CN117263763A - Method for treating xylene isomerization raw material - Google Patents
Method for treating xylene isomerization raw material Download PDFInfo
- Publication number
- CN117263763A CN117263763A CN202210676995.8A CN202210676995A CN117263763A CN 117263763 A CN117263763 A CN 117263763A CN 202210676995 A CN202210676995 A CN 202210676995A CN 117263763 A CN117263763 A CN 117263763A
- Authority
- CN
- China
- Prior art keywords
- carrier
- mass
- hydrogen
- xylene
- raw material
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 94
- 239000008096 xylene Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 71
- 239000002994 raw material Substances 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 79
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 17
- 150000002367 halogens Chemical class 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 23
- 229920006395 saturated elastomer Polymers 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000006386 neutralization reaction Methods 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- -1 aluminum alkoxide Chemical class 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- 150000004645 aluminates Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 26
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 20
- 239000000243 solution Substances 0.000 description 21
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000004927 clay Substances 0.000 description 16
- 238000005470 impregnation Methods 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000002808 molecular sieve Substances 0.000 description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 101150116295 CAT2 gene Proteins 0.000 description 6
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 6
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 4
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 3
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XTCQUBCCCSJAKJ-UHFFFAOYSA-N ethylbenzene Chemical compound CCC1=CC=CC=C1.CCC1=CC=CC=C1 XTCQUBCCCSJAKJ-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
- C07C7/14841—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for treating xylene isomerization raw materials, which comprises the following steps: (1) Mixing the xylene isomerization raw material with hydrogen to obtain a hydrogen-soluble xylene isomerization raw material; (2) Contacting the hydroxylene isomerization feedstock from step (1) with a hydrofining catalyst under liquid phase hydrogenation conditions; the hydrofining catalyst comprises gamma-Al 2 O 3 As carrier, based on dry Al 2 O 3 The hydrofining catalyst further comprises an Al catalyst supported on the carrier by mass 2 O 3 0.01 to 10 mass% of main active component, 0.01 to 5 mass% of auxiliary agent and 0.1 to 3 mass% of halogen of the carrier. The method of the invention can efficiently utilize dissolved hydrogen and can efficientlyThe method of the invention has higher olefin removal rate and high-efficiency oxygenate removal rate, and has low aromatic hydrocarbon loss rate.
Description
Technical Field
The invention relates to the technical field of catalytic hydrogenation, in particular to a method for treating xylene isomerization raw materials.
Background
The arene united device is an industrial device for producing important chemical products such as Paraxylene (PX), o-xylene and the like. Typical aromatics complex, as shown in FIG. 2, generally comprises units such as catalytic reforming (abbreviated reforming), aromatics extraction (abbreviated extraction), disproportionation, transalkylation (abbreviated disproportionation), PX adsorption separation, xylene rectification, xylene isomerization, and the like. The reforming, extraction and disproportionation unit is a device for providing mixed xylene raw materials, and the xylene isomerization is a unit containing reaction conversion in the aromatic hydrocarbon combination device, and ethylbenzene is converted into xylene while the xylene isomerization reaction is carried out so as to increase the yield of PX. The xylene isomerization catalyst is generally prepared by taking alumina and zeolite as carriers and loading noble metal Pt. In order to ensure a long-period stable operation of the isomerization catalyst, it is necessary to strictly control water, sulfur, olefins, oxygenates, and the like in the xylene isomerization feedstock.
For dehydration and desulfurization, strict control is required from the upstream of the device, or molecular sieve and hydrofining desulfurization facilities are adopted. While clay, modified clay, molecular sieve refined catalyst and the like can be adopted for removing trace olefin, the initial stage of use can lead to demethylation or ethyl reaction, and xylene loss is caused. For the C8+ mixed aromatic hydrocarbon fraction, the clay replacement frequency is higher and higher due to the fact that the fraction is rich in indan, colloid and other heavy components which are easy to inactivate clay, and some granular clay used by enterprises needs to be replaced even once a week, so that the labor intensity is very high, and the clay consumption is also very high. The abandoned clay contains a certain amount of heavy aromatic hydrocarbon, the landfill or burning treatment can bring serious pollution to the environment, and the post-treatment cost is high, so that the comprehensive utilization cost of the clay is high. In recent years, there are also methods for non-hydrogenation catalytic olefin removal using a catalyst containing molecular sieve, which have a service life longer than that of granular clay, but which still have environmental problems such as relatively short single-pass service life, need for continuous catalyst removal regeneration and post-treatment landfill. In addition, because the reaction mechanisms of the granular clay and the refined catalyst containing the molecular sieve are basically similar, the alkylation, superposition, condensation and other reactions are mainly carried out to remove olefin, so that the content of heavy aromatic hydrocarbon with low utilization value in the reaction product is increased, and the dry point of the reaction product is increased. Therefore, there is an urgent need for an environmentally friendly dealkenation catalyst to completely replace the industrial granular clay and molecular sieve-containing refined catalyst.
