WO1998010863A1 - Catalyseur pour l'hydrogenation selective de melanges d'hydrocarbures hautement insatures dans un compose a base d'olefine - Google Patents
Catalyseur pour l'hydrogenation selective de melanges d'hydrocarbures hautement insatures dans un compose a base d'olefine Download PDFInfo
- Publication number
- WO1998010863A1 WO1998010863A1 PCT/JP1997/003196 JP9703196W WO9810863A1 WO 1998010863 A1 WO1998010863 A1 WO 1998010863A1 JP 9703196 W JP9703196 W JP 9703196W WO 9810863 A1 WO9810863 A1 WO 9810863A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- palladium
- catalyst
- hydrogen
- alumina
- reaction
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 223
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 80
- -1 olefin compound Chemical class 0.000 title claims abstract description 33
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 22
- 229930195735 unsaturated hydrocarbon Natural products 0.000 title claims abstract description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 369
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 185
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000001257 hydrogen Substances 0.000 claims abstract description 79
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 79
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000003795 desorption Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims description 43
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 34
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 26
- 239000005977 Ethylene Substances 0.000 claims description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 24
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 24
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 12
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 10
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000013081 microcrystal Substances 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 3
- 238000007086 side reaction Methods 0.000 abstract description 12
- 239000003575 carbonaceous material Substances 0.000 abstract description 7
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- 230000000704 physical effect Effects 0.000 description 38
- 239000000243 solution Substances 0.000 description 27
- 230000009467 reduction Effects 0.000 description 24
- 150000002941 palladium compounds Chemical class 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- 239000002994 raw material Substances 0.000 description 19
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 11
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 7
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- 238000005406 washing Methods 0.000 description 6
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 5
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- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 4
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- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 3
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 239000004280 Sodium formate Substances 0.000 description 3
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
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- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
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- SSORSZACHCNXSJ-UHFFFAOYSA-N 2-[2-(3,4-dichlorophenyl)-3-[2-(2-hydroxypropylamino)pyrimidin-4-yl]imidazol-4-yl]acetonitrile Chemical compound ClC=1C=C(C=CC=1Cl)C=1N(C(=CN=1)CC#N)C1=NC(=NC=C1)NCC(C)O SSORSZACHCNXSJ-UHFFFAOYSA-N 0.000 description 2
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- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- 229940062097 nitrogen 90 % Drugs 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- ALWUDBGJBKUAME-UHFFFAOYSA-N palladium;sodium;hydrochloride Chemical compound [Na].Cl.[Pd] ALWUDBGJBKUAME-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UNWZKBKTIYBBRV-UHFFFAOYSA-N tetraazanium;tetrachloride Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Cl-].[Cl-].[Cl-].[Cl-] UNWZKBKTIYBBRV-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—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
-
- B01J35/30—
-
- B01J35/60—
-
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B01J35/392—
-
- B01J35/613—
-
- B01J35/615—
Definitions
- the reaction Since the palladium-based catalyst used in the selective hydrogenation reaction has not only high selectivity but also excellent activity, the reaction starts at a low temperature, and the carbonaceous substance on the catalyst surface which occurs as another side reaction When the activity decreases due to adhesion or the like and the reaction efficiency deteriorates, the reaction temperature is gradually increased to operate while preventing highly unsaturated hydrocarbon compounds from being unreacted in the production system. When the temperature rises to near the critical point where the hydrogenation reaction of the compounds becomes active, the reaction is interrupted, the catalyst is regenerated and reused.
- the acetylene compound is significantly higher, Usually, the amount of the olefin compound is much larger than that of the olefin compound, so the hydrogenation of the olefin compound also occurs in parallel with the hydrogenation of the acetylene compound. It is preferable for the yield of the target compound to be a catalyst that does not cause the addition reaction as much as possible.In addition, a carbonaceous substance is precipitated on the catalyst by polymerization of highly unsaturated compounds as another side reaction.
- EP 7227776 and US Pat. No. 5,489,655 disclose palladium.
- ⁇ The ability to add silver and aluminum fluoride to the alumina catalyst.
- EP 689872 states that palladium ⁇ Adds silver to the alumina catalyst and then reduces the catalyst by liquid phase reduction.
- the ability to prepare is described in French Patent No. 27200956 as adding a Group I element of the Periodic Table and an alkali or alkaline earth element to a palladium-alumina catalyst.
- Japanese Patent Publication No. 26035578 discloses the addition of gold to a palladium-alumina catalyst.
- a mixture of three kinds of alumina hydrates is calcined at a high temperature as a carrier alumina of a palladium-alumina catalyst. That is, JP-B No. 5 8 - be used 0 1 7 8 3 Table area 5 5 during No. 5 as a carrier for the palladium 'alumina catalyst 1 2 0 alumina m 2 Z g, JP-B
- the size of the palladium crystal of the palladium-alumina catalyst is specified to be at least 50 A or more in JP-B No. 63-3-0 17 8 13 and JP-B No. 54-135 711.
- a palladium-alumina catalyst contains silver as a promoter component, and the carrier has a surface area of 3 to 7 It is disclosed that the thickness of the palladium-supporting layer is 300 microns or less with ⁇ 2 alumina of m 2 / g.
- the only one that discloses improvement in the physical properties of palladium, which is an active ingredient, is to make the crystallite size of palladium 5 OA or more.
- the morphology and chemical properties of the particles were analyzed from the crystallographic viewpoint, and the change in the interaction between palladium and hydrogen caused by the difference in the palladium microcrystal plane and the effect on the catalyst selectivity were considered.
- the palladium-alumina catalyst is a catalyst for selectively hydrogenating highly unsaturated hydrocarbon compounds as impurities contained in the olefin compounds obtained by naphtha steam cracking.
