CN115259985A - Method for catalyzing selective hydrogenation of acetylene by using monatomic catalyst - Google Patents
Method for catalyzing selective hydrogenation of acetylene by using monatomic catalyst Download PDFInfo
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- CN115259985A CN115259985A CN202211036279.XA CN202211036279A CN115259985A CN 115259985 A CN115259985 A CN 115259985A CN 202211036279 A CN202211036279 A CN 202211036279A CN 115259985 A CN115259985 A CN 115259985A
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- Prior art keywords
- catalyst
- acetylene
- solution
- nitrogen
- palladium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 21
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title abstract description 40
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 38
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005977 Ethylene Substances 0.000 claims abstract description 24
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical group 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 129
- -1 nitrogen-containing compound Chemical class 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 26
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical group [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 claims 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 12
- 229910052763 palladium Inorganic materials 0.000 description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 45
- 238000001035 drying Methods 0.000 description 23
- 238000005470 impregnation Methods 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000011701 zinc Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 229910052709 silver Inorganic materials 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- CAMRHYBKQTWSCM-UHFFFAOYSA-N oxocyanamide Chemical compound O=NC#N CAMRHYBKQTWSCM-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- SLIOYUPLNYLSSR-UHFFFAOYSA-J tetrachloroplatinum;hydrate;dihydrochloride Chemical compound O.Cl.Cl.Cl[Pt](Cl)(Cl)Cl SLIOYUPLNYLSSR-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B01J35/23—
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/48—Silver or gold
- C07C2523/50—Silver
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/60—Platinum group metals with zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/644—Arsenic, antimony or bismuth
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
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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
Abstract
The invention relates to a method for catalyzing selective hydrogenation of acetylene by using a monatomic catalyst, which comprises the step of converting acetylene in an acetylene-containing atmosphere into ethylene by selective hydrogenation in the presence of hydrogen and a catalyst, wherein the catalyst is selected from Pd 1 M/Al 2 O 3 The catalyst is characterized in that Pd exists in a single atomic site state, M is a promoter, M is selected from transition metals, preferably one or more of Ni, ag, co, zn and Bi in combination, and the carrier is alumina, wherein the loading amount of an active component Pd is 0.015-3.0 wt% based on the total weight of the catalyst, and the loading amount of M is 0-5wt% based on the total weight of the catalyst. The catalyst treated by the method keeps higher conversion rate and selectivity of selective hydrogenation of acetylene under the condition of low noble metal loading.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a catalyst applied to acetylene selective hydrogenation reaction and a preparation method thereof.
Background
Polyethylene is produced industrially by polymerization of ethylene, which is one of the most widely used polymeric materials. Industrially, ethylene is separated from gases produced in petroleum refineries and petrochemical plants, however, the ethylene feed for polymerization typically contains small amounts (-1%) of acetylene, which poisons the ziegler-natta catalyst for ethylene polymerization and reduces the quality of the polyethylene product produced. In industrial production, a small amount of acetylene in the ethylene feed gas needs to be reduced to ppm level for polymerization.
The selective hydrogenation of acetylene to ethylene is a desirable method for removing acetylene from ethylene feed gas. The process employs a supported palladium catalyst which is required to hydrogenate acetylene to ethylene from an ethylene/acetylene mixture with high selectivity without over-hydrogenation to ethane. Pure palladium nanocrystals are generally very poor in selectivity for high acetylene conversion in the presence of ethylene. For this reason, pure palladium metal is often surface modified, deposited as a second metal/metal oxide, alloyed to improve its selectivity. However, the industry requires that acetylene in the ethylene/acetylene mixed gas is reduced to ppm level, and under the condition of high acetylene conversion, the currently used Pd-based catalyst in the industry is easy to excessively hydrogenate the acetylene to generate ethylene and the raw material gas to generate ethane, so that the reaction selectivity is sharply reduced.