The other olefin removing method mainly adopts a selective hydrogenation process, wherein the process is to selectively hydrogenate the olefin in the mixed aromatic hydrocarbon under the hydrogenation condition, and the deep mild hydrogenation is realized to remove the olefin in the aromatic hydrocarbon under the condition that the aromatic hydrocarbon is not saturated by hydrogenation. Unlike clay and molecular sieve-containing catalyst, the hydrogenation process is adopted to eliminate olefin and the dry point of the reaction product is not raised. One is to use the catalyst containing non-noble metal (such as Co-Mo or Ni-Mo) to catalyze the hydrogenation method, need higher reaction temperature (280-320 ℃) and lower space velocity (1-2 h-1), aromatic hydrocarbon loss is large, and catalyst life is short, need regeneration or replacement in several months, this craft and catalyst have been eliminated at present. The other is a low-temperature hydrogenation process adopting a noble metal (Pd and Pt) hydrofining catalyst, the reaction severity is lower, the reaction temperature is 120-170 ℃, the reaction pressure is 1.0-2.4 MPa, the aromatic hydrocarbon loss is less than 0.5w%, and the catalyst can stably operate for a long period. The deactivated catalyst is regenerated by adopting an external regeneration mode, and noble metals such as Pd, pt and the like of the waste catalyst can be entrusted to the recovery enterprises with hazardous waste treatment qualification for high-efficiency recovery. In addition, in view of the trace amount of peroxy compounds in the xylene isomerization feed, the hydrofining mode must also be employed in view of an efficient removal mode. Therefore, comprehensively considering the aspects of long-term investment, long-term stable operation, economic and social benefits, environmental protection and the like, the adoption of the hydrodeolefine process and the catalyst for the raw material for isomerizing the paraxylene is a necessary trend of future development.
Chinese patent CN102911721a discloses a method for liquid phase selective hydrodeolefination of reformate feedstock, which adopts a method that under hydrogenation conditions, a liquid phase mixture enters a multistage conventional hydrogenation reactor in stages; the mixture enters a catalyst bed zone for reaction in sections, part of the reaction product coming out of the bottom of the reactor is circularly mixed with fresh raw materials, and the part of the reaction product is discharged from a reaction system to a subsequent separation device; the ratio of the circulating liquid hydrogenation product to the raw material is 1:1-5:1 by volume; the hydrogenation process conditions are as follows: the reaction temperature is 80-180 ℃, the pressure is 1.5-2.0 MPa, and the space velocity of fresh feeding volume is 2.0-4.0 h -1 。
CN201210440412.8 discloses a process for the dealkenation of reformate feedstock. The raw material of the reformed oil is firstly subjected to shallow hydrogenation under the process conditions of high airspeed, low hydrogen-oil ratio, low temperature and low pressure, the bromine index in the produced oil is controlled, and the hydrogenated oil enters a clay tower for adsorption refining.
How to design a method with simple and environment-friendly starting process to efficiently remove olefin and oxygen-containing compounds in xylene isomerization raw materials under low aromatic hydrocarbon loss so as to completely replace non-hydro-dealkenation technologies such as clay, molecular sieves and the like is a technical problem to be solved at present.
Disclosure of Invention
The invention provides a method for treating a dimethylbenzene isomerization raw material, which aims to solve the technical problems of high catalyst replacement frequency, serious pollution, environmental protection and high dimethylbenzene loss in the prior art when olefin in the dimethylbenzene isomerization raw material is removed through clay, molecular sieve and the like.
The present invention provides a process for treating a xylene isomerized feedstock comprising: (1) Mixing xylene isomerization raw material with hydrogen to obtain hydrogen-soluble xylene iso-formStructuring the raw material; (2) Contacting the hydroxylene isomerization feedstock from step (1) with a hydrofining catalyst under liquid phase hydrogenation conditions; the hydrofining catalyst comprises gamma-Al 2 O 3 As carrier, based on dry Al 2 O 3 The hydrofining catalyst further comprises an Al catalyst supported on the carrier by mass 2 O 3 0.01 to 10 mass% of main active component, 0.01 to 5 mass% of auxiliary agent and 0.1 to 3 mass% of halogen of the carrier; the main active component is VIII B group element, and the auxiliary agent is rare earth element; the Al is 2 O 3 In the carrier, the pore volume of pores with a pore diameter of 10nm or more is 90% or more.
Optionally, the mixing in step (1) is performed in a gas-liquid mixer; the gas-liquid mixer is a static mixer or a dynamic mixer; the hydrogen-soluble xylene isomerization feedstock from step (1) is a saturated hydrogen-soluble xylene isomerization feedstock.
Optionally, the contacting reaction in step (2) is performed in a hydrogenation reactor.
Optionally, the aspect ratio of the hydrogenation reactor is not higher than 2; preferably, the hydrogenation reactor is a fixed bed reactor; preferably, the fixed bed reactor is a fixed bed isothermal reactor or a fixed bed adiabatic reactor.
Optionally, the liquid phase hydrogenation conditions in step (2) comprise: the reaction temperature is 80-150 ℃, the pressure is 1.5-3.0 MPa, and the weight airspeed is 50-150.0 h -1 Hydrogen oil volume ratio (0.05-50): 1.
optionally, the liquid phase hydrogenation conditions in step (2) comprise: the reaction temperature is 100-130 ℃, the pressure is 1.8-2.5 MPa, and the weight airspeed is 80-120.0 h -1 Hydrogen oil volume ratio (0.5-20): 1.
optionally, the main active component is selected from one or more than two of Ni, ru, rh, pd and Pt, the auxiliary agent is selected from one or more than two of La, ce, sm, eu, Y and Yb, and halogen is chlorine; on dry basis of Al 2 O 3 The mass ratio of the main active component is 0.05-5%, the mass ratio of the auxiliary agent is 0.10-1.0%, and the mass ratio of the halogen is calculated by the mass of the carrierThe weight ratio is 0.5-1.5%.
