, the modified molecular sieve, the matrix, the binder and the composite auxiliary agent are mixed and pulped to obtain slurry with the solid content of about 20-50 wt%, generally, the catalyst microspheres with the particle size of about 20-200nm can be obtained by drying (such as spray drying) and forming, and then, the multi-step drying and roasting operation can be carried out, for example, the catalyst microspheres can be dried for 12-50h at about 20-50 ℃, dried for 12-50h at 100-200 ℃ and roasted for 1-12h at 500-700 ℃ in sequence to obtain the alkane cracking catalyst; in addition, hydrothermal aging treatment can be further carried out, for example, hydrothermal aging treatment is carried out at the temperature of 500-800 ℃, and the final alkane cracking catalyst product is obtained.
According to the research of the invention, the yield of propylene can be further improved by selecting the alkane cracking catalyst, and the molecular sieve is modified by utilizing a plurality of metal elements and nonmetal elements, so that the acid strength and the acid density of the molecular sieve carrier are controlled in a targeted manner, the alkane cracking catalyst has acid centers of different types such as super acid, strong acid, weak acid and the like, the adsorption capacity of olefin and alkane can be simultaneously improved, the cracking efficiency of hydrocarbon which is difficult to crack such as alkane and the like can be particularly improved, and the cracking method can achieve better yield of propylene while improving the conversion rate of raw materials. In addition, the synergistic effect of the specific composite auxiliary agent is introduced, so that the wear resistance of the catalyst is improved while the catalytic performance is ensured, and the service life of the catalyst is prolonged.
In the invention, the raw material composition of the olefin cracking catalyst comprises 20-50 wt% of modified composite molecular sieve, 1-50 wt% of matrix and 3-35 wt% of binder, wherein the modified composite molecular sieve is obtained by silanizing a composite molecular sieve formed by at least two molecular sieves, and then modifying by nonmetallic elements and metallic elements; the at least two molecular sieves can be selected from at least two of HZSM-5, USY molecular sieve, SAPO34 and beta molecular sieve, the matrix comprises at least one of pseudo-boehmite, kaolin, titanium dioxide and zirconia, and the binder comprises at least one of alumina sol, silica sol, sesbania powder and the like.
Specifically, the modified composite molecular sieve can be prepared according to the following processes: mixing the pretreated SAPO-34 molecular sieve, ZSM-5 molecular sieve, beta molecular sieve and USY molecular sieve according to the mass ratio of 0-30:50-80:0-30:0-50 to prepare the composite molecular sieve at least comprising two molecular sieves, wherein the pretreatment is used for expanding pores of the molecular sieves so as to be beneficial to subsequent nonmetal and metal modification and improve the performance of the catalyst, and specifically comprises the following steps: respectively treating a ZSM-5 molecular sieve, a beta molecular sieve and a USY molecular sieve by using alkali, and treating an SAPO-34 molecular sieve by using acid; wherein, the alkali treatment operation can adopt the conventional mode in the field, for example, alkali liquor with higher concentration (for example, common alkali liquor with 0.4mol/L-0.8 mol/L) with concentration of more than 0.4mol/L is used to desiliconize and expand the molecular sieve, then ammonium ion exchange is carried out to recover the acidity of the molecular sieve, and the specific process can refer to the alkali treatment process of the alkane cracking catalyst part, and is not described herein again; the acid treatment is generally carried out by using an acid solution having a concentration of 0.02mol/L to 0.1mol/L, and the acid used may be an inorganic acid such as nitric acid.
And then, drying and dehydrating the composite molecular sieve in an inert gas atmosphere, and then performing silanization treatment, wherein the dosage of a silanization reagent is 0.1-1.0mL/g of the composite molecular sieve. The silylating agent may be selected from compounds of the formula
Wherein R1 is selected from alkyl of C1-C3 or phenyl; r2 is selected from hydrogen, hydroxy, C1-C3 alkyl, C1-C3 alkoxy, or phenyl;
in the specific implementation, the silanization reagent is dissolved in an anhydrous nonpolar solvent in advance, and the composite molecular sieve is subjected to silanization treatment after high-temperature dehydration, wherein the silanization treatment temperature is 120 ℃ and 250 ℃, and the treatment time is 0.5-5 hours.
The modified composite molecular sieve can be obtained by sequentially modifying the composite molecular sieve subjected to silanization treatment by adopting a conventional method in the field such as an impregnation method and the like with a non-metal element and a metal element, and the specific modification process can be similar or identical to the non-metal modification and metal modification treatment process of the alkane cracking catalyst part, so that redundant description is omitted. Specifically, the non-metallic element may be selected from at least one of group va, group VIA and group IIA of the periodic table, and further may be selected from one or more of P, S, F and Cl, with an element loading of 0.01 to 3 wt% (based on the mass of the catalyst); the metal element can be selected from at least one of IA group, IIA group, IB group, VIB group, VIIB group, VIII group and lanthanide series of the periodic table, and further can be selected from one or more of Na, K, Mg, Ca, La, Ce, Cu, Ag, Ni, Co, Fe, Mn and Cr, and the element loading is 0.01-3 wt% (based on the mass of the catalyst).
After the selection and modification of the raw material components are completed, the preparation of the olefin cracking catalyst can be completed according to conventional operations, for example, the modified composite molecular sieve, the matrix and the binder can be mixed and pulped, and aged and roasted to obtain the olefin cracking catalyst, and the conditions of drying, roasting, hydrothermal aging and the like related to the preparation process can also refer to the preparation process of the alkane cracking catalyst, which is not described in detail herein. In the present invention, "wt%" represents a mass content unless otherwise specified.
