CN115739139A - Niobium-based carrier and preparation method thereof, niobium-based supported catalyst and preparation method thereof, and monocyclic aromatic hydrocarbon production method - Google Patents
Niobium-based carrier and preparation method thereof, niobium-based supported catalyst and preparation method thereof, and monocyclic aromatic hydrocarbon production method Download PDFInfo
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- CN115739139A CN115739139A CN202111056598.2A CN202111056598A CN115739139A CN 115739139 A CN115739139 A CN 115739139A CN 202111056598 A CN202111056598 A CN 202111056598A CN 115739139 A CN115739139 A CN 115739139A
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- Prior art keywords
- niobium
- source
- carrier
- aromatic hydrocarbon
- catalyst
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000010955 niobium Substances 0.000 title claims abstract description 93
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008096 xylene Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 16
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 9
- QISGROBHHFQWKS-UHFFFAOYSA-N [C].[Nb] Chemical compound [C].[Nb] QISGROBHHFQWKS-UHFFFAOYSA-N 0.000 claims abstract description 7
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 claims abstract description 7
- LIZIAPBBPRPPLV-UHFFFAOYSA-N niobium silicon Chemical compound [Si].[Nb] LIZIAPBBPRPPLV-UHFFFAOYSA-N 0.000 claims abstract description 6
- PEQFPKIXNHTCSJ-UHFFFAOYSA-N alumane;niobium Chemical compound [AlH3].[Nb] PEQFPKIXNHTCSJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 73
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 45
- 239000006259 organic additive Substances 0.000 claims description 31
- 229910052710 silicon Inorganic materials 0.000 claims description 30
- 239000010703 silicon Substances 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 29
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- 238000005470 impregnation Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 24
- 229910052684 Cerium Inorganic materials 0.000 claims description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims description 23
- 239000011574 phosphorus Substances 0.000 claims description 23
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 150000004706 metal oxides Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000006900 dealkylation reaction Methods 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- MLVHQYFKMSFVJZ-UHFFFAOYSA-M CCC[N+](CC)(CCC)CCC.[F-] Chemical compound CCC[N+](CC)(CCC)CCC.[F-] MLVHQYFKMSFVJZ-UHFFFAOYSA-M 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- FDHRGQIRBRQMPF-UHFFFAOYSA-N 2h-pyridin-1-amine Chemical compound NN1CC=CC=C1 FDHRGQIRBRQMPF-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 230000020335 dealkylation Effects 0.000 claims description 4
- DAFQXFQQULLFEE-UHFFFAOYSA-M ethyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](CC)(CCC)CCC DAFQXFQQULLFEE-UHFFFAOYSA-M 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- MQZUUFKWLJGBFY-UHFFFAOYSA-M diethyl(dimethyl)azanium;fluoride Chemical compound [F-].CC[N+](C)(C)CC MQZUUFKWLJGBFY-UHFFFAOYSA-M 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000003927 aminopyridines Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 claims description 2
- 150000004950 naphthalene Chemical class 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- 239000000523 sample Substances 0.000 description 11
- 230000009467 reduction Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000000243 solution Substances 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 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002790 naphthalenes Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Chemical compound O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 description 2
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Chemical compound [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 239000013643 reference control Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 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
- 108091007643 Phosphate carriers Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DUSBUJMVTRZABV-UHFFFAOYSA-M [O-2].O[Nb+4].[O-2] Chemical compound [O-2].O[Nb+4].[O-2] DUSBUJMVTRZABV-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002821 niobium Chemical class 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Images
Classifications
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- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of industrial catalysis, in particular to a niobium-based carrier and a preparation method thereofThe carrier contains niobium oxide, niobium phosphate, niobium-silicon mixed oxide, niobium-aluminum mixed oxide, porous carbon-niobium material, ceOx-NbOy and TiO 2 -NbOz, the relative crystallinity of the carrier is more than 1%, and the specific surface area is not less than 120m 2 (ii) in terms of/g. The niobium-based carrier provided by the invention has high specific surface area and high crystallinity, is a microscopic nano material, is beneficial to uniform modification and loading of active components, and can efficiently disperse the loaded active components through surface bond energy. The catalyst prepared from the niobium-based carrier has an outstanding effect on treating xylene tower bottoms, and shows more excellent reaction activity and product monocyclic aromatic selectivity in practical application.
Description
Technical Field
The invention relates to the technical field of industrial catalysis, in particular to a niobium-based carrier and a preparation method thereof, a niobium-based supported catalyst and a preparation method thereof, and a monocyclic aromatic hydrocarbon production method.
Background
The aromatic hydrocarbon conversion technology is an important basis of aromatic hydrocarbon complete system engineering, and a low-value aromatic hydrocarbon raw material is used for producing a high-value monocyclic aromatic hydrocarbon product. In recent years, with the popularization and application of new energy technologies, the gasoline consumption market is expected to show a descending trend in the future. In addition, as the quality of the gasoline is upgraded, the limit on the content of aromatic hydrocarbons, particularly heavy aromatic hydrocarbons, in the gasoline is further reduced.
The traditional aromatic hydrocarbon combination device generally comprises a xylene tower, wherein the material in the xylene tower can be partially circulated back to a disproportionation reaction device for feeding, all the material in the xylene tower is difficult to be completely circulated back to the feeding for composition, and due to the limitation of the prior art, the active component in the composition of the conventional catalyst is difficult to adapt to the complex component of the material in the xylene tower under high concentration. On one hand, the poor aromatic hydrocarbon raw material is not fully burnt, which is easy to cause larger pollution, the cracking product is complex, the selectivity is poor, the yield is low (US 2020017772A 1), and the conversion requirements of high efficiency and environmental protection are difficult to meet. On the other hand, the supply of monocyclic aromatic hydrocarbon products such as p-xylene is short, and the inferior heavy aromatic hydrocarbon is converted into BTX chemical products, so that the method is an effective technical route for realizing upgrading and utilization of the inferior heavy aromatic hydrocarbon. The technology for producing the monocyclic aromatic hydrocarbon by catalytic conversion of the xylene column bottoms of a new generation is developed, high-value-added chemicals are efficiently produced with high selectivity, and the method has important significance for optimizing the product structure, reducing the accumulation of inferior materials and improving the economic benefit of an aromatic hydrocarbon device.
In heterogeneous catalyst systems, "molecular pen" catalysts are designed to match the reaction steps using a rigorous manufacturing process, but this elaborate construction is very demanding and difficult to implement (Science, 2020, doi 10.1126/Science. Aaw 1108).
Disclosure of Invention
The invention aims to overcome the defects that the conventional catalyst in the prior art is difficult to adapt to complex components of xylene tower bottoms under high concentration, the complex components are used as composition feeding materials, all the xylene tower bottoms are difficult to completely circulate back to disproportionation reaction, and the catalytic performance needs to be further improved, and provides a niobium-based carrier, a preparation method thereof, a niobium-based supported catalyst, a preparation method thereof and a monocyclic aromatic hydrocarbon production method.
