CN114471570B - Naphthalene selective hydrogenation catalyst and preparation method and application thereof - Google Patents
Naphthalene selective hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN114471570B CN114471570B CN202011148428.2A CN202011148428A CN114471570B CN 114471570 B CN114471570 B CN 114471570B CN 202011148428 A CN202011148428 A CN 202011148428A CN 114471570 B CN114471570 B CN 114471570B
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- China
- Prior art keywords
- selective hydrogenation
- hydrogenation catalyst
- naphthalene
- catalyst
- metal element
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- 239000003054 catalyst Substances 0.000 title claims abstract description 169
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 21
- 230000002829 reductive effect Effects 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 71
- 239000010949 copper Substances 0.000 claims description 42
- 238000001478 photoelectron diffraction Methods 0.000 claims description 39
- 238000001228 spectrum Methods 0.000 claims description 34
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- 229910052802 copper Inorganic materials 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000008139 complexing agent Substances 0.000 claims description 14
- 230000000536 complexating effect Effects 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000004696 coordination complex Chemical class 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 18
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012854 evaluation process Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 8
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 8
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 150000001879 copper Chemical class 0.000 description 6
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 6
- 150000002815 nickel Chemical class 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 2
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 2
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- WGACMNAUEGCUHG-VYBOCCTBSA-N (2s)-2-[[(2s)-2-[[(2s)-2-acetamidopropanoyl]amino]propanoyl]amino]-n-[(2s)-6-amino-1-[[(2s)-1-[(2s)-2-[[(2s)-1-[[(2s)-5-amino-1-[[(2s)-1-[[(2s)-1-[[(2s)-6-amino-1-[[(2s)-1-amino-3-(4-hydroxyphenyl)-1-oxopropan-2-yl]amino]-1-oxohexan-2-yl]amino]-3-hydroxy- Chemical compound CC(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CO)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCCCN)C(=O)N[C@H](C(N)=O)CC1=CC=C(O)C=C1 WGACMNAUEGCUHG-VYBOCCTBSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- GIGQFSYNIXPBCE-UHFFFAOYSA-N alumane;platinum Chemical compound [AlH3].[Pt] GIGQFSYNIXPBCE-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XZUAPPXGIFNDRA-UHFFFAOYSA-N ethane-1,2-diamine;hydrate Chemical compound O.NCCN XZUAPPXGIFNDRA-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 108010074544 myelin peptide amide-12 Proteins 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- -1 softener Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for producing tetrahydronaphthalene through naphthalene selective hydrogenation, and a preparation method and application thereof, wherein the catalyst comprises 1-30 parts of one or more than one of non-noble metals selected from VIII groups; 1 to 20 parts of one or more metals selected from group IB metals; the carrier with the content of 50-98 parts is selected from one or more of silicon dioxide or aluminum oxide. The catalyst has obvious performance advantages in the reaction of producing tetrahydronaphthalene by naphthalene selective hydrogenation, compared with a vulcanized catalyst, the metal catalyst does not need a presulfiding process before use, the tail gas does not need to be treated, the operation in the driving process is simple, and the cost is obviously reduced.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a naphthalene selective hydrogenation catalyst, and a preparation method and application thereof.
Background
Tetrahydronaphthalene, also known as tetralin, is a cycloaliphatic aromatic hydrocarbon. It is a colorless liquid with naphthalene smell and is also an important derivative of naphthalene. Tetrahydronaphthalene is insoluble in water, is miscible with all common solvents, is an ideal high-boiling point solvent, can dissolve grease, oxidized linseed oil, rubber, wax, asphalt, phenolic resin, naphthalene, iodine, paint and the like, and is widely applied to preparing intermediate alpha naphthol of pesticide Ding Weiyin; also used for producing lubricants and reducing the viscosity of high viscosity oils; mixing with alcohol and benzene as fuel for internal combustion engine; also used as degreasing agent, softener, absorbent of low boiling point organic compound vapor, insect repellent and substitute of turpentine.
The production process of tetrahydronaphthalene mainly originates from naphthalene hydrogenation, naphthalene hydrogenation is a two-stage series reaction, first, the first benzene ring is hydrogenated to generate the target product tetrahydronaphthalene, but at the same time, the second benzene ring is hydrogenated to generate the side reaction of decalin, so the control of the selectivity of the hydrogenation process is particularly critical for improving the yield of tetrahydronaphthalene. At present, because of the difficult problem of hydrogenation selectivity control, the research on the production of tetrahydronaphthalene by naphthalene hydrogenation is less, and the selectivity of the tetrahydronaphthalene is lower.