In addition, because the storage amount of the global noble metal palladium is extremely low, the waste of palladium is avoided in the chemical industry, the utilization rate of palladium is improved, and the monatomic catalyst and the application thereof attract attention in the industry. CN104689816A discloses a Pd/ZnO monatomic catalyst and uses the Pd/ZnO monatomic catalyst in the selective hydrogenation reaction of acetylene. The noble metal content of the catalyst is still relatively high, although the claims refer to noble metal contents of 0.3% to 4%, the examples show a noble metal Pd content of 1%, indicating that the catalyst costs are still high.
It is a pursuit of the industry to further reduce the amount of noble metal used and maintain reasonable conversion and selectivity.
Disclosure of Invention
The invention discloses a method for selectively hydrogenating acetylene, which comprises the step of converting acetylene in an acetylene-containing atmosphere into ethylene by selective hydrogenation in the presence of hydrogen and a catalyst, wherein the catalyst is selected from Pd 1 M/Al 2 O 3 A catalyst.
The acetylene atmosphere comprises pure acetylene atmosphere or mixed atmosphere containing acetylene and ethylene. Further preferably, the reaction atmosphere is an ethylene/acetylene/ethane mixed atmosphere.
The Pd 1 M/Al 2 O 3 The catalyst comprises an active component Pd, wherein the Pd exists in a single-atom site state, M is a cocatalyst, M is selected from transition metals, preferably one or a combination of more of Ni, ag, co, zn and Bi, and a carrier is alumina, wherein the loading amount of the active component Pd is 0.015-3.0 wt% based on the total weight of the catalyst, and the loading amount of M is 0% -5wt% based on the total weight of the catalyst.
The method for selectively hydrogenating acetylene comprises the step of converting acetylene in acetylene-containing atmosphere into ethylene by selective hydrogenation in the presence of hydrogen and a catalyst, wherein the catalyst is selected from Pd 1 /Al 2 O 3 The catalyst, pd in the single atom site state, with 0% of promoter M content, i.e. promoter is not needed.
In the method, the loading amount of the active component Pd is 0.015-3.0 wt%, preferably 0.015-0.05 wt% based on the total weight of the catalyst.
Further, the Pd 1 M/Al 2 O 3 The monatomic catalyst is prepared by a method characterized in that,
s1, dipping a Pd salt solution and/or an M metal salt solution on a carrier, and carrying out solid-liquid separation to obtain a solid product;
s2, treating the solid product obtained in the step 1 by using a nitrogen-containing compound solution;
and S3, calcining to obtain the monatomic catalyst.
The Pd salt or Pd complex used in the invention is selected from palladium nitrate, palladium acetate, chloropalladate, palladium acetylacetonate or an ammonia complex of the above compounds.
The M metal salt is soluble salt of M metal, and is selected from nitrate, chloride, sulfate, organic acid salt, or complex.
In step S2, the treatment comprises soaking or flushing the catalyst precursor with a nitrogen-containing compound, followed by solid-liquid separation to obtain a solid product. The nitrogen-containing compound is a nitrogen-containing organic or inorganic compound, the solution is a nitrogen-containing compound solution, and the nitrogen-containing compound is NH 3 Dimethylformamide, urea, C 1-20 Alkane amines, C 2-20 Olefin amines, C 1-20 Alkanediamine, C 1-20 Alkane triamine, C 4-20 Cycloalkane amine, C 4-20 Cycloalkane diamine, C 4-20 Nitrogen-containing heterocycles, C 6 - 20 An aromatic amine; preferably NH 3 Dimethylformamide, urea, C 1-6 Alkane amine, C 1-6 Alkanediamine, C 6-20 An aromatic amine; preferably, the solution is a solution of ammonia, an imidazole compound or a pyrrole compound.
The application also discloses a Pd 1 M/Al 2 O 3 The application of the catalyst is characterized in that the catalyst is applied to removing acetylene in ethylene gas, wherein the load of an active component Pd is 0.015-3.0 wt%, preferably 0.015-0.05 wt% based on the total weight of the catalyst, and the load of M is 0-5wt% based on the total weight of the catalyst.