The inventor develops a catalyst technology by research and application of a novel niobium-based material, pertinently uses a poor heavy aromatic hydrocarbon mixture at a xylene column kettle as a single raw material, and researches how to maximize yield increase of a monocyclic aromatic hydrocarbon product; researches show that the functionalized catalyst generally needs to effectively improve the mass transfer and adsorption activation rates and effectively generate a synergistic catalytic effect, wherein the high dispersion and partial controllable crystallization stabilization of active components are the most critical research contents, are beneficial to the selectivity of the catalyst and exist on the surface of the catalyst in a stable 'dotted' form; in addition, the stability of the common alumina carrier after the active component is loaded is poor, even physical or chemical methods such as a metal coating agent and a complexing agent are needed, and the process operation difficulty is high. Based on this, the inventors have further studied to provide the present invention.
In order to achieve the above objects, the present invention provides in a first aspect a niobium-based support comprising niobium oxide, niobium phosphate, niobium-silicon mixed oxide, niobium-aluminum mixed oxide, porous carbon-niobium material, ceOx-NbOy and TiO 2 At least one of NbOz, the relative crystallinity of the carrier is more than 1%, and the specific surface area is not less than 50m 2 /g。
In a second aspect, the present invention provides a method for preparing a niobium-based carrier, the method comprising:
performing crystallization reaction on a niobium source, an organic additive and at least one of an optional phosphorus source, a silicon source, an aluminum source, a carbon source, a cerium source and a titanium source by a solid phase method, a hydrothermal method or an irradiation method;
in the solid phase method, the crystallization reaction conditions comprise: the temperature is 120-600 ℃,
in the hydrothermal method, crystallization reaction conditions comprise: the temperature is 80-220 ℃, and the liquid-solid ratio is 2-30;
in the irradiation method, the crystallization reaction conditions comprise: the irradiation intensity is 200-1000 microwatts/cm 2 ；
Wherein, the adding amount of the organic additive is 2-50wt% based on the total amount of the raw materials.
The third aspect of the present invention provides a niobium-based supported catalyst, which comprises a carrier and an active component; the support is selected from the niobium-based support of the first aspect or the niobium-based support prepared by the method of the second aspect.
A fourth aspect of the present invention provides a method for producing the niobium-based supported catalyst according to the third aspect, the method comprising:
the active ingredient is introduced into the support by impregnation, ion exchange, precipitation or physical kneading, and is then optionally dried and calcined.
The fifth aspect of the present invention provides a method for producing monocyclic aromatic hydrocarbons, which comprises: and under the dealkylation condition, contacting the heavy aromatic hydrocarbon mixture with a catalyst, wherein the catalyst is the niobium-based supported catalyst of the third aspect or the niobium-based supported catalyst prepared by the method of the fourth aspect.
The niobium-based carrier provided by the invention has proper high specific surface area and high crystallinity, is a microscopic nano material, is beneficial to uniform modification and loading of active components, and can efficiently disperse the loaded active components through surface bond energy. In contrast, the carrier in the prior art generally has a small specific surface area under the condition of high crystallinity, or has low crystallinity and is amorphous under the condition of large specific surface area. Compared with common oxide carriers such as alumina and the like, the niobium-based carrier disclosed by the invention is weak in sensitivity to water, good in stability after being loaded with active components, and has the advantages of large treatment capacity on inferior raw materials, good selectivity of reaction products, high concentration of monocyclic high-added-value aromatic hydrocarbons and the like.
The specific niobium-based carrier is adopted in the niobium-based supported catalyst provided by the invention, so that the high dispersion of active components can be realized, and the niobium-based supported catalyst exists on the surface of the carrier in a stable 'dotted' form, so that the mass transfer and adsorption activation rate of the catalyst can be effectively improved, a synergistic catalytic effect is effectively generated, the catalytic activity and stability of the catalyst are greatly improved, the technical problems are well solved, and the niobium-based supported catalyst has excellent reaction performance in a complex xylene tower residue conversion reaction.
The method for producing the monocyclic aromatic hydrocarbon adopts the specific catalyst, can efficiently convert heavy aromatic hydrocarbon mixture (such as xylene tower residue) into BTX monocyclic aromatic hydrocarbon liquid-phase product through the selective saturation and high-selectivity dealkylation effects of aromatic rings, solves the problems of active site poisoning and coking of the traditional alumina carrier catalyst under the high-temperature reaction condition, and can adapt to the reaction working condition of high airspeed. Compared with the prior art which adopts the forms of partial mixed feeding, composite bed catalyst and the like, the method has better operability.
The catalyst provided by the invention is formed controllably by uniformly loading the active component on the specific niobium-based carrier after modification, the technical cost is controllable, the treatment effect on the xylene column residue is outstanding, and the catalyst shows more excellent reaction activity and the selectivity of the product monocyclic aromatic hydrocarbon in practical application. The catalyst provided by the invention can show more excellent comprehensive performance and stability in practical application according to the actual composition and production requirements of complex raw materials, and can be used in industrial production.
Drawings
FIG. 1 is an FE-SEM photograph of a niobium-based support of example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, MOn is an oxide form of M, n is the number of O atoms satisfying the valence of M, and n is hereinafter x, y, z, or the like. For example, ceOx refers to a multivalent oxide of Ce, nbOy refers to a multivalent oxide of Nb (including but not limited to at least one of niobium monoxide, niobium dioxide, niobium trioxide, niobium pentoxide), and NbOz refers to the same or different crystalline form of the oxide as NbOy.
First aspect of the inventionA niobium-based carrier is provided, which comprises niobium oxide and niobium phosphate (i.e., nbOxPO) 4 ) Niobium-silicon mixed oxide, niobium-aluminum mixed oxide, porous carbon-niobium material, ceOx-NbOy and TiO 2 -NbOz, the relative crystallinity of the carrier is more than 1%, and the specific surface area is not less than 120m 2 /g。
In the present invention, the niobium-silicon mixed oxide refers to a mixed crystalline oxide containing niobium and silicon, and the specific mixed form thereof is not limited in any way, and may be, for example, a mixture of niobium oxide and silicon oxide. The niobium-aluminum mixed oxide refers to a mixed crystalline oxide containing niobium and aluminum, and the present invention is not limited to any particular form of mixing thereof, and may be, for example, a mixture of niobium oxide and aluminum oxide, specifically, a mechanical mixing of their respective crystals. The porous carbon niobium material refers to a product of niobium oxide crystal growth with a carbon material as a substrate, such as a porous hollow carbon nanosphere. The CeOx-NbOy refers to a crystalline mixture of oxides of Ce and Nb. The TiO is 2 -NbOz refers to a mixture of oxides of Ti and Nb.