In the invention, the alkane-rich raw material refers to a light hydrocarbon raw material with alkane as a main component, and the olefin-rich raw material refers to a light hydrocarbon raw material with olefin as a main component. In order to facilitate the yield of light olefins such as propylene, in one embodiment of the present invention, the alkane content in the alkane-rich raw material is generally not lower than 40 wt%, and further not lower than 50 wt%, or 60 wt%, or 70 wt%; the olefin content of the olefin-rich feedstock is generally not less than 30 wt%, and may further be not less than 40 wt%. Of course, the present invention is not limited to the above-mentioned limited range (for example, some light hydrocarbon raw materials with alkane content less than 40 wt% can be used as alkane-rich raw materials), but according to the research of the present invention, the yield of light olefins such as propylene can be increased within the above-mentioned limited range.
The light hydrocarbon raw material of the present invention may be fractions or oil products from different processes, and specifically may be a C4+ light hydrocarbon raw material (such as C4+ gasoline fraction, etc.), in some embodiments of the present invention, the light hydrocarbon raw material may be naphtha, catalytic pyrolysis gasoline, pressurized gas oil, a steam cracking byproduct C4 component or light pyrolysis gasoline, a FCC unit or a C4 component of a cracking unit, a methanol to olefins unit (MTO unit) byproduct C4+ olefin component, etc., and during a specific operation process, the light hydrocarbon raw material may be catalytically cracked as an alkane-rich raw material or an alkene-rich raw material according to the alkane and olefin contents therein; of course, C4-C10, C4-C8 or C4-C6 alkane such as heptane can be selected as the alkane-rich raw material, and C4-C10, C4-C8 or C4-C6 alkene can be selected as the alkene-rich raw material.
The riser (the first riser/the second riser) may be an equal linear velocity riser, a variable diameter riser, an equal diameter riser, etc., and a nozzle may be generally disposed at a material inlet (such as a raw material inlet, a fresh cracking catalyst inlet, a regenerated catalyst inlet, etc.) of the riser, so that the corresponding raw material, catalyst, etc. are sprayed into the riser through the nozzle, thereby facilitating a material mixing reaction; the nozzle may be a hollow cone nozzle, a solid cone nozzle, a square nozzle, a rectangular nozzle, an elliptical nozzle, a fan nozzle, a cylindrical flow (direct flow) nozzle, a two-fluid nozzle, a multi-fluid nozzle, etc., which are commonly used in the art. In addition, the acute included angle between the material inlet of each riser and the axis of each riser is 30-60 degrees, and the acute included angle can ensure that the materials entering the interior of the riser reactor are mixed more fully, thereby being more beneficial to cracking reaction.
In still another aspect of the present invention, there is provided a multi-zone coupling control multi-stage catalytic cracking apparatus, comprising: the device comprises a first riser, a second riser, a steam stripping device, a settler and a regenerator, wherein the steam stripping device is internally provided with a first subarea and a second subarea which are mutually independent; the lower part of the stripping device is provided with a stripping gas inlet communicated with the first partition and the second partition, a material outlet of the first lifting pipe is communicated with the material inlet of the first partition, a spent catalyst outlet of the first partition is communicated with a spent catalyst inlet of the first regeneration partition, a regenerated catalyst outlet of the first regeneration partition is communicated with a regenerated catalyst inlet of the first lifting pipe, a material outlet of the second lifting pipe is communicated with a material inlet of the second partition, a spent catalyst outlet of the second partition is communicated with a spent catalyst inlet of the second regeneration partition, and a regenerated catalyst outlet of the second regeneration partition is communicated with a regenerated catalyst inlet of the second lifting pipe.
In the catalytic cracking device provided by the invention, the first riser, the first reaction zone and the first regeneration zone form one path of reaction-stripping-regeneration route which can be used for the independent cracking reaction of the alkane-rich raw material, and the second riser, the second reaction zone and the second regeneration zone form the other path of reaction-stripping-regeneration route which can be used for the independent cracking reaction of the alkene-rich raw material.
Specifically, the stripping device may be a conventional stripper in the art or a reactor having a stripping function, and may be selected as needed. In specific implementation, for example, the stripping device may be divided into a first partition and a second partition by using a structure such as a partition (the structure such as the partition is disposed at the middle position of the stripping device along the axial direction of the stripping device), and the partitioned stripping device may be connected to the settler by using a conventional assembly method in the art, so that both the first partition and the second partition are communicated with the settler; the dense phase zone of the regenerator can be divided into a first regeneration zone and a second regeneration zone by a partition plate and other structures, and the partition plate and other structures are arranged in the middle of the dense phase zone along the axial direction of the dense phase zone, so that the first regeneration zone and the second regeneration zone are both communicated with the dilute phase zone of the regenerator.
Furthermore, an outer heat compensator is arranged outside the regenerator, a first pre-combustion area and a second pre-combustion area which are independent of each other are arranged inside the outer heat compensator, a spent catalyst outlet of the first sub-area is communicated with a spent catalyst inlet of the first regeneration area through the first pre-combustion area, and a spent catalyst outlet of the second sub-area is communicated with a spent catalyst inlet of the second regeneration area through the second pre-combustion area.
In the present invention, the above-mentioned apparatus can be assembled/modified by the conventional method in the art, and if not specifically mentioned, the structures/components/apparatuses, etc. can be communicated with each other by the structures such as pipes/tubes, etc. commonly used in the art.
