EP2155392A2 - Katalysator zur selektiven hydrierung acetylenischer kohlenwasserstoffe und verfahren zu seiner herstellung - Google Patents
Katalysator zur selektiven hydrierung acetylenischer kohlenwasserstoffe und verfahren zu seiner herstellungInfo
- Publication number
- EP2155392A2 EP2155392A2 EP08758898A EP08758898A EP2155392A2 EP 2155392 A2 EP2155392 A2 EP 2155392A2 EP 08758898 A EP08758898 A EP 08758898A EP 08758898 A EP08758898 A EP 08758898A EP 2155392 A2 EP2155392 A2 EP 2155392A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- carrier
- palladium
- metal compound
- active metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052751 metal Inorganic materials 0.000 claims abstract description 91
- 239000002184 metal Substances 0.000 claims abstract description 91
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 45
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims description 42
- 239000011149 active material Substances 0.000 claims description 25
- 238000009826 distribution Methods 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 13
- 230000000737 periodic effect Effects 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 150000002941 palladium compounds Chemical class 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229940100890 silver compound Drugs 0.000 claims description 6
- 150000003379 silver compounds Chemical class 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 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
- 150000002148 esters Chemical class 0.000 claims 1
- 150000002344 gold compounds Chemical class 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 abstract description 28
- 239000004332 silver Substances 0.000 abstract description 28
- 239000000243 solution Substances 0.000 description 50
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 28
- 239000000523 sample Substances 0.000 description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 17
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 15
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 230000035515 penetration Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- -1 polyethylene Polymers 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002083 X-ray spectrum Methods 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000003901 oxalic acid esters Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018089 Al Ka Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 241000158147 Sator Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000010457 zeolite 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group 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
- B01J23/48—Silver or gold
-
- 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
-
- 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
-
- B01J35/30—
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
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- B01J35/393—
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- B01J35/397—
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- B01J35/613—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
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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
- C07C2523/54—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
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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
Definitions
- the invention relates to a process for the preparation of a catalyst, in particular for the selective reduction of acetylenic compounds in hydrocarbon streams, a catalyst obtained by the process for the selective reduction of acetylenic compounds in hydrocarbon streams, and its use for the selective reduction of acetylenic compounds in hydrocarbon streams.
- Ethylene and propylene are important monomers for the production of plastics such as polyethylene or polypropylene.
- Ethylene and propylene are primarily derived from petroleum or petroleum products by thermal or catalytic cracking of long chain hydrocarbons.
- the ethylene or propylene obtained from the cracking product still contains small amounts of acetylenic compounds, such as acetylene or propyne.
- these acetylenic compounds must be removed become.
- the acetylene concentration must be reduced to a concentration of less than 5 ppm.
- the acetylene can be selectively hydrogenated to ethylene.
- acetylene should be removed as completely as possible by reaction with ethylene.
- the hydrogenation of ethylene to ethane must be prevented.
- the hydrogenation is carried out within a temperature range which is limited by the "clean-up temperature” and the “runaway temperature".
- a “clean-up temperature” is understood to mean the temperature at which an appreciable hydrogenation of acetylene to ethylene is observed.
- a “runaway temperature” is the temperature at which a significant hydrogenation of ethylene to ethane begins. The temperatures can be determined, for example, by measuring the hydrogen consumption of a defined gas mixture containing acetylene and ethylene, as a function of the temperature.
- palladium catalysts are used, which may also contain promoters, such as silver or alkali metals.
- the palladium and optionally the promoters, in particular silver are applied to an inert and temperature-resistant carrier material in the form of a shell.
- the preparation takes place in such a way that suitable salts of palladium or of a promoter, for example palladium nitrate and silver nitrate, are applied in the form of aqueous solutions to a porous support.
- the impregnation can be carried out in separate steps with a solution of the palladium compound and a solution of the silver compound. But it is also possible to apply palladium and silver in a common impregnation step on the carrier.
- the impregnated carrier is then calved ziniert and reduced to convert the catalyst into the activated form.
- DE 31 19 850 describes a process for the selective hydrogenation of a diolefin having at least 4 carbon atoms in a hydrocarbon mixture.
- the hydrogenation is carried out with hydrogen over a catalyst which simultaneously contains palladium and silver.
- the weight ratio of silver to palladium is 0.7: 1 to 3: 1.
- the catalyst is prepared by co-impregnating a support with an aqueous solution of palladium and silver salts.
- No. 5,648,576 describes a process for the selective gas-phase hydrogenation of acetylenic hydrocarbons (C 2 -C 3 ) into the corresponding ethylenic hydrocarbons.
- the catalyst is prepared by co-impregnating the support with an aqueous solution of the corresponding metal salts.
- EP 0 064 301 discloses a catalyst for the selective gas phase hydrogenation of acetylene.
- the preparation of the catalyst is carried out by two-stage application of palladium and silver.