- the selectivity has been improved by the improvement of physical properties, but it is not enough, and the selectivity is further reduced by further suppressing the hydrogenation of the olefin compound as a side reaction that occurs concurrently or sequentially during the reaction.
- the selectivity of the catalyst is influenced by the surface area, pore volume, or crystal size of the constituent components as the basic physical properties, but if multiple reactions occur simultaneously or sequentially, Since the catalyst is required to promote only the reaction, it is considered necessary that the surface of the catalyst as a reaction field has a physical or crystallographic structure suitable for the reaction to be promoted. .
- the present inventors focused on the crystallographic structure of palladium microcrystals as an active ingredient of the catalyst, and focused on the type of raw palladium and their use as carriers. Examine the treatment method after loading, examine the resulting catalyst for the exposed surface of palladium microcrystals by X-ray diffraction, adsorb hydrogen to the catalyst, desorb it by heating, and observe the situation Analysis of the catalyst's ability to absorb hydrogen, and the relationship between the physical and chemical properties of these fine particles of palladium and the performance of the selective hydrogenation of highly unsaturated hydrocarbon compounds in the olefin compounds. .
- a palladium-based catalyst that selectively hydrogenates highly unsaturated hydrocarbon compounds in the olefin compounds is prepared by supporting various palladium compound raw materials on a carrier, followed by drying, calcining, reducing, etc., and the activity of the catalyst.
- the selectivity is affected by the type of palladium compound raw material used, the type of carrier, the method of supporting the palladium raw material on the carrier, the drying, calcination, and reduction methods.
- the palladium raw material may be any compound that is soluble in water and does not contain any components that will eventually remain on the catalyst and cause poisons in the catalyst.
- palladium compounds can be used, palladium chloride, palladium sodium chloride, palladium nitrate, palladium sulfate, tetrachloride palladium salts, dichlorodiamminepalladium, and palladium anion, which are usually easily available, can be used.
- Min complex salts, dinitropolyammine palladium, and the like are used.
- Materials used as carriers are porous inorganic oxides, such as silica, alumina, and titanium oxide.In particular, alumina is generally used, and a method for improving catalyst selectivity by improving the physical properties of the catalyst.
- the most suitable carrier is selected as appropriate depending on the type of reaction desired, the method of preparing the catalyst to be applied, and the like.
- the palladium raw material is supported on a carrier by adding a carrier to an aqueous solution of a palladium compound, using a soaking method using the adsorption action of the carrier, the pore volume of the carrier An aqueous solution of a palladium compound is filled therein to physically carry a palladium compound, which is carried out by an immersion method, an impregnation method, or a spray method in which an aqueous solution of a palladium compound is sprinkled on a carrier.
- the palladium compound After the palladium compound is supported on the carrier, it is dried and calcined.These treatments are usually performed in the air.
- the calcination is related to the size of the palladium particles carried on the carrier, and as a result, the Since it affects the activity and selectivity, it is necessary to carefully select and carry out the firing temperature.
- the catalyst is reduced.
- This reduction treatment is usually performed in a gas phase under heating with hydrogen, but as a separate reduction method, a liquid phase is used, and water-soluble organic compounds, hydrazine, and sodium boron boron are used.
- the reduction can be carried out by a dry method or the like. In this case, the palladium material supported on a carrier may be directly reduced. After drying and calcining, the liquid phase reduction is also possible.
- the shape of the palladium fine particles usually supported on a carrier has a spherical shape, and a feature that the (111) plane is mainly grown crystallographically can be seen.
- the desorption peak is confirmed in the temperature range of 40 to 90 and the temperature range of 120 to 17 O:
- the former desorption amount is 1.5 to 2.5 times the latter desorption amount, and a large amount of weakly chemisorbed hydrogen is present in palladium.
- the present inventors have focused on a treatment method carried out after supporting a palladium compound raw material on a carrier, as one of the studies conducted, and in an inert gas stream instead of ordinary firing in air, or Heat treatment was performed at a relatively high temperature in a reducing gas stream, and the finally obtained catalyst was examined for its exposed surface of palladium microcrystals by X-ray diffraction.Hydrogen was adsorbed on the catalyst, followed by thermal desorption. Analysis of the adsorption of the catalyst to hydrogen by observing the situation, and the relationship between the physical and chemical properties of these palladium fine particles and the performance of the selective hydrogenation reaction of highly unsaturated hydrocarbon compounds in the olefin compound. Examined.
- the exposed crystal planes of palladium fine particles were examined by X-ray diffraction.
- the (100) plane and the (110) plane have mainly grown crystal forms.
- the desorption peak temperature was in the temperature range of 40 to 90 and 120 to 170 as in the case of the normal catalyst.
- the amount of desorbed hydrogen in the latter was 1.5 to 2.5 times that of the former, confirming that the proportion of strongly adsorbed hydrogen was increasing, unlike ordinary catalysts.
- the resulting catalyst was subjected to a selective hydrogenation reaction of highly unsaturated compounds in the olefin compounds in a fixed bed pressurized flow reactor, and after loading palladium chloride on an alumina carrier by a usual preparation method.
- the performance of the catalyst of the present invention was compared with that of a catalyst obtained by drying, calcining in air, and then reducing with hydrogen.
- the catalyst according to the present invention usually lost more by hydrogenation of olefin compounds as a side reaction than the catalyst. And the precipitation of carbonaceous material due to the polymerization of the highly unsaturated hydrocarbon compound on the catalyst was considerably small.
- the type of the gas is not limited when the process is performed in an inert gas stream.However, from the viewpoint of practicality, the atmosphere of nitrogen, carbon dioxide, or steam When the heat treatment is performed in a reducing gas stream, hydrogen gas or a gas obtained by diluting hydrogen gas with an inert gas is used.