Definition and interpretation:
the separation state in the monoatomic site state, the monoatomic distribution, the monoatomic morphology, or the monoatomic level in the present invention means a state in which the metal atoms (ions) of the active metal elements are separated from each other independently, and the metal-metal bonds or the metal-O-metal bonds that are directly connected to each other are not formed between the active metal atoms, and are dispersed in the atomic level or in the monoatomic site state. Metals dispersed in the monoatomic site state may exist in the atomic state, may exist in the ionic state, and more may exist between the atomic and ionic states (the bond length is between two bond lengths). In the metal nanocrystalline, metal atoms in the same nanocrystalline are mutually bonded and do not belong to a monoatomic state or a monoatomic separation state defined by the invention; for the oxide nanocrystals formed by metal and oxygen, although the metals are separated by oxygen, there is a possibility that the metals inside are directly connected to each other, and the above-mentioned metal-state metal nanocrystals are formed after the reduction reaction, which also does not belong to the monoatomic site state or the monoatomic separation state defined in the present invention. The metals in the monatomic site state protected by the present invention are theoretically completely independent of each other. However, random deviations from batch-to-batch manufacturing operating condition control do not preclude the presence of small amounts of agglomerated metal species, such as clusters containing one-site numbers of atoms or ions, in the resulting product; it is not excluded that part of the metal is present in the nanocrystalline state. In other words, it is possible that the active metal exists in a single-atom-site dispersed state in the catalyst of the present invention, while a cluster state containing an aggregation of metal atoms exists in part, and/or a part of the metal assumes a nanocrystalline state. And the monatomic state is transformed to the cluster and/or nano-state as the external environment changes. The monatomic state as claimed herein requires a certain proportion of monatomic noble metal in the catalyst in the different forms of presence, such as monatomic noble metal monatomic, noble metal clusters, noble metal nanocrystals, for example, higher than 10%, preferably higher than 20%, particularly preferably higher than 50%. However, the method is limited to the current technical means, and only relatively rough statistical means can be used, a large number of randomly selected different local areas in a catalyst test sample can be analyzed and represented by a high-resolution spherical aberration electron microscope, the existence states of various forms of precious metals can be randomly selected for statistical analysis, or a catalyst sample can be analyzed by an X-ray absorption fine structure spectrum (EXAFS) capable of representing the overall information of the sample, so that the ratio of metal and other atom bonding signals to metal-metal bonding signals is obtained, and the approximate ratio of the single atom state is determined. It is to be noted that the product exhibits an improvement in performance substantially as long as the catalyst product having only a partial monoatomic state is obtained by using the technique of the present invention in the product.
Alkanolamine means that the alkane bears one amino function, alkanediamine means that the alkane bears two amino functions, alkanetriamine means that the alkane bears three amino functions, the said alkane being optionally substituted by one or more C 1-6 Alkyl radical, C 4-20 Cycloalkane of C 6-20 Aromatic groups, or the C-C bond in the alkane can be replaced by unsaturated alkene or alkyne to form an unsaturated carbon chain; c mentioned above 6-20 The aromatic cyclic amine means an aromatic cyclic amine compound having 6 to 20 carbon atoms, wherein the aromatic group includes aromatic and heteroaromatic groups, and the heteroaromatic group means a compound having the characteristic of 2n +4 having an aromatic group, while a part of the ring carbon atoms are replaced by heteroatoms, which are O and N atoms. C 4-20 The nitrogen-containing heterocyclic ring represents a ring nitrogen-containing heterocyclic ring containing 4 to 20 atoms; c 4-20 By cycloalkaneamine or cycloalkanediamine is meant a cycloalkane containing 4 to 20 ring carbon atoms, the cycloalkane containing one or two amine functional groups. The above-mentioned cycloalkane, nitrogen-containing heterocycle, aromatic ring is a single-or fused-ring heterocycle, which may be further substituted with C 1-6 Alkane substitution.
Complexes, also referred to as complexes, include complexes of noble or transition metals with ligands, common ligands including halogens (fluorine, chlorine, bromine, iodine), nitro, nitroso, cyanide, ammonia, water molecules or organic groups, and common complexes are chloro complexes, ammino complexes, cyano complexes, and the like, including chloroplatinic acid, chloroplatinate, chloroplatinic acid hydrate. See handbook of synthesis of precious metal compounds and complexes (essence) (residual jiangmin, 2009, chemical industry press).
Advantageous effects
The method for catalyzing the selective hydrogenation of acetylene by using the monatomic catalyst disclosed by the invention has the following advantages:
1. the active metal palladium in the catalyst is dispersed on the carrier in a single atom site form, the metal load is low and is further reduced to 0.015-0.03wt%, the atomic catalysis efficiency of metal atoms is high, and the cost of the catalyst is greatly reduced.
2. The invention uses a new treatment method to further improve the conversion rate and selectivity of the monatomic noble metal catalyst.
3. The catalyst shows excellent catalytic performance in selective hydrogenation of acetylene and has good activity, selectivity and stability.
4. The catalyst carrier of the invention uses alumina carrier which is commonly adopted in industry, effectively reduces the cost of the catalyst and has excellent industrial application prospect.
Detailed Description
Example 1: 0.015wt% Palladium-on-alumina catalyst
An aqueous solution of Pd of 0.002 g/g concentration was prepared in advance from a palladium nitrate solution, 7.5 g was taken and diluted to 54 g with water, and then 100 g of carrier Al was added 2 O 3 Then carrying out equal-volume impregnation to ensure that palladium is fully adsorbed on the surface of the carrier, drying at 120 ℃ overnight, carrying out equal-volume impregnation by using 2wt% diluted ammonia water, drying at 120 ℃ overnight again, and roasting at 400 ℃ for 1 h to obtain the palladium-loaded Al 2 O 3 The catalyst for selective hydrogenation of acetylene is marked as Pd (0.015%)/Al 2 O 3 。
Example 2: 0.030wt% Palladium-on-alumina catalyst
An aqueous solution of Pd of 0.002 g/g concentration was prepared in advance from a palladium nitrate solution, 15.0 g was taken and diluted to 54 g with water, and then 100 g of carrier Al was added 2 O 3 Then carrying out equal-volume impregnation to ensure that palladium is fully adsorbed on the surface of the carrier, drying at 120 ℃ overnight, carrying out equal-volume impregnation by using 2wt% diluted ammonia water, drying at 120 ℃ overnight again, and roasting at 400 ℃ for 1 h to obtain the palladium-loaded Al 2 O 3 The catalyst for selective hydrogenation of acetylene of (1) is marked as Pd (0.030%)/Al 2 O 3 。
Example 3: catalyst of 0.015wt% palladium, 0.09% silver-loaded alumina
Preparing Pd and Ag aqueous solutions with concentrations of 0.002 g/g and 0.02 g/g with palladium nitrate solution and silver nitrate respectively in advance, taking 7.5 g and 4.5 g respectively and diluting to 54 g with water,then 100 g of carrier Al are added 2 O 3 Then, equal-volume impregnation is carried out to ensure that palladium and silver are fully adsorbed on the surface of the carrier, drying is carried out at 120 ℃ overnight, equal-volume impregnation is carried out by using 2wt% diluted ammonia water, drying is carried out at 120 ℃ overnight again, and roasting is carried out at 400 ℃ for 1 h to obtain the palladium and silver loaded Al 2 O 3 The catalyst is marked as Pd (0.015%) Ag (0.09%)/Al 2 O 3 。
Example 4: catalyst of 0.030wt% palladium, 0.18% silver on alumina
Preparing Pd and Ag aqueous solutions with concentrations of 0.002 g/g and 0.02 g/g with palladium nitrate solution and silver nitrate, respectively, taking 15.0 g and 9.0 g respectively, diluting with water to 54 g, and adding 100 g of carrier Al 2 O 3 Then, equal-volume impregnation is carried out to ensure that palladium and silver are fully adsorbed on the surface of the carrier, drying is carried out at 120 ℃ overnight, equal-volume impregnation is carried out by using 2wt% diluted ammonia water, drying is carried out at 120 ℃ overnight again, and roasting is carried out at 400 ℃ for 1 h to obtain the palladium and silver loaded Al 2 O 3 The catalyst for selective hydrogenation of acetylene of (1) is marked by Pd (0.030%) Ag (0.18%)/Al 2 O 3 。