Preferably, the relative crystallinity of the support is from 1 to 100%, more preferably from 5 to 100%, even more preferably from 15 to 80%.
In the invention, the determination of the relative crystallinity is completed by relying on an XRD characterization technology, and the specific test method comprises the following steps: the light source is Cu target Kalpha ray, the tube voltage is 40kV, the tube current is 30mA, the scanning speed is 2 degrees/min, and the diffraction pattern is recorded in the range of 2 theta being 5-80 degrees.
Preferably, the specific surface area of the carrier is 120 to 700m 2 A/g, more preferably 200 to 600m 2 /g。
In the present invention, the specific surface area is obtained by analyzing and measuring by means of low-temperature nitrogen adsorption and desorption, which is well known to those skilled in the art and will not be described herein.
According to the invention, preferably, the amount of surface hydroxyl groups of the support is between 0.2 and 30 mol/m 2 Preferably 0.5 to 20 mol/m 2 More preferably 1 to 20 mol/m 2 . Under the preferable scheme, the reaction activity of the catalyst prepared by the carrier is improved, and the catalyst isThe product, when used, is monocyclic aromatic selective.
In the invention, the hydroxyl quantity is obtained by testing an infrared spectrum (FT-IR) on an NICOLET6700 Fourier transform infrared spectrometer of Nicolet company in America, and the specific testing method comprises the following steps: tabletting the pure sample, dewatering, cooling to room temperature, and obtaining a spectral resolution of 4.0cm -1 Scanning range 4000cm -1 -400cm -1 The detector is MCT/A, and the scanning times are 32 times. In the hydroxyl infrared testing process, a sample is firstly activated in an in-situ pool at 450 ℃ for 1h in vacuum, then is sequentially cooled to 400 ℃, 300 ℃, 200 ℃ and room temperature (reference control sample detection temperature) in situ, and after the temperature points are balanced for 5min, the hydroxyl infrared spectrogram at the corresponding temperature is tested by in-situ diffuse reflection Fourier transform infrared spectrum scanning.
According to the invention, the niobium is preferably present in an amount of 5 to 100% by weight, more preferably 15 to 60% by weight, based on the total amount of oxides of the support on a dry basis, in moles.
The niobium-based carrier provided by the invention has high specific surface area and high crystallinity, and can efficiently carry active components through surface bonds with high dispersion, thereby improving the reaction performance of the obtained catalyst.
In a second aspect, the present invention provides a method for preparing a niobium-based carrier, the method comprising: performing crystallization reaction on a niobium source, an organic additive and at least one of an optional phosphorus source, a silicon source, an aluminum source, a carbon source, a cerium source and a titanium source by a solid phase method, a hydrothermal method or an irradiation method;
in the solid phase method, the crystallization reaction conditions comprise: the temperature is 120-600 ℃,
in the hydrothermal method, crystallization reaction conditions comprise: the temperature is 80-220 ℃, and the liquid-solid ratio is 2-30;
in the irradiation method, the crystallization reaction conditions comprise: the irradiation intensity is 200-1000 microwatts/cm 2 ；
Wherein, the adding amount of the organic additive is 2-50wt% based on the total amount of the raw materials.
In the present invention, the "optional at least one of a phosphorus source, a silicon source, an aluminum source, a carbon source, a cerium source, and a titanium source" means that at least one of the phosphorus source, the silicon source, the aluminum source, the carbon source, the cerium source, and the titanium source may be introduced, or at least one of the phosphorus source, the silicon source, the aluminum source, the carbon source, the cerium source, and the titanium source may not be introduced. The person skilled in the art can freely choose them according to the actual requirements.
In the present invention, the niobium source and the optional phosphorus source, silicon source, aluminum source, carbon source, cerium source and titanium source are used in amounts such that the niobium-based carrier of the first aspect is obtained, which is not described herein again.
In the invention, the selectable range of the niobium source is wide, as long as the niobium element can be introduced and converted by the method to obtain the required carrier; preferably, the niobium source is selected from at least one of niobium oxide, niobium oxalate, niobium nitrate, and niobic acid. The niobic acid may be dry niobic acid or wet niobic acid, and the invention is not limited thereto.
In the present invention, the specific types of the phosphorus source, the silicon source, the aluminum source, the carbon source, the cerium source or the titanium source may be those that can be converted by the above method to obtain the desired vector; preferably, the phosphorus source, the silicon source, the aluminum source, the carbon source, the cerium source or the titanium source is at least one selected from oxides, acids, salts and esters each independently containing a phosphorus element, a silicon element, an aluminum element, a carbon element, a cerium element or a titanium element. For example, the phosphorus source may preferably be at least one of phosphoric acid, aluminum dihydrogen phosphate, and elemental phosphorus. The silicon source may be an organic silicon source and/or an inorganic silicon source, and is preferably at least one of silicon dioxide, silicon powder, white carbon black, silica sol, water glass, silicon oil and silicon ester, wherein a person skilled in the art can freely select the concentration of silicon dioxide in the silica sol according to a requirement, and a person skilled in the art can select a specific type of silicon ester according to a requirement as long as the silicon source can be converted into silicon oxide. The aluminum source may preferably be at least one of aluminum sulfate, aluminum nitrate, pseudoboehmite, aluminum hydride, alumina sol, sodium metaaluminate, and aluminum dihydrogen phosphate, wherein the concentration of the alumina sol may be freely selected by those skilled in the art as desired. The carbon source may preferably be at least one material of carbon nanotubes, carbon nanofibers, nanocarbon spheres, and silicon carbide. The cerium source may preferably be at least one of cerium ammonium nitrate, cerium nitrate, and cerium zirconium powder. The titanium source may preferably be at least one of butyl titanate, titanium oxide and titanium silicalite.
In the invention, the introduced organic additive plays the roles of a crystal structure directing agent and a template in the nucleation and crystal growth processes. Preferably, the organic additive is selected from at least one of quaternary ammonium salt, quaternary ammonium base, urotropin, imidazole and aminopyridine. The quaternary ammonium salt may be, for example, a chloride salt, a bromide salt, a fluoride salt, an iodide salt, or an alkyl-substituted quaternary ammonium salt, and specifically, cetyl trimethyl ammonium bromide may be mentioned. The quaternary ammonium hydroxide may be, for example, an alkyl-substituted quaternary ammonium hydroxide, and specifically may be at least one of tetraethylammonium hydroxide, dimethyldiethylammonium hydroxide, tetrapropylammonium hydroxide and ethyltripropylammonium hydroxide.
More preferably, the organic additive is at least one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, tetraethylammonium fluoride, ethyltripropylammonium fluoride, tetraethylammonium hydroxide, dimethyldiethylammonium fluoride, tetrapropylammonium hydroxide, ethyltripropylammonium hydroxide, urotropin, imidazole, n-aminopyridine, wherein n is 1, 2, 3 or 4. By adopting the preferred scheme of the invention, the performance of the catalyst prepared by the obtained carrier, especially the selectivity of the monocyclic aromatic hydrocarbon, can be improved.