The implementation of the invention has at least the following advantages:
the multi-region coupling control multistage catalytic cracking method based on the properties of the raw materials provided by the invention has the advantages that based on the characteristics and cracking principles of different types of hydrocarbons, the paraffin-rich raw materials and the olefin-rich raw materials are independently reacted in the two lifting pipes respectively, and the catalysts used in the two reactions are independently regenerated and circularly participate in respective cracking reactions by matching with the zoned regenerator, the reaction-regeneration process design aiming at the light hydrocarbon raw materials can achieve higher yield of low-carbon olefins such as propylene and the like, and simultaneously has lower yield of byproducts such as dry gas, coke and the like, and researches show that by adopting the catalytic cracking method, the yield of the propylene can reach more than 32 percent, the yield of the ethylene can reach more than 21 percent (the total yield of the two olefins reaches more than 53 percent), the yield of the coke is basically not higher than 0.1 percent, and the yield of the dry gas is basically; meanwhile, the method can adjust and control the respective reaction conditions of the two raw materials according to the hydrocarbon type, so that the two raw materials are cracked under respective proper conditions, thereby ensuring high target product yield and low byproduct yield and having lower energy consumption; in addition, the light hydrocarbon raw material can be from a byproduct of cracking processing of the heavy raw material, so that the catalytic cracking method can be used as a downstream treatment process of a cracking treatment product of the existing heavy raw material, high yield of low-carbon olefins such as propylene and the like is realized, and the utilization rate of the heavy raw material can be further improved.
The multi-region coupling control multistage catalytic cracking device provided by the invention can realize independent reaction of two different light hydrocarbon raw materials (such as the alkane-rich raw material and the olefin-rich raw material), namely two independent closed reaction-catalyst regeneration routes are formed, reaction conditions can be specifically regulated and controlled according to the properties of the hydrocarbon raw materials, and the device has the advantages of simple structure, small occupied area, easiness in operation and contribution to actual industrial application.
Drawings
FIG. 1 is a schematic view of a multi-zone coupled multi-stage catalytic cracking apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic view of a multi-zone coupled multi-stage catalytic cracking unit according to another embodiment of the present invention;
FIG. 3 is a schematic view of a multi-zone coupled multi-stage catalytic cracking apparatus according to still another embodiment of the present invention;
description of reference numerals:
1. a first riser; 2. a second riser; 3. a fluidized bed reactor; 31. a first reaction zone; 32. a second reaction zone; 3', a stripper; 31', a first stripping zone; 32', a second stripping zone; 4. a settler; 5. a regenerator; 51. a first regeneration zone; 52. a second regeneration zone; 6. an external heat compensator; a1, paraffin-rich feedstock; a2, olefin-rich feedstock; b1, product of the first cleavage reaction; b2, product of the second cleavage reaction; c1, a first oil and gas product; c2, a second oil and gas product; d1, a first catalyst to be regenerated; d2, a second spent catalyst; e1, first regenerated catalyst; e2, second regenerated catalyst; f. stripping gas; g. a cleavage product; h. regenerating gas; i. flue gas.
Detailed Description
The present invention will be described in more detail with reference to examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
Example 1
FIG. 1 is a schematic diagram of a multi-zone coupled multi-stage catalytic cracking apparatus according to an embodiment of the present invention, the apparatus comprising: a first riser 1, a second riser 2, a stripper 3 'provided with a first stripping zone (i.e. a first subarea) 31' and a second stripping zone (i.e. a second subarea) 32 'inside which are independent from each other, a settler 4 arranged at the upper part of the stripper 3' and communicated with the first stripping zone 31 'and the second stripping zone 32', and a regenerator 5 provided with a first regeneration zone 51 and a second regeneration zone 52 inside which are independent from each other; the first riser 1, the first stripping zone 31 'and the first regeneration zone 51 form one path of reaction-stripping-regeneration route for the independent cracking reaction of the alkane-rich raw material, and the second riser 2, the second stripping zone 32' and the second regeneration zone 52 form the other path of reaction-stripping-regeneration route for the independent cracking reaction of the alkane-rich raw material.
Specifically, the bottom of the stripper is provided with a stripping gas inlet communicated with the first stripping zone 31 'and the second stripping zone 32' for introducing a stripping gas f to strip the spent catalyst in the first stripping zone 31 'and the second stripping zone 32'.
The dense phase zone of the regenerator 5 is divided into the first regeneration zone 51 and the second regeneration zone 52 by a partition, and the partition is arranged at the middle position of the dense phase zone along the axial direction of the dense phase zone, so that the first regeneration zone 51 and the second regeneration zone 52 are both communicated with the dilute phase zone at the upper part of the regenerator 5; the bottom of the dense phase zone of the regenerator is provided with a regeneration gas inlet communicated with the first regeneration zone 51 and the second regeneration zone 52 and used for introducing regeneration gas h into the first regeneration zone 51 and the second regeneration zone 52, and the top of the dilute phase zone of the regenerator is provided with a flue gas outlet used for discharging flue gas i generated in the regenerator.
An outer heat compensator 6 is arranged outside the regenerator 5, a first pre-combustion area and a second pre-combustion area which are independent from each other are arranged inside the outer heat compensator 6, a spent catalyst outlet of the first stripping area 31 'is communicated with a spent catalyst inlet of the first regeneration area 51 through the first pre-combustion area, and a spent catalyst outlet of the second stripping area 32' is communicated with a spent catalyst inlet of the second regeneration area 52 through the second pre-combustion area; and fuel distributors are arranged above the spent catalyst inlet of the first pre-combustion zone and above the spent catalyst inlet of the second pre-combustion zone.