CN200310106565 discloses a process for synthesizing decalin by intermittent hydrogenation, which comprises using naphthalene as raw material, and on nickel catalyst, at 6 MPa-12 MPa, 180-220 deg.C, liquid hourly space velocity of 0.5h -1 ～1.0h -1 Under the condition, the conversion rate of naphthalene is more than 98%, and the yield of decalin is 98%. However, this process is a batch operation, is inefficient, and is not suitable for the production of tetrahydronaphthalene. CN200510041404.6 discloses a process for producing decalin by continuous hydrogenation, which comprises using decalin or tetrahydronaphthalene as naphthalene solvent, platinum-aluminum or nickel-aluminum catalyst, and liquid hourly space velocity of 0.1h at 2-15 MPa and 120-280 DEG C -1 ～5.0h -1 Hydrogen oil volume ratio is 1-3000Under the piece, the naphthalene conversion rate is 70% -99%, but the method is not suitable for producing tetrahydronaphthalene.
CN102838438 discloses a process for synthesizing tetralin, which comprises using naphthalene as raw material, using sulfuration type NiMo containing 10-80% ZSM-5 molecular sieve as catalyst, hydrogen partial pressure 0.5-20 MPa, 200-400 deg.C, volume space velocity 0.5h in fixed bed reactor -1 ～10h -1 Under the condition of 200-1000 volume ratio of hydrogen to oil, the conversion rate of naphthalene reaches 91.7%, and the selectivity of target product tetrahydronaphthalene reaches 97.8%. The method can obtain tetrahydronaphthalene with high selectivity, but a sulfide type catalyst is needed. CN109550525 discloses a pre-sulfiding method for catalysts for preparing tetrahydronaphthalene, and also relates to a method for producing tetrahydronaphthalene using sulfiding catalysts. Before use, the sulfide catalyst needs to undergo a presulfiding process, namely, the oxide catalyst precursor adopts a vulcanizing agent such as dimethyl disulfide (DMDS) and the like, and has catalytic activity after presulfiding at 200-400 ℃. The operation of the pre-vulcanization process is complex, and the use of the vulcanizing agent can bring about environmental problems such as hydrogen sulfide-containing tail gas treatment.
CN104741124a discloses an aluminum-based intermetallic compound for naphthalene selective hydrogenation catalyst and a preparation method thereof, wherein the Ni-Al intermetallic compound is used as a hydrogenation catalyst, and vulcanization is not needed before the catalyst is used for hydrogenation reaction, but the preparation process is complex, a strong reducing agent of naphthalene lithium is needed, and the catalyst has the problems of high cost and environmental protection of waste liquid.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the existing hydrogenation catalyst tetrahydronaphthalene has low selectivity and sulfide catalyst pretreatment is complex, and the like, and a naphthalene selective hydrogenation metal catalyst and a preparation method and application thereof are provided, namely the first aim of the invention is to provide a naphthalene selective hydrogenation catalyst which comprises the following components in parts by weight:
1 to 30 parts of VIII group non-noble metal element;
1 to 20 parts of IB group metal element;
50-98 parts of carrier.
According to some embodiments of the invention, the group VIII non-noble metal element comprises one or more of nickel, iron, cobalt.
According to some embodiments of the invention, the group VIII non-noble metal element comprises nickel.
According to some embodiments of the invention, the nickel content comprises 5.0 parts to 20 parts by weight.
According to some embodiments of the invention, the group IB metal element comprises one or more of Cu, ag, au.
According to some embodiments of the invention, the group IB metal element comprises copper.
According to some embodiments of the invention, the copper content comprises 3.0 parts to 12.0 parts by weight.
According to some embodiments of the invention, the photoelectron diffraction energy spectrum peak of the VIII group non-noble metal element in the naphthalene selective hydrogenation catalyst is shifted from 0.5 to 2.0eV to the high binding energy direction of the photoelectron diffraction energy spectrum peak in the presence of the VIII group non-noble metal element alone. According to some specific embodiments of the present invention, the photoelectron diffraction energy spectrum peak of the Ni element in the naphthalene selective hydrogenation catalyst is shifted from 0.5eV to 2.0eV toward the high binding energy of the photoelectron diffraction energy spectrum peak in the presence of the Ni element alone; according to some more specific embodiments of the invention, the photoelectron diffraction energy spectrum peak of the Ni element in the naphthalene selective hydrogenation catalyst is shifted by 1.6eV to the high binding energy direction of the photoelectron diffraction energy spectrum peak in the presence of the Ni element alone. Wherein the photoelectron diffraction spectrum peak in the presence of the non-noble metal element of the VIII group alone or the photoelectron diffraction spectrum peak in the presence of the Ni element alone refers to the photoelectron diffraction spectrum peak containing only the non-noble metal element of the VIII group or the Ni element as an active element.