- the heat treatment temperature is in the range of 500 to 1200, preferably in the range of 600 to 100, and at a temperature of 500 ° C. or less, (100) and (110) ) No crystal plane growth was observed, and at temperatures above 1200 X: the catalyst was physically degraded and no good catalyst could be obtained.
- the catalyst When the heat treatment atmosphere is an inert gas stream, the catalyst needs to be reduced. Usually, it is preferable to reduce the catalyst in a hydrogen gas stream like the catalyst, and the reduction is performed in a temperature range of 100 to 500 in the temperature range of 1 to 2 It is needless to say that when the heat treatment atmosphere is a reducing airflow, the catalyst need not be reduced.
- the crystal of the palladium fine particles had a crystal form in which the (100) plane and the (110) plane mainly grew, and were subjected to thermal desorption after adsorbing hydrogen.
- the desorption peak temperature can be seen in the temperature range of 40 to 90 :, and 120 to 170 as in the case of the normal catalyst. 1.5 to 2.5 times
- the catalyst had a surface area per unit weight of 1 to 100 II ⁇ Z g ⁇ palladium.
- the palladium raw materials that can be used here need only be decomposed by heat treatment and do not contain components that will eventually remain on the catalyst and cause poisoning of the catalyst.
- Palladium chloride, palladium nitrate, palladium tetrachloride Ammonium oxalate and the like can be used, and the amount of palladium supported on the carrier is in the range of 0.02 to 3.0 wt.%.
- Alumina is preferable as the carrier, and any shape of alumina can be used.However, since this catalyst is used in a molded body, when powdered alumina is used as a starting material, it is molded during the catalyst production process. Molding after carrying palladium will result in palladium being uniformly distributed in the molded body, and the palladium present inside will not be used effectively. It is desirable to use a molded product such as an extruded product or a spherical product having a gear-shaped cross section in the direction, and it is possible to use a molded product having a surface area of 1 to 350 Zg.
- Catalysts with palladium particles exhibiting a different crystal surface growth state than conventional catalysts and having a high rate of strongly adsorbing hydrogen are reduced after the palladium compound raw material is supported on a carrier and heat-treated in an inert gas stream.
- it can be obtained by heat treatment also serving as palladium reduction in a reducing gas stream, but can also be obtained by carrying out a liquid phase reduction after supporting a specific palladium compound on a carrier.
- the carrier use is made of an alumina molded product such as a tablet having a surface area in the range of 1 to 350 Hi 2 / g, an extruded product having a columnar or diametrical cross section in a gear shape, or a spherical product.
- the raw materials that can be used as the specific palladium compound include dinitropolyammine palladiums, dichlorodiammine palladiums, and the like, and 0.2 to 3.0 as palladium on a carrier. wt.%, and the loading of these palladium compounds on the carrier is carried out by a soaking method, a spraying method, a dipping method, or an impregnation method. After the loading operation is completed, the palladium compound is dried or directly without drying. The desired catalyst is obtained by liquid phase reduction, followed by washing and drying. Is prepared.
- the range of the reaction in which these catalysts show high selectivity is not limited by the number of carbon atoms of the reactants, but is not limited to acetylene in ethylene, propagen and methylacetylene in propylene, butadiene and ethylacetylene in butene, and decomposed gasoline. It can be applied to the selective hydrogenation of gens and the like. In the petrochemical industry, the selective hydrogenation reaction of highly unsaturated hydrocarbon compounds contained in various olefins has different reaction conditions depending on the carbon number of the reactants.
- the reaction initiation temperature is 50 to At 70, the reaction temperature is gradually increased as the activity decreases, the reaction is stopped when the temperature reaches 90 to 15 O :, the catalyst is regenerated, and the reaction is restarted.
- the maximum temperature rise due to the heat of reaction is 40-45 t: preferably 20-30 or less.
- the pressure is 5-35 kg / cm 2 -G, SV 40 0 0-8 0 0 0 (1 / H r)
- the reaction temperature is 25 to 120: pressure and 30 kg / cm2 * G, SV
- the condition is 200-350-350 (1 / Hr), hydrogen / acetylene molar ratio of 1.1-3.0, and when the activity decreases, it is similar to the front-end method.
- the hydrogenation reaction is performed within a reaction temperature range of 25 to 120 while regenerating is repeated.
- the reaction temperature is 20 to 40, Pressure: 20 to 70 kg / cm2-G, LHSV to 10 (lZHr), hydrogen / (molybdenum + methylacetylene) molar ratio ⁇ 3.0 is usually used for gas phase reaction.
- the reaction is carried out at a reaction temperature of 20 to 40 while repeating regeneration.
- the selective hydrogenation reaction of butadiene and ethylacetylene in butene and the selective hydrogenation reaction of gens in decomposed gasoline are carried out in the liquid phase.
- 150 t pressure 14 ⁇ 70 kg / cni2 * G, LH SV ⁇ 10 (lZHr), hydrogen
- the reaction is carried out while repeating the regeneration at a reaction temperature in the range of 40-150 ⁇ , as in the case of the gas phase reaction.
- the catalyst of the present invention When the catalyst of the present invention is used for these reactions performed in the petrochemical industry, the loss of the olefins as the target product by hydrogenation of the olefin compounds as a side reaction is extremely small, and Since carbonaceous substances are less likely to precipitate on the catalyst due to the polymerization of the highly unsaturated hydrocarbon compound as another side reaction, the catalyst can be operated stably for a long period of time with less catalyst regeneration frequency than conventional catalysts. The invention's effect
- the exposed crystal surface of the palladium fine particles obtained by the present invention is defined as (1) (0) plane and (110) plane, and desorption peaks due to the heating of adsorbed hydrogen are observed in the temperature range of 40 to 90: and 120 to 170 ° C, former
- the catalyst in which the ratio of the amount of hydrogen desorbed in the temperature range of 4 to 6: 3 to 7 in the latter temperature range shows excellent performance for the selective hydrogenation reaction of highly unsaturated hydrocarbon compounds, It can improve the yield rate and enable long-term non-recycling operations, and the economic effect when practically used is very large.