Further preferably, the organic additive is at least one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, tetraethylammonium fluoride, ethyltripropylammonium fluoride, tetraethylammonium hydroxide, dimethyldiethylammonium fluoride, tetrapropylammonium hydroxide, ethyltripropylammonium hydroxide, n-aminopyridine, wherein n is 1, 2, 3 or 4.
In the present invention, the organic additive is preferably added in an amount of 3 to 30wt%, more preferably 10 to 25wt%, further preferably 15 to 25wt%, and further preferably 20 to 25wt%, based on the total amount of the raw materials.
In the present invention, the hydrothermal method has a conventional meaning in the art, and can be carried out according to a method existing in the art as long as a niobium-based support having the aforementioned specific crystallinity and specific surface area can be produced. According to a preferred embodiment of the present invention, the hydrothermal process comprises: performing hydrothermal crystallization on a niobium source, an organic additive and at least one of an optional phosphorus source, a silicon source, an aluminum source, a carbon source, a cerium source and a titanium source with water.
Preferably, the conditions of the hydrothermal crystallization include: the temperature is 120-220 deg.C, and the time is 0.5-200h, preferably 20-60h.
Preferably, in the hydrothermal crystallization, the liquid-solid ratio is 5-30, and more preferably 5-15. Under the preferable scheme, the crystallization reaction is promoted, so that the crystallinity and the specific surface area of the obtained carrier are improved, and the consumption of raw materials is saved.
Preferably, the hydrothermal crystallization is performed under autogenous pressure.
In the present invention, the self-generated pressure refers to the pressure generated by the system itself without additional control of pressure.
In the present invention, the solid phase method has a conventional meaning in the art, and may be carried out according to a conventional method in the art as long as a niobium-based support having the above-mentioned specific crystallinity and specific surface area can be produced. For example, in one embodiment, the solid phase method comprises: mixing a niobium source, an organic additive and at least one of an optional phosphorus source, a silicon source, an aluminum source, a carbon source, a cerium source and a titanium source, grinding, and then carrying out crystallization reaction.
In the solid phase method, preferably, the crystallization reaction conditions include: the temperature is 200-550 deg.C, and the time is 0.5-200h, preferably 1-30h.
In the solid phase method, preferably, the crystallization reaction is performed under autogenous pressure or under vacuum conditions.
The grinding is more advantageous for the crystallization reaction, the size of the particles obtained by grinding is not particularly limited, and those skilled in the art can appropriately select the size by actual conditions.
In the present invention, the irradiation method has a conventional meaning in the art, and may be performed according to a method existing in the art as long as a niobium-based support having the aforementioned specific crystallinity and specific surface area can be prepared. For example, in one embodiment, the irradiation process comprises: under the condition of microwave irradiation, a niobium source, an organic additive and at least one of an optional phosphorus source, a silicon source, an aluminum source, a carbon source, a cerium source and a titanium source are subjected to crystallization reaction.
In the present invention, preferably, the irradiation method includes: firstly, mixing all the raw materials, and then carrying out crystallization reaction under the microwave irradiation condition.
Preferably, the microwave irradiation conditions include: the irradiation intensity is 200-500 microwatts/cm 2 The irradiation time is 1-12h.
In the irradiation method of the present invention, the treatment may be performed at a certain irradiation intensity or at a gradient irradiation intensity, and the present invention is not limited thereto, and those skilled in the art can freely select the irradiation intensity as long as the preparation of the carrier having the composition is facilitated.
The preparation method provided by the invention can be used for preparing the niobium-based carrier with high crystallinity and high specific surface area, and is beneficial to uniform modification and loading of active components.
The third aspect of the present invention provides a niobium-based supported catalyst, which comprises a carrier and an active component; the support is selected from the niobium-based support of the first aspect or the niobium-based support prepared by the method of the second aspect.
According to the present invention, preferably, the active component is a metal and/or a metal oxide.
In a particularly preferred embodiment, the metal is selected from at least one of group VIII metals, group VIIB metals and group IB metals. More preferably, the metal is selected from at least one of Fe, co, ni, ru, rh, pd, os, ir, pt, re, au, ag and Cu, and further preferably, the metal is selected from at least one of Ni, pt and Re.
In a more preferred embodiment, the metal is selected from at least one of group VIII metals and at least one of group VIIB metals, further preferably the metal is selected from at least one of Fe, co, ni, ru, rh, pd and Re.
By adopting the preferable scheme of the specific metal, more excellent reaction activity and monocyclic aromatic hydrocarbon selectivity of the product are shown in the xylene column bottom material treatment.
Preferably, the metal is present in an amount of 0.001 to 10wt%, more preferably 0.01 to 5wt%, based on the total amount of catalyst. Preferably, the support is present in an amount of 90 to 99.999 wt%, more preferably 95 to 99.99 wt%, calculated as oxide, based on the total amount of catalyst.
In a particularly preferred embodiment, the metal oxide is selected from at least one of lanthanide metal oxides, group IIIB metal oxides, group IVB metal oxides, group VB metal oxides, group VIB metal oxides, group IIIA metal oxides, group IVA metal oxides, and group VA metal oxides, more preferably an oxide of at least one of La, pr, nd, ti, V, cr, zr, sn, bi, W, Y, mo, al, ga, and In, and even more preferably an oxide of at least one of Ti, V, cr, zr, sn, bi, W, Y, and Mo. By adopting the preferable scheme of the invention, more excellent reaction activity and monocyclic aromatic hydrocarbon selectivity of the product are shown in the xylene tower residue treatment.
Preferably, the metal oxide is present in an amount of 0.001 to 40 wt%, more preferably 3 to 30wt%, based on the total amount of the catalyst. Preferably, the support is present in an amount of 60 to 99.999 wt%, more preferably 70 to 97 wt%, calculated as oxide, based on the total amount of catalyst.
The catalyst provided by the invention has excellent reaction activity and stability, solves the problems of active site poisoning and coking of the traditional alumina carrier catalyst under the high-temperature reaction condition in the presence of hydrogen, and can adapt to the reaction working condition with high airspeed.
The catalyst provided by the invention is preferably reduced before use, the reduction can be carried out immediately after the preparation of the catalyst, or the catalyst can be stored for a certain time after the preparation, and the catalyst is uniformly reduced before useThe reducing agent is used for reduction. The method for reduction can be selected by those skilled in the art according to actual requirements, for example, the method for reduction can be a room temperature irradiation reduction method, and can also be a high temperature reduction (preferably hydrogen-containing atmosphere, more preferably H) 2 /N 2 Atmosphere, invention for H 2 The content is not particularly limited and can be freely selected by those skilled in the art according to actual needs). The room temperature irradiation reduction method and the high temperature reduction method can be carried out according to the corresponding methods in the prior art, and are not described herein again for the prior art. More preferably, the hydrogen-containing atmosphere is provided by hydrogen and an inert gas, which may be any one of nitrogen, neon, helium and argon.
A fourth aspect of the present invention provides a method for producing the niobium-based supported catalyst according to the third aspect, the method comprising: the active ingredient is introduced into the support by impregnation, ion exchange, precipitation or physical kneading, optionally followed by drying and calcination.
In the present invention, preferably, an impregnation method is used, and more preferably, an equal volume impregnation method is used. By adopting the preferred scheme of the invention, the active ingredients are more favorably and uniformly dispersed on the carrier with high efficiency. In the present invention, the isometric impregnation method has a conventional meaning in the field, that is, impregnation is performed by using an impregnation solution with a volume equal to the water absorption capacity of the carrier, which is a conventional method in the field and is not described herein again.
According to a first preferred embodiment of the invention, an impregnation method is used, in particular comprising: impregnating the carrier with an impregnation solution containing an active component precursor, shaping, and optionally drying and calcining.
The present invention is not limited to the kind of the active component precursor as long as the active component can be supported on the carrier. For example, the active component precursor may be a salt (preferably an acid salt) or a complex of the corresponding active component, the salt may be at least one of nitrate, acetate, chlorate, ammonium salt, sulfate and the like, for example, at least one of ammonium dimolybdate, chloroplatinic acid, ammonium perrhenate and nickel nitrate, and the complex may be any one of existing complexes containing the active component, which will not be described in detail herein. The optional ranges of the active ingredients herein are the same as those of the active ingredients of the aforementioned third aspect, and are not described herein again.
Preferably, the active component precursor is used in an amount such that the content of the active component in the prepared catalyst satisfies the desired corresponding content.
Preferably, the impregnation liquid further contains a solvent.
The solvent of the present invention can be selected from a wide range as long as the active component precursor can be dissolved or dispersed in the solvent. Preferably, the solvent is selected from at least one of water, alcohol amine, acid, thioether and ketone.
More preferably, the solvent is selected from at least one of water, methanol, ethanol, ethanolamine, ethyl sulfide, isopropanol, acetone, acetic acid and citric acid.
Further preferably, the impregnation liquid further contains a surfactant and/or a complexing agent. The present invention does not have any limitation on the kinds of the surfactant, such as sodium polyacrylate, and the complexing agent, such as EDTA (i.e., ethylenediaminetetraacetic acid) and disodium ethylenediaminetetraacetate, as long as the active component precursor can be dissolved or dispersed in the solvent. In the present invention, the amount of the surfactant and the complexing agent in the impregnation liquid is not limited as long as the active component precursor can be dissolved or dispersed in the solvent, and for example, the molar ratio of the total amount of the surfactant and/or the complexing agent to the solvent may preferably be 0.1 to 10.
In the present invention, the amounts of the solvent, the surfactant and the complexing agent in the impregnation solution are not limited, as long as the active component precursor can be dissolved or dispersed in the solvent, and those skilled in the art can freely select the amount according to the requirements. For example, the molar ratio of the total amount of the active components, calculated as oxides, to the solvent may preferably be from 1.
According to the present invention, there is no limitation on the conditions of the impregnation, and the impregnation may be performed once or multiple times, as long as a desired amount of the active component precursor can be loaded on the carrier, and may be any impregnation method existing in the art, and will not be described herein again.
The molding method of the present invention is not limited in any way, and can be carried out according to any molding method known in the art, as long as the molding can be carried out to obtain the catalyst in a desired shape, for example, kneading molding. Preferably, a binder is introduced in the forming. The kind and amount of the binder, which may be, for example, aluminum dihydrogen phosphate, etc., are not particularly limited in the present invention, and may be freely selected by those skilled in the art as long as molding can be performed.
In the present invention, the ion exchange method has a conventional meaning in the art, and can be performed according to the existing ion exchange method in the art as long as it is capable of introducing the active ingredient into the carrier, and will not be described herein again.
In the present invention, the precipitation method has a conventional meaning in the art, and can be performed according to the existing precipitation method in the art as long as the active ingredient can be introduced into the carrier, and thus, the details are not described herein.
In the present invention, the physical kneading method has a conventional meaning in the art, and may be performed according to a method existing in the art as long as the active ingredient can be introduced into the carrier. For example, in one particularly preferred embodiment, the method comprises: the carrier, the active component precursor and optionally water are kneaded to form a shape, and then the optional drying and baking are performed.
The amount of the water used in the present invention is not limited, as long as the active component precursor can be dissolved and kneading molding is facilitated, and those skilled in the art can freely select the water according to actual requirements.
In the invention, after the active component is introduced into the carrier, the active component can be dried and then roasted; or directly roasting. The former is preferred. The conditions for said drying are not subject to any restrictions by the present invention and can be freely chosen by the person skilled in the art according to the actual requirements.
Preferably, the conditions of the calcination include: the roasting temperature is 300-700 ℃, and the roasting time is 0.5-12h.
Preferably, the roasting conditions further include: heating to the roasting temperature at a heating rate of 0.1-20 ℃/min.
In the present invention, preferably, the calcination is performed in an oxygen-containing atmosphere or an inert atmosphere. The oxygen-containing atmosphere may be any one of air, oxygen-deficient atmosphere and oxygen-enriched atmosphere. The inert atmosphere may be any one of nitrogen, neon, helium and argon.
The preparation method of the niobium-based supported catalyst provided by the invention solves the matching problem of the catalytic effect and various synthesis parameters in the preparation process of the catalyst.
The fifth aspect of the present invention provides a method for producing a monocyclic aromatic hydrocarbon, comprising: under dealkylation conditions, the heavy aromatic hydrocarbon mixture is contacted with a catalyst, wherein the catalyst is the niobium-based supported catalyst of the third aspect or the niobium-based supported catalyst prepared by the method of the fourth aspect.
In a particularly preferred embodiment, the heavy aromatics blend is xylene column bottoms, more preferably xylene column bottoms of an aromatics complex. In the present invention, the xylene column bottoms of the aromatics complex have conventional definitions in the art. The catalyst of the invention is especially suitable for composing complicated, high-concentration and poor-quality xylene tower residue.
In the present invention, said C 9 + The aromatic hydrocarbon refers to a mixed material containing heavy aromatic hydrocarbons with more than C9. Preferably, the heavy aromatics blend contains C 9 + Aromatic hydrocarbon of said C 9 + The content of aromatic hydrocarbons is not less than 95% by weight. Said C is 9 + The aromatic hydrocarbon means an aromatic hydrocarbon having not less than 9 carbon atoms.
More preferably, the heavy aromatic hydrocarbon mixture also contains C9-C12 heavy non-aromatic hydrocarbons, and the content of the C9-C12 heavy non-aromatic hydrocarbons is not more than 3 wt%. The heavy non-aromatic hydrocarbon of C9-C12 refers to the non-aromatic hydrocarbon with the C number of 9-12.
More preferably, the heavy aromatic hydrocarbon mixture also contains C9-C14 heavy aromatic hydrocarbons and/or naphthalene series, and the total content of the C9-C14 heavy aromatic hydrocarbons and/or the naphthalene series is not more than 2wt%. The heavy aromatic hydrocarbon of C9-C14 refers to the heavy aromatic hydrocarbon with 9-14C atoms. The naphthalene series substance refers to naphthalene and derivatives thereof.
According to the present invention, preferably, the dealkylation reaction conditions include: under the condition of hydrogen, the hydrogen-hydrocarbon molar ratio is 0.5-30, and the weight space velocity of the heavy aromatic hydrocarbon mixture is 0.1-10h -1 The reaction pressure is 0-50MPa, and the reaction temperature is 200-600 ℃. In the present invention, the hydrogen-hydrocarbon molar ratio means a molar ratio of hydrogen gas to the raw material hydrocarbon in terms of C atoms.
The method for producing the monocyclic aromatic hydrocarbon can realize that the yield of the monocyclic aromatic hydrocarbon product is increased to the maximum extent by taking the poor-quality heavy aromatic hydrocarbon mixture (namely the xylene tower residue) of the xylene tower residue as a single raw material, can efficiently produce the monocyclic aromatic hydrocarbon product, improves the economy of the production process, and can adapt to the reaction working condition of high airspeed.
The present invention will be described in detail below by way of examples.
In the following examples, the relative crystallinity was determined by XRD characterization technique, and the specific test method was: the light source is Cu target Kalpha ray, the tube voltage is 40kV, the tube current is 30mA, the scanning speed is 2 degrees/min, and the diffraction pattern is recorded in the range of 2 theta being 5-80 degrees.
In the following examples, the specific surface area was determined by analysis using a low-temperature nitrogen adsorption and desorption method.
In the following examples, the hydroxyl content was measured by infrared spectroscopy (FT-IR) on a Nicolet6700 fourier transform infrared spectrometer, nicolet corporation, usa, using the specific test method: tabletting the pure sample, dewatering, cooling to room temperature, and obtaining a spectral resolution of 4.0cm -1 Scanning range 4000cm -1 -400cm -1 The detector is MCT/A, and the scanning times are 32 times. In the hydroxyl infrared testing process, a sample is firstly activated in vacuum for 1 hour at 450 ℃ in an in-situ pool, then is sequentially cooled to 400 ℃, 300 ℃, 200 ℃ and room temperature (reference control sample detection temperature) in situ, and after the temperature points are balanced for 5 minutes, in-situ diffuse reflection Fourier transform infrared spectrum scanning is carried out to test a hydroxyl infrared spectrogram at corresponding temperature.
The particle size was measured by malvern particle sizer.
Example 1
Preparation of niobium-based carrier: firstly, a niobium phosphate carrier is synthesized by a solid phase method (the specific surface area, the crystallinity and the hydroxyl content of the carrier are shown in table 1, and an FE-SEM image is shown in figure 1), and the specific synthesis method comprises the following steps: mixing a niobium source (specifically niobium oxalate), a phosphorus source (specifically phosphoric acid) and an organic additive (ethyl tripropyl ammonium fluoride), grinding (grinding to enable the particle size to be 20 nm), and then carrying out crystallization reaction for 3 hours at 250 ℃; wherein the molar ratio of the niobium source calculated by the niobium element to the phosphorus source calculated by the phosphorus element is 1: and 1, the adding amount of the organic additive is 25wt% based on the total amount of the raw materials.
Preparation of the catalyst: the niobium phosphate support was then added in an equal volume impregnation to a mixed solution containing ammonium perrhenate and nickel nitrate in a molar ratio of 2, to ethanolamine, sodium polyacrylate (NaPA: mw ≈ 2100) and EDTA in a molar ratio of 1.
After the impregnation is finished, tabletting and forming are carried out, then the temperature is raised to 580 ℃ at the rate of 2 ℃/min in the air atmosphere for roasting for 3 hours, and the obtained product is put into a furnace for roasting in H 2 The reduction was carried out at 450 ℃ for 3 hours to obtain catalyst A1.
Example 2
Hydrothermal synthesis of TiO using CTAB (hexadecyltrimethylammonium bromide) 2 The specific surface area, crystallinity and hydroxyl group content of the-NbOx carrier are shown in Table 1, and the specific method comprises the following steps: carrying out hydrothermal crystallization on a niobium source (niobic acid), a titanium source (specifically butyl titanate), an organic additive (CTAB) and water at 180 ℃ for 30 hours, wherein the liquid-solid ratio (namely the weight ratio of the water to the total amount of the niobium source, the titanium source and the organic additive) is 16, then filtering, and drying at 150 ℃ for 6 hours; wherein the molar ratio of the niobium source calculated by the niobium element to the titanium source calculated by the titanium element is 2:1, taking the total amount of all raw materials as a reference, and adding the organic additiveIs 15wt%.
The carrier is added into a chloroplatinic acid-ethanol solution in an equal-volume impregnation mode, the dosage of the chloroplatinic acid is such that the mass fraction of the platinum of the prepared catalyst after reduction is 0.05wt% compared with the carrier, and the molar ratio of the platinum metal to the solvent (namely ethanol) is 1.
Kneading the impregnated sample with 49 g of aluminum dihydrogen phosphate, molding, heating the molded sample to 550 ℃ at a heating rate of 1.5 ℃/min in an air atmosphere, roasting for 4 hours, and calcining in H 2 The reaction was carried out at 400 ℃ for 6 hours to obtain catalyst A2.
Example 3
Adding quaternary ammonium salt water to synthesize the niobium-silicon mixed oxide carrier (the specific surface area, the crystallinity and the hydroxyl content of the carrier are shown in table 1) by a thermal synthesis method, which comprises the following steps: carrying out hydrothermal crystallization on a niobium source (specifically niobic acid), a silicon source (specifically active white carbon black), an organic additive (specifically ethyl tripropyl ammonium fluoride) and water at 200 ℃ for 48 hours, wherein the liquid-solid ratio (namely the weight ratio of the water to the total amount of the niobium source, the silicon source and the organic additive) is 10, then filtering, and drying at 90 ℃ for 4 hours; wherein the molar ratio of the niobium source calculated by the niobium element to the silicon source calculated by the silicon element is 1:1, the adding amount of the organic additive is 22wt% based on the total amount of the raw materials.
And then adding the carrier into an ammonium dimolybdate aqueous solution by a physical kneading method for kneading and molding, wherein the using amount of the ammonium dimolybdate is such that the mass fraction of the molybdenum oxide compared with the carrier is 3wt%, and the concentration of the ammonium dimolybdate in the ammonium dimolybdate aqueous solution is 15wt%. The molded sample is heated to 500 ℃ in the air atmosphere at a heating rate of 2.5 ℃/min and is roasted for 3.5 hours to obtain the catalyst A3.
Example 4
The procedure of example 1 was followed except that the carrier was different, specifically, ceOx-NbOy carrier (the specific surface area, crystallinity and hydroxyl group amount of the carrier are shown in Table 1) was synthesized by the solid phase method by the following specific synthesis method: mixing a niobium source (specifically niobium oxalate), a cerium source (specifically ammonium ceric nitrate) and an organic additive (specifically dimethyl diethyl ammonium hydroxide), grinding, and then performing a crystallization reaction at 400 ℃ for 20 hours; wherein the molar ratio of the niobium source calculated by the niobium element to the cerium source calculated by the cerium element is 0.5:1, the adding amount of the organic additive is 16wt% based on the total amount of the raw materials.
Example 5
The procedure was followed as in example 1 except that the support was different, specifically, a porous carbon niobium support was synthesized by a solid phase method (the specific surface area, crystallinity and hydroxyl group amount of the support are shown in Table 1) by the following specific synthesis method: mixing a niobium source (specifically wet niobic acid), a porous carbon niobium material (namely porous hollow carbon nanospheres) and an organic additive (specifically n-aminopyridine, n = 2), grinding, and then carrying out crystallization reaction for 5 hours at 500 ℃; wherein the molar ratio of the niobium source calculated by the niobium element to the carbon source calculated by the carbon element is 1.5:1, the adding amount of the organic additive is 24wt% based on the total amount of the raw materials.
Example 6
The procedure was carried out as in example 2, except that the organic additive was used in an amount of 10% by weight, and the specific surface area, crystallinity and amount of hydroxyl groups of the obtained carrier were as shown in Table 1.
Example 7
The procedure was carried out in accordance with the procedure of example 2 except that the liquid-solid ratio was 30 and the specific surface area, crystallinity and amount of hydroxyl groups of the obtained carrier were as shown in Table 1.
Example 8
The procedure of example 2 was followed, except that hydrothermal crystallization was carried out at 80 ℃ for 200 hours, and the specific surface area, crystallinity and hydroxyl group amount of the obtained carrier were as shown in Table 1.
Comparative example 1
The procedure was followed as in example 1, except that a pseudo-boehmite (PB) sample (having a specific surface area, a crystallinity and an amount of hydroxyl groups shown in Table 1) was used in place of the niobium phosphate support in example 1. Catalyst B1 was obtained.
Comparative example 2
The procedure is as in example 2, except that a sample of gamma-alumina (having a specific surface area, crystallinity and hydroxyl group content as shown in Table 1) is used in place of the TiO of example 2 2 -a NbOx support. Catalyst B2 was obtained.
Comparative example 3
The procedure is as in example 1, except that the niobium-based support is prepared by a different method, specifically: neutralizing with a niobium solution (commercial niobium solution, containing 3wt% HF) in a precipitation tank with aqueous ammonia to obtain Nb (OH) 5 Precipitating, pumping into a filter press for solid-liquid separation, washing with dilute ammonia water, filtering to remove fluoride ions, washing with pure water, blow-drying with air of 0.6-0.7Mpa to obtain a wet product, drying in a hot air circulation drying oven to obtain niobium hydroxide, and roasting to obtain the niobium-based carrier, wherein the amount of the niobium solution is used for preparing the required amount of the niobium-based carrier; this niobium-based support was then used in the same amount as in example 1 to prepare a catalyst according to the procedure of example 1, to obtain catalyst B3.
TABLE 1
| Source of vector | Specific surface area, m 2 /g | Relative degree of crystallinity,% | Amount of hydroxyl groups, mol/m 2 |
| Example 1 | 320 | 15 | 10 |
| Example 2 | 180 | 80 | 8 |
| Example 3 | 350 | 50 | 20 |
| Example 4 | 300 | 30 | 4.5 |
| Example 5 | 290 | 70 | 6 |
| Example 6 | 240 | 65 | 10 |
| Example 7 | 160 | 90 | 2 |
| Example 8 | 300 | 8 | 0.8 |
| Comparative example 1 | 330 | 4 | 2 |
| Comparative example 2 | 185 | 30 | 0.4 |
| Comparative example 3 | 350 | 0 | 0.5 |
Test example
The catalysts prepared in the above examples and comparative examples were evaluated on a continuous microreactor in a fixed bed reactor having a diameter of 25X 1200mm and a loading of 20.0 g, respectively.
Before evaluation, the catalyst was first sulfided for 6h at 280 ℃ and 3.0MPa in a toluene feed containing dimethyldisulfide (DMDS) at a concentration of 10ppm as elemental sulfur, and then switched to the normal evaluation feed.
The xylene column bottoms (composition: 60wt% C9 aromatics, 38wt% C10 aromatics, remainder C) 10 + Heavy aromatics and naphthalene series) as raw materials, the raw materials are contacted with a bed layer containing the catalyst, and the evaluation conditions are as follows: space velocity WHSV of raw material =1.5h -1 The pressure of a reaction system is 4MPa, the reaction temperature is 450 ℃, and the molar ratio H of hydrogen to hydrocarbon (namely hydrogen and raw materials calculated by C atoms) 2 and/HC =5. The reaction performance of the catalyst was calculated from the raw material composition and the product composition, and the results of the specific evaluation of the catalyst are shown in table 2, in which the conversion and B + T + X are data indicating that the reaction index was substantially stable.
TABLE 2
* The conversion in the table is the total mass conversion of the xylene column bottoms, conversion = (total weight of raw material-C in product) 9 + Total aromatics)/total weight of feedstock x 100%.
* B + T + X in the table is the sum of the mass percentages of benzene, toluene and xylene in the liquid phase product.
The results in table 2 show that the catalyst prepared by the invention has outstanding effect on treating xylene column bottoms, and shows excellent reaction activity and product monocyclic aromatic selectivity. Among these, it is clear from comparative example 2 and examples 7 to 8 that the preferable hydrothermal conditions are preferable.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A niobium-based carrier, which contains niobium oxide, niobium phosphate, niobium-silicon mixed oxide, niobium-aluminum mixed oxide, porous carbon-niobium material, ceOx-NbOy and TiO 2 -NbOz, the relative crystallinity of the carrier is more than 1%, and the specific surface area is not less than 120m 2 /g。
2. The niobium-based carrier according to claim 1, wherein the relative crystallinity of said carrier is 1 to 100%, more preferably 5 to 100%, further preferably 15 to 80%;
and/or the specific surface area of the carrier is 120-700m 2 A/g, more preferably 200 to 600m 2 /g。
3. The niobium-based support according to claim 1 or 2, wherein the amount of surface hydroxyl groups of the support is from 0.2 to 30 mol/m 2 Preferably 0.5 to 20 mol/m 2 More preferably 1 to 20 mol/m 2 。
4. A method of making a niobium-based support, the method comprising:
performing crystallization reaction on a niobium source, an organic additive and at least one of an optional phosphorus source, a silicon source, an aluminum source, a carbon source, a cerium source and a titanium source by a solid phase method, a hydrothermal method or an irradiation method;
in the solid phase method, the crystallization reaction conditions comprise: the temperature is 120-600 ℃;
in the hydrothermal method, crystallization reaction conditions comprise: the temperature is 80-220 ℃, and the liquid-solid ratio is 2-30;
in the irradiation method, the crystallization reaction conditions comprise: the irradiation intensity is 200-1000 microwatts/cm 2 ；
Wherein the adding amount of the organic additive is 2-50wt% based on the total amount of the raw materials.
5. The production method according to claim 4, wherein the niobium source is at least one selected from the group consisting of niobium oxide, niobium oxalate, niobium nitrate, and niobic acid;
and/or the phosphorus source, the silicon source, the aluminum source, the carbon source, the cerium source or the titanium source are at least one selected from oxides, acids, salts and esters containing phosphorus, silicon, aluminum, carbon, cerium or titanium, respectively;
preferably, the organic additive is selected from at least one of quaternary ammonium salts, quaternary ammonium bases, urotropin, imidazole and aminopyridine, more preferably at least one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, tetraethylammonium fluoride, ethyltripropylammonium fluoride, tetraethylammonium hydroxide, dimethyldiethylammonium fluoride, tetrapropylammonium hydroxide, ethyltripropylammonium hydroxide, urotropin, imidazole, n-aminopyridine, wherein n is 1, 2, 3 or 4;
and/or the organic additive is added in an amount of 3 to 30wt%, more preferably 10 to 25wt%, based on the total amount of the respective raw materials.
6. The preparation process according to claim 4 or 5, wherein the hydrothermal process comprises: carrying out hydrothermal crystallization on a niobium source, an organic additive and at least one of an optional phosphorus source, a silicon source, an aluminum source, a carbon source, a cerium source and a titanium source with water;
preferably, the conditions of the hydrothermal crystallization include: the temperature is 120-220 ℃, and the time is 0.5-200h;
and/or, the conditions of the hydrothermal crystallization comprise: the liquid-solid ratio is 5-30;
and/or, the hydrothermal crystallization is carried out under autogenous pressure.
7. The production method according to claim 4 or 5, wherein the solid phase method comprises: mixing a niobium source, an organic additive and at least one of an optional phosphorus source, a silicon source, an aluminum source, a carbon source, a cerium source and a titanium source, grinding, and then carrying out crystallization reaction;
preferably, the crystallization reaction conditions include: the temperature is 200-550 ℃, and the time is 0.5-200h;
and/or, the crystallization reaction is carried out under autogenous pressure or under vacuum conditions.
8. The production method according to claim 4 or 5, wherein the irradiation method includes: under the microwave irradiation condition, carrying out crystallization reaction on a niobium source, an organic additive and at least one of an optional phosphorus source, a silicon source, an aluminum source, a carbon source, a cerium source and a titanium source;
preferably, the microwave irradiation conditions are: the irradiation intensity is 200-500 microwatts/cm 2 The irradiation time is 1-12h.
9. A niobium-based supported catalyst, which comprises a carrier and an active component; the support is selected from the niobium-based support of any one of claims 1 to 3 or the niobium-based support prepared by the method of any one of claims 4 to 8;
preferably, the active component is a metal and/or metal oxide;
preferably, the metal is selected from at least one of group VIII, VIIB and IB metals, more preferably at least one of Fe, co, ni, ru, rh, pd, os, ir, pt, re, au, ag and Cu;
and/or the metal content is from 0.001 to 10% by weight, more preferably from 0.01 to 5% by weight, based on the total amount of catalyst;
preferably, the metal oxide is selected from at least one of lanthanide metal oxides, group IIIB metal oxides, group IVB metal oxides, group VB metal oxides, group VIB metal oxides, group IIIA metal oxides, group IVA metal oxides, and group VA metal oxides, more preferably an oxide of at least one of La, pr, nd, ti, V, cr, zr, sn, bi, W, Y, mo, al, ga, and In;
and/or the metal oxide is present in an amount of 0.001 to 40 wt%, more preferably 3 to 30wt%, based on the total amount of the catalyst.
10. The method for producing the niobium-based supported catalyst as claimed in claim 9, which comprises:
introducing the active component into the carrier by impregnation, ion exchange, precipitation or physical kneading, and optionally drying and calcining;
preferably, an impregnation method is used, and further preferably, an equal volume impregnation method is used.
11. The method of claim 10, wherein the method comprises: impregnating the carrier with impregnation liquid containing an active component precursor, forming, and optionally drying and roasting;
preferably, the impregnation liquid further contains a solvent, wherein the solvent is at least one selected from water, methanol, ethanol, ethanolamine, ethyl sulfide, isopropanol, acetone, acetic acid and citric acid; more preferably, the impregnation liquid also contains a surfactant and/or a complexing agent;
preferably, the conditions of the calcination include: the roasting temperature is 300-700 ℃, and the roasting time is 0.5-12h;
preferably, the roasting conditions further include: heating to the roasting temperature at a heating rate of 0.1-20 ℃/min;
and/or, the calcination is carried out in an oxygen-containing atmosphere or an inert atmosphere.
12. A method for producing monocyclic aromatic hydrocarbons, the method comprising: under dealkylation conditions, contacting a heavy aromatic hydrocarbon mixture with a catalyst, wherein the catalyst is the niobium-based supported catalyst of claim 9 or the niobium-based supported catalyst prepared by the method of claim 10 or 11;
preferably, the heavy aromatic hydrocarbon mixture is xylene tower residue of an aromatic hydrocarbon combined device;
preferably, the heavy aromatics blend contains C 9 + Aromatic hydrocarbon, said C 9 + The content of aromatic hydrocarbon is not less than 95 wt%;
more preferably, the heavy aromatic hydrocarbon mixture also contains C9-C12 heavy non-aromatic hydrocarbons, wherein the content of the C9-C12 heavy non-aromatic hydrocarbons is not more than 3 wt%;
and/or the heavy aromatic hydrocarbon mixed material contains C9-C14 heavy aromatic hydrocarbons and/or naphthalene series substances, and the total content of the C9-C14 heavy aromatic hydrocarbons and/or the naphthalene series substances is not more than 2 wt%;
preferably, the dealkylation reaction conditions include: under the condition of hydrogen, the hydrogen-hydrocarbon molar ratio is 0.5-30, and the weight space velocity of the heavy aromatic hydrocarbon mixture is 0.1-10h -1 The reaction pressure is 0-50MPa, and the reaction temperature is 200-600 ℃.
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