- the present invention therefore has, in a first aspect, the object of providing a process for the preparation of a catalyst for the selective reduction of acetylenic compounds, in particular acetylene and propyne, in hydrocarbon streams, the catalyst avoiding the disadvantages of the prior art and a continuous and uniform hydrogenation over a long period of time without frequent catalyst regeneration.
- the catalyst should have the widest possible temperature window between "clean-up temperature” and "runaway temperature", wherein the temperature window should not change significantly over the lifetime of the catalyst.
- this object is achieved according to the invention by a method having the features of patent claim 1.
- Advantageous embodiments are the subject of the dependent claims.
- the at least one active metal from group 8 of the Periodic Table, preferably palladium, and (if present) the at least one promoter metal from group IB of the Periodic Table, preferably silver, are applied to a support by (co) precipitation.
- the solvent used here is a mixture of water and at least one further organic solvent in which at least one active metal compound is present.
- An element of group 8 of the Periodic Table of the Elements and (if present) at least one promoter metal compound of an element of group IB of the Periodic Table of the Elements are dissolved.
- Catalysts can be prepared by the combined use of water and at least one organic solvent in which the active metals are present in very finely divided form, wherein at least 90% of the active metal particles and / or the promoter metal particles have a size of less than 6 nm.
- the advantageous effects of the invention are already evident in the absence of a promoter metal (such as silver), ie when using only one or more active metals.
- at least one active metal and at least one promoter metal is used.
- the particles of the active material formed from the active metal and optionally the promoter metal can be applied to the carrier by the impregnation in a very thin shell.
- the penetration depth can be varied via the water content of the impregnating solution.
- the penetration depth of the impregnating solution also increases.
- the particles of the active metal or of the active material preferably show a very narrow particle size distribution. This is favored by the inventive method surprisingly.
- the active metal and the promoter metal is predominantly, ie preferably more than 50%, of the particles of the active material applied to the support together in the form of an alloy, so that intimate contact between the catalytically active metal and the promoter metal is achieved.
- the catalyst shows a significantly reduced tendency to form by-products, which are obtained in the form of polymers on the surface of the catalyst. As a result, the catalyst shows a significantly extended stability of its properties, so that the cycles between a regeneration of the catalyst could be significantly extended.
- an impregnating solution which contains as solvent a mixture of water and at least one water-miscible organic solvent in which at least one active metal compound of an element of group 8 of the Periodic Table of Elements and preferably at least one promoter metal compound of an element of group IB of the Periodic Table of the Elements is solved;
- the carrier is impregnated with the impregnating solution.
- the impregnated carrier is calcined.
- the catalyst is preferably reduced, this being carried out in a separate step, for example after the calcination or only in the reactor itself, for example when the catalyst is "started up". can be made. Preference is given to a reduction with hydrogen before starting the catalyst.
- an impregnating solution is first prepared.
- the solvent used is a mixture of water and a water-miscible organic solvent.
- the organic solvent should preferably be completely miscible with the water, so that no multi-phase system is formed.
- the organic solvent may be both a pure compound and a mixture of several organic solvents. Preferably, for simplicity, only a single organic solvent is used.
- At least one active metal compound and at least one promoter metal compound are dissolved in the solvent mixture. In the preparation of the impregnating solution can proceed in any way per se. Thus, the at least one active metal compound or the at least one promoter metal compound can be dissolved in water and the other compound in the organic solvent and then combined the two solutions.
- the solvent may be at about room temperature. But it is also possible to heat the solvent to accelerate the dissolution process.
- the organic solvent and the at least one active metal compound and the at least one promoter metal compound are preferably selected such that the most concentrated possible solution of the at least one active metal or promoter metal compound is obtained.
- Suitable active metal or promoter metal compounds are, for example, the carbonates, hydrogencarbonates, nitrates, salts of organic acids, such as, for example, acetates, oxalates, citrates or else acetylacetonates.
- the anions of the active metal or promoter metal salts are preferably selected so that the most concentrated impregnating solution can be prepared.
- a silver compound suitable as a promoter metal compound is, for example, silver nitrate.
- a palladium compound suitable as an active metal compound is, for example, palladium acetate, palladium acetylacetonate, palladium citrate, palladium oxalate or mixtures thereof.
- a carrier is provided.
- any solid supports can be used. It is possible to use customary supports which are already known for the preparation of catalysts for the selective hydrogenation of acetylenic compounds.
- it is a porous or channeled carrier.
- the carrier can also consist of a largely or completely non-porous material which has a (porous) coating which can be impregnated.
- supports are therefore also to be understood as coatings or coated materials Suitable supports are, for example, Al 2 O 3 , in particular ⁇ -Al 2 O 3 , clays, aluminum silicates, SiO 2 , ZrO 2 , TiO 2 , SiC, ZnO or any mixtures thereof, wherein Al 2 O 3 is particularly preferred
- the support preferably has a specific surface area in the range from 1 to 60 m 2 / g, preferably from 3 to 35 m 2 / g
- the pore volume of the support is preferably 0.1 to 1.5 ml / g, particularly preferably 0.2 to 1.0 ml / g
- the average pore diameter of the carrier is preferably 10 to 300 ⁇ , particularly preferably 30 to 200 ⁇ .
- the carrier may have any shape.
- the support is particularly preferably provided in the form of a shaped article or a coating (see above).
- the shape of the molding can be chosen arbitrarily per se.
- a suitable embodiment is, for example, according to a preferred aspect, a tablet or a pellet.
- the material carrying the coating consists of any desired channels which have a cross-section of between 0.01 and 15 mm 2 or, for example, highly fired ceramics, for example in ring form.
- the carrier may also contain a conventional binder and further additives, such as, for example, pore formers.
- the skilled person can fall back on his knowledge for the production of such moldings.
- the carrier is then impregnated with the impregnating solution.
- the carrier can be impregnated with the impregnating solution.
- the "incipient wetness" method is preferably used, in which the at least one active metal compound and the at least one promoter metal compound are dissolved in a volume of solvent which corresponds approximately to the pore volume of the carrier.
- the pore volume does not have to be fully utilized. For example, it is also possible to use only 80 to 90% of the pore volume of the carrier.
- the at least one active metal compound and the at least one promoter metal compound can also be dissolved in a volume of solvent which is greater than the pore volume of the carrier, wherein excess impregnating solution is discharged or the solvent is evaporated.
- spray the impregnating solution onto the carrier wherein the carrier is preferably moved during spraying.
- the impregnation is carried out in a manner such that both the active metal compound and the promoter metal compound are concentrated in a thin shell at the edge of the support.
- the support e.g. a tablet or a pellet, while spraying the solution and simultaneously dried by a gas stream.
- the layer thickness is predetermined by the coating according to a preferred aspect of the invention.
- the impregnating solution may preferably be passed either through the existing channels, or a differently shaped coated carrier may be impregnated by spraying.
- the impregnated carrier is preferably dried.
- the drying can be carried out after the impregnation or preferably already carried out during the impregnation. Drying already during the impregnation is preferred because then very thin shells are obtained.
- the drying can be carried out by conventional methods, for example by drying the impregnated support in an oven. Preferably, the drying is carried out in such a way that the impregnated carrier is dried in a gas stream, wherein the impregnated carrier is preferably moved.
- the gas for drying air can be used.
- an inert gas stream such as, for example, a nitrogen stream
- the drying is preferably carried out at room temperature, so that no decomposition tion of at least one active metal or promoter metal compound occurs.
- the temperature used for drying is preferably in the range of 15 to 120 ° C., more preferably in the range of 25 to 100 ° C.
- the preferably dried, impregnated carrier is then calcined to fix the at least one active metal or promoter metal compound on the carrier.
- the calcining is carried out in conventional equipment, for example an oven, such as a rotary kiln.
- an oven such as a rotary kiln.
- the temperature is preferably not chosen too high in order, for example, to prevent a confluence of the reduced metal particles on the surface of the carrier.
- the calcination is preferably carried out in an oxygen-containing atmosphere, particularly preferably under the ingress of air. However, it is also possible to carry out the calcination in whole or in part under an inert gas atmosphere.
- the calcining can initially be carried out under an inert gas atmosphere and then under air.
- the duration during which the calcination is carried out depends on the amount of catalyst to be calcined and on the calcination temperature and can be determined by the skilled worker by means of appropriate series experiments.
- the calcination time is preferably selected in the range from 1 to 20 hours, more preferably 2 to 10 hours.
- compounds of Group 8 elements of the Periodic Table of the Elements may be used, with ruthenium, rhodium, palladium, osmium, iridium and platinum being preferred. Palladium is particularly preferred
- promoter metal compounds it is possible to use compounds of the elements of group IB of the Periodic Table of the Elements, namely copper, silver and gold, silver being particularly preferred. is awarded. In a preferred embodiment, silver is partially or wholly replaced by gold.
- the impregnating solution is prepared in such a way that at least a first solution is prepared by the promoter metal compound, preferably silver compound, dissolved in water, a second solution is prepared by the active metal compound, preferably palladium compound, in one dissolved organic solvent, and at least the first solution is combined with the second solution. It has been found that in this way after calcination and reduction, metal particles with a very small diameter are obtained.
- the amount of water and the amount of organic solvent is preferably chosen such that the most concentrated impregnating solution is obtained.
- the activity of the catalyst can be favorably influenced if the proportion of the organic solvent is not chosen too low.
- the layer thickness (penetration depth of the impregnating solution) can be adjusted via the water content. The more water in the solution, the greater the layer thickness.
- the invention therefore relates to a method for adjusting the penetration depth of an impregnating solution into a carrier, wherein the impregnating solution contains an organic solvent as described herein and water, and wherein the penetration depth is influenced by the water content of the impregnating solution.
- the ratio (v / v) between water and the at least one organic solvent in the impregnating solution is between 9.95: 0.05 and 0.05: 9.95, preferably between 0.1: 9.9 and 2: 8, more preferably between 0.1: 9.9 and 1: 9.
- the proportion of water in the impregnating solution, based on the total weight of water and organic solvent between about 0.05 and 10 wt .-%.
- the organic solvent can be chosen arbitrarily per se, preference being given to those solvents which can be completely removed from the support by drying and calcining.
- the at least one organic solvent is selected from the group of ketones, carboxylic acids, carboxylic acid esters, alcohols and ethers, with ketones and ethers being particularly preferred.
- a ketone suitable as the organic solvent is, for example, acetone or ethyl methyl ketone.
- a suitable carboxylic acid is, for example, formic acid or acetic acid; a suitable carboxylic acid ester is, for example, methyl acetate.
- alcohols both monohydric and polyhydric alcohols can be used. Suitable monohydric alcohols are, for example, ethanol or butanol. Suitable polyhydric alcohols are, for example, glycol or glycerol or else polyethylene or polypropylene glycols.
- Suitable ethers are, for example, diisopropyl ether or tetrahydrofuran, with cyclic ethers being preferred. Particularly preferred organic solvents are acetone and tetrahydrofuran.
- the at least one organic solvent preferably has a boiling point at atmospheric pressure of less than 150 0 C, more preferably less than 100 0 C, particularly preferably less than 80 0 C. , However, the organic solvent should not have too high volatility at room temperature to facilitate handling.
- the at least one organic solvent preferably has a boiling point at normal pressure of more than 50 ° C.
- the properties of the catalyst can be favorably influenced if the calcining is carried out at not too high a temperature.
- the inventors believe that at lower temperatures the combustion of the organic solvent is incomplete and therefore carbonaceous residues remain on the catalyst which partially poison the catalyst and thereby increase the selectivity of the catalyst.
- the temperature for the calcination lower than 400 0 C, preferably lower than 350 0 C, particularly preferably selected in the range of 200 to 300 0 C.
- the impregnating solution contains the at least one active metal compound, preferably at least one palladium compound, and the at least one promoter metal compound, preferably at least one silver compound, preferably in a ratio close to the ratio desired for the at least one active metal compound and the at least one promoter metal compound in the final catalyst is or is equal to this.
- the at least one promoter metal compound and the at least one active metal compound in the impregnating solution in a molar ratio promoter metal / active metal (Ag / Pd) in the range of 1: 1 to 10: 1, preferably zugt 1: 1 to 7: 1, particularly preferably 1.5: 1 to 6: 1 included.
- the concentration of the at least one active metal compound, preferably palladium compound, in the impregnating solution is preferably chosen such that the amount of the active metal compound, calculated as metal and based on the weight of the carrier or coating, is between 0.001 and 1% by weight, preferably 0.005 to 0.8, more preferably 0.01 to 0.5 wt .-% is.
- the concentration of the at least one promoter metal compound, preferably silver compound, in the impregnation solution is preferably selected such that the amount of the promoter metal compound, calculated as metal and based on the weight of the carrier (or the coating to be impregnated), is between 0.001 and 1 wt. %, preferably 0.005 to 0.8, particularly preferably 0.01 to 0.5 wt .-% is.
- the catalyst may contain other metal compounds.
- compounds of the alkali metals and alkaline earth metals are preferred.
- Preferred alkali metals are sodium and potassium.
- a preferred alkaline earth metal is magnesium.
- Suitable compounds are, for example, nitrates, hydroxides, carbonates, acetates, acetylacetonates, oxalates, or citrates of the metals.
- the amount of the further metal compound, in particular alkali metal compound, is so selected that the catalyst contains the at least one further metal, calculated as metal oxide and based on the weight of the catalyst in an amount of 0.05 to 0.2 wt .-%.
- the atomic ratio of the at least one further metal to active metal is preferably between 2: 1 and 20: 1, preferably 4: 1 and 15: 1. According to a preferred embodiment, however, the catalyst contains no further metals besides active metal and promoter metal.
- the process of the present invention results in a catalyst for the selective hydrogenation of acetylenic compounds in hydrocarbon streams which tolerates a relatively wide temperature range within which selectivity remains high, i.e., in the range of 0.9 to 10.8. No or only a small proportion of the ethylenic compounds is reduced, and the long operating times allowed before a regeneration of the catalyst is required to maintain the productivity of the corresponding plant.
- the invention therefore also provides a catalyst for the selective hydrogenation of acetylenic compounds in hydrocarbon streams, as can be obtained, for example, by the process described above.
- the catalyst comprises a support and supported particles of an active material comprising at least the active metal and the silver, wherein at least 90% of the particles of the active material have a diameter of less than 6 nm.
- At least 75%, preferably at least 80%, more preferably at least 85%, most preferably at least 90% of the particles of the active material are formed from an alloy containing both the active metal and the promoter metal.
- the inventors believe that the high activity of the catalyst is promoted with high selectivity, in particular by the specific distribution of the active components in the shell and the small size of the particles of the active material, whereby a large catalytic surface area is available for diffusion-controlled reactions which favorably influences the activity of the catalyst.
- the catalyst may also contain other metals or metal compounds. Suitable metal compounds are, for example, alkali metal compounds, such as sodium or potassium compounds. These compounds of the other metals are preferably present in the form of their oxides on the support.
- the particle size and the particle size distribution of the active material can be determined, for example, by means of which the number and size of the particles of the active material are determined and the corresponding values are statistically evaluated. At least 150 particles are evaluated on the basis of electron micrographs with a magnification factor of 150,000. The particle diameter is the longest dimension of the particles that can be seen from the electron micrographs.
- the particles of the active material of the catalyst preferably have an average particle diameter (unweighted arithmetic mean) of less than 5.5 nm, more preferably less than 4.5 nm.
- Carbon monoxide shows characteristic bands on adsorption on palladium, each of which can be assigned to different types of coordination of CO at the surface. Assuming the model of a densest packing of spheres to which CO molecules are bound, the CO molecule can be bound to a single palladium atom (top), bridging two palladium atoms (bridge), or bridging three palladium atoms (hollow).
- the carbon monoxide is preferably adsorbed in such a way that it is adsorbed on three palladium atoms, that is arranged on the gap in the packing of the palladium atoms. Only when the degree of cloudiness is high will the energetically unfavorable positions (top and bridge) be occupied. When silver atoms are introduced into the palladium, fewer positions are available at which the CO can coordinate to three palladium atoms in vacancy, thus favoring positions with increasing silver content at which the CO is only coordinated to a palladium atom (top).
- the ratio of the intensity of the bands which can be assigned to the adsorption on the gap (hollow) or to a single palladium atom (top) changes. From the ratio of the intensities can therefore be inferred conversely on the degree of alloying. Further, the wavenumber at which adsorption of a CO molecule to a single palladium atom changes depending on the degree of alloying. For pure palladium, the band is observed for the adsorption of a CO molecule on a single palladium atom (top) at 2070 - 2065 cm -1 . As the degree of alloying increases, a shift to wavenumbers in the range of 2055-2050 cm -1 is observed.
- both the active metal and the promoter metal are concentrated in a very thin shell.
- At least 90% by weight of the active metal is contained in a shell of the support which, measured from the outer surface of the support (or the coating), has a layer thickness of at most 250 ⁇ m, preferably at most 200 ⁇ m, particularly preferably 150 ⁇ m.
- the promoter metal (s) is also present in the above distribution. The inventors assume that the high selectivity of the catalyst is achieved by the very thin shell and the specific distribution of the active components, since the molecules diffusing into the catalyst, for example acetylene or ethylene, can only come in contact with the active material for a very short time.
- the active metal preferably has a very pronounced concentration maximum on the outer edge of the shell.
- the highest concentration of the active metal (s), and preferably also of the promoter (s) according to this particularly preferred embodiment of the invention within 80 microns, preferably 60 .mu.m, in particular 50 microns calculated from the surface (outer surface) of the carrier ( or the coating).
- the highest concentration lies directly on the surface of the carrier (or of the coating) and decreases toward the interior of the carrier (or of the coating).
- both the active metal and the promoter metal can be concentrated within a very thin shell in the carrier material. It is preferred that in the catalyst of the invention, the active metal and the promoter metal in the volume of the carrier form a common concentration maximum at the outer edge of the carrier (see above).
- the particle size distribution of the active material, in particular of the active metal (eg palladium) and preferably also of the promoter metal (eg silver), according to a particularly preferred embodiment has a maximum with a half-width of less than 4 nm. The half-width can be determined by plotting the number of particles against their diameter, so that a curve with a maximum of the particle size distribution is obtained. The half-width then corresponds to the width of the peak of the maximum in 50% of its height, measured from the zero value.
- the distribution of the active metal and promoter metal in the support can be determined by making a cut of the catalyst, for example, by sanding the support accordingly. In the electron microscope, the spatial distribution of the active metal or the promoter metal can then be determined with the aid of WDX spectroscopy (wavelength-dispersive X-ray diffraction). In this case, a measuring head is guided over the sample, which is sensitive to the active metal, preferably palladium, or the promoter metal, preferably silver, so that their distribution in the surface can be determined.
- WDX spectroscopy wavelength-dispersive X-ray diffraction
- the electron beam microprobe is a combination of scanning electron microscope (SEM) and X-ray fluorescence spectrometer.
- SEM scanning electron microscope
- X-ray fluorescence spectrometer X-ray fluorescence spectrometer.
- a finely focused electron beam strikes the sample.
- this beam can be used to image the sample.
- the existing elements can be identified and their mass concentration can be determined.
- the identification of the elements and the determination of the concentrations are as follows: The electron beam strikes the sample at the measuring point and penetrates into the material.
- the penetration depth is of the order of 1 to 3 ⁇ m and can be changed by the excitation voltage of the electron beam (at higher excitation voltage, the penetration depth is greater).
- the irradiated electrons interact with the atoms of the sample. In this case, the electrons are decelerated and it is emitted a continuous brake spectrum whose upper limit is determined by the excitation voltage of the electron beam.
- the following process occurs: An electron ejects an electron from the electron shell of an atom. This results in a shell (viewed in the drilling model), a hole that is immediately filled again by an electron from a higher shell. This electron gives off in the form of an X-ray photon the energy that corresponds to the energy difference of the two shells.
- the emitted photon can be absorbed by an electron from the electron shell, which then leaves the envelope as an "Auger electron", or leave the electron shell and emerge from the sample.
- the totality of the thus generated and emitted from the sample X-ray photons forms the so-called "characteristic X-ray spectrum ", which consists of lines with discrete energies. Since the energy levels of the electrons are characteristic of each element, it can be determined from the energies of the characteristic lines which elements are in the sample. In addition, it can be determined from the intensities of the lines in which concentrations the elements are present.
- the X-ray radiation issuing isotropically from the sample must be analyzed.
- Wavelength Dispersive Analysis A bundle of rays is faded out from the emitted X-radiation, so that it is focused on an analyzer. Crystal of a spectrometer falls. Depending on the orientation of this crystal to the incident radiation, a fixed wavelength is reflected from the surface (Bragg condition) and the reflected beam is registered with a detector (gas flow meter, scintillation counter).
- the catalyst contains the active metal, in particular palladium, in an amount in the range of 0.001 to 1 wt .-%, preferably 0.01 to 0.8 wt .-%, based on the weight of the catalyst or the coating.
- the catalyst contains the promoter metal, in particular silver, in an amount of 0.001 to 1 wt .-%, preferably 0.005 to 0.8 wt .-%, based on the weight of the catalyst or the coating.
- the catalyst comprises a porous inorganic support, wherein all conventional support materials can be selected per se.
- the inorganic carrier material is preferably selected from the group consisting of aluminum silicates, SiO 2 , Al 2 O 3 , zeolites, kieselguhr, TiO 2 , ZrO 2 , ZnO, SiC and mixtures thereof.
- all chemically inert, abrasion-stable and temperature-stable support materials are suitable in addition to those mentioned here.
- Al 2 O 3 more preferably (X-Al 2 O 3 , is preferably used as the inorganic support material.
- the catalyst preferably has a specific surface area, measured by BET, of 1 to 80 m 2 / g, preferably 2 to 45 m 2 / g.
- the catalyst further preferably has a CO adsorption in the range from 1,000 to 5,000 ⁇ mol / g, based on the palladium. A method of measuring CO adsorption will be described later.
- the catalyst can be provided in any desired form, preference being given to formation as a shaped body (or coating, see above). All geometries known to those skilled in the art, such as, for example, spheres, cylinders, tablets, stars, and the corresponding hollow bodies, are possible. Suitable coatings, for example, are all highly fired ceramic or metallic supports with arbitrarily shaped channels or highly burned moldings, e.g. Rings.
- the shaped body is designed as a sphere or tablet, since in this shaping, the layer of the active material can be formed very precisely.
- the size of the molded body varies depending on the particular process conditions and can be easily adapted by the person skilled in the art.
- the moldings can be used with uniform shape or as mixtures of different geometries.
- the dimensions of the moldings are chosen in the range suitable for such applications.
- spheres having a diameter of 1 to 20 mm, preferably 2 to 15 mm, or tablets having a diameter and a height in the range of 1 to 20 mm, preferably 2 to 15 mm, are suitable.
- the catalyst may also contain further promoters.
- the further promoter is preferably selected from the group which is formed from the compounds of alkali and alkaline earth metals.
- the catalyst according to the invention has a high activity and selectivity in the hydrogenation of acetylenic compounds in hydrocarbon streams.
- the invention therefore also relates in one aspect to the use of the above-described catalyst for the selective hydrogenation of acetylenic hydrocarbons in hydrocarbon streams.
- other uses of the catalyst according to the invention are also covered, in particular other selective hydrogenations such as, for example, dienes.
- the catalyst according to the invention is particularly suitable for the selective hydrogenation of alkynes and dienes having a carbon number of 2 to 5, in particular in mixtures of hydrocarbons, as obtained in cracking.
- the hydrogenation can be carried out in the gas phase or else in a mixed gaseous and liquid phase.
- Such methods are known per se to the person skilled in the art.
- the reaction parameters for example the hydrocarbon throughput, the temperature and the pressure are chosen analogously to known methods.
- the catalyst is suitable for the selective hydrogenation of acetylene in ethylene streams (C2) and propyne in propylene streams (C3).
- the hydrogen is suitably used in 0.8 to 5 times, preferably 0.95 to 2 times the amount required for the stoichiometric conversion.
- the hydrogenation process can be carried out in one or more stages.
- a space velocity of the C2 stream based on the catalyst volume in the range of 500 to 10,000 m 3 / m 3 , a temperature of 0 to 250 0 C and a pressure of 0.01 to 50 bar are set.
- the space velocity is suitably 1 to 50 m 3 / m 3 .
- Fig. 1 different IR spectra of samples of a catalyst with different Ag / Pd ratio on which CO has been adsorbed;
- FIG. 3 shows a wavelength-dispersive X-ray spectrum (WDX) of a catalyst according to the invention.
- the particle size distribution is determined by means of transmission electron microscopy (TEM).
- TEM transmission electron microscopy
- the samples are first reduced. This will be a sample of Catalyst in its oxidic form under helium (100 ml / min) heated to 80 0 C and dried for 30 min. Thereafter, the sample is reduced at this temperature for 1 hour in hydrogen (10 ml / min).
- the samples thus obtained are transferred directly to the electron microscope.
- the samples are treated with ultrasound and collected particles are collected on a grid.
- Each 7 images are used for particle analysis.
- the images are processed using commercially available image processing software. This does not affect the number and size of the particles. At intervals of 1 nm, the number and size of the particles were counted. At least 150 particles are measured at a magnification factor of 150,000 (see above).
- the catalyst was first embedded in resin and then ground down to the point at which it was to be measured. These silicon carbide discs with a grain size between 100-4000 (4000 to last) and the lubricant isopropanol are used.
- the JXA8900 microprobe from Jeol which was used to measure the catalysts, has 5 wavelength dispersive spectrometers, each with 2 different analyzers that can be switched by software. This makes it possible to measure up to 5 X-ray lines simultaneously. By the simultaneous measurement one is sure that the X-ray lines actually come from the same sample site. In the measurement of the catalysts it was possible to measure the lines Pd L ⁇ l, Ag L ⁇ 1, Al Ka, O Ka and C Ka simultaneously. The beam parameters of the measurement were: beam voltage 20 kV beam current 20 n ⁇ measuring time:
- the corresponding available lines are used for the measurement.
- the sample is first oxidized in a sample chamber at 400 ° C. in a mixture of 80% N 2 and 20% O 2 for 1 hour in order to remove organic contaminants. Subsequently, the sample is first rinsed with pure N 2 for 30 minutes at the same temperature and then reduced in hydrogen flow (40 ml / min) for 1 hour. The prepared sample is reacted with CO. For this purpose, 5 pulses (15 mbar) CO are introduced into the sample chamber and after 15 minutes the chamber is flushed with hydrogen. The sample is kept for 30 minutes at 400 0 C under a hydrogen atmosphere. The adsorbed CO reacts quantitatively with hydrogen to methane. The amount of methane produced can be determined by means of an FID.
- the determination of the Pd / Ag alloy content is made by measuring the nature of the CO bond on the catalyst surface.
- the sample preparation is analogous to the measurement of CO adsorption, but without reduction of the bound CO to methane. After introducing the CO into the measuring chamber, the sample is cooled to room temperature over a period of 60 minutes. The CO 2 -type catalyst samples are then measured in the IR spectrometer. The peaks observed in the IR transmission spectrum can be assigned to different binding states of the CO molecule to the palladium layer.
- the peak maximum for linear bonding (linear, "top” (1)) of the CO molecule is 2065-2070 cm -1 , bridging (bridged (edge) b (e)) for 1950- 1965 cm '1 and with multiple bridging (hollow (h)) at about 1910 cm “1 .
- the peaks shift accordingly.
- the degree of alloying can then be determined Peak areas l / ((h + b (e)) one can estimate the alloy formation: the larger this ratio, the higher the proportion of alloyed metal particles.
- the degree of alloying can then be determined from the peak ratio for linearly bound CO at the wave number of the pure palladium sample and at the wave number of the sample with silver and palladium. For this purpose, the contribution of each peak to the total area of the on top peak is determined.
- Fig. 1 shows by way of example an IR spectrum of catalyst samples with different Ag / Pd ratio on which CO has been adsorbed. It can be clearly seen that in comparison with the pure Pd catalyst, the proportion of linearly bound CO is increased in both bimetallic samples. This is especially evident in the sample with the increased metal loading (blue curve). This is due to the fact that by the addition of Silver less hollow and bridge sites (3 or 2 contiguous Pd surface atoms) are available for the adsorption of CO. The adsorption of CO on the bimetallic catalysts is therefore predominantly in a linear geometry on isolated Pd surface atoms.
- Example 2.1 150 ml of solution containing palladium nitrate (0.072% by weight) and silver nitrate (0.08% by weight) are applied to 250 g of alumina tablets measuring 2 ⁇ 4 mm by means of a ball coater. The mixture was then dried and calcined as in Example 2.1, ie, the coated support bodies were dried for 1 hour at 80 0 C under a stream of nitrogen and then calcined at 300 0 C for 3 h. Catalyst D has a CO adsorption of 700 ⁇ mol CO / g Pd.
- 150 ml of solution containing palladium nitrate (0.072% by weight) are applied to 250 g of alumina tablets measuring 2x4 mm by means of a ball coater.
- the coated carrier bodies are incubated for 1 hour at 80 ° C. under an embroidery Dried stream and then calcined at 300 0 C for 3 h.
- Example 1 of EP 0 780 155 150 ml of nitric acid solution containing palladium nitrate (0.09% by weight) and silver nitrate (0.135% by weight) are sprayed onto 250 g alumina tablets measuring 2 ⁇ 4 mm. The coated support bodies are calcined for 1 hour at 120 ° C. and then under air at 750 ° C. for 3 hours.
- the catalyst according to the invention has a narrow particle size distribution both on the tablet-like (Example 2.1.) Support material and on the spherical support material (Example 2.3) with a maximum at approximately 3.5 nm.
- the comparative catalyst D (Example 2.4) has a very broad particle size distribution and only a local maximum at about 5.5 nm.
- the catalyst according to the invention is thus present in a more precisely defined, narrow size distribution. This ensures constant properties in the use of the catalyst according to the invention in the hydrogenation of acetylenic hydrocarbons.
- the narrow particle size distribution also makes it possible to use a broader temperature window ( ⁇ T), higher selectivities and lifetime in comparison to bimetallic catalysts with Pd / Ag, for example catalysts produced according to EP 0 780 155, Example 1. 2.8 Determination of the operating temperature window and the selectivity
- the temperature is raised until the cleanup temperature is reached.
- the clean-up temperature is the temperature at which a C 2 H 2 concentration ⁇ 25 ppm in the exit gas is measured.
- the runaway temperature is defined as the temperature at which exotherm occurs and the hydrogen consumption is> 4%.
- the selectivity is calculated as follows:
- Fig. 3 shows the distribution of the catalytically active elements palladium and silver in the shell of the catalyst. As can be seen in the WDX spectrum, the elements silver and palladium are both consistently present on the catalyst up to a shell depth of 150 ⁇ m. The high accumulation of silver and palladium on the outer shell edge has a favorable effect on the performance of the catalyst.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102007025315A DE102007025315A1 (de) | 2007-05-31 | 2007-05-31 | Katalysator zur selektiven Hydrierung acetylenischer Kohlenwasserstoffe und Verfahren zu seiner Herstellung |
PCT/EP2008/004327 WO2008145387A2 (de) | 2007-05-31 | 2008-05-30 | Katalysator zur selektiven hydrierung acetylenischer kohlenwasserstoffe und verfahren zu seiner herstellung |
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EP2155392A2 true EP2155392A2 (de) | 2010-02-24 |
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EP08758898A Withdrawn EP2155392A2 (de) | 2007-05-31 | 2008-05-30 | Katalysator zur selektiven hydrierung acetylenischer kohlenwasserstoffe und verfahren zu seiner herstellung |
Country Status (9)
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US (1) | US20100217052A1 (zh) |
EP (1) | EP2155392A2 (zh) |
JP (1) | JP5323060B2 (zh) |
KR (1) | KR20100041714A (zh) |
CN (1) | CN101730588A (zh) |
DE (1) | DE102007025315A1 (zh) |
RU (1) | RU2009145197A (zh) |
TW (1) | TW200916189A (zh) |
WO (1) | WO2008145387A2 (zh) |
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2007
- 2007-05-31 DE DE102007025315A patent/DE102007025315A1/de not_active Ceased
-
2008
- 2008-05-29 TW TW097119794A patent/TW200916189A/zh unknown
- 2008-05-30 EP EP08758898A patent/EP2155392A2/de not_active Withdrawn
- 2008-05-30 RU RU2009145197/04A patent/RU2009145197A/ru unknown
- 2008-05-30 KR KR1020097027581A patent/KR20100041714A/ko not_active IP Right Cessation
- 2008-05-30 WO PCT/EP2008/004327 patent/WO2008145387A2/de active Application Filing
- 2008-05-30 CN CN200880018334A patent/CN101730588A/zh active Pending
- 2008-05-30 JP JP2010509739A patent/JP5323060B2/ja not_active Expired - Fee Related
- 2008-05-30 US US12/601,985 patent/US20100217052A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO2008145387A3 * |
Also Published As
Publication number | Publication date |
---|---|
JP5323060B2 (ja) | 2013-10-23 |
CN101730588A (zh) | 2010-06-09 |
JP2010527776A (ja) | 2010-08-19 |
KR20100041714A (ko) | 2010-04-22 |
RU2009145197A (ru) | 2011-07-10 |
US20100217052A1 (en) | 2010-08-26 |
TW200916189A (en) | 2009-04-16 |
DE102007025315A1 (de) | 2008-12-11 |
WO2008145387A3 (de) | 2009-03-12 |
WO2008145387A2 (de) | 2008-12-04 |
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