- the crystal plane measurement of palladium microcrystals is performed by X-ray diffraction measurement of the catalyst, and based on the half width of the (200), (220), and (111) diffraction peaks of palladium.
- the (100), (110), and (111) plane crystallite diameters were calculated, and the amount of hydrogen desorbed by the adsorption and desorption of hydrogen on palladium was measured using the catalyst.
- Hydrogen treatment at 110 ° C for 60 minutes, then cooling at 30 and storing in a stream of hydrogen for 60 minutes to remove the hydrogen adsorbed on the catalyst,
- Desorption is carried out by heating to 300 ° C at 3 / min, and the amount of the desorption is measured by measuring the amount of desorption.
- the palladium surface area is measured by reducing the catalyst with hydrogen and then degassing at 300.
- carbon monoxide was adsorbed with 11 O :, and calculated from the obtained adsorption amount by the following formula.
- the catalyst was tested after a reduction treatment in advance.
- the reduction and test conditions were as follows.
- the method of calculating activity and selectivity differs between the tail-end method and the front-end method, and the calculation method is as follows.
- Acetylene (Inlet acetylene concentration – Outlet acetylene concentration)
- Ethylene (Outlet ethylene concentration – Inlet ethylene concentration) Stability of performance: Measure the weight of poly produced in the catalyst after the test, and determine the carbon per acetylene conversion amount of lg. Calculate the amount.
- the light-off temperature means the temperature at which ethylene begins to be rapidly hydrogenated, and can be measured as a rapid rise in the temperature above the catalyst layer.
- the gas was analyzed by FID using a gas chromatograph.
- the catalyst reduction and test conditions are as follows.
- Fluorene gain (mo) out. ⁇ Pyrene concentration (mo) One inlet propylene concentration (mo) Selective hydrogenation test of 1.3-butadiene in C4 fraction
- Catalyst reduction and test conditions are as follows
- Gen conversion The gen number in the raw material before and after the reaction was maleated using maleic anhydride, and the unreacted maleic anhydride was quantified by titration analysis.
- Bromine value conversion After treating the bromine value in the raw materials before and after the reaction with an excess of potassium bromide-bromide acid solution standard solution, excess bromine is reduced with iodide force solution, and the liberated iodine is reduced to sulfur. It was determined by titration with sodium sulfate.
- Example 11 This intermediate is placed in an electric furnace replaced with nitrogen gas, heated to 100,000 over 5 hours while flowing 100 cc of nitrogen gas per minute, and then fired at 100,000 for 4 hours.
- the catalyst of Example 11 was prepared according to Example 1. The components of the resulting catalyst, physical properties were measured, and a performance test was conducted under the conditions I and ⁇ . The palladium content, the palladium surface area, and the palladium crystal plane were measured. Table 1 shows the measurement results of the amount of desorbed hydrogen from the catalyst, and Table 13 shows the performance test results of the selective hydrogenation of acetylene in ethylene.
- Example 11 Palladium chloride-supported alumina as an intermediate in Example 11 was placed in a closed reaction tube, replaced with a mixed gas of 10% hydrogen and 90 nitrogen, and then flowed at 100 cc per minute for the mixed gas.
- the catalyst of Example 12 was prepared by raising the temperature to 1000 over 5 hours and calcining at 1000 ° C. for 4 hours, and further, the components, physical properties and conditions of the obtained catalyst I
- the performance test was conducted under the conditions (1) and (2), and the measurement results of palladium content, palladium surface area, and palladium crystal surface are shown in Table 11, the measurement results of the amount of desorbed hydrogen of the catalyst are shown in Table 1, and the acetylene selection in ethylene
- the performance test results of the hydrogenation reaction were as shown in Table 13.
- Example 11 Palladium chloride-supported alumina as an intermediate in Example 11 was placed in a closed reaction tube, replaced with hydrogen gas, and then flowed through 100 cc for 1 minute. After heating to 100 ° C, the catalyst of Example 13 was prepared by calcining at 100 ° C for 4 hours, and the performance test was performed according to the components of the resulting catalyst, measurement of physical properties, and conditions I and ⁇ . Table 1 shows the measurement results of the palladium content, palladium surface area, and palladium crystal plane, and Table 1 shows the measurement results of the amount of desorbed hydrogen of the catalyst. The performance test results of the selective hydrogenation reaction of acetylene in ethylene was as shown in Table 13. Comparative Example 1 1
- Example 11 Palladium chloride-supported alumina as an intermediate in Example 11 was placed in an electric furnace, heated in air to 100 over 5 hours, and calcined at 100 Ot: for 4 hours. Thus, the catalyst of Comparative Example 11 was prepared. The components of the obtained catalyst, physical properties were measured, and performance tests were performed under the conditions I and ⁇ . The results of the palladium content, palladium surface area, and palladium crystal plane measurement were as follows. Table 1 shows the measurement results of the amount of desorbed hydrogen from the catalyst, and Table 13 shows the performance test results of the selective hydrogenation of acetylene in ethylene.
- Example 14 This intermediate was placed in an electric furnace replaced with nitrogen gas, and the temperature was raised to 100 ° C over 5 hours while flowing 100 cc of nitrogen gas per minute.
- the catalyst of Example 14 was prepared by calcining for a period of time, and a performance test was conducted according to the components, physical properties, and conditions of the obtained catalyst. The results of palladium content, palladium surface area, and palladium crystal plane measurement results were as follows. Table 1 shows the measurement results of the amount of desorbed hydrogen of the catalyst, and Table 14 shows the performance test results of the hydrogenation reaction of provagen and methylacetylene in propylene.