Optionally, the Al 2 O 3 The specific surface area of the carrier is 100-300 m 2 /g; the Al is 2 O 3 The pore volume of the carrier is 0.4-1.0 mL/g; at the Al 2 O 3 In the pore size distribution of the carrier, the pore size is smaller than<10nm, pore diameter of 10-20 nm and pore diameter>The pore volume of the pores at 20nm is respectively<10%, 20-40%>50％。
Optionally, the Al 2 O 3 The carrier is made of Al 2 O 3 Is prepared by steam treatment, al 2 O 3 The aluminum hydroxide is baked or formed by an aluminum sol oil column; aluminum hydroxide is prepared by an aluminum alkoxide hydrolysis method, an aluminate neutralization precipitation method, an aluminum salt neutralization method and/or an aluminum sol neutralization method.
Optionally, the bromine index in the xylene isomerized feedstock is from 10 to 100mgBr/100g and/or the oxygenate content is from 5 to 30ug/g based on the total weight of the xylene isomerized feedstock.
The invention has the following beneficial effects:
(1) In the method, the xylene isomerization raw material is fully mixed and dissolved with hydrogen, so that the dissolved hydrogen is effectively utilized;
(2) The hydrofining catalyst in the method has high activity, and can efficiently lead olefin and oxygen-containing compounds in the dimethylbenzene isomerization raw material to react with hydrogen so as to be removed, so that the method has higher olefin removal rate and high-efficiency oxygen-containing compound removal rate, and the loss rate of aromatic hydrocarbon is low;
(3) The method has simple starting process and is environment-friendly, and can completely replace non-hydro-dealkenation technologies such as clay, molecular sieves and the like.
Drawings
FIG. 1 is a process flow diagram of one embodiment of the process of the present invention for treating a xylene isomerization feedstock;
FIG. 2 is a flow diagram of an aromatics complex;
reference numerals illustrate:
a1 circularly isomerizing raw materials; a2, outsourcing supplementary raw materials;
a xylene isomerization feed; b hydrogen; a gas-liquid mixer;
a D isomerization reaction feeding preheater; e, a hydrogenation reactor;
f isomerisation product high temperature separation tank.
Detailed Description
The present application is further described in detail below by way of the accompanying drawings and examples. The features and advantages of the present application will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not collide with each other.
The present invention provides a process for treating a xylene isomerized feedstock comprising: (1) Mixing the xylene isomerization raw material with hydrogen to obtain a hydrogen-soluble xylene isomerization raw material; (2) Contacting the hydroxylene isomerization feedstock from step (1) with a hydrofining catalyst under liquid phase hydrogenation conditions; the hydrofining catalyst comprises gamma-Al 2 O 3 As carrier, based on dry Al 2 O 3 The hydrofining catalyst further comprises an Al catalyst supported on the carrier by mass 2 O 3 0.01 to 10 mass% of main active component, 0.01 to 5 mass% of auxiliary agent and 0.1 to 3 mass% of halogen of the carrier; the main active component is VIII B group element, and the auxiliary agent is rare earth element; the Al is 2 O 3 In the carrier, the pore volume of pores with a pore diameter of 10nm or more is 90% or more.
In the aromatic hydrocarbon combination device, as shown in fig. 2, the cyclic isomerization raw material A1 and the outsourced supplementary raw material A2 together form the xylene isomerization raw material, the xylene isomerization raw material enters an isomerization unit to be isomerized under the action of an isomerization catalyst, and o-xylene and m-xylene can be converted into p-xylene through an isomerization reaction, so that ethylbenzene is converted into p-xylene. However, xylene isomerization feedstocks contain small or trace amounts of olefins and oxygenates, the presence of which can adversely affect the isomerization catalyst and, in turn, the isomerization reaction. Therefore, the cyclic isomerization raw material A1 and the outsourced supplementary raw material A2 need to be treated according to the method of the invention before entering an isomerization unit, so that the olefin and the oxygen-containing compound in the dimethylbenzene isomerization raw material are efficiently removed, and the isomerization reaction can be better carried out.
In the method for treating the xylene isomerization raw material, the xylene isomerization raw material is fully mixed and dissolved with hydrogen to obtain the hydrogen-dissolved xylene isomerization raw material, and then the hydrogen-dissolved xylene isomerization raw material is subjected to a liquid-phase hydrogenation process under the catalysis of the hydrofining catalyst; firstly, the removal rate of olefin and oxygen-containing compounds in the dimethylbenzene isomerization raw material is greatly improved, secondly, the consumption of hydrogen is reduced, and then the dimethylbenzene isomerization device is stably and fully operated; third, the aromatic hydrocarbon loss rate is low.
According to one embodiment, the mixing in step (1) is performed in a gas-liquid mixer; the gas-liquid mixer is a static mixer or a dynamic mixer; the hydrogen-soluble xylene isomerization feedstock from step (1) is a saturated hydrogen-soluble xylene isomerization feedstock.
It should be noted that the gas-liquid mixer may be one or more, wherein the static mixer may be one or a combination of several of SV, SK, SX, SH, SL type static mixers; the dynamic mixer may be one or several selected from mixing pump, vortex mixer, supercritical mixer and stirring mixer. Both the xylene isomerization feed and the hydrogen can be fed continuously. When the xylene isomerization raw material is mixed with hydrogen by the gas-liquid mixer, the hydrogen and the xylene isomerization raw material are preferably continuously or continuously introduced into the gas-liquid mixer, so that the xylene isomerization raw material and the hydrogen can be rapidly and fully mixed and dissolved to obtain the saturated hydrogen-dissolved xylene isomerization raw material.