The multi-zone coupling control multi-stage catalytic cracking method based on the raw material property by using the catalytic cracking device of the embodiment is briefly described as follows:
mixing preheated (or not preheated) alkane-rich raw material a1 with first atomized steam (steam) according to a certain mass ratio, then enabling the mixture to enter a first riser 1 with an alkane cracking catalyst to carry out a first cracking reaction, enabling a product b1 of the first cracking reaction to enter a first stripping zone 31 ', enabling a first oil-gas product c1 in the product to go upwards and enter a settler 4 in the first stripping zone 31', outputting the product from the settler 4 after gas-solid separation, enabling a first catalyst d1 to go downwards and enter a first regeneration zone 51 for regeneration after steam stripping treatment, and obtaining a first regenerated catalyst e 1; returning the first regenerated catalyst e1 to the first riser 1 to participate in the first cracking reaction, forming a first cycle;
mixing a preheated (or not preheated) olefin-rich raw material a2 with second atomized steam (steam) according to a certain proportion, then enabling the mixture to enter a second riser 2 with an olefin cracking catalyst to generate a second cracking reaction, enabling a product b2 of the second cracking reaction to enter a second stripping zone 32 ', enabling a second oil gas product c2 in the product to ascend into a settler 4 in the second stripping zone 32', outputting the product from the settler 4 after gas-solid separation, enabling a second spent catalyst d2 to descend, performing steam stripping treatment, and then enabling the product to enter a second regeneration zone 52 for regeneration to obtain a second regenerated catalyst e 2; the second regenerated catalyst e2 is returned to the second riser 2 to participate in the second cracking reaction, forming a second cycle.
The method can realize the zoned cracking of the alkane-rich raw material and the alkene-rich raw material and the zoned regeneration treatment of the first spent catalyst and the second spent catalyst, and the direct implementation of the burning may be difficult to meet the regeneration of the catalysts in consideration of the small coking content on the surfaces of the catalysts in the cracking process, and the spent catalysts from two circulations (namely the first spent catalyst and the second spent catalyst) can be completely or partially respectively sent into the first pre-combustion area and the second pre-combustion area of the external heat compensator 6, contacted with the fuel introduced through the fuel distributor and subjected to the pre-combustion treatment (coke and other combustion promoters are attached to the surfaces of the spent catalysts) and then enter the corresponding regeneration areas for regeneration.
The first oil gas product and the second oil gas product obtained by gas-solid separation are converged and output from the top of the settler 4 to become a cracking product g.
The obtained cracked product can be introduced into a product separation device (not shown) for further treatment such as fractionation and the like to obtain products such as dry gas, liquefied gas, gasoline, diesel oil, oil slurry and the like, and can also be further refined to obtain low-carbon olefin products such as propylene and the like.
Example 2
FIG. 2 is a schematic diagram of a multi-zone coupling control multi-stage catalytic cracking unit according to an embodiment of the present invention, which is different from the catalytic cracking unit shown in FIG. 1 in that: in this embodiment, the stripper 3' is replaced by a fluidized bed reactor 3 having a first reaction zone (i.e., a first partition) 31 and a second reaction zone (i.e., a second partition) 32, which are independent of each other, and the lower portion of the fluidized bed reactor 3 is provided with a stripping gas inlet communicated with the first reaction zone 31 and the second reaction zone 32, for introducing a stripping gas f to strip the spent catalyst in the first reaction zone 31 and the second reaction zone 32; the first riser 1, the first reaction zone 31 and the first regeneration zone 51 form a path of reaction-stripping-regeneration for the independent cracking reaction of the alkane-rich raw material, and the second riser 2, the second reaction zone 32 and the second regeneration zone 52 form another path of reaction-stripping-regeneration for the independent cracking reaction of the alkene-rich raw material.
The multi-zone coupling control multi-stage catalytic cracking method based on the raw material property using the catalytic cracking unit of this embodiment is different from that of example 1 in that:
the product b1 of the first cracking reaction enters the first reaction zone 31 to carry out a third cracking reaction, a first oil gas product c1 in the third cracking reaction product ascends to enter the settler 4, is output from the settler 4 after gas-solid separation, and a first catalyst d1 to be regenerated descends and enters the first regeneration zone 51 for regeneration after being subjected to steam stripping treatment;
the product b2 of the second cracking reaction enters the second reaction zone 32 to carry out a fourth cracking reaction, a second oil gas product c2 in the fourth cracking reaction product ascends to enter the settler 4, is output from the settler 4 after gas-solid separation, and a second spent catalyst d2 descends and enters the second regeneration zone 52 for regeneration after steam stripping treatment.
Example 3
FIG. 3 is a schematic diagram of a multi-zone coupling control multi-stage catalytic cracking unit according to an embodiment of the present invention, which is different from the catalytic cracking unit shown in FIG. 2 in that: in this embodiment, the regenerated catalyst outlet of the first regeneration zone 51 is also in communication with the first reaction zone 31, and the regenerated catalyst outlet of the second regeneration zone 52 is also in communication with the second reaction zone 32.
The multi-zone coupling control multi-stage catalytic cracking method based on the raw material property using the catalytic cracking unit of this embodiment is different from that of example 2 in that:
returning a portion of the first regenerated catalyst e1 to the first riser 1 to participate in the first cracking reaction, forming a first cycle; returning a portion of the first regenerated catalyst e1 to the first reaction zone 31 for participation in a third cracking reaction, forming a third cycle;
returning a part of the second regenerated catalyst e2 to the second riser 2 to participate in the second cracking reaction, so as to form a second cycle; a portion of the second regenerated catalyst e2 is returned to the second reaction zone 32 for participation in the fourth cracking reaction, forming a fourth cycle.