- Example 14 The palladium chloride-supported alumina as an intermediate in Example 14 was placed in a closed reaction tube, and was replaced with a mixed gas of 10% hydrogen and 90% nitrogen.
- the catalyst of Example 15 was heated at a temperature of 100 ° C. over 5 hours while flowing at 0 cc, and calcined at 100 ° C. for 4 hours.
- Table 11 After performing a performance test using the prepared catalyst components, measurement of physical properties and conditions m, the results of palladium content, palladium surface area, and palladium crystal plane measurement are shown in Table 11, and the amount of desorbed hydrogen in the catalyst was measured.
- Table-2 the performance test results of the hydrogenation reaction of provadene and methylacetylene in propylene are shown in Table-14.
- Example 14 Palladium chloride-supported alumina as an intermediate in Example 14 was placed in a hermetically sealed reaction tube, and after being replaced with hydrogen gas, 100 ° C. was flowed over 100 minutes per minute while flowing 100 cc. After raising the temperature to C, the catalyst of Example 16 was prepared by calcining at 1000 for 4 hours, and the obtained catalyst was subjected to a performance test by measuring the components, physical properties, and conditions. Table 1 shows the measurement results of the palladium content, palladium surface area, and palladium crystal plane.Table 12 shows the measurement results of the amount of desorbed hydrogen of the catalyst. The performance test results of the hydrogenation reaction of provagen and methylacetylene in propylene are shown in Table 11. It was as shown in Table 1-4.
- Example 14 Palladium chloride-supported alumina as an intermediate in Example 14 was placed in an electric furnace, heated in air to 100 over 5 hours, and calcined at 100 for 4 hours.
- the catalyst of Comparative Example 12 was prepared, and a performance test was performed according to the components, physical properties, and conditions of the obtained catalyst.
- the results of palladium content, palladium surface area, and palladium crystal plane measurement are shown in Table 11.
- Table 2 shows the measurement results of the amount of desorbed hydrogen of the catalyst
- Table 14 shows the performance test results of the hydrogenation reaction of provadene and methylacetylene in propylene.
- a 0 mg, 150 g alumina carrier having a diameter of 3 mm was immersed and held for 1 hour to carry a palladium compound on the carrier to obtain an alumina-supported tetrachloroammonium palladium ammonium salt as an intermediate.
- This intermediate was placed in an electric furnace replaced with nitrogen gas, the temperature was raised to 100 over 5 hours while flowing 100 cc of nitrogen gas per minute, and then calcined at 100 for 4 hours.
- the catalyst of Example 17 was prepared, and the components of the obtained catalyst, physical properties were measured, and a performance test was performed under the condition IV.
- Table 2 shows the measurement results of the amount of desorbed hydrogen from the catalyst
- Table 15 shows the performance test results of the selective hydrogenation reaction of 1,3-butadiene in butene.
- the alumina having tetrachloroammonium palladium obtained obtained in Example-7 was dried with 110 at 20 ° C., and then placed in an electric furnace. The temperature was raised to 1000 ° C. in air for 5 hours.
- the catalyst of Comparative Example 13 was prepared by calcining at 00 0 for 4 hours, and the components of the obtained catalyst, physical properties were measured, and performance tests were performed under condition IV.
- Table 1 shows the measurement results of the palladium crystal plane
- Table 2 shows the measurement results of the amount of desorbed hydrogen of the catalyst
- Table 5 shows the results of the performance test of the selective hydrogenation of 1,3-butadiene in butene. It was as shown.
- a 150-cc palladium nitrate solution having a palladium content of 3 g / 1 was weighed into a 300-cc beaker, and a 3 mm-diameter alumina carrier having a surface area of 3 mm was immersed in this solution for 1 hour. by supporting palladium compounds by on connexion carrier to hold, after substitution with 1 1 0 2 0 hours after drying sealable H 2 gas placed in a reaction tube, while supplying 1 0 0 cc per minute of hydrogen After raising the temperature to 900 in 5 hours, the catalyst of Example 18 was prepared by calcining at 900 ° C. for 4 hours.The components, physical properties and conditions of the obtained catalyst were further measured.
- Example 18 The catalyst of Comparative Example 14 was prepared by calcination in air instead of calcination under hydrogen flow in Example 8, and the obtained catalyst was subjected to component tests, physical property measurements and performance tests under condition IV.
- Table 1 shows the measurement results of palladium content, palladium content, palladium surface area, and palladium crystal plane.
- Table 1 shows the measurement results of the amount of desorbed hydrogen of the catalyst, and the performance test of the selective hydrogenation reaction of 1,3-butadiene in butene. The results are shown in Table 5 and the results of hydrogenation of the decomposed gasoline are shown in Table 16.
- 83 cc of a 1: 1 aqueous solution of sodium tetracyanopalladate was placed in a spray container and sprayed for 5 minutes. After the spraying is completed, stop the rotation and let stand for 10 minutes.After drying in air for 11 hours for 20 hours, put it in an electric furnace replaced with nitrogen gas, and supply nitrogen gas at 100 cc / min. After the temperature was raised to 800 over time, the mixture was calcined at 800 for 4 hours to obtain a palladium-supported alumina as an intermediate.
- Example 19 sodium boron hydride was dissolved in pure water to prepare a 5% reducing solution of 162 cc.
- the above-mentioned palladium compound was immersed in this reduced solution at room temperature for 1 hour to perform palladium reduction, further washed with water, and dried in air at 110 for 20 hours to prepare a catalyst of Example 19, which was obtained.
- the composition, physical properties, and performance tests were performed on the catalyst under the conditions V.
- the measurement results of the palladium content, palladium surface area, and palladium crystal plane are shown in Table 11, and the measurement results of the amount of desorbed hydrogen of the catalyst are shown in Table 1.