According to one embodiment, the contacting reaction in step (2) is performed in a hydrogenation reactor.
As a preferred embodiment, the aspect ratio of the hydrogenation reactor is not higher than 2; preferably, the hydrogenation reactor is a fixed bed reactor; preferably, the fixed bed reactor is a fixed bed isothermal reactor or a fixed bed adiabatic reactor. By selecting the appropriate aspect ratio reactor and internals, the reactor pressure drop can be reduced.
Preferably, as shown in fig. 1, the method of the present invention may further comprise the steps of:
the xylene isomerization raw material A and the hydrogen B are fully mixed and dissolved in a gas-liquid mixer C to obtain a saturated hydrogen-soluble xylene isomerization raw material, the saturated hydrogen-soluble xylene isomerization raw material is preheated by an isomerization reaction feed preheater D and then enters a hydrogenation reactor E, and olefin, oxygen-containing compounds in the saturated hydrogen-soluble xylene isomerization raw material and hydrogen are subjected to hydrogenation reaction under the catalysis of a hydrofining catalyst, so that the olefin and the oxygen-containing compounds in the xylene isomerization raw material are respectively converted into alkane, water and the like and are further removed. In addition, the isomerisation product can be sent to an isomerisation product high temperature separation tank F for separation and purification, and the residue after the purification of the product is used as part of xylene isomerisation raw material (for example, can be used as recycle isomerisation raw material A1 in FIG. 2) to be sent to an isomerisation reaction feed preheater D for preheating and then sent to a hydrogenation reactor E. The isomerization feed preheater D may be embodied as an electric heater or a vapor heat exchanger.
According to one embodiment, the liquid phase hydrogenation conditions in step (2) comprise: the reaction temperature is 80-150 ℃, the pressure is 1.5-3.0 MPa, and the weight airspeed is 50-150.0 h -1 Hydrogen oil volume ratio (0.05-50): 1.
according to a preferred embodiment, the liquid phase hydrogenation conditions in step (2) comprise: the reaction temperature is 100-130 ℃, the pressure is 1.8-2.5 MPa, and the weight airspeed is 80-120.0 h -1 Hydrogen oil volume ratio (0.5-20): 1.
the xylene isomerization feed may contain one or more of toluene, cumene, C8 non-aromatics, ethylbenzene, para-xylene, ortho-xylene, meta-xylene, C9 aromatics, and the like, and a quantity of olefins and/or oxygenates, according to one embodiment. Toluene, cumene, C8 non-aromatics, ethylbenzene, para-xylene, ortho-xylene, meta-xylene, C9 aromatics, etc. are substantially non-reactive under the process conditions of the present application and olefins and/or oxygenates therein are removed by conversion to alkanes and/or water. By olefin is meant, according to one embodiment, an olefin having a carbon number of from C8 to C12, including mono-, di-or multiolefins. The oxygen-containing compound refers to, for example, benzoyl peroxide, cumene hydroperoxide, and the like.
According to one embodiment, the bromine index in the xylene isomerisation feedstock may be in the range of from 10 to 100mgBr/100g and/or the oxygenate content may be in the range of from 5 to 30ug/g based on the total weight of the xylene isomerisation feedstock.
In the method, the hydrofining catalyst is used as a catalyst, the xylene isomerization raw material is treated under the conditions, the bromine index of the obtained treated xylene isomerization raw material product is less than 10mgBr/100g of oil, the aromatic hydrocarbon loss is less than 0.1w%, the olefin removal rate is more than 98%, and the peroxide removal rate is 100%. Namely, the method of the invention can reduce the loss of aromatic hydrocarbon by controlling the conditions, obtain higher olefin removal rate and high-efficiency oxygen-containing compound removal rate by selecting the hydrofining catalyst with high activity, and reduce investment cost by increasing airspeed.
Hydrofinishing catalysts useful herein include gamma-Al 2 O 3 As carrier, based on dry Al 2 O 3 The hydrofining catalyst further comprises an Al catalyst supported on the carrier by mass 2 O 3 0.01 to 10 mass% of main active component, 0.01 to 5 mass% of auxiliary agent and 0.1 to 3 mass% of halogen of the carrier; the main active component is VIII B group element, and the auxiliary agent is rare earth element; the Al is 2 O 3 In the carrier, the pore volume of pores with a pore diameter of 10nm or more is 90% or more.
Based on one embodiment, the main active component is selected from one or more than two of Ni, ru, rh, pd and Pt, the auxiliary agent is selected from one or more than two of La, ce, sm, eu, Y and Yb, and halogen is chlorine; on dry basis of Al 2 O 3 The mass ratio of the main active component to the carrier is 0.05-5%, the mass ratio of the auxiliary agent to the carrier is 0.10-1.0%, and the mass ratio of the halogen to the carrier is 0.5-1.5%.
According to one embodiment, the Al 2 O 3 The specific surface area of the carrier is 100-300 m 2 /g; the Al is 2 O 3 The pore volume of the carrier is 0.4-1.0 mL/g; at the Al 2 O 3 In the pore size distribution of the carrier, the pore size is smaller than<10nm, pore diameter of 10-20 nm and pore diameter>The pore volume of the pores at 20nm is respectively<10%, 20-40%>50％。
The hydrorefining catalyst has a specific molecular weight as that of Al 2 O 3 The same specific surface area, pore volume and pore size distribution of the support.