In the relevant experiments/comparative experiments of the following application examples, the compositions of the alkane cracking catalysts used and the methods for their preparation were, unless otherwise specified, as follows:
1. preparation of ZSM-5
Firstly, ethyl orthosilicate, sodium aluminate, tetrapropylammonium hydroxide, ammonia water and water are mixed according to 100SiO2:1Al2O3:20TPABr:120NH3·H2O:2000H2Mixing the molar ratio of O, crystallizing at 80 ℃ for 12h, crystallizing at 180 ℃ for 48h to obtain ZSM-5 with the grain size of 500-3000nm and the molar ratio of silicon to aluminum of 100, washing, filtering, drying at 120 ℃ for 12h, and roasting at 600 ℃ for 10h to obtain the molecular sieve ZSM-5.
2. Alkali treatment of catalyst supports
Mixing the molecular sieve ZSM-5 with 0.4mol/L NaOH solution according to the mass ratio of 1:6, then exchanging for 2h at the temperature of 90 ℃, then washing the mixture to be neutral, then drying for 12h at the temperature of 120 ℃ and roasting for 2h at the temperature of 540 ℃.
Mixing a ZSM-5 molecular sieve with 1mol/L ammonium nitrate solution according to the mass ratio of 1:10, then carrying out ammonium exchange for 4h at the temperature of 90 ℃, then washing the mixture to be neutral, then drying the mixture for 12h at the temperature of 120 ℃ and roasting the mixture for 2h at the temperature of 540 ℃ in sequence to obtain the catalyst carrier HZSM-5.
3. Modification of non-metallic elements
According to alkali-treated HZSM-5 with NH4H2PO4And (NH)4)2SO4The mixed solution is dipped with P and S on HZSM-5 with the mass ratio of 0.5:1 to obtain the load of P of 0.8 wt% and the load of S of 0.5 wt%, and then the mixture is aged for 6h at room temperature, dried for 12h at the temperature of 120 ℃ and roasted for 4h at the temperature of 540 ℃.
4. Hydrothermal treatment
Carrying out hydrothermal treatment on the nonmetal element impregnated and modified HZSM-5 for 4h at the temperature of 550 ℃ in a steam atmosphere.
5. Modification of metallic elements
5.1 impregnation of Nb
Firstly (NH)4)3[NbO(C2O4)]Heating the aqueous solution to 60 ℃ to dissolve the aqueous solution, then soaking the HZSM-5 subjected to the hydrothermal treatment according to the mass ratio of 1:0.4 to obtain the Nb loading of 0.2 wt%, aging at room temperature for 6h, drying at 120 ℃ for 12h, and roasting at 540 ℃ for 4 h.
5.2 impregnation of Mn, Mg and La
Mixing MnCl2、MgCl2And La (NO)3)3Adding the mixture into a 4mol/L citric acid solution, soaking Mn, Mg and La on Nb-loaded HZSM-5 according to the mass ratio of citric acid to HZSM-5 of 0.3:1 to obtain the load of Mn of 1.8 wt%, the load of Mg of 1.5 wt% and the load of La of 0.5 wt%, and then sequentially aging at room temperature for 6h, drying at 120 ℃ for 12h and roasting at 540 ℃ for 4h to obtain the modified HZSM-5.
6. Preparation of alkane cracking catalyst
Mixing modified HZSM-5, a matrix (comprising kaolin, pseudo-boehmite and ZrO in a mass ratio of 7:3: 1), silica sol, sesbania powder, methyl cellulose and nitric acid according to the mass fractions of 40%, 30%, 15%, 4%, 10% and 1%, adding water to prepare slurry with the solid content of 35 wt%, spray-drying and forming to obtain catalyst microspheres with the particle size of 20-200nm, roasting at 600 ℃ for 4 hours, and performing hydrothermal aging treatment at 650 ℃ in a steam atmosphere for 8 hours to obtain the alkane cracking catalyst.
In the relevant experiments/comparative experiments in the following application examples, the olefin cracking catalysts used had the following composition and their preparation, unless otherwise specified:
1. pretreatment of
(1) Alkali treatment of HZSM-5 molecular sieve and USY molecular sieve
Mixing HZSM-5 molecular sieve (with the particle size of 0.5-2 mu m and the silica-alumina ratio of 25) and 0.5mol/L NaOH solution according to the mass ratio of 1:6, then exchanging for 2h at the temperature of 80 ℃, then washing the mixture to be neutral, then drying for 12h at the temperature of 110 ℃ and roasting for 2h at the temperature of 550 ℃.
Mixing the roasted ZSM-5 molecular sieve with 0.1M ammonium nitrate solution according to the mass ratio of 1:6, then carrying out ammonium exchange at the temperature of 80 ℃ for 2h, and then washing the mixture to be neutral; and performing ammonium exchange again in the same operation, and drying at 120 ℃ for 12h (without roasting) after the ammonium exchange twice to obtain the alkali-treated HZSM-5 molecular sieve.
And (3) carrying out alkali treatment on the USY molecular sieve according to the method to obtain the alkali-treated USY molecular sieve (the granularity is micron and the silica-alumina ratio is 5).