According to some embodiments of the invention, the photoelectron diffraction spectrum peak of the group IB metal element is shifted from 0.2 to 0.5eV toward the high binding energy of the photoelectron diffraction spectrum peak in the presence of the group VIII non-noble metal element alone. According to some embodiments of the invention, the photoelectron diffraction energy spectrum peak of the Cu element in the naphthalene selective hydrogenation catalyst moves 0.2-0.5 eV towards the high binding energy direction in the presence of the Cu element alone; according to some more specific embodiments of the invention, the photoelectron diffraction energy spectrum peak of the Cu element in the naphthalene selective hydrogenation catalyst is shifted to the high binding energy direction in the presence of the Cu element alone by 0.5eV. Wherein the photoelectron diffraction spectrum peak in the presence of the group IB metal element alone or the photoelectron diffraction spectrum peak in the presence of the Cu element alone refers to the photoelectron diffraction spectrum peak containing only the group IB metal element or the Cu element as an active element.
The invention also aims to provide a preparation method of the naphthalene selective hydrogenation catalyst, which comprises the steps of preparing the non-noble metal element compound of VIII family, the metal element compound of IB family and the complexing agent into a metal complexing solution, loading the metal complexing solution onto a catalyst carrier, and drying and roasting the metal complexing solution to obtain the naphthalene selective hydrogenation catalyst.
According to some embodiments of the invention, the complexing agent comprises a polyamine complexing agent; preferably the complexing agent comprises an aqueous solution of an organic amine or inorganic ammonia; more preferably, the complexing agent comprises an aqueous solution of ethylenediamine.
According to some embodiments of the invention, the group VIII non-noble metal element compound comprises a nickel-containing compound; preferably comprising one or more of nickel chloride, nickel nitrate, nickel sulphate and nickel carbonate, preferably nickel nitrate.
According to some embodiments of the invention, the group IB metal element compound comprises a copper-containing compound, preferably comprising one or more of copper chloride, copper nitrate, copper sulfate and basic copper carbonate, preferably copper nitrate.
According to some embodiments of the invention, the loading method comprises one or both of an immersion method, a precipitation method.
According to some embodiments of the invention, the impregnation method comprises mixing or spraying the metal complexing solution onto a catalyst support; preferably, the saturated adsorption amount of the metal complexing solution and the carrier is 1:1.
According to some embodiments of the invention, the precipitation method comprises reacting the metal complex solution with a precipitant solution to deposit a precipitate on a catalyst support; preferably, the precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, ammonium carbonate, basic sodium carbonate, ammonia water, preferably ammonium carbonate. More preferably, the saturated adsorption amount of the metal complexing solution and the carrier is 10:1-1:1.
According to some embodiments of the invention, the catalyst support comprises, for example, fully kneading silica, alkali, extrusion aid and water, extruding into strips, drying and calcining to obtain the catalyst support. Preferably, the catalyst support may comprise, for example, silica, alumina, all-silica molecular sieves.
According to some specific embodiments of the invention, the silicon dioxide is powdery substance with the weight content of silicon dioxide being more than 99%, and the weight content of the silicon dioxide in the catalyst is 73-92 parts; the silicon dioxide is selected from one or more of white carbon black, silica gel and colloidal silicon dioxide; the alkali is selected from one or more of sodium hydroxide and potassium hydroxide, preferably sodium hydroxide, and the addition amount of the alkali is 0.1 to 10.0 parts, preferably 1.0 to 5.0 parts of the weight of the carrier dry basis; the extrusion aid is a substance which is favorable for extrusion molding, and can be selected from one or more of starch, hydroxymethyl cellulose and sesbania powder, preferably sesbania powder, and the addition amount of the extrusion aid is 1.0-10.0 parts, preferably 1.0-5.0 parts, of the weight of the carrier dry basis.
According to some embodiments of the present invention, the loading manner may be one or both of an impregnation method and a deposition precipitation method, and the complex solution containing nickel and copper may be prepared by a conventional method, that is, a nickel-containing compound and a copper-containing compound are dissolved in an aqueous solution containing organic amine of a complexing agent or inorganic ammonia, and the nickel-containing compound is one or more selected from nickel chloride, nickel nitrate, nickel sulfate and nickel carbonate, preferably nickel nitrate; the copper-containing compound is selected from one or more of copper chloride, copper nitrate, copper sulfate and basic copper carbonate, preferably copper nitrate.
According to some embodiments of the invention, the impregnation method comprises an isovolumetric impregnation method, i.e. the volume of the nickel-and copper-containing solutions formulated as saturated adsorption amounts of the catalyst support is directly mixed or sprayed onto the catalyst support.
According to some embodiments of the invention, the volume of the solution containing nickel and copper prepared in the deposition precipitation method is 1-10 times of the water absorption rate of the carrier, the solution containing active metal nickel and copper acts with a precipitant solution, and the precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, ammonium carbonate, basic sodium carbonate and ammonia water, preferably ammonium carbonate, for deposition precipitation on the catalyst carrier.
According to some embodiments of the invention, the drying conditions of the catalyst support and the catalyst may be the same, and the calcination conditions of the catalyst support and the catalyst.
According to some embodiments of the invention, the drying conditions of the catalyst carrier and the catalyst comprise maintaining the temperature of 50 ℃ to 300 ℃ for 1h to 48h, and the roasting conditions of the catalyst carrier and the catalyst are maintained at 300 ℃ to 700 ℃ for 0.5h to 10.0h.
According to some embodiments of the invention, the method for preparing naphthalene selective hydrogenation catalyst further comprises a step of reducing and activating the naphthalene selective hydrogenation catalyst into active metal in a reducing atmosphere before use; preferably, the reduction activation condition comprises hydrogen partial pressure of 0.1 MPa-5.0 MPa, reaction temperature of 150-350 ℃ and volume space velocity of 50h -1 ～300h -1 The reduction time is 1-12 h.
It is a further object of the present invention to provide a process for producing tetrahydronaphthalene by selective hydrogenation of naphthalene using a fixed bed adiabatic reactor comprising the steps of:
in the presence of naphthalene selective hydrogenation catalyst which is subjected to reduction activation treatment, the reaction temperature is 100 ℃ to 350 ℃, the reaction pressure is 0.5MPa to 5.0MPa, and the volume space velocity is 0.5h -1 And (3) under the conditions of 5.0h < -1 > and 50-1000 hydrogen-oil ratio, the raw material naphthalene undergoes hydrogenation reaction to obtain tetrahydronaphthalene.
According to some embodiments of the invention, the reaction is carried out in a fixed bed adiabatic reactor.
It is a further object of the present invention to provide the use of the above catalyst in naphthalene selective hydrogenation to obtain tetrahydronaphthalene.
Compared with the prior art, the invention has the following beneficial effects:
(1) The hydrogenation catalyst adopted by the method has the active components in a metal state, noble metals are not used, only hydrogen is introduced for reduction before use, and the hydrogen is excessive in the reaction process, so that the active center can be effectively maintained. Compared with the traditional sulfuration type catalyst, the method has the advantages that the problems of complex operation, sulfur-containing gas treatment, activity reduction caused by catalyst sulfur loss in the reaction process and the like caused by the sulfuration process are avoided. The operation difficulty and the reaction severity are obviously reduced.
(2) The hydrogenation catalyst contains nickel and copper bimetal, after hydrogen reduction, the nickel and copper have synergistic effect, and compared with a single metal active center, the bimetal system has higher hydrogenation activity;
(3) The acidity of the catalyst can cause the further deep hydrogenation of tetrahydronaphthalene to decalin and the cracking of saturated rings of naphthalene hydrogenation products to occur, while the traditional sulfided catalyst carrier usually contains a large number of ZSM-5, MOR, Y and other molecular sieves, and the strong acid center of the catalyst carrier inevitably causes side reactions, so that the selectivity of tetrahydronaphthalene is reduced. In order to solve the problem of side reaction caused by acidity of the catalyst, the hydrogenation catalyst carrier in the technology is silicon dioxide and does not contain an acidic center, so that the side reaction is inhibited to the greatest extent. The pore diameter of the silicon dioxide carrier is mesoporous, which is favorable for the diffusion of reactants and product molecules, and further is favorable for improving the selectivity of target product tetrahydronaphthalene;
(4) The method adopts a specific hydrogenation catalyst, can adopt a fixed bed to continuously produce the tetrahydronaphthalene under proper reaction conditions, and has higher naphthalene conversion rate and tetrahydronaphthalene selectivity.
The naphthalene selective hydrogenation catalyst with special components and proportions and the method for obtaining tetrahydronaphthalene by using the naphthalene selective hydrogenation catalyst have the advantages of no need of presulfiding process, no need of treatment of tail gas, high catalytic activity and high naphthalene conversion rate, and the preparation method of the naphthalene selective hydrogenation catalyst is simple and easy to carry out, and is suitable for large-scale production and application.
Drawings
FIG. 1 is an XRD diffraction pattern of a naphthalene selective hydrogenation catalyst prepared in accordance with one embodiment of the invention;
FIG. 2 is a Cu photoelectron diffraction spectrum of a naphthalene selective hydrogenation catalyst prepared according to one embodiment of the present invention;
FIG. 3 is a diffraction pattern of Ni photoelectron diffraction spectra of a naphthalene selective hydrogenation catalyst prepared according to an embodiment of this invention.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
The performance of the invention is measured according to the following method:
the catalyst of the invention is evaluated by adopting a 100ml fixed bed adiabatic reactor, the catalyst loading amount is 100ml, and the catalyst is subjected to reduction and activation treatment before feeding, and the reduction conditions and evaluation conditions are shown in table 1. After 2 hours of feeding reaction, the composition analysis is carried out on the product, and the conversion rate of naphthalene and the selectivity of tetrahydronaphthalene are calculated by the following specific calculation method:
naphthalene conversion = [ weight of naphthalene in raw material-weight of naphthalene in product ]/weight of naphthalene in raw material ]
Tetrahydronaphthalene selectivity = (moles of tetrahydronaphthalene in product/moles of naphthalene converted) ×100%.
XPS (X-ray photoelectron Spectrometry) analysis method: the composition of the catalyst element and the analysis and analysis of valence state adopt a Kratos AXIS Ultra DLD X-ray photoelectron spectrometer, and the minimum energy spectrum beam spot is 15 mu m; energy resolution ± 1%; the analysis chamber vacuum was < 7X 10-8Pa.
Example 1
The catalyst of this example was prepared as follows:
(1) Taking 76.1 g of white carbon black, 5 g of sodium hydroxide, 6 g of sesbania powder and a proper amount of water, fully kneading, extruding into cylindrical strips (with the diameter of 1.2 mm), drying at 120 ℃ for 8 hours and roasting at 550 ℃ for 3 hours to obtain a catalyst carrier;
(2) Taking 74.3 g of nickel nitrate hexahydrate and 19 g of copper nitrate trihydrate, dissolving into an ethylenediamine water solution with the concentration of 45wt.% to prepare a complexing impregnation solution, preparing a catalyst by an isovolumetric impregnation method, spraying the salt solution onto the carrier prepared in the step (1) in a rotary pot, stirring for 1 hour in a rotary way, drying at 110 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to prepare the catalyst, wherein the composition of the catalyst is as follows: nickel/copper/silica=15/5/80 (weight), numbered Cat-1, the hydrogenation evaluation process conditions of the catalyst were: the reaction temperature is 170 ℃, the reaction pressure is 2.5MPa, and the volume space velocity is 2.5h -1 The hydrogen to oil ratio was 500, and the results are shown in Table 1.
XRD diffraction analysis is carried out on the catalyst prepared in the example 1, as shown in fig. 1, the catalyst in the example 1 has no obvious diffraction peaks of Ni, cu and oxides thereof in XRD diffraction, which indicates that active metals such as Ni, cu and the like or precursors thereof are in a high dispersion state on the catalyst, and the high dispersion state catalyst has high catalyst activity.
XPS analysis was performed on the catalyst Cat-1 prepared in example 1 and single-component catalysts in which Cu and Ni elements exist separately, respectively, to determine the interaction between Cu and Ni elements in the catalyst prepared in the invention:
as shown in FIG. 2, the Cu element photoelectron diffraction spectrum of the catalyst Cat-1 prepared in example 1, wherein the binding energy of the photoelectron diffraction peak of the Cu element is 933.6eV, is shifted by 0.5eV in the high binding energy direction of the photoelectron diffraction peak of the catalyst Cat-1 of the present invention compared with the binding energy 933.1eV of the photoelectron diffraction peak of the catalyst containing only Cu element (example 9).
As shown in FIG. 3, the catalyst Cat-1 prepared in example 1 has a Ni element photoelectron diffraction spectrum, wherein the binding energy of the photoelectron diffraction peak of Ni element is 856.6eV, and the photoelectron diffraction peak of the catalyst Cat-1 in example 1 of the present invention is shifted by 1.6eV to the high binding energy of the photoelectron diffraction peak of the catalyst containing only Ni element (example 8) compared with the binding energy 855.0eV of the photoelectron diffraction peak of the catalyst containing only Ni element (example 8).
The XPS binding energy change condition corresponds to the surface states of Cu element and Ni element of the catalyst surface active components, and XPS of the Cu element and the Ni element moves towards the high binding energy direction, so that the strong interaction exists between the catalyst active elements Ni and Cu, the Ni-Cu alloy active center exists after reduction, and the catalyst has high activity and high reaction selectivity relative to the catalyst with the elements existing independently.
Example 2
The catalyst of this example was prepared in the same manner as in example 1 except that the silicon source used was silica gel and the catalyst composition was the same: nickel/copper/silica=15/5/80 (wt.), cat-2, and the hydrogenation evaluation process conditions of the catalyst were the same as in example 1, and the results are shown in table 1.
Example 3
The catalyst of this example was prepared in the same manner as in example 1 except that the nickel salt used was nickel chloride and the catalyst composition was the same: nickel/copper/silica=15/5/80 (wt.), cat-3, and the hydrogenation evaluation conditions of the catalyst were the same as in example 1, and the results are shown in table 1.
Example 4
The catalyst of this example was prepared in the same manner as in example 1 except that the copper salt used was cupric chloride and the catalyst composition was the same: nickel/copper/silica=15/5/80 (wt.), cat-4, and the hydrogenation evaluation process conditions of the catalyst were the same as in example 1, and the results are shown in table 1.
Example 5
The catalyst of this example was prepared in the same manner as in example 1 except that the copper salt used was cupric chloride and the nickel salt was nickel chloride, and the catalyst composition was the same: nickel/copper/silica=15/5/80 (wt.), cat-5, and the hydrogenation evaluation process conditions of the catalyst were the same as in example 1, and the results are shown in table 1.
Example 6
The preparation method of the catalyst in this embodiment is the same as that in embodiment 1, except that the ratio of nickel salt to copper salt is different, and the composition of the catalyst is different, and the composition of the obtained catalyst is: nickel/copper/silica=10/10/80 (wt.), cat-6, and the hydrogenation evaluation process conditions of the catalyst were the same as in example 1, and the results are shown in table 1.
Example 7
The preparation method of the catalyst in this embodiment is the same as that in embodiment 1, except that the ratio of nickel salt to copper salt is different, and the composition of the catalyst is different, and the composition of the obtained catalyst is: nickel/copper/silica=5/15/80 (wt.), cat-7, and the hydrogenation evaluation process conditions of the catalyst were the same as in example 1, and the results are shown in table 1.
Example 8
The catalyst of this example was prepared in the same manner as in example 1 except that the catalyst composition was different, and the composition of the catalyst obtained was: nickel/silica=20/80 (wt.), cat-8, and the hydrogenation evaluation process conditions of the catalyst were the same as in example 1, and the results are shown in table 1.
Example 9
The catalyst of this example was prepared in the same manner as in example 1 except that the catalyst composition was different, and the composition of the catalyst obtained was: copper/silica=20/80 (wt.), and the hydrogenation evaluation process conditions of the catalyst were the same as in example 1, and the results are shown in table 1.
Comparative example 1
The comparative example was prepared as in example 1, except that the active ingredient loading process was by precipitation.
Taking 74.3 g of nickel nitrate hexahydrate and 19 g of copper nitrate trihydrate, dissolving the nickel nitrate hexahydrate and the copper nitrate hexahydrate into 68.2 g of water to prepare a salt solution, preparing 0.1M ammonium carbonate solution, stirring at 50 ℃, adding the solution into a beaker containing 80 g of carrier and 20 g of water in parallel, controlling the pH value to be 8-9 in the liquid adding process, aging at 50 ℃ for 2 hours after the dripping is finished, filtering and washing the obtained slurry, drying at 110 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to prepare the catalyst, wherein the catalyst comprises the following components: nickel/copper/silica=15/5/80 (wt.), cat-10, and the hydrogenation evaluation process conditions of the catalyst were the same as in example 1, and the results are shown in table 1.
Comparative example 2
The preparation method of the catalyst of the comparative example is the same as that of comparative example 1, except that copper salt is cupric chloride, nickel salt is nickel chloride, and the catalyst has the same composition: nickel/copper/silica=15/5/80 (wt.), cat-11, and the hydrogenation evaluation conditions of the catalyst were the same as in example 1, and the results are shown in table 1.
Comparative example 3
The preparation method of the carrier of the catalyst of this comparative example was the same as in example 1, except that the composition was different, and 2 g of molybdenum trioxide was added during the molding process. The active component loading method is an isovolumetric impregnation method, the metal salt solution only contains nickel salt and does not contain copper salt, and the preparation process is the same as in example 8, so that the composition of nickel/molybdenum trioxide/silicon dioxide=20/2/78 (weight) is obtained, and the number is Cat-12.
The comparative example is a sulfided catalyst, and before use, dimethyl disulfide is used as a sulfiding agent for heating up and presulfiding under the following conditions: hydrogen partial pressure 2.0MPa, temperature 320 ℃, vulcanizing agent content 3.0wt%, vulcanizing volume airspeed 1.0h -1 Hydrogen oil volume ratio 400 and vulcanizing time 12h. The hydrogenation evaluation process conditions of the catalyst are the same as in example 1, and the results are shown in Table 1.
Table 1 evaluation results of different catalysts
| Examples | Catalyst numbering | Naphthalene conversion, wt% | Tetrahydronaphthalene selectivity, mol% |
| 1 | Cat-1 | 95.4 | 98.6 |
| 2 | Cat-2 | 94.8 | 98.5 |
| 3 | Cat-3 | 92.0 | 94.1 |
| 4 | Cat-4 | 90.9 | 93.6 |
| 5 | Cat-5 | 90.1 | 87.4 |
| 6 | Cat-6 | 78.1 | 98.9 |
| 7 | Cat-7 | 45.2 | 99.5 |
| 8 | Cat-8 | 90.6 | 91.3 |
| 9 | Cat-9 | 3.2 | 99.9 |
| 10 | Cat-10 | 85.4 | 97.8 |
| 11 | Cat-11 | 78.8 | 87.1 |
| 12 | Cat-12 | 86.7 | 96.5 |
As can be seen from the results in Table 1, the metal catalyst Cat-1 of the present invention has very good reaction performance in the reaction of producing tetrahydronaphthalene by naphthalene selective hydrogenation, and both naphthalene conversion rate and target product tetrahydronaphthalene selectivity are more than 95%. Compared with the sulfided catalyst Cat-12 of the comparative example, the catalyst of the invention has significantly higher naphthalene conversion (95.4%) than the comparative example naphthalene conversion (86.7%) under the condition that the selectivity of tetrahydronaphthalene is basically equivalent.
The result shows that the catalyst has obvious performance advantages in the reaction of producing tetrahydronaphthalene by naphthalene selective hydrogenation, compared with a vulcanized catalyst, the metal catalyst does not need a presulfiding process before use, the tail gas does not need to be treated, the operation in the driving process is simple, and the cost is obviously reduced.
Claims (17)
1. A naphthalene selective hydrogenation catalyst comprising the following components by weight:
5.0 to 20 parts of VIII group non-noble metal element;
3.0 to 12.0 parts of IB group metal element;
50-98 parts of carrier; wherein the group VIII non-noble metal element comprises nickel; the group IB metal element comprises copper; the support comprises a silica support;
the combination energy of the photoelectron diffraction energy spectrum peak of the VIII family non-noble metal element in the naphthalene selective hydrogenation catalyst is shifted to the high combination energy direction of the photoelectron diffraction energy spectrum peak in the independent existence of the VIII family non-noble metal element by 0.5-2.0 eV; and/or the binding energy of the photoelectron diffraction energy spectrum peak of the IB group metal element to the photoelectron diffraction energy spectrum peak of the IB group metal element is shifted to the high binding energy direction of the photoelectron diffraction energy spectrum peak in the presence of the IB group metal element by 0.2-0.5 eV;
the naphthalene selective hydrogenation catalyst is prepared by preparing a metal complexing solution from a VIII group non-noble metal element compound, an IB group metal element compound and a complexing agent, loading the metal complexing solution onto a catalyst carrier, and drying and roasting the metal complexing solution; the complexing agent comprises a polyamine complexing agent.
2. The naphthalene selective hydrogenation catalyst according to claim 1, wherein the photoelectron diffraction energy spectrum peak of Ni element in said naphthalene selective hydrogenation catalyst is shifted from 0.5eV to 2.0eV to the high binding energy direction of the photoelectron diffraction energy spectrum peak in the presence of Ni element alone; and/or the photoelectron diffraction energy spectrum peak of the Cu element in the naphthalene selective hydrogenation catalyst moves 0.2-0.5 eV towards the high combination energy direction of the photoelectron diffraction energy spectrum peak in the presence of the Cu element alone.
3. The naphthalene selective hydrogenation catalyst according to claim 2, wherein the photoelectron diffraction energy spectrum peak of Ni element in said naphthalene selective hydrogenation catalyst is shifted by 1.2 to 2.0eV to the high binding energy direction of the photoelectron diffraction energy spectrum peak in the presence of Ni element alone; and/or the photon diffraction energy spectrum peak of Cu element in the naphthalene selective hydrogenation catalyst is shifted to the high combination energy direction of the photoelectron diffraction energy spectrum peak in the presence of Cu element alone by 0.3-0.5 eV.
4. A method for preparing a naphthalene selective hydrogenation catalyst according to any one of claims 1 to 3, comprising preparing a metal complex solution from a non-noble metal element compound of group VIII, a metal element compound of group IB and a complexing agent, loading the metal complex solution onto a catalyst carrier, and drying and roasting the metal complex solution;
the complexing agent comprises a polyamine complexing agent;
the group VIII non-noble metal element compound includes a nickel-containing compound; the group IB metal element compound comprises a copper-containing compound.
5. The method for preparing a naphthalene selective hydrogenation catalyst according to claim 4, wherein said complexing agent comprises an aqueous solution of an organic amine or inorganic ammonia.
6. The method for preparing a naphthalene selective hydrogenation catalyst according to claim 5, wherein said complexing agent comprises an aqueous solution of ethylenediamine.
7. The method for producing a naphthalene selective hydrogenation catalyst according to any of claims 4 to 6, wherein said group VIII non-noble metal element compound comprises one or more of nickel chloride, nickel nitrate, nickel sulfate and nickel carbonate, and/or said group IB metal element compound comprises one or more of copper chloride, copper nitrate, copper sulfate and basic copper carbonate.
8. The method for producing a naphthalene selective hydrogenation catalyst according to claim 7, wherein said group VIII non-noble metal element compound comprises nickel nitrate and/or said group IB metal element compound comprises copper nitrate.
9. The method for producing a naphthalene selective hydrogenation catalyst according to any of claims 4 to 6, wherein said supporting comprises one or both of an impregnation method and a precipitation method; and/or the impregnation method comprises mixing or spraying the metal complexing solution onto a catalyst support; and/or the deposition precipitation method comprises the steps of enabling the metal complexing solution to act with a precipitator solution to deposit and precipitate on the catalyst carrier.
10. The method for preparing naphthalene selective hydrogenation catalyst according to claim 9, wherein said precipitant is one or more selected from sodium hydroxide, potassium hydroxide, ammonium carbonate, basic sodium carbonate, and ammonia water.
11. The method for preparing naphthalene selective hydrogenation catalyst according to claim 10, wherein said precipitant is selected from ammonium carbonate.
12. The method for producing a naphthalene selective hydrogenation catalyst according to any of claims 4 to 6, wherein the saturated adsorption amount of said metal complex solution and carrier is 1:1; and/or the saturated adsorption quantity of the metal complexing solution and the carrier is 10:1-1:1.
13. The method for producing a naphthalene selective hydrogenation catalyst according to any of claims 4 to 6, wherein said drying condition is 50 ℃ to 300 ℃ for 1h to 48h; and/or the roasting condition is 300-700 ℃ and maintained for 0.5-10.0 h.
14. The method for producing a naphthalene selective hydrogenation catalyst according to any of claims 4 to 6, wherein said catalyst further comprises a step of reductive activation to an active metal under a reducing atmosphere before use.
15. The method for preparing naphthalene selective hydrogenation catalyst according to claim 14, wherein said reductive activation conditions comprise hydrogen partial pressure of 0.1 MPa-5.0 MPa, reaction temperature of 150 ℃ to 350 ℃ and volume space velocity of 50h -1 ～300h -1 The reduction time is 1-12 h.
16. A method for producing tetrahydronaphthalene by naphthalene selective hydrogenation, which is characterized by comprising the following steps: in the presence of the naphthalene selective hydrogenation catalyst according to any one of claims 1-3 after reduction and activation treatment, the reaction temperature is 100-350 ℃, the reaction pressure is 0.5-5.0 MPa, and the volume space velocity is 0.5h -1 ～5.0h -1 And under the condition of hydrogen-oil ratio of 50-1000, the raw material naphthalene is hydrogenated to obtain tetrahydronaphthalene.
17. The method of claim 16, wherein the reaction is accomplished in a fixed bed adiabatic reactor.
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