Example 5: catalyst of 0.015wt% palladium, 0.015% nickel on alumina
Aqueous solutions of Pd and Ni with concentrations of 0.002 g/g and 0.005 g/g are prepared in advance from a palladium nitrate solution and nickel nitrate hexahydrate respectively, 4.5 g and 1.8 g are taken respectively and diluted to 32 g with water, and then 60 g of carrier Al is added 2 O 3 Then, equal-volume impregnation is carried out to ensure that palladium and nickel are fully adsorbed on the surface of the carrier, drying is carried out at 120 ℃ overnight, equal-volume impregnation is carried out by using 2wt% diluted ammonia water, drying is carried out at 120 ℃ overnight again, and roasting is carried out at 400 ℃ for 1 h to obtain the palladium and nickel loaded Al 2 O 3 The catalyst is marked as Pd (0.015%) Ni (0.015%)/Al 2 O 3 。
Example 6: 0.015wt% palladium, 0.030% nickel on alumina catalyst
Pd and Ni aqueous solutions with the concentrations of 0.002 g/g and 0.005 g/g are prepared in advance from a palladium nitrate solution and nickel nitrate hexahydrate respectively, 4.5 g and 3.6 g are taken respectively and diluted to 32 g by waterFollowed by the addition of 60 g of carrier Al 2 O 3 Then, equal-volume impregnation is carried out to ensure that palladium and nickel are fully adsorbed on the surface of the carrier, drying is carried out at 120 ℃ overnight, equal-volume impregnation is carried out by using 2wt% diluted ammonia water, drying is carried out at 120 ℃ overnight again, and roasting is carried out at 400 ℃ for 1 h to obtain the palladium and nickel loaded Al 2 O 3 The catalyst is marked as Pd (0.015%) Ni (0.030%)/Al 2 O 3 。
Example 7: catalyst of 0.015wt% palladium, 0.150% nickel on alumina
Preparing Pd and Ni aqueous solutions with the concentrations of 0.002 g/g and 0.005 g/g by using a palladium nitrate solution and nickel nitrate hexahydrate respectively in advance, taking 4.5 g and 18.0 g respectively, diluting the solutions to 32 g by using water, and then adding 60 g of carrier Al 2 O 3 Then carrying out equal-volume impregnation to ensure that palladium and nickel are fully adsorbed on the surface of the carrier, drying at 120 ℃ overnight, carrying out equal-volume impregnation by using 2wt% diluted ammonia water, drying at 120 ℃ overnight again, and roasting at 400 ℃ for 1 h to obtain the palladium and nickel loaded Al 2 O 3 The catalyst is marked as Pd (0.015%) Ni (0.150%)/Al 2 O 3 。
Example 8: catalyst of 0.015wt% palladium, 0.015wt% nickel, 0.20% zinc-loaded alumina
Preparing Pd, ni and Zn aqueous solutions with concentrations of 0.002 g/g, 0.005 g/g and 0.02 g/g by using a palladium nitrate solution, nickel nitrate hexahydrate and nickel nitrate hexahydrate in advance, taking 6.0 g of Zn aqueous solution, diluting the solution to 32 g by using water, and adding 60 g of carrier Al 2 O 3 Then soaking in equal volume to make zinc be fully adsorbed on the surface of carrier, drying at 120 deg.C overnight, then roasting at 400 deg.C for 1 h to obtain zinc-treated Al 2 O 3 Support, labelled Zn/Al 2 O 3 . Then 4.125 g and 1.65 g of aqueous solutions of Pd and Ni are taken respectively and diluted to 27 g by water, and 55 g of carrier Zn/Al is added 2 O 3 Then carrying out equal-volume impregnation to ensure that palladium and nickel are fully adsorbed on the surface of the carrier, drying at 120 ℃ overnight, carrying out equal-volume impregnation by using 2wt% diluted ammonia water, drying at 120 ℃ overnight again, and roasting at 400 ℃ for 1 h to obtain the palladium-nickel-based catalystAl supported by palladium, nickel and zinc 2 O 3 The catalyst for selective hydrogenation of acetylene is marked as Pd (0.015%), ni (0.015%), zn (0.20%)/Al 2 O 3 。
Example 9: catalyst of 0.015wt% palladium, 0.015wt% nickel, 0.20 wt% bismuth-supported alumina
Preparing 0.002 g/g, 0.005 g/g and 0.02 g/g aqueous solutions of Pd, ni and Bi (wherein Bi needs to be added with HCl for dissolution) by using a palladium nitrate solution, nickel nitrate hexahydrate and bismuth chloride in advance, respectively, firstly taking 6.0 g of aqueous solution of Bi, diluting the aqueous solution of Bi to 32 g by using water, and then adding 60 g of carrier Al 2 O 3 Then soaking in the same volume to make bismuth fully adsorbed on the surface of the carrier, drying at 120 deg.C overnight, and roasting at 400 deg.C for 1 h to obtain bismuth-treated Al 2 O 3 Support, marked Bi/Al 2 O 3 . Then 4.125 g and 1.65 g of aqueous solutions of Pd and Ni are taken respectively and diluted to 27 g by water, and 55 g of carrier Bi/Al is added 2 O 3 Then carrying out equal-volume impregnation to ensure that palladium and nickel are fully adsorbed on the surface of the carrier, drying at 120 ℃ overnight, carrying out equal-volume impregnation by using 2wt% diluted ammonia water, drying at 120 ℃ overnight again, and roasting at 400 ℃ for 1 h to obtain the palladium, nickel and bismuth loaded Al 2 O 3 Is marked as Pd (0.015%) Ni (0.015%) Bi (0.20%)/Al 2 O 3 。
Example 10: catalyst of 0.015wt% palladium, 0.015wt% nickel, 0.10% zinc, 0.10% bismuth-loaded alumina
Preparing 0.002 g/g, 0.005 g, 0.02 g/g and 0.02 g/g aqueous solutions of Pd, ni, zn and Bi (wherein Bi needs to be added with HCl for dissolution) by using a palladium nitrate solution, a nickel nitrate hexahydrate and bismuth chloride in advance, respectively, firstly taking 3.0 g and 3.0 g aqueous solutions of Zn and Bi respectively, diluting the aqueous solutions of Zn and Bi to 32 g by using water, and then adding 60 g of carrier Al 2 O 3 Then carrying out equal-volume impregnation to ensure that zinc is fully adsorbed on the surface of the carrier, drying at 120 ℃ overnight, and then roasting at 400 ℃ for 1 h to obtain the Al2O3 carrier treated by zinc and bismuth, wherein the carrier is marked as ZnBi/Al 2 O 3 . Then 4.125 g and 1.65 g of aqueous solutions of Pd and Ni are taken and usedDiluting with water to 27 g, and adding 55 g of ZnBi/Al as a carrier 2 O 3 Then carrying out equal-volume impregnation to ensure that palladium and nickel are fully adsorbed on the surface of the carrier, drying at 120 ℃ overnight, carrying out equal-volume impregnation by using 2wt% diluted ammonia water, drying at 120 ℃ overnight again, and roasting at 400 ℃ for 1 h to obtain the Al loaded with palladium, nickel, zinc and bismuth 2 O 3 The catalyst for selective hydrogenation of acetylene is marked as Pd (0.015%), ni (0.015%), zn (0.10%), bi (0.10%)/Al 2 O 3 。
Application test example:
the test method comprises the following steps: the catalytic hydrogenation reaction is carried out in the mixed atmosphere of ethylene/acetylene/ethane (C) 2 H 4 93% by weight, C 2 H 2 0.4% of C 2 H 6 6% of H 2 Accounting for 0.6%). The reaction temperature is 60-90 ℃. The catalyst dosage is 5 mL, and the space velocity is 6000mL/g.h.
TABLE 1 test results
* The selectivity calculation of the present invention is defined as: s = [ C ] 2 H 4 (out)- C 2 H 4 (in)]/[ C 2 H 2 (in)- C 2 H 2 (out)]
* Description of the drawings: in the case of selectivities greater than 100%, either from instrumental errors or from the dehydrogenation of ethane to ethylene.
And (4) conclusion:
the monatomic catalyst treated by the method has excellent acetylene selective hydrogenation activity and selectivity under the condition of low palladium consumption, still has high selectivity under the condition of acetylene conversion rate close to 100 percent, has lower use cost and has high industrial application prospect.