(2) Acid-treated SAPO-34 molecular sieves
SAPO-34 molecular sieve (with micron-sized particle size) and 0.05mol/L HNO3The solution is prepared by mixing the following components in a mass ratio of 1:6, mixing, maintaining at about 80 ℃ for about 2 hours, washing to be neutral, drying at 110 ℃ for 2 hours, and roasting at 550 ℃ for 4 hours to obtain the SAPO-34 molecular sieve subjected to acid treatment.
2. Preparation of composite molecular sieves
Mixing the HZSM-5 molecular sieve subjected to alkali treatment, the USY molecular sieve subjected to alkali treatment and the SAPO-34 molecular sieve subjected to acid treatment in a ratio of 5:2:1 to obtain the HZSM-5/USY/SAPO-34 composite molecular sieve.
3. Composite molecular sieve for silanization treatment
And (3) filling the composite molecular sieve obtained in the step (2) into a reaction tube for olefin cracking, introducing nitrogen at 350 ℃ at a volume flow of 1L/min, purging for 1 hour, and performing high-temperature dehydration and drying on the composite molecular sieve.
And (3) cooling the dehydrated composite molecular sieve to 200 ℃, and pumping methyldiethoxysilane into a composite molecular sieve bed layer under the nitrogen flow of 300 mL/min: cyclohexane volume ratio 1: 50 of silanization reagent, wherein the pump flow rate is 0.1mL/min, and the adding amount of silanization reagent is 0.5mL of methyldiethoxysilane/g of composite molecular sieve.
After the feeding is finished, the silanization reaction is kept for 2 hours, then the temperature of the system is continuously increased to 400 ℃, nitrogen is continuously introduced, the flow rate of the nitrogen is 1L/min, and the high-temperature purging is carried out for 1 hour.
System for filtering and recovering cyclohexane solvent after silanization treatmentPlacing the composite molecular sieve in a muffle furnace to be roasted for 4 hours at 540 ℃, and setting the programmed temperature rise to 4 ℃/min; adding 0.05mol/L HNO into the roasted composite molecular sieve3The solution was acid-washed and maintained at 80 ℃ for 2 hours (in order to wash away silicon oxide and prevent pore blocking), to obtain a silanized composite molecular sieve.
4. Modified composite molecular sieve
(4.1) nonmetallic element modified composite molecular sieve
And (3) carrying out equal-volume impregnation on the silanized composite molecular sieve obtained in the step (3) by using a diammonium hydrogen phosphate solution at room temperature for about 1 hour, wherein the load of P is 1%, aging at room temperature for 12 hours after the impregnation is finished, then placing the composite molecular sieve in a drying oven for drying at 120 ℃ for 12 hours, then placing the composite molecular sieve in a muffle furnace for roasting at 540 ℃ for 4 hours, and cooling to obtain the non-metal element modified composite molecular sieve.
(4.2) Metal element modified composite molecular sieve
And (4) adding the nonmetal element modified composite molecular sieve obtained in the step (4.1) into a lanthanum nitrate solution, and soaking for about 1 hour at room temperature in an equal volume mode, wherein the loading amount of La is 1%, so as to obtain a soaking mixture. After the impregnation is finished, the aging is continued for 12 hours at room temperature, then the mixture is placed in an oven to be dried for 12 hours at 120 ℃, and then the mixture is placed in a muffle furnace to be roasted for 4 hours at 540 ℃, and the mixture is cooled to obtain the metal element modified composite molecular sieve (namely the modified composite molecular sieve).
5. Preparation of olefin cracking catalyst
And (3) mixing and pulping the modified composite molecular sieve obtained in the step (4) with kaolin, pseudo-boehmite, titanium dioxide, alumina sol and sesbania powder according to the dry basis mass ratio of 40:30:10:5:14:1, and stirring for 4 hours by adopting an electric mechanical stirrer to obtain a uniform mixture containing the modified composite molecular sieve, the matrix and the binder.
The uniform mixture is aged for 12 hours at room temperature, and then dried for 12 hours at 120 ℃ and roasted for 4 hours at 540 ℃. And then carrying out hydrothermal aging on the calcined catalyst for 6h at the temperature of 600 ℃ in the atmosphere of 100% of water vapor to obtain the olefin cracking catalyst.
Application examples
Wherein:
in comparative experiment 1, a1 and a2 are mixed according to the mass ratio of 1:1, so that 50 percent of mixed raw materials are fed from a first lifting pipe and 50 percent of mixed raw materials are fed from a second lifting pipe, and the rest conditions are the same as those in experiment 2;
in comparative experiment 2, the temperature of the first cracking reaction was 730 ℃, the temperature of the second cracking reaction was 680 ℃, and the rest conditions were the same as those in experiment 2;
in comparative experiment 3, the temperature of the first cracking reaction was 470 ℃, the temperature of the second cracking reaction was 450 ℃, and the rest conditions were the same as those in experiment 2;
in comparative experiment 4, the temperature of the first cracking reaction was 730 ℃, the temperature of the second cracking reaction was 680 ℃, and the rest conditions were the same as those in experiment 3;
in comparative experiment 5, the temperature of the first cleavage reaction was 470 deg.C, the temperature of the second cleavage reaction was 450 deg.C, and the remaining conditions were the same as those in experiment 3.
