JP6151685B2 - エポキシ化触媒の製造方法及びそれを用いたエポキシ化方法 - Google Patents
エポキシ化触媒の製造方法及びそれを用いたエポキシ化方法 Download PDFInfo
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- JP6151685B2 JP6151685B2 JP2014514486A JP2014514486A JP6151685B2 JP 6151685 B2 JP6151685 B2 JP 6151685B2 JP 2014514486 A JP2014514486 A JP 2014514486A JP 2014514486 A JP2014514486 A JP 2014514486A JP 6151685 B2 JP6151685 B2 JP 6151685B2
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- Prior art keywords
- catalyst
- epoxidation
- solution
- manganese
- support
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- 238000006735 epoxidation reaction Methods 0.000 title claims description 80
- 238000000034 method Methods 0.000 title claims description 80
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 238000005470 impregnation Methods 0.000 claims description 64
- 239000011572 manganese Substances 0.000 claims description 56
- 229910052709 silver Inorganic materials 0.000 claims description 49
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 48
- 239000004332 silver Substances 0.000 claims description 47
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 46
- 229910052748 manganese Inorganic materials 0.000 claims description 46
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- 239000011734 sodium Substances 0.000 claims description 28
- 229910052708 sodium Inorganic materials 0.000 claims description 22
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 18
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 15
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 8
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- 239000012633 leachable Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 235000014872 manganese citrate Nutrition 0.000 description 1
- 239000011564 manganese citrate Substances 0.000 description 1
- OKVGBKABWITJQA-UHFFFAOYSA-L manganese dithionate Chemical compound [Mn+2].[O-]S(=O)(=O)S([O-])(=O)=O OKVGBKABWITJQA-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical class [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003281 rhenium Chemical class 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WVRJUMZHKISIJD-UHFFFAOYSA-N tetraazanium;disulfate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WVRJUMZHKISIJD-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