Claims (10)
1. A process for the selective hydrogenation of acetylene comprising the selective hydrogenation of acetylene in an acetylene containing atmosphere to ethylene in the presence of hydrogen and a catalyst selected from Pd 1 M/Al 2 O 3 A catalyst,
the acetylene atmosphere comprises pure acetylene atmosphere or mixed atmosphere containing acetylene and ethylene, and further preferably, the reaction atmosphere is ethylene/acetylene/ethane mixed atmosphere.
2. The method of claim 1, wherein the Pd is 1 M/Al 2 O 3 The catalyst comprises an active component Pd, wherein the Pd exists in a single-atom site state, the M is a promoter, the M is selected from transition metals, preferably one or a combination of more of Ni, ag, co, zn and Bi, and a carrier is alumina, wherein the loading amount of the active component Pd is 0.015-3.0 wt% based on the total weight of the catalyst, and the loading amount of the M is 0-5wt% based on the total weight of the catalyst.
3. The method as set forth in claim 2, wherein the Pd content is 0.015 to 0.05wt%, and the M content is 0%.
4. The method of claim 1, wherein the catalyst is prepared by the following method: the monatomic catalyst is prepared by dipping a Pd salt solution and/or an M metal salt solution on a carrier, carrying out solid-liquid separation, treating by using a nitrogen-containing compound solution, and calcining.
5. The method of claim 4, wherein the catalyst is prepared by the steps of:
s1, dipping a Pd salt or Pd complex solution and/or an M metal salt solution on a carrier, and carrying out solid-liquid separation to obtain a solid product;
s2, treating the solid product obtained in the step 1 by using a nitrogen-containing compound solution;
s3, calcining to obtain the monatomic catalyst;
the Pd salt or Pd complex is selected from palladium nitrate, palladium acetate, chloropalladate, palladium acetylacetonate or an ammonia complex of the compounds; the M metal salt is soluble salt of M metal, and is selected from nitrate, chloride, sulfate, organic acid salt or complex; the nitrogen-containing compound is a nitrogen-containing organic or inorganic compound, and the solution is a solution of the nitrogen-containing compound.
6. The process of claim 4 or 5, S2, wherein the treatment comprises soaking or rinsing the catalyst precursor with a nitrogen-containing compound, followed by solid-liquid separation to obtain a solid product.
7. The method of claim 6, wherein the solution is a solution of a nitrogen-containing compound that is NH 3 Dimethylformamide, urea, C 1-20 Alkane amines, C 2-20 Alkylene amines, C 1-20 Alkanediamine, C 1-20 Alkane triamine, C 4-20 Cycloalkane amine, C 4-20 Cycloalkane diamine, C 4-20 Nitrogen-containing heterocycles, C 6 - 20 An aromatic amine.
8. The method according to claim 7, wherein the solution of the nitrogen-containing compound is a solution of ammonia, an imidazole compound or a pyrrole compound.
9. Pd 1 M/Al 2 O 3 The application of the catalyst is applied to removing acetylene in ethylene gas, wherein Pd exists in a single-atom site state, M is a cocatalyst, M is selected from transition metals and is selected from one or a combination of more of Ni, ag, co, zn and Bi, and a carrier is alumina, wherein the loading amount of an active component Pd is 0.015-3.0 wt% based on the total weight of the catalyst, and the loading amount of M is 0-5% based on the total weight of the catalyst.
10. Use according to claim 9, wherein the Pd content is 0.015-0.05 wt% and the loading of M is 0%.
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Effective date of registration: 20231218 Address after: North 4th Floor, Building 4 (3 # B), Phase II of Hefei Innovation and Entrepreneurship Park, No. 268 Furong Road, Shushan District, Hefei City, Anhui Province, 230051 Patentee after: Hefei Danyuan Catalytic Technology Co.,Ltd. Address before: Room 310, third floor, block B, No. 7, Fengxian Middle Road (incubation building), Haidian District, Beijing 100094 Patentee before: Beijing Single Atom Catalysis Technology Co.,Ltd. |
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