TABLE 1 composition of alkane rich feed a1
TABLE 2 composition of olefin-rich feedstock b1
TABLE 3 EXPERIMENTAL 1-3 CATALYTIC CRACKING CONDITIONS
TABLE 4 test results of tests 1-3 and comparative tests 1-5
Claims (10)
1. A multi-zone coupling control multistage catalytic cracking method based on raw material properties is characterized in that a light hydrocarbon raw material is used as a cracking raw material, the light hydrocarbon raw material comprises an alkane-rich raw material and an olefin-rich raw material, a reaction device comprising a first riser and a second riser and a regenerator internally provided with a first regeneration zone and a second regeneration zone which are independent of each other are adopted, and the method comprises the following steps:
enabling the alkane-rich raw material to enter a first lifting pipe to contact with an alkane cracking catalyst to generate a first cracking reaction, and performing gas-solid separation on a product of the first cracking reaction to respectively obtain a first oil-gas product and a first catalyst to be generated; allowing the first catalyst to be regenerated to enter a first regeneration area for regeneration after steam stripping to obtain a first regenerated catalyst; returning at least a portion of the first regenerated catalyst to the first riser to form a first cycle;
enabling the olefin-rich raw material to enter a second lifting pipe to contact with an olefin cracking catalyst to generate a second cracking reaction, and performing gas-solid separation on a product of the second cracking reaction to respectively obtain a second oil gas product and a second spent catalyst; allowing the second spent catalyst to enter a second regeneration zone for regeneration after steam stripping to obtain a second regenerated catalyst; returning at least a portion of the second regenerated catalyst to the second riser to form a second cycle;
and collecting the separated first oil gas product and the second oil gas product to obtain a cracking product.
2. The catalytic cracking process of claim 1, wherein the reaction conditions of the first riser are: the reaction temperature is 500-; the reaction conditions of the second riser are as follows: the reaction temperature is 480 ℃ and 650 ℃, the reaction pressure is 0.1-0.4MPa, the catalyst-oil ratio is 3-30, and the retention time is 0.3-6 s.
3. The catalytic cracking method according to claim 1 or 2, wherein the reaction apparatus further comprises a fluidized-bed reactor in which a first reaction zone and a second reaction zone are provided independently of each other, the method further comprising:
enabling the product of the first cracking reaction to enter the first reaction zone to carry out a third cracking reaction, and carrying out gas-solid separation on the product of the third cracking reaction to respectively obtain the first oil-gas product and a first catalyst to be generated;
and enabling the product of the second cracking reaction to enter the second reaction zone to carry out a fourth cracking reaction, and carrying out gas-solid separation on the product of the fourth cracking reaction to respectively obtain the second oil gas product and a second spent catalyst.
4. The catalytic cracking process of claim 3, wherein the reaction conditions of the fluidized bed reactor are: the mass space velocity is 5-25h-1The bed linear velocity is 0.1-0.5m/s, and the reaction temperature is 600-650 ℃.
5. A catalytic cracking process according to claim 3 or 4, characterized in that part of the first regenerated catalyst is returned to the first reaction zone to form a third cycle; and/or, returning a portion of the second regenerated catalyst to the second reaction zone to form a fourth cycle.
6. The catalytic cracking method of claim 1 or 2, wherein the raw material composition of the alkane cracking catalyst comprises 20-50 wt% of the modified molecular sieve, 1-50 wt% of the matrix, 3-35 wt% of the binder and 3-15 wt% of the composite auxiliary agent; wherein,
the modified molecular sieve is obtained by carrying out alkali treatment on the molecular sieve and then carrying out non-metal element modification and metal element modification treatment on the molecular sieve;
the non-metallic elements are selected from at least two non-metallic elements in IIIA group, VA group, VIA group and VIIA group of the periodic table;
the metal elements are at least three elements selected from IIA group, IVB group, VB group, VIB group, VIIB group, VIII group and lanthanide series of the periodic table, and at least comprise one transition metal element except lanthanide series;
the composite auxiliary agent comprises inorganic acid and cellulose.
7. The catalytic cracking process of claim 1 or 6, wherein the olefin cracking catalyst has a feedstock composition comprising 20 to 50 wt% of the modified composite molecular sieve, 1 to 50 wt% of the matrix, and 3 to 35 wt% of the binder; the modified composite molecular sieve is obtained by silanizing a composite molecular sieve formed by at least two molecular sieves, and then modifying by using non-metallic elements and metallic elements; the at least two molecular sieves are selected from at least two of HZSM-5, USY molecular sieve, SAPO34 and beta molecular sieve.
8. A catalytic cracking process according to claim 1, characterized in that the regeneration conditions in the regenerator are: the temperature is 600 ℃ and 850 ℃, and the linear velocity of the regeneration gas is 0.5-30 m/s. Preferably, the regeneration gas is an oxygen-containing gas having an oxygen content of from 10 to 35 wt.%.
9. The catalytic cracking process of claim 1 or 8, wherein at least a part of the first catalyst to be regenerated is brought into contact with the fuel and subjected to a pre-combustion treatment before entering the first regeneration zone; and/or, enabling at least part of the second spent catalyst to contact with fuel, pre-burning the second spent catalyst, and then entering a second regeneration zone; wherein, the pre-combustion treatment is carried out by an outer heat compensator arranged outside the regenerator, and the pre-combustion conditions in the outer heat compensator are as follows: the temperature is 400 ℃ and 800 ℃, the absolute pressure is 0.05-0.4MPa, and the oxygen content is 0.005-7 wt%.