- Table 2 shows the performance test results of the hydrogenation reaction of cracked gasoline.
- Example 10 Palladium-supported alumina calcined at 800 in Example 19 for 4 hours was added with 162 cc of pure water, 0.14 g of viscous soda, and 7 cc of formalin solution.
- the catalyst of Example 10 was prepared by immersing in a reducing solution warmed at 60 ° C. for 1 hour, performing palladium reduction, further washing with water, and drying at 110 ° C. for 20 hours.
- Catalyst components, physical properties and conditions V Table 1 shows the measurement results of the palladium content, palladium surface area, and palladium crystal plane, Table 2 shows the measurement results of the amount of desorbed hydrogen of the catalyst, and the hydrogenation reaction of cracked gasoline. The performance test results are as shown in Table 16.
- Example 1 Palladium-supported alumina before firing at 800 ° C for 4 hours in Example 9 was placed in an electric furnace, heated to 900 in air for 4 hours, and then fired at 900 for 4 hours.
- the catalyst of Comparative Example 15 was prepared in exactly the same manner as in Example 10 except that the catalyst of Comparative Example 15 was prepared, and the components, physical properties and conditions of the obtained catalyst were measured.
- performance tests were performed using V, the measurement results of palladium content, palladium surface area, and palladium crystal plane are shown in Table 11, the measurement results of the amount of desorbed hydrogen of the catalyst are shown in Table 1, and the hydrogenation of decomposed gasoline The performance test results of the reaction were as shown in Table 16.
- Example 11 The catalyst of Example 11 was prepared, and the components of the resulting catalyst, physical properties were measured, and performance tests were performed under the conditions ⁇ and ⁇ .
- the results of measurement of the palladium content, palladium surface area, and palladium crystal plane were as follows. Table 1 shows the measurement results of the amount of desorbed hydrogen of the catalyst, and Table 13 shows the performance test results of the selective hydrogenation of acetylene in ethylene.
- Example 11 The catalyst of Example 12 was prepared, and the components of the obtained catalyst, physical properties were measured, and performance tests were performed under the conditions I and ⁇ . The results of measurement of the palladium content, palladium surface area, and palladium crystal plane were obtained. Table 1 shows the measurement results of the amount of desorbed hydrogen of the catalyst, and Table 13 shows the performance test results of the acetylene selective hydrogenation reaction in ethylene.
- a 150 cc dinitrodiammine palladium nitric acid solution with a palladium content of 3 g / 1 was weighed into a 300 cc beaker, and a 3 mm diameter surface area of 20 OmZ ⁇ g was added to this solution.
- the alumina carrier was immersed and held for one hour, whereby a palladium compound was supported on the carrier, and dinitrodiammine palladium on alumina as an intermediate was obtained.
- Example 13 The catalyst of Example 13 was prepared, and the physical properties of the resulting catalyst were measured and performance tests were performed under conditions II, IV, and V. Results of measurement of palladium content, palladium surface area, and palladium crystal plane Table 1 shows the measurement results of the amount of desorbed hydrogen in the catalyst. Table 1 shows the performance test results of the selective hydrogenation reaction of propane and methylacetylene in propylene. Table 1 shows the results of 1,3-butadiene in butene. Table 5 shows the performance test results of the selective hydrogenation reaction, and Table 6 shows the performance test results of the selective hydrogenation reaction of cracked gasoline.
- Example 11 was performed in the same manner as in Example 11 except that the palladium concentration of the dinitrogenamine palladium mononitrate solution of 11 was changed to 3 g / I.
- the catalyst of No. 4 was prepared, and a performance test was conducted according to the components, physical properties and conditions of the obtained catalyst. The results of the measurement of the palladium content, palladium surface area, and palladium crystal plane are shown in Table 1-1. The measurement results of the amount of desorbed hydrogen are shown in Table 12, and the performance test results of the selective hydrogenation reaction of provagen and methylacetylene in propylene are shown in Table 14.
- the catalyst of Example 11 was prepared in the same manner as in Example 12 except that the concentration of palladium in the dinitrodiammine palladium mononitrate solution of Example 11 was changed to 3 g Zl.
- a performance test was performed on the components, physical properties and conditions of the catalysts obtained.
- Table 1 shows the measurement results of palladium content, palladium surface area, and palladium crystal plane, and Table 1 shows the measurement results of the amount of desorbed hydrogen of the catalyst.
- Table 2 shows the performance test results of the selective hydrogenation reaction of provagen and methylacetylene in propylene.
- Example 1 The intermediate of 12 was dried at 11 Ot: for 20 hours, placed in an electric furnace, heated to 900 over 5 hours in air, and calcined at 900 for 4 hours.
- the catalyst of Comparative Example 16 was prepared, and the components of the resulting catalyst, physical properties were measured, and performance tests were performed under the conditions I and ⁇ .
- the measurement results of the palladium content, palladium surface area, and palladium crystal plane were as follows. Table 1 shows the measurement results of the amount of desorbed hydrogen of the catalyst, and Table 13 shows the performance test results of the acetylene selective hydrogenation reaction in ethylene.
- Example 13 The intermediate of 13 was dried at 110 for 20 hours, placed in an electric furnace, heated to 900 in air for 5 hours, and then calcined at 900 for 4 hours.
- Example 17 The catalyst of Example 7 was prepared, and the obtained catalyst was subjected to a measurement of the components, physical properties, and performance tests performed under the conditions I, IV, and V. The palladium content, palladium surface area, and palladium crystal plane were measured. Table 1 shows the results, Table 2 shows the results of measurement of the amount of desorbed hydrogen of the catalyst, and Table 14 shows the performance test results of the selective hydrogenation reaction of propane and methylacetylene in propylene. 3 — The performance test results of the selective hydrogenation reaction of butadiene are shown in Table 5 and the performance test results of the selective hydrogenation reaction of decomposed gasoline are shown in Table 6. It was as shown.