-
- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/024—Multiple impregnation or coating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(1) Z*=塩化エチル当量(ppmv)/エタン当量(モル%)
によって表される。式中、塩化エチル当量は、供給物流中の有機塩化物の濃度で、反応器供給物流中に存在するその有機塩化物とほぼ同じ触媒塩化効力をもたらす塩化エチル濃度(ppmv単位)であり、また、エタン当量は、供給物流中の炭化水素を含有する非塩化物の濃度で、供給物流中の炭化水素を含有する非塩化物とほぼ同じ触媒脱塩化効力をもたらすエタン濃度(モル%単位)である。
(2) Z*=(ECL+2*EDC+VCL)/(C2H6+0.01*C2H4)
として定義することができる。式中、ECL、EDC、及びVCLは、反応器の供給物流中のそれぞれ塩化エチル(C2H5Cl)、二塩化エチレン(Cl−CH2−CH2−Cl)及び塩化ビニル(H2C=CH−Cl)のppmv単位の濃度である。C2H6及びC2H4は、反応器供給物流中のそれぞれエタン及びエチレンのモル%単位の濃度である。
触媒1(比較)は、下記に述べるように調製し、すべての助触媒を二回目の銀の含浸の間に加えた。担体A(10.30g)の一回目の含浸は、米国特許出願公開第2009/177000号明細書中の「Catalyst Preparation」の欄に記載されているように調製した約30mLの銀−アミン−シュウ酸溶液(銀26.6重量%)を使用して行った。
触媒3(本発明)は、前記触媒1と同一の目標配合処方により調製した。前記触媒1との唯一の違いは、ナトリウム助触媒を、一回目のAg含浸の間に、銀溶液に加えたことである。その他の助触媒は、すべて二回目のAg含浸の間に加えた。含浸工程の間に銀−アミ−シュウ酸溶液に加えた助触媒溶液の量と、銀の吸収量及び加えた助触媒の量に基づいて最終的に算出した組成とを、表2に示す。
触媒4(比較)は、前記触媒1と同一の目標配合処方により調製した。前記触媒1との唯一の違いは、ナトリウム助触媒と、((NH4)2EDTAと錯体を形成させた)マンガン助触媒とを、一回目のAg含浸の間に、溶液に加えたことである。残りの助触媒は、二回目のAg含浸の間に銀−アミン−シュウ酸溶液に加えた。前記含浸工程の間に銀−アミン−シュウ酸溶液に加えた助触媒溶液の量と、銀の吸収量及び加えた助触媒溶液の量に基づいて算出した最終組成とを、表2に示す。
触媒5(比較)は、助触媒をすべて二回目の銀含浸の間に加えて調製した。二回目の含浸の間に銀−アミン−シュウ酸溶液に加えた助触媒溶液の量と、銀の吸収量及び加えた助触媒溶液の量に基づいて算出した最終組成とを、表2に示す。
触媒7(本発明)は、触媒1と同一の目標配合処方により調製した。前記触媒1との唯一の違いは、ナトリウム助触媒及びリチウム助触媒を、一回目のAg含浸の間に銀溶液に加えたことである。その他の助触媒は、二回目のAg含浸の間に加えた。含浸工程の間に銀−アミン−シュウ酸溶液に加えた助触媒溶液の量と、銀の吸収量及び加えた助触媒溶液の量に基づいて算出した触媒7の最終組成とを、表2に示す。
触媒8(本発明)は、触媒1と同一の目標配合処方により調製した。前記触媒1との唯一の違いは、マンガン助触媒を、Ag溶液の含浸の前に、露出した担体に加えたことである。この触媒の調製は、下記の工程からなる。Mn溶液は、0.0348gの硝酸第一マンガン溶液(溶液1g当たりMn 0.1552g)を30gの脱イオン水に加えることにより調製した。上記溶液を用いて、10.13gの担体(支持体番号A)に真空含浸した。過剰の溶液を排出した後、担体を焙焼した。次いで、25.60重量%のAgを含有する銀−アミン−シュウ酸溶液を用いて、二回目の真空含浸を行った。Ag含浸後の触媒の重量は13.16g、すなわち23.07%のAg装填量であった。次いで、42.3gの銀−アミン−シュウ酸溶液に、0.0902gのCsOH溶液(溶液1g当たりCs 0.4564g)と、0.0944gの酢酸リチウム溶液(溶液1g当たりLi 0.023g)と、0.0375gの酢酸ナトリウム溶液(溶液1g当たりNa 0.071g)と、0.8042gの過レニウム酸アンモニウム溶液(溶液1g当たりRe 0.0359g)と、0.0366gの硫酸アンモニウム溶液(溶液1g当たりSO4 0.2789g)と、0.0357gの硝酸第一マンガン溶液(溶液1g当たりMn 0.1552g)と、を加えて調製した溶液を用いて、焙焼した触媒丸剤のもう一回の含浸を行った。この含浸工程における含浸、排出及び焙焼の各工程は、前回の含浸と同じように行った。排出及び焙焼の後に算出した最終触媒重量は15.79gであった。銀の吸収量及び加えた助触媒溶液の量に基づいて算出した触媒8の組成は、Ag:35.71重量%、Cs:627ppm、Li:33ppm、Na:41ppm、Re:439ppm、SO4:155ppm、Mn:82ppmであった。
触媒9(比較)は、Agの含浸を一回だけ行って調製した。18.76重量%のAgを含有する42.0gの銀−アミン−シュウ酸溶液に、0.0541gのCsOH溶液(溶液1g当たりCs 0.4564g)と、0.0605gの酢酸リチウム溶液(溶液1g当たりLi 0.023g)と、0.0245gの酢酸ナトリウム溶液(溶液1g当たりNa 0.071g)と、0.4823gの過レニウム酸アンモニウム溶液(溶液1g当たりRe 0.0359g)と、0.0212gの硫酸アンモニウム溶液(溶液1g当たりSO4 0.2789g)と、0.0238gの硝酸第一マンガン溶液(溶液1g当たりMn 0.1552g)と、0.0947gのジアンモニウムEDTA溶液(溶液1g当たりEDTA 0.4128g)と、を加えて調製した溶液を用いて、10.34gの担体の丸剤(支持体番号A)に含浸させた。含浸、排出及び焙焼の各工程は、前回の調製と同じように行った。排出及び焙焼の後、最終触媒重量は12.30gであった。銀の吸収量及び加えた助触媒溶液の量に基づいて算出した触媒9の組成は、Ag:15.94重量%、Cs:499ppm、Li:28ppm、Na:35ppm、Re:350ppm、SO4:120ppm、Mn:75ppmであった。
本開示は以下も包含する。
[1] 支持体と、少なくとも1種類の触媒種と、マンガンと、少なくとも1種類のアルカリ金属及び/又は助触媒とを含むエポキシ化触媒の製造方法であって、
前記マンガンの少なくとも一部を、前記少なくとも1種類のアルカリ金属及び/又は助触媒とは別の含浸工程において含浸させる工程を含む、前記製造方法。
[2] 前記マンガンが、前記少なくとも1種類の触媒種と共に含浸される、上記態様1に記載の製造方法。
[3] 前記少なくとも1種類のアルカリ金属及び/又は助触媒が、ナトリウム、セシウム、リチウム、硫酸塩又はこれらの組合せを含む、上記態様1に記載の製造方法。
[4] 前記少なくとも1種類のアルカリ金属及び/又は助触媒が、ナトリウムを含み、前記マンガンとは別の工程において含浸される、上記態様1に記載の製造方法。
[5] 前記マンガンが、Mn−EDTA錯体を含む、上記態様1に記載の製造方法。
[6] 前記少なくとも1種類のアルカリ金属及び/又は助触媒がレニウムを含む、上記態様1に記載の製造方法。
[7] 前記触媒種が銀を含む、上記態様1に記載の製造方法。
[8] 上記態様1に記載の製造方法によって調製されたエポキシ化触媒。
[9] 上記態様1に記載の製造方法によって調製されたエポキシ化触媒の存在下で、酸素供給源とアルキレンを接触させる工程を含む、1種類又は複数種類のアルキレンのエポキシ化方法。
[10] 前記アルキレンがエチレンを含む、上記態様8に記載の製造方法。
[11] 1,2−ジオール、1,2−ジオールエーテル、1,2−カーボナート又はアルカノールアミンの製造方法であって、上記態様6に記載の製造方法によって調製されたアルキレンオキシドを、前記1,2−ジオール、1,2−ジオールエーテル、1,2−カーボナート又はアルカノールアミンに転化させる工程を含む、前記製造方法。
Claims (4)
- 支持体と、銀と、マンガンと、ナトリウムとを含むエポキシ化触媒の製造方法であって、
ナトリウムにより前記支持体を含浸する工程の前に、マンガンにより前記支持体を含浸する工程と、
マンガンによる含浸と同時に、銀により前記支持体を含浸する工程と、
を含み、
前記触媒は、ナトリウム及びマンガンに加えて、少なくとも1種類のアルカリ金属及び/又は助触媒を更に含む、前記製造方法。 - 少なくとも1種類の更なるアルカリ金属及び/又は助触媒がレニウムを含む、請求項1に記載の製造方法。
- 前記触媒は、マンガンにより前記支持体を含浸する工程とナトリウムにより前記支持体を含浸する工程との間に、600℃を超えない昇温に曝される、請求項1に記載の製造方法。
- 支持体と、銀と、マンガンと、ナトリウムとを含むエポキシ化触媒の製造方法であって、
ナトリウムとは別に、マンガンにより前記支持体を含浸する工程と、
前記触媒を、各含浸の間において、600℃を超えない昇温に曝す工程と、
を含み、
前記マンガンの含浸の前に、前記銀の少なくとも一部と同時に、前記ナトリウムを前記支持体に含浸させる、前記製造方法。
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