10. A multi-zone coupled control multi-stage catalytic cracking unit, comprising: the device comprises a first riser, a second riser, a steam stripping device, a settler and a regenerator, wherein the steam stripping device is internally provided with a first subarea and a second subarea which are mutually independent; the lower part of the stripping device is provided with a stripping gas inlet communicated with a first partition and a second partition, a material outlet of the first lifting pipe is communicated with the material inlet of the first partition, a spent catalyst outlet of the first partition is communicated with a spent catalyst inlet of the first regeneration partition, a regenerated catalyst outlet of the first regeneration partition is communicated with a regenerated catalyst inlet of the first lifting pipe, a material outlet of the second lifting pipe is communicated with a material inlet of the second partition, a spent catalyst outlet of the second partition is communicated with a spent catalyst inlet of the second regeneration partition, and a regenerated catalyst outlet of the second regeneration partition is communicated with a regenerated catalyst inlet of the second lifting pipe.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011130960.1A CN112322334A (en) | 2020-10-21 | 2020-10-21 | Multi-zone coupling control multistage catalytic cracking method and device based on raw material properties |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011130960.1A CN112322334A (en) | 2020-10-21 | 2020-10-21 | Multi-zone coupling control multistage catalytic cracking method and device based on raw material properties |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112322334A true CN112322334A (en) | 2021-02-05 |
Family
ID=74310804
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011130960.1A Pending CN112322334A (en) | 2020-10-21 | 2020-10-21 | Multi-zone coupling control multistage catalytic cracking method and device based on raw material properties |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112322334A (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1915516A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalytic cracking fluid bed catalyst containing molecular sieve |
US20120296146A1 (en) * | 2008-12-22 | 2012-11-22 | Uop Llc | Fluid catalytic cracking process |
CN107971010A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons |
CN109705905A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of method and apparatus of low-carbon olefines high-output |
CN111482199A (en) * | 2020-04-26 | 2020-08-04 | 中国石油大学(北京) | Olefin cracking catalyst, preparation method thereof and olefin cracking method |
-
2020
- 2020-10-21 CN CN202011130960.1A patent/CN112322334A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1915516A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalytic cracking fluid bed catalyst containing molecular sieve |
US20120296146A1 (en) * | 2008-12-22 | 2012-11-22 | Uop Llc | Fluid catalytic cracking process |
CN107971010A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons |
CN109705905A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of method and apparatus of low-carbon olefines high-output |
CN111482199A (en) * | 2020-04-26 | 2020-08-04 | 中国石油大学(北京) | Olefin cracking catalyst, preparation method thereof and olefin cracking method |
Non-Patent Citations (6)
Title |
---|
中国化工学会石油化工学会组织: "《有机化工原理大全 第1卷》", 31 December 1989, 化学工业出版社 * |
何杰等: "《工业催化》", 31 August 2014, 中国矿业大学出版社 * |
刘建周: "《工业催化工程》", 30 June 2018, 中国矿业大学出版社有限责任公司 * |
张德义: "《含硫原油加工技术》", 30 July 2003, 中国石化出版社 * |
张继光: "《催化剂制备过程技术》", 30 June 2004, 中国石化出版社 * |
李春年: "《渣油加工工艺》", 30 April 2002, 中国石化出版社 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111482199B (en) | Olefin cracking catalyst, preparation method thereof and olefin cracking method | |
CN102531821B (en) | Method for catalyzing catalytic cracking reaction of methanol coupled with naphtha using modified ZSM-5 molecular sieve based catalyst | |
TWI647011B (en) | Phosphorus-containing fcc catalyst | |
JP7386226B2 (en) | Hydrocarbon oil catalytic cracking method, reactor and system | |
US20110266197A1 (en) | Method of production of light olefins in catalytic cracking units with energy deficiency | |
CN102816583B (en) | Method for improving productivity of ethylene and propylene in catalytic cracking process | |
CN112457874B (en) | Method for controlling multistage catalytic cracking according to multi-zone partition coupling bed layers of raw material types | |
JP7354228B2 (en) | Catalytic cracking method and system for hydrocarbon oil | |
CN111100702B (en) | Method and system for producing clean gasoline from sulfur-containing light oil | |
CN102816591B (en) | Catalytic cracking method | |
CN102816589B (en) | Hydrocarbon oil catalytic cracking method | |
CN112322330A (en) | Method for controlling multistage catalytic cracking by using double-zone and zone coupling bed layer according to properties of raw materials | |
CN112322331A (en) | Three-zone series cooperative control multi-stage catalytic cracking method according to raw material types | |
CN112322325A (en) | Multi-bed-layer partition cooperative control multi-stage catalytic cracking method according to raw material types | |
CN112322334A (en) | Multi-zone coupling control multistage catalytic cracking method and device based on raw material properties | |
CN112322338A (en) | Multi-zone coupling control multistage catalytic cracking method and device based on raw material types | |
CN112322324A (en) | Multi-zone coupling control multistage catalytic cracking method and device based on raw material types | |
CN112322321A (en) | Multi-zone coupling control multistage catalytic cracking method and device based on raw material properties | |
CN111100701B (en) | Method for adsorption desulfurization and hydrocarbon conversion of sulfur-containing light raw oil | |
CN112322327A (en) | Method for double-bed-layer partition cooperative control of multistage catalytic cracking according to properties of raw materials | |
CN112322323A (en) | Method for controlling multi-stage catalytic reactions using multi-zone parallel coupled beds of feedstock type | |
CN112322329A (en) | Double-zone parallel cooperative control multi-stage catalytic cracking method according to properties of raw materials | |
CN112322336A (en) | Three-zone parallel cooperative control multi-stage catalytic cracking method according to types of raw materials | |
CN112322326A (en) | Method for controlling multistage catalytic cracking by virtue of double-zone cooperative control coupling bed layer according to properties of raw materials | |
CN102816590B (en) | Method for producing low-carbon olefin through petroleum hydrocarbon oil catalytic cracking |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |