WO2010035325A1 - 1,3-ブタジエン中のアセチレン類化合物の選択水素化用触媒およびその製造方法並びにその使用方法 - Google Patents
1,3-ブタジエン中のアセチレン類化合物の選択水素化用触媒およびその製造方法並びにその使用方法 Download PDFInfo
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- WO2010035325A1 WO2010035325A1 PCT/JP2008/067355 JP2008067355W WO2010035325A1 WO 2010035325 A1 WO2010035325 A1 WO 2010035325A1 JP 2008067355 W JP2008067355 W JP 2008067355W WO 2010035325 A1 WO2010035325 A1 WO 2010035325A1
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- Prior art keywords
- catalyst
- compound
- butadiene
- palladium
- acetylene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- -1 acetylene compound Chemical class 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 150000001622 bismuth compounds Chemical class 0.000 claims description 7
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 150000002941 palladium compounds Chemical class 0.000 claims description 6
- 150000003498 tellurium compounds Chemical class 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 19
- 229910052797 bismuth Inorganic materials 0.000 abstract description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004230 steam cracking Methods 0.000 abstract description 4
- 229910052714 tellurium Inorganic materials 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 34
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000009467 reduction Effects 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 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 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000007086 side 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
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical compound [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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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
-
- 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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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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
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
Definitions
- the present invention relates to a catalyst applied to a reaction for selectively hydrogenating an acetylene compound contained in a C4 hydrocarbon compound reservoir mainly containing 1,3-butadiene to obtain high-purity 1,3-butadiene. And a manufacturing method thereof and a method of using the same.
- olefin compounds as basic raw materials for petrochemical industry are usually produced by naphtha steam cracking, but they contain highly unsaturated hydrocarbon compounds, which are used as raw materials for polymer chemical industry. In order to do so, these compounds must be removed.
- olefin compounds such as ethylene, propylene, butadiene, isoprene and the like
- the loss of useful materials such as ethylene, propylene, butenes, butadiene, isoprene and the like in the feed stream is reduced.
- the palladium-based catalyst used in the selective hydrogenation reaction is not only highly selective but also highly active, so adjusting the reaction temperature prevents side reactions and unreacted highly unsaturated hydrocarbon compounds.
- palladium catalysts are used, the acetylene compounds are significantly higher in the reactivity of olefin compounds and acetylene compounds.
- Olefin compounds as side reactions are preferably catalysts that do not cause hydrogenation reaction as much as possible in terms of the yield of the target compound.
- carbonaceous materials obtained by polymerization of highly unsaturated compounds are preferably used. Precipitation on the catalyst also occurs, and it is preferable that the polymerization material is as little as possible because the frequency of regeneration of the catalyst can be reduced.
- C4 acetylene compounds such as vinyl acetylene and ethyl acetylene in a C4 hydrocarbon compound reservoir mainly containing 1,3-butadiene by hydrogenation
- butadiene is also hydrogenated to remove butene.
- Arise butadiene is useful as a polymer raw material, and its loss causes many losses economically, so it is preferable to reduce it as much as possible.
- Patent Document 1 it has been reported in Patent Document 1 that the selectivity is improved by adding Ag to the catalyst composition as an improvement in the performance of the palladium-based catalyst. Moreover, in the catalyst composition of patent document 2, it is reported that selectivity improves by adding Ag and Bi to Pd.
- Patent Document 3 reports a catalyst to which Te or Sb is added in order to suppress the elution of Pd in a high-concentration butadiene stream. However, although the elution of Pd is suppressed, there is no description about the improvement of the selectivity.
- the present invention relates to palladium / alumina reported so far as a catalyst for selectively hydrogenating acetylene compounds contained in a C4 hydrocarbon compound reservoir mainly containing 1,3-butadiene obtained by steam cracking or the like.
- the catalyst improves the selectivity by adding a cocatalyst component, but it is for solving the problems of the prior art that were not satisfactory in practice.
- an object of the present invention is to provide a catalyst for selectively hydrogenating a trace amount of acetylene compounds contained in a C4 hydrocarbon compound reservoir mainly containing 1,3-butadiene having a high selectivity sufficiently satisfactory for practical use. It aims at providing the manufacturing method and its usage.