- Example 16 The catalyst of Example 16 was prepared, and the components of the obtained catalyst, physical properties were measured, and performance tests were conducted under the conditions I and II. The palladium content, the palladium surface area, and the palladium crystal face were measured. Table 1 shows the measurement results, Table 2 shows the measurement results of the amount of desorbed hydrogen of the catalyst, and Table 13 shows the performance test results of the selective hydrogenation of acetylene in ethylene.
- the catalyst of Example 17 was prepared in the same manner as in Example 16 except that the palladium concentration of the dinitrotetraamminepalladium solution in Example 16 was changed to 3 g / 1, and the catalyst of Example 17 was further obtained.
- a performance test was conducted according to the components, physical properties, and conditions (1) .
- Table 1 shows the measurement results of the palladium content, palladium surface area, and palladium crystal plane, and Table 1 shows the measurement results of the amount of desorbed hydrogen of the catalyst.
- the performance test results of the selective hydrogenation reaction of provadene and methylacetylene in propylene are as shown in Table 14.
- Example 1 The intermediate of 16 was dried at 110 for 20 hours, placed in an electric furnace, heated to 900 over 5 hours in air, and calcined at 900 for 4 hours. Therefore, the catalyst of Comparative Example 18 was prepared, and the obtained catalyst was tested for its components, physical properties, and under the conditions I and ⁇ . Table 1 shows the measurement results of the amount of desorbed hydrogen of the catalyst, and Table 3 shows the performance test results of the selective hydrogenation of acetylene in ethylene. Comparative Example 1 9
- Example 1 Dinitrotetraammine palladium-supported alumina as an intermediate of 17 was dried at 110 for 20 hours, placed in an electric furnace, and heated in air for 5 hours to 900, and then heated to 900.
- the catalyst of Comparative Example 1-9 was prepared by calcining at room temperature for 4 hours, and performance tests were performed according to the components, physical properties, and conditions of the obtained catalyst. The palladium content, palladium surface area, and palladium crystal plane were measured. The results are shown in Table 11, the measurement results of the amount of desorbed hydrogen of the catalyst are shown in Table 12, and the performance test results of the selective hydrogenation reaction of propane and methylacetylene in propylene are shown in Table 14.
- This intermediate is added to a 5% aqueous sodium formate solution (162 cc), immersed in a reducing solution heated to 60 for 1 hour, palladium reduced, washed with water, and dried in air at 110 for 20 hours. Then, the catalyst of Example 18 was prepared, and the components of the obtained catalyst, physical properties were measured, and performance tests were carried out under the conditions I and ⁇ . The results of measurement of the palladium content, palladium surface area, and palladium crystal plane were obtained. Table 1 shows the results of the measurement of the amount of desorbed hydrogen of the catalyst, and Table 13 shows the results of the performance test of the selective hydrogenation of acetylene in ethylene.
- Example 18 A palladium-supported alumina dried at 110 in 210 for 20 hours was further subjected to the same heat treatment as in Example 18 except that the alumina-treated alumina was further heated at 25 O: in air for 2 hours.
- Example 19 The catalyst of Example 19 was prepared, and the components of the resulting catalyst, physical properties were measured, and performance tests were carried out under the conditions I and ⁇ . The results of the measurement of the palladium content, palladium surface area, and palladium crystal plane were shown in the table. Table 1 shows the measurement results of the amount of desorbed hydrogen of the catalyst. The performance test results of the selective hydrogenation of acetylene in benzene are shown in Table 13.
- Example 18 Except for using a palladium chloride aqueous solution having a palladium concentration of 0.3 g / 1 and an aqueous palladium chloride solution of 150 cc in place of the palladium concentration of 0.3 g / 1 and an aqueous solution of dinitrodiammine / palladium chloride having a concentration of 150 g / l,
- the catalyst of Comparative Example 10 was prepared in exactly the same manner as in Example 18 and the components of the resulting catalyst, physical properties were measured, and performance tests were carried out under the conditions I and II.
- Table 1 shows the measurement results of palladium surface area and palladium crystal plane
- Table 12 shows the measurement results of the amount of desorbed hydrogen in the catalyst
- Table 13 shows the performance test results of the acetylene selective hydrogenation reaction in ethylene. It was as shown.
- Example 18 Except for using 150 g of a palladium concentration of 3.0 g / 1 and 150 g of an aqueous dinitamine palladium diammine palladium solution of 150 g in place of 0.3 g of a dinitrodiammine palladium aqueous solution of 150 g of a palladium concentration of 0.3 g,
- the catalyst of Example 20 was prepared in exactly the same manner as in Example 18 and the components of the resulting catalyst, physical properties were measured, and a performance test was conducted under the conditions of ffl.
- Table 1 shows the measurement results of the palladium crystal plane
- Table 2 shows the measurement results of the amount of desorbed hydrogen of the catalyst
- Table 14 shows the performance test results of the selective hydrogenation reaction of propylene and methyl acetylene in propylene. It was.
- Example 1 Except for using 150 cc of a palladium chloride aqueous solution having a palladium concentration of 3.0 O g Zl instead of 150 cc of a 0.3 g / l aqueous solution of dinitrodiammimpalladium having a palladium concentration of 0.3 g / l,
- the catalyst of Comparative Example 11 was prepared in exactly the same manner as in Example 18 and a performance test was carried out according to the components, physical properties, and conditions of the obtained catalyst.
- Table 1 Contents of catalysts open to palladium, surface area, and crystal plane measurement results
- Example 1 1 0.05 17 (100), (110) faces mainly grow
- Example 1 2 23
- Comparative Example 1 15 (HI) plane mainly grows
- Comparative Example 1 2 // 12 (111) plane mainly grows Example 1 ⁇ 0.330 30 (100), (110) plane mainly grows Comparative Example 1 3 27 (111) plane mainly grows Example -8 0.30 34 (100). (I 10) face mainly grows Comparative Example 1 4 40 (111) face mainly grows Example 1 9 1.0 27 (100), (110) face mainly grows Example -10 /, 33
- Comparative Example 1 5 // 35 (111) plane mainly grows and fails ⁇ i U. U ⁇ ⁇ M 1 ⁇ UU ⁇ il ⁇ , JF USiij J 1 t. I— ⁇ 3 sz Example-2 0.05 32 //
- Comparative Example 1 8 35 (111) plane mainly grows Example-17 0.30 25 (100). (110) plane mainly grows Comparative Example 9 39 (111) plane mainly grows Example 1 18 0.03 70 (100). (110) plane is mainly growing.
- Comparative Example 1 10 110 (111) plane mainly grows Example 1 20 0.30 50 (100), (110) plane mainly grows Comparative Example 1 11 120 (1 I 1) plane mainly grows Table 1 Measurement results of the amount of desorbed hydrogen from the catalyst
- Example 1 1 3 5: 6 5 ⁇ ⁇ ⁇ Example 4 0: 6.0
- Example-13 4. 0: 6.0 it Example-c ⁇ ) 7.5: 2.5
- Example-! 95 33 0. 035 40 22
- Example- 2 98 35 0. 032 39 24
- Example- 3 95 32 0. 037 1 21
- Comparative example- 1 95 23 0.068 39 14
- Example- 11 90 36 0. 035 42
- Example-12 95 34 0.04 42
- Comparative Example-6 96 23 0.070 39 13
- Example-16 95 36 0.039 42
- Comparative Example-8 95 25 0.073 40 13
- Example-18 97 33 0. 035 39 21
- Comparative Example-10 98 23 0.080 42 12
- Table 4 Selective hydrogenation reaction results of provagen and methylacetylene in propylene
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP51349598A JP3409072B2 (ja) | 1996-09-11 | 1997-09-10 | オレフィン化合物類中の高不飽和炭化水素化合物選択水素添加用触媒 |
DE69720235T DE69720235T2 (de) | 1996-09-11 | 1997-09-10 | Katalysator zur selektiven hydrierung von mehrfach ungesättigtem kohlenwasserstoff in einer olefinverbindung |
EP97940338A EP0933129B1 (en) | 1996-09-11 | 1997-09-10 | Catalyst for selective hydrogenation of highly unsaturated hydrocarbon compound in olefin compound |
US09/254,497 US6084140A (en) | 1996-09-11 | 1997-09-11 | Catalyst for selective hydrogenation of highly unsaturated hydrocarbon compound in olefin compound |
Applications Claiming Priority (2)
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JP8/261216 | 1996-09-11 | ||
JP26121696 | 1996-09-11 |
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WO1998010863A1 true WO1998010863A1 (fr) | 1998-03-19 |
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PCT/JP1997/003196 WO1998010863A1 (fr) | 1996-09-11 | 1997-09-10 | Catalyseur pour l'hydrogenation selective de melanges d'hydrocarbures hautement insatures dans un compose a base d'olefine |
Country Status (6)
Country | Link |
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US (1) | US6084140A (ja) |
EP (1) | EP0933129B1 (ja) |
JP (1) | JP3409072B2 (ja) |
KR (1) | KR100333350B1 (ja) |
DE (1) | DE69720235T2 (ja) |
WO (1) | WO1998010863A1 (ja) |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59123539A (ja) * | 1982-12-28 | 1984-07-17 | Mitsubishi Chem Ind Ltd | 選択的水素添加用触媒 |
JPH08229392A (ja) * | 1995-01-09 | 1996-09-10 | Basf Ag | パラジウム−担体触媒 |
JPH09313936A (ja) * | 1996-05-29 | 1997-12-09 | Nissan Gaadoraa Shokubai Kk | ▲c4▼留分中のジオレフィン類及びアセチレン類の選択水添触媒製造法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4686314A (en) * | 1984-09-28 | 1987-08-11 | The Dow Chemical Company | Catalysts having alkoxide-modified supports |
-
1997
- 1997-09-10 DE DE69720235T patent/DE69720235T2/de not_active Expired - Lifetime
- 1997-09-10 JP JP51349598A patent/JP3409072B2/ja not_active Expired - Lifetime
- 1997-09-10 EP EP97940338A patent/EP0933129B1/en not_active Expired - Lifetime
- 1997-09-10 KR KR1019997002006A patent/KR100333350B1/ko not_active IP Right Cessation
- 1997-09-10 WO PCT/JP1997/003196 patent/WO1998010863A1/ja active IP Right Grant
- 1997-09-11 US US09/254,497 patent/US6084140A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59123539A (ja) * | 1982-12-28 | 1984-07-17 | Mitsubishi Chem Ind Ltd | 選択的水素添加用触媒 |
JPH08229392A (ja) * | 1995-01-09 | 1996-09-10 | Basf Ag | パラジウム−担体触媒 |
JPH09313936A (ja) * | 1996-05-29 | 1997-12-09 | Nissan Gaadoraa Shokubai Kk | ▲c4▼留分中のジオレフィン類及びアセチレン類の選択水添触媒製造法 |
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EP0933129A4 (en) | 2000-04-19 |
US6084140A (en) | 2000-07-04 |
DE69720235T2 (de) | 2004-02-12 |
KR20000036028A (ko) | 2000-06-26 |
EP0933129B1 (en) | 2003-03-26 |
DE69720235D1 (de) | 2003-04-30 |
JP3409072B2 (ja) | 2003-05-19 |
KR100333350B1 (ko) | 2002-05-25 |
EP0933129A1 (en) | 1999-08-04 |
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