According to one embodiment, the Al 2 O 3 The carrier is made of Al 2 O 3 Is prepared by steam treatment, al 2 O 3 The aluminum hydroxide is baked or formed by an aluminum sol oil column; aluminum hydroxide is prepared by an aluminum alkoxide hydrolysis method, an aluminate neutralization precipitation method, an aluminum salt neutralization method and/or an aluminum sol neutralization method. Preferably, the aluminium hydroxide is prepared by aluminate neutralisation precipitation.
Al is used as 2 O 3 When the pseudo-boehmite powder is prepared by baking aluminum hydroxide, an aluminum alkoxide hydrolysis method, an aluminate neutralization precipitation method, an aluminum salt neutralization method, an aluminum sol neutralization method and the like can be adopted to produce the pseudo-boehmite powder; then, pseudo-boehmite powder is firstly mixed with bonding forming auxiliary agents such as sesbania powder, nitric acid, acetic acid, citric acid and the like, extruded, dried and roasted to obtain Al 2 O 3 . The Al is 2 O 3 Treated by water vapor to obtain Al 2 O 3 A carrier.
The steam treatment includes: to saturate or oversaturateSaturated steam passes through Al at 500-700 DEG C 2 O 3 0.5 to 8 hours by Al 2 O 3 The mass of the water vapor is Al 2 O 3 0.5 to 5 times of the mass; the temperature of the saturated or supersaturated water vapor is 100-150 ℃.
The water vapor treatment may be used to make Al 2 O 3 Obtaining more large pore channels, especially performing steam high temperature treatment according to the above conditions to obtain Al 2 O 3 The pore volume of the pores with the pore diameter of more than 10nm in the carrier accounts for more than 90 percent; specifically, al 2 O 3 The specific surface area of the carrier is 100-300 m 2 /g，Al 2 O 3 The pore volume of the carrier is 0.4-1.0 mL/g, and the pore diameter is smaller than<10nm, pore diameter of 10-20 nm and pore diameter>The pore volume of the pores at 20nm is respectively<10%, 20-40%>50％。
Al obtained by the method 2 O 3 The carrier can be prepared into a hydrofining catalyst by the following method: by letting Al 2 O 3 The carrier is contacted with a precursor solution (impregnating solution) for impregnation, so that a loaded carrier is obtained; the solute of the precursor solution comprises a compound of a VIII B element, a compound of a rare earth element and halogen acid; and drying, activating and reducing the loaded carrier sequentially.
The compound of the group VIII B element is selected from one or more of chloride, nitrate, acetate, carbonate, sulfate, hydroxide, formate, acetate, nitrite and nitrite, preferably chloride; the compound of the rare earth element is selected from one or more of chloride, nitrate and oxide, preferably chloride; the halogen acid is hydrochloric acid.
The drying temperature is 60-200 ℃ and the drying time is 2-8 hours; the activation is carried out in an air atmosphere at the temperature of 400-650 ℃ for 2-8 hours with the volume ratio of gas/agent of 600-1500: 1, a step of; the reduction is carried out in a hydrogen atmosphere at a temperature of 400-600 ℃ for 2-6 hours with a gas/agent volume ratio of 600-1200: 1.
impregnation can incorporate the active ingredient, auxiliary agent and halogen, and may be by means of partial impregnation and co-impregnation, as well as by means of saturated impregnation or supersaturated impregnation. Precursor solution or impregnating solution and Al during impregnation 2 O 3 The liquid/solid volume ratio of the carrier is (1.0-4.0): 1, preferably (1.2 to 2.0): 1. suitable impregnation temperatures are from 25 to 70℃and preferably from 20 to 50 ℃. The precursor solution or the impregnating solution contains a compound of a group VIIIB element and a compound of a rare earth element, and in addition, the impregnating solution is prepared to contain halogen acid, preferably hydrochloric acid, so as to introduce the halogen component and uniformly distribute the metal component on the whole carrier. Excess impregnating solution after supersaturation may be removed by filtration or evaporation of the solvent in vacuo. The method of evaporating the solvent in vacuo may be carried out using a rotary vacuum evaporator.
The specific impregnation method can be as follows: preparing water-soluble compound containing active components (including the above-mentioned active components, adjuvant and halogen) into precursor solution or impregnating solution, impregnating Al under the condition of 0.001-0.10 MPa and rotating 2 O 3 The carrier, the liquid/solid volume ratio of the impregnating solution to the carrier may be (1.2-1.8): 1, the rotational linear velocity may be 0.01 to 2.0 m/s. The pressure of vacuum spin impregnation is preferably 0.001 to 0.09MPa, the vacuum spin impregnation is performed while heating, the vacuum spin impregnation is performed at a heating temperature of preferably 50 to 100 ℃, more preferably 60 to 80 ℃, the spin rate is preferably not too fast, and the spin line speed is preferably 0.02 to 0.8 m/s, more preferably 0.05 to 0.5 m/s. The impregnation time is preferably 1 to 8 hours, more preferably 2 to 4 hours. After vacuum rotary impregnation, the moisture in the impregnation liquid is basically evaporated, and the catalyst is in a dry state, and the loaded carrier can be directly taken out for drying, activating and reducing.
The activation may be firing under the above conditions in an air atmosphere, and the reduction may be firing under the above conditions in a hydrogen atmosphere. Can be loaded on Al by activation 2 O 3 The metallic element in the active element compound of the carrier is converted to an oxidized state, and the nonmetallic element (such as nitrate in nickel nitrate) is convertedFor gas removal, the activated oxidation state metal can be reduced by reduction.
The reduced sulfiding may also be included in the preparation of the hydrofinishing catalyst. Sulfiding refers to roasting the reduced catalyst together with a sulfiding agent, which may be dimethyl disulfide, carbon disulfide, sulfide and other sulfur-containing organic compounds. For catalysts with Ni and other metals as active components, the metals are converted into sulfide states through a vulcanization process, so that the catalysts have higher hydrogenation activity, stability and selectivity. For catalysts with active components containing noble metals (such as one or more of Ru, rh, pd and Pt), part of active sites can be passivated through sulfuration treatment, so that the catalytic activity is properly reduced, and further side reactions are reduced, in particular, hydrogenation reaction of aromatic hydrocarbon is avoided when olefin and oxygen-containing compounds are removed through hydrogenation, and the loss of aromatic hydrocarbon is reduced.
The invention is illustrated in further detail by the following examples.
In the following examples, materials or reagents used were commercially available and rotary vacuum evaporators were produced by Shanghai Asia Biochemical instruments. The following examples and comparative examples use xylene isomerate oil of the composition shown in table 1 below as the xylene isomerate feed.
TABLE 1
| Component name | Unit (B) | Composition of the composition |
| C 8 Non-aromatic hydrocarbon | Mass percent of | 2.16 |
| Toluene (toluene) | Mass percent of | 0.27 |
| Ethylbenzene (ethylbenzene) | Mass percent of | 21.40 |
| Para-xylene | Mass percent of | 6.35 |
| Meta-xylene | Mass percent of | 58.89 |
| Ortho-xylene | Mass percent of | 10.87 |
| Cumene (isopropyl benzene) | Mass percent of | 0.02 |
| C 9 Aromatic hydrocarbons | Mass percent of | 0.04 |
| Olefin (bromine index) | mgBr/100g | 50 |
| Oxygen-containing compound | ug/g | 22 |
Example 1
(1) Preparation of Al 2 O 3 And (3) a carrier: the aluminum hydroxide powder is pseudo-boehmite powder produced by the long-term division company of China petrochemical catalyst Co by adopting a sodium metaaluminate and aluminum sulfate precipitation method, and the aluminum hydroxide powder is prepared according to the following steps: sesbania powder: nitric acid: acetic acid: citric acid: the mass ratio of water is 100:1.5:1:4:5: mixing the above materials, extruding, drying at 120deg.C for 12 hr, and calcining at 620 deg.C for 4 hr to obtain Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Al is mixed with 2 O 3 Controlling the gas-agent ratio of water vapor and carrier at 750 ℃ to be 1200/1, introducing 150 ℃ saturated water vapor for 4 hours to prepare Al 2 O 3 Vector S-1;
(2) Preparing a hydrofining catalyst: 100g of the above Al is taken 2 O 3 The carrier S-1 is prepared by preparing nickel nitrate, palladium chloride, yttrium chloride, hydrochloric acid and water into an impregnating solution, wherein the impregnating solution contains 2.0 mass percent of Ni, 0.20 mass percent of Pd, 0.30 mass percent of Y and 1.8 mass percent of Cl, and the dry basis of Al 2 O 3 The mass of the carrier S-1 is taken as a reference, and Al is made 2 O 3 The carrier S-1 is dispersed in the impregnating solution, and the liquid/solid volume ratio is 1.7; pouring the impregnating solution with the carrier dispersed into a 500 ml flask, impregnating for 3 hours on a rotary vacuum evaporator at 30 ℃, 0.008MPa and a rotating linear speed of 0.04 m/s, vacuumizing at 70 ℃ to enable the solid to be dry, and drying at 120 ℃ for 12 hours; activating in dry air at 500 deg.C with gas/agent volume ratio of 1000 for 4 hr, and then using H at 485 deg.C with gas/agent volume ratio of 600 2 Reducing for 4 hours to obtain a catalyst Cat-1;
(3) Introducing the xylene isomerization raw material and hydrogen into a gas-liquid mixer shown in the figure 1 at the same time to obtain a saturated hydrogen-dissolved xylene isomerization raw material; filling a fixed bed axial reactor with 1.0 g of catalyst Cat-1; at a reaction temperature of 115 ℃ and a pressure of 2.0MPa, the feed weight space velocity is 150h -1 The hydrogen/oil volume ratio was 20: under the condition of 1, the saturated hydrogen-dissolved xylene isomerization raw material enters a fixed bed axial reactor and is catalyzed by a catalyst Cat-1The reaction is carried out.
Example 2
(1) Spherical Al is prepared according to an aluminum sol oil column forming method 2 O 3 Vector S-2;
200g of aluminum powder is weighed and added into 2500g of 10% hydrochloric acid aqueous solution by mass fraction, aluminum sol is prepared by heating and dissolving at 95 ℃, 5% pseudo-boehmite by mass of the aluminum sol and 600g of 35% hexamethylenetetramine aqueous solution by mass fraction are added, uniformly mixed, then the mixture is dripped into an oil column with the temperature of 90 ℃ through a dispersing drip tray, and aging is carried out for 6 hours at 120 ℃ and 0.60MPa after molding is finished. Washing the aged gel pellets with pure water until no chloride ion is detected, filtering to remove residual liquid, drying at 120deg.C for 12 hr, and calcining at 750deg.C in muffle furnace for 8 hr to obtain spherical Al 2 O 3 Vector S-2;
(2) Catalyst Cat-2 was prepared by the method of step (2) in example 1, except that the carrier used was Al 2 O 3 Vector S-2, in step (2) H 2 After reduction, catalyst Cat-2 was subjected to conventional sulfidation by adding 0.1 mass% hydrogen sulfide in a hydrogen atmosphere at 420-430 ℃ based on the mass of catalyst Cat-2;
(3) Introducing the xylene isomerization raw material and hydrogen into a gas-liquid mixer shown in the figure 1 at the same time to obtain a saturated hydrogen-dissolved xylene isomerization raw material; filling a fixed bed axial reactor with 1.0 g of catalyst Cat-2; at a reaction temperature of 120 ℃ and a pressure of 2.2MPa, the weight space velocity of the feed is 120h -1 The hydrogen/oil volume ratio was 10: under the condition of 1, the saturated hydrogen-dissolved xylene isomerization raw material enters a fixed bed axial reactor to react under the catalysis of a catalyst Cat-2.
Example 3
(1) Al prepared in step (1) of example 1 2 O 3 The carrier S-1 is used as a carrier;
(2) A hydrofinishing catalyst was prepared according to example 1, step (2), except that: the immersion liquid (aqueous solution) was prepared from palladium chloride, platinum chloride, ruthenium chloride, cerium chloride, ytterbium chloride and hydrochloric acid, and the immersion liquid contained 0.15 mass% Pd, 0.10 mass% Pt, 0.30 mass% Ru, 0.15 mass% Ce, 0.15 mass% Yb and Cl 1.6 mass% based on dry Al 2 O 3 The mass of the carrier S-1 is used as a reference to prepare a catalyst Cat-3;
(3) Introducing the xylene isomerization raw material and hydrogen into a gas-liquid mixer shown in the figure 1 at the same time to obtain saturated hydrogen-dissolved xylene isomerization raw material; filling a fixed bed axial reactor with 1.0 g of catalyst Cat-3; at 130 ℃ and 2.5MPa, the weight space velocity of the feed is 130h -1 The hydrogen/oil volume ratio was 5: under the condition of 1, the saturated hydrogen-dissolved xylene isomerization raw material enters a fixed bed axial reactor to react under the catalysis of a catalyst Cat-3.
Example 4
(1) Al prepared in step (1) of example 1 2 O 3 The carrier S-1 is used as a carrier;
(2) A hydrofinishing catalyst was prepared according to example 1, step (2), except that: will be
Nickel nitrate, palladium chloride, rhodium chloride, samarium chloride and hydrochloric acid are prepared into an impregnating solution (aqueous solution), and the impregnating solution contains 1 mass percent of Ni, 0.10 mass percent of Pd, 0.1 mass percent of Rh, 0.20 mass percent of Sm and 1.7 mass percent of Cl, and the impregnating solution is prepared into an aqueous solution by using dry basis of Al 2 O 3 The mass of the carrier S-1 is used as a reference to prepare a catalyst Cat-4;
(3) Introducing the xylene isomerization raw material and hydrogen into a gas-liquid mixer shown in the figure 1 at the same time to obtain saturated hydrogen-dissolved xylene isomerization raw material; filling a fixed bed axial reactor with 1.0 g of catalyst Cat-4; at a reaction temperature of 100 ℃, a pressure of 3.0MPa and a feed weight space velocity of 140h -1 The hydrogen/oil volume ratio was 30: under the condition of 1, the saturated hydrogen-dissolved xylene isomerization raw material enters a fixed bed axial reactor to react under the catalysis of a catalyst Cat-4.
Comparative example 1
(1) Comparative catalyst DBCat-1 was prepared according to comparative patent CN1448474A, example 1 and CN201210440412.8 Table 2;
dissolving chloroplatinic acid and palladium chloride in deionized water, taking the mass of a dry alumina carrier as a reference, wherein the impregnating solution contains 0.18 mass percent of Pd and 0.08 mass percent of Pt, placing the alumina carrier in the impregnating solution for impregnation, then drying at 120 ℃ for 8-10 hours, and roasting at 450 ℃ in air for 4-6 hours to obtain a catalyst DBCat-1;
(2) 1.0 g of catalyst DBCat-1 was charged in a 10mL medium test evaluation device, the reaction temperature was 130℃and the pressure was 1.5MPa, and the feed volume space velocity was 7.0h -1 The hydrogen/oil volume ratio was 20:1, simultaneously introducing a dimethylbenzene isomerization raw material and hydrogen into a 10mL medium-sized test evaluation device, and carrying out reaction under the catalysis of a catalyst DBCat-1.
The composition of the catalysts in examples 1-4 and comparative example 1 above is shown in Table 2 below:
TABLE 2
Test example 1
For Al respectively 2 O 3 Carriers S-1, al 2 O 3 The specific surface area, pore volume and pore size of the support S-2 and the catalyst DBCat-1 were measured, respectively, and the measurement results are shown in Table 3 below.
Wherein the specific surface area, pore volume and pore distribution of the carrier are obtained by adopting low-temperature N on an ASAP2400 static adsorption instrument manufactured by Micromeritics company 2 The adsorption method was used to measure the specific surface area and pore distribution by BET method and t-plot method. By way of example only,<the pore volume distribution of 6nm refers to the percentage of the total pore volume of pores with a pore diameter less than 6nm in the total pore volume of the support.
TABLE 3 Table 3
Test example 2
The oxygen content and the xylene content of the raw materials or reaction products of examples 1 to 4 and comparative example 1 were respectively detected by high performance liquid chromatography, the bromine index of the raw materials or reaction products was detected by an electric quantity method, and then the olefin removal rate, the oxygenate removal rate and the xylene loss rate were calculated as shown in the following table 4. Wherein the olefin removal rate is calculated by the formula (feed bromine index-reaction product bromine index)/feed bromine index of 100%, the oxygenate removal rate is calculated by the formula (feed oxygen content-reaction product oxygen content)/feed oxygen content of 100%, and the xylene loss rate is calculated by the formula (feed xylene content-reaction product xylene content)/feed xylene content of 100%.
TABLE 4 Table 4
| Catalyst | Olefin removal rate, mass% | Oxygen-containing compound removal rate, mass% | Xylene loss rate, mass% |
| Cat-1 | 98.00 | 100.00 | 0.01 |
| Cat-2 | 98.12 | 100.00 | 0.01 |
| Cat-3 | 98.14 | 100.00 | 0.01 |
| Cat-4 | 98.15 | 100.00 | 0.01 |
| DBCat-1 | 75.12 | 80.00 | 0.5 |
As can be seen from Table 4, the process of the present invention has a higher olefin removal rate, a lower aromatics loss rate, and a high efficient oxygenate removal rate.
In the description of the present application, it should be noted that the directions or positional relationships indicated by the terms "upper", "lower", "inner", "outer", "front", "rear", "left", "right", etc. are based on the directions or positional relationships in the working state of the present application, are merely for convenience of description and simplification of description, and do not indicate or imply that the apparatus or element to be referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present application.
In the description of the present application, it should be noted that the terms "mounted," "connected," and "connected" are to be construed broadly, unless explicitly specified and limited otherwise. The specific meaning of the terms in this application will be understood by those of ordinary skill in the art in a specific context.
The present application has been described in connection with the preferred embodiments, but these embodiments are merely exemplary and serve only as illustrations. On the basis of this, many alternatives and improvements can be made to the present application, which fall within the scope of protection of the present application.
Claims (10)
1. A method of treating a xylene isomerization feedstock, comprising:
(1) Mixing the xylene isomerization raw material with hydrogen to obtain a hydrogen-soluble xylene isomerization raw material;
(2) Contacting the hydroxylene isomerization feedstock from step (1) with a hydrofining catalyst under liquid phase hydrogenation conditions;
the hydrofining catalyst comprises gamma-Al 2 O 3 As carrier, based on dry Al 2 O 3 The hydrofining catalyst further comprises an Al catalyst supported on the carrier by mass 2 O 3 0.01 to 10 mass% of main active component, 0.01 to 5 mass% of auxiliary agent and 0.1 to 3 mass% of halogen of the carrier; the main active component is VIII B group element, and the auxiliary agent is rare earth element; the Al is 2 O 3 In the carrier, the pore volume of pores with a pore diameter of 10nm or more is 90% or more.
2. The method of claim 1, wherein the mixing in step (1) is performed in a gas-liquid mixer;
the gas-liquid mixer is a static mixer or a dynamic mixer;
the hydrogen-soluble xylene isomerization feedstock from step (1) is a saturated hydrogen-soluble xylene isomerization feedstock.
3. The process of claim 2, wherein the contacting in step (2) is performed in a hydrogenation reactor.
4. The process of claim 3, wherein the aspect ratio of the hydrogenation reactor is no higher than 2;
preferably, the hydrogenation reactor is a fixed bed reactor;
preferably, the fixed bed reactor is a fixed bed isothermal reactor or a fixed bed adiabatic reactor.
5. The process of claim 4, wherein the liquid phase hydrogenation conditions in step (2) comprise:
the reaction temperature is 80-150 ℃, the pressure is 1.5-3.0 MPa, and the weight airspeed is 50-150.0 h -1 Hydrogen oil volume ratio (0.05-50): 1.
6. the process of claim 5, wherein the liquid phase hydrogenation conditions in step (2) comprise:
the reaction temperature is 100-130 ℃, the pressure is 1.8-2.5 MPa, and the weight airspeed is 80-120.0 h -1 Hydrogen oil volume ratio (0.5-20): 1.
7. the method of claim 6, wherein the main active component is selected from one or more of Ni, ru, rh, pd and Pt, the auxiliary is selected from one or more of La, ce, sm, eu, Y and Yb, and halogen is chlorine;
on dry basis of Al 2 O 3 The mass ratio of the main active component to the carrier is 0.05-5%, the mass ratio of the auxiliary agent to the carrier is 0.10-1.0%, and the mass ratio of the halogen to the carrier is 0.5-1.5%.
8. The method according to claim 7, wherein the Al 2 O 3 The specific surface area of the carrier is 100-300 m 2 /g；
The Al is 2 O 3 The pore volume of the carrier is 0.4-1.0 mL/g;
at the Al 2 O 3 In the pore size distribution of the carrier, the pore size is smaller than<10nm, pore diameter of 10-20 nm and pore diameter>The pore volume of the pores at 20nm is respectively<10%, 20-40%>50％。
9. The method of claim 8, wherein the Al 2 O 3 The carrier is made of Al 2 O 3 Is prepared by steam treatment, al 2 O 3 The aluminum hydroxide is baked or formed by an aluminum sol oil column;
aluminum hydroxide is prepared by an aluminum alkoxide hydrolysis method, an aluminate neutralization precipitation method, an aluminum salt neutralization method and/or an aluminum sol neutralization method.
10. The process according to claim 1, wherein the bromine index in the xylene isomerisation feed is from 10 to 100mgBr/100g and/or the oxygenate content is from 5 to 30ug/g based on the total weight of the xylene isomerisation feed.
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