- 1,3-butadiene is hydrogenated by adding a new promoter component to the palladium catalyst and further reducing it with hydrogen at a high temperature. It has been found that a catalyst with a small amount, that is, a high selectivity can be produced.
- the present invention relates to a catalyst for hydrogenating an acetylene compound in 1,3-butadiene containing palladium, bismuth or palladium, bismuth and tellurium and hydrogenating at high temperature, and a method for producing and using the same. I will provide a.
- 1,3-butadiene is selectively used in a selective hydrogenation reaction of acetylene compounds such as vinylacetylene and ethylacetylene contained in a trace amount in a C4 hydrocarbon compound reservoir mainly containing 1,3-butadiene. It is possible to carry out without loss due to hydrogenation, and it is possible to provide a catalyst having a very high level of selectivity, a method for producing the same, and a method for using the same.
- FIG.1 (a) is a figure which shows the catalyst physical property which measured the catalyst of Example 1 with the XRD measuring apparatus.
- FIG.1 (b) is a figure which shows the catalyst physical property which measured the catalyst of the comparative example 4 with the XRD measuring apparatus.
- a palladium compound is supported on an inorganic carrier, treated with a reducing agent, dried or calcined in air, introduced with a metal compound, dried or calcined, and then reduced in an air stream containing high-temperature hydrogen.
- a metal compound dried or calcined, and then reduced in an air stream containing high-temperature hydrogen.
- the palladium raw material of the catalyst composition of the present invention is not particularly limited as long as it does not contain components that are decomposed by heat treatment and finally remain on the catalyst and become catalyst poisons, but palladium chloride, palladium nitrate, tetrachloro Inorganic and organic compounds such as palladium and palladium acetonato can be used, and the palladium content supported on the support is in the range of 0.01 to 1% by weight based on the total weight of the catalyst composition.
- metal oxides such as alumina, silica, titania, silica alumina and the like can be used, and alumina is particularly preferable.
- Alumina can be used in the form of tablets, cylinders, extruded products, spherical products, etc., and the surface area can be in the range of 1 to 350 m 2 / g.
- a carrier liquid containing palladium To support palladium on the carrier, prepare a carrier liquid containing palladium, soak the carrier in the carrier liquid, spray the carrier liquid on the carrier, spray the carrier liquid in a liquid volume that matches the water absorption amount of the carrier. It is carried out by an impregnation method in which a holding liquid is prepared and the entire amount is contained in the carrier. After palladium loading, it is reduced without drying or firing or drying.
- the reduction method is performed by hydrogen or liquid phase reduction.
- an aqueous solution of a reducing agent such as formalin, sodium formate or silicon hydride can be used. After the reduction, the solution is washed with water, dried or calcined.
- the firing or reduction temperature here is not particularly limited, and is carried out in the range of room temperature to 600 ° C.
- the thickness of the palladium layer from the outer surface of the catalyst is about 400 micrometers or less, high selectivity can be obtained with little butadiene loss.
- the metal compound as the promoter component of the present invention contains bismuth, and can be used as an inorganic salt such as nitrate or chloride, or an organic salt such as acetate.
- the bismuth compound content is included in the range of about 0.01 to 10% by weight, more preferably in the range of 0.1 to 6% by weight, based on the total weight of the catalyst composition.
- the weight ratio of the bismuth compound to the palladium compound is preferably from 0.1 to 10, more preferably from 0.5 to 8.
- a tellurium compound can be further added to the bismuth compound.
- the tellurium compound can be used as an oxo acid such as tellurate, an inorganic salt such as chloride, or an oxide.
- the tellurium compound content is in the range of about 0.01 to 0.1% by weight, more preferably about 0.01 to 0.05% by weight, based on the total weight of the catalyst composition.
- the support of the promoter component on the carrier is carried out by the soaking method, the spray method, the impregnation method, etc. as in the case of palladium.
- These metal compounds can be supported on the support simultaneously with palladium, but a promoter component can be further added to the support on which palladium is supported.
- the firing temperature is not particularly limited, and is carried out in the range of room temperature to 800 ° C.
- the gas used for the reduction may contain an inert gas such as nitrogen in hydrogen.
- the reduction can be carried out in the range of 250 to 600 ° C, preferably in the range of 300 to 500 ° C. It is important to reduce at a high temperature in this hydrogen stream, and the selectivity decreases at about 150 ° C., which is normally used. Further, as described in Patent Document 2, even when silver is added to the catalyst component, practically sufficient selectivity cannot be obtained by hydrogen reduction at a low temperature. As this cause, believe to be due to Pd and the cocatalyst component by reduction at high temperature PdBi, compounds such as PdBi 2 produced by alloying.
- the active component obtained by alloying the metal is generated by high-temperature reduction in a hydrogen stream, and is a catalyst that is essentially different from the known catalyst.
- the novel catalyst having this physical property selectively hydrogenates a trace amount of C4 acetylenes such as vinyl acetylene and ethyl acetylene in a C4 hydrocarbon compound reservoir rich in 1,3-butadiene.
- either a fixed bed reactor or a fluidized bed reactor may be used, and the reaction is carried out in any of a gas phase, a liquid phase, and a mixed phase. May be.
- a gas phase reaction a mixture of an acetylene compound and an olefin compound such as 1,3-butadiene and hydrogen gas are introduced into a carrier gas from the inlet of a reactor filled with the catalyst of the present invention. In this case, the abundance ratio of olefinic compounds can be increased at the outlet of the reactor.
- the C4 hydrocarbon compound reservoir mainly containing 1,3-butadiene in which the catalyst of the present invention is used includes butane, isobutane, butene, isobutene, 1,3-butadiene, 1,2-butadiene, ethylacetylene, It contains vinyl acetylene and a small amount of C3 and C5 hydrocarbons, and mainly contains 30 to 60% of 1,3-butadiene and 0.1 to 5% of vinyl acetylene and ethyl acetylene.
- reaction temperature 40 to 100 ° C. pressure 0.5 to 5 MPa
- LHSV 1 to 20 h ⁇ 1
- hydrogen / acetylenes 0. It is carried out under the conditions of 5 to 2.
- the acetylene conversion rate was determined by the following equation by measuring the concentrations of vinyl acetylene and ethyl acetylene in the liquid before and after the reaction by gas chromatography.
- the butadiene loss rate was determined from the following equation by measuring the concentration of 1,3-butadiene in the raw material and the liquid after the reaction using a gas chromatograph.
- the catalyst for selective hydrogenation according to the present invention has a small amount of hydrocarbons obtained by steam cracking or the like, especially in a C4 hydrocarbon compound reservoir that has been very difficult to separate because it contains a large amount of 1,3-butadiene.
- acetylene hydrocarbons can be selectively hydrogenated and excessive hydrogenation reactions can be prevented, minimizing the loss of useful resources and being very advantageous in industrial cracking processes.
- the cost for producing the final raw material for the polymer chemical industry can be greatly reduced.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
触媒量=30ml
LHSV=10h-1
圧力=2.9MPa
反応温度=35℃
水素/アセチレン類=1.0
リサイクル比=0.5~1.0
リサイクル比は、原料を希釈するために反応後の液を原料に混合する割合である。
リサイクル比=反応後液量(ml/h)/原料液量(ml/h)
ビニルアセチレン=0.3~0.5%
エチルアセチレン=0.13~1.16%
1,3-ブタジエン=44%
1-ブテン=18%
t-2-ブテン=5%
c-2-ブテン=4%
i-ブテン=24%
N-ブタン=4%
アセチレン転化率は、反応前及び反応後の液中のビニルアセチレンおよびエチルアセチレンの濃度をガスクロマトグラフにより測定し、次式により求めた。
Claims (8)
- 1,3-ブタジエンを含むC4炭化水素化合物溜中のアセチレン類化合物の選択水素化用触媒であって、無機担体に坦持されたパラジウム化合物とパラジウム以外の金属化合物とを含有し水素を含む気流中で還元されたことを特徴とするアセチレン類化合物選択水素化用触媒。
- 金属化合物は、ビスマス化合物あるいはビスマス化合物およびテルル化合物からなることを特徴とする請求項1記載の触媒。
- 触媒全重量に基づき、パラジウム化合物の含有量は0.01~1重量%であり、ビスマス化合物の含有量は0.01~10重量%であり、パラジウム化合物に対するビスマス化合物の重量比は0.1~10であることを特徴とする請求項2記載の触媒。
- 触媒全重量に基づき、テルル化合物の含有量は0.01~0.1重量%であることを特徴とする請求項3記載の触媒。
- 250~600℃で還元されたことを特徴とする請求項1記載の触媒。
- C4炭化水素化合物溜中に1,3-ブタジエンが30~60%含まれ、アセチレン類化合物が0.1~5%含まれることを特徴とする請求項1記載の触媒。
- 請求項1~6に記載の触媒を製造する方法であって、パラジウム化合物を無機担体に担持させ、還元剤で処理し、空気中で乾燥または焼成し、金属化合物を導入し、乾燥または焼成した後、高温の水素を含む気流中で還元することにより製造することを特徴とする方法。
- 1,3-ブタジエンを含むC4炭化水素化合物溜中のアセチレン類化合物を選択水素化してオレフィン化合物に転化するために使用される請求項1に記載の触媒の使用方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2008/067355 WO2010035325A1 (ja) | 2008-09-25 | 2008-09-25 | 1,3-ブタジエン中のアセチレン類化合物の選択水素化用触媒およびその製造方法並びにその使用方法 |
KR1020117008859A KR101478398B1 (ko) | 2008-09-25 | 2008-09-25 | 1,3-부타디엔 중의 아세틸렌류 화합물의 선택적 수소화용 촉매 및 그의 제조방법 및 그의 사용방법 |
EP08877066A EP2329879A4 (en) | 2008-09-25 | 2008-09-25 | CATALYST FOR THE SELECTIVE HYDROGENATION OF ACETYLENE COMPOUNDS TO 1,3-BUTADIENES, METHOD OF MANUFACTURING THEREOF, AND USE METHOD THEREFOR |
CN2008801313241A CN102164669A (zh) | 2008-09-25 | 2008-09-25 | 1,3-丁二烯中的炔类化合物的选择氢化用催化剂及其制造方法、和其使用方法 |
US13/121,163 US20120123174A1 (en) | 2008-09-25 | 2008-09-25 | Catalyst for selective hydrogenation of acetylene compounds |
JP2010530656A JP5346030B2 (ja) | 2008-09-25 | 2008-09-25 | 1,3−ブタジエン中のアセチレン類化合物の選択水素化用触媒およびその製造方法並びにその使用方法 |
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PCT/JP2008/067355 WO2010035325A1 (ja) | 2008-09-25 | 2008-09-25 | 1,3-ブタジエン中のアセチレン類化合物の選択水素化用触媒およびその製造方法並びにその使用方法 |
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US (1) | US20120123174A1 (ja) |
EP (1) | EP2329879A4 (ja) |
JP (1) | JP5346030B2 (ja) |
KR (1) | KR101478398B1 (ja) |
CN (1) | CN102164669A (ja) |
WO (1) | WO2010035325A1 (ja) |
Cited By (2)
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---|---|---|---|---|
JP2011020116A (ja) * | 2009-06-18 | 2011-02-03 | Univ Of Electro-Communications | 遷移元素触媒およびその製造方法、並びに選択的水素添加方法 |
WO2017170421A1 (ja) * | 2016-03-31 | 2017-10-05 | 日本ゼオン株式会社 | 水素化方法 |
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- 2008-09-25 EP EP08877066A patent/EP2329879A4/en not_active Withdrawn
- 2008-09-25 KR KR1020117008859A patent/KR101478398B1/ko active IP Right Grant
- 2008-09-25 CN CN2008801313241A patent/CN102164669A/zh active Pending
- 2008-09-25 WO PCT/JP2008/067355 patent/WO2010035325A1/ja active Application Filing
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Also Published As
Publication number | Publication date |
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EP2329879A1 (en) | 2011-06-08 |
KR101478398B1 (ko) | 2014-12-31 |
CN102164669A (zh) | 2011-08-24 |
US20120123174A1 (en) | 2012-05-17 |
JP5346030B2 (ja) | 2013-11-20 |
KR20110057246A (ko) | 2011-05-31 |
JPWO2010035325A1 (ja) | 2012-02-16 |
EP2329879A4 (en) | 2012-07-11 |
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