JP2012514628A - アンモオキシム化方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 19
- 150000003624 transition metals Chemical group 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 125000004429 atom Chemical group 0.000 claims abstract description 16
- 150000002576 ketones Chemical class 0.000 claims abstract description 15
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 12
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 37
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 26
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 22
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 15
- 150000002923 oximes Chemical group 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 229910017119 AlPO Inorganic materials 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000010936 titanium Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- -1 cyclohexane oxime Chemical class 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000003997 cyclic ketones Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- VTWKXBJHBHYJBI-VURMDHGXSA-N (nz)-n-benzylidenehydroxylamine Chemical compound O\N=C/C1=CC=CC=C1 VTWKXBJHBHYJBI-VURMDHGXSA-N 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003325 tomography Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
【選択図】 図1
Description
M1M2AlPO (I)
又は
M1M2SAlPO (II)
(式中、M1及びM2は、互いに異なり、それぞれレドックス触媒能を有する遷移金属原子を表し;
リン原子の一部は他の等価原子によって置換されていてよい)
を有する。
M1M2AlPO−5 (I)
(式中、M1は、レドックス触媒能を有する少なくとも1種類の遷移金属原子であり;
M2は、(IV)の酸化状態の少なくとも1種類の金属であり;
M1及びM2は互いに異なり;M1M2AlPO−5タイプの構造中のリン原子の一定割合はM2原子によって置換されている)
を有するアルミノホスフェートベースのレドックス触媒の存在下でアンモニア及び酸素と反応させることを特徴とするレドックスアンモオキシム化方法が提供される。
M1M2AlPO−5 (I)
(式中、M1は、レドックス触媒能を有する少なくとも1種類の遷移金属原子であり;
M2は、(IV)の酸化状態の少なくとも1種類の金属であり;
M1及びM2は互いに異なり;M1M2AlPO−5タイプの構造中のリン原子の一定割合はM2原子によって置換されている)
を有するアルミノホスフェートベースのレドックス触媒が提供される。
M1M2SiAlPO−5 (II)
(式中、M1は、レドックス触媒能を有する少なくとも1種類の遷移金属原子であり;
M2は、(IV)の酸化状態の少なくとも1種類の金属であり;
M1及びM2は互いに異なり;M1M2AlPO−5タイプの構造中のリン原子の一定割合はM2原子によって置換されている)
を有する。
M1M2AlPO−5 (I)
(式中、M1は、レドックス触媒能を有する少なくとも1種類の遷移金属原子であり;
M2は、(IV)の酸化状態の少なくとも1種類の金属であり;
M1及びM2は互いに異なり;M1M2AlPO−5タイプの構造中のリン原子の一定割合はM2原子によって置換されている)
を有するアルミノホスフェートベースのレドックス触媒が提供される。
水酸化アルミニウム(約0.053モル)及びリン酸(0.098モル)をPTFEビーカー内で20mLの水と混合し、20分間攪拌状態に保持して均一な混合物を得た。2金属AlPOに関しては、2種類の金属前駆体を2つの別々のビーカー内で溶解し、攪拌状態に保持した後、アルミニウム/リン混合物に同時に滴加した。得られたゲルを30分間静置して均一化した後、構造規定剤を水の残りと一緒に滴加し、激しい攪拌状態に1時間保持した。次に、ゲルを3つのテフロンライニングオートクレーブ中に分け、140〜200℃において2時間結晶化させた(AFI骨格)。
PEEK及びPTFEでライニングした0.1LのParr 4590反応器及び4843 Parrコントローラーの混合装置内において高圧で触媒反応を行い、炎イオン化検出器(FID)を有するVarian Star 3400CXガスクロマトグラフを用いて触媒反応の結果を得た。この方法においては、80℃の初期カラム温度、7分間の保持時間、10分間の保持時間で220℃の最終カラム温度、及び3℃/分の温度上昇速度を用いた。
下記にアンモオキシム化ゲル組成データを列記する。
触媒(1g)を10g(0.101モル)のシクロヘキサノンと共に反応容器に加えた後、密封し、30barの窒素で20分間パージした。圧力を解除し、23.8g(0.204モル)の水酸化アンモニウム(水中30%)をシリンジによって加えた後、30barの空気を加えた。830rpmで攪拌しながら反応容器を60℃に加熱し、試料を20分間隔で取り出した。試料を遠心分離した後、0.2μLをガスクロマトグラフ中に注入した。
か焼した試料について触媒反応試験を行って、シクロヘキサノンのアンモオキシム化を示した。これらの結果を下表5に示す。
Claims (18)
- ケトン又はアルデヒドを、定性一般式(I):
M1M2AlPO−5 (I)
(式中、M1は、レドックス触媒能を有する少なくとも1種類の遷移金属原子であり;
M2は、(IV)の酸化状態の少なくとも1種類の金属原子であり;
M1及びM2は互いに異なり;M1M2AlPO−5タイプの構造中のリン原子の一定割合はM2原子によって置換されている)
を有するアルミノホスフェートベースのレドックス触媒の存在下でアンモニア及び酸素と反応させることを特徴とするレドックスアンモオキシム化方法。 - M2が(IV)の酸化状態の少なくとも1種類の遷移金属である、請求項1に記載の方法。
- M2が、Ge(IV)、Sn(IV)、Ti(IV)、Re(IV)、V(IV)、及びこれらの混合物から選択される、請求項1又は2に記載の方法。
- M2がTi(IV)である、請求項3に記載の方法。
- 触媒が、CoIIITiIVAlPO−5、MnIIITiIVAlPO−5、FeIIITiIVAlPO−5、CrVITiIVAlPO−5、CuIIITiIVAlPO−5、VVTiIVAlPO−5、及びRuIIITiIVAlPO−5から選択される、請求項4に記載の方法。
- 触媒が、CoIIITiIVAlPO−5、MnIIITiIVAlPO−5、及びFeIIITiIVAlPO−5から選択される、請求項5に記載の方法。
- M1が、Co(III)、Mn(III)、Fe(III)、Cr(VI)、Cu(III)、V(V)、及びRu(III)から選択される、請求項1〜6のいずれかに記載の方法。
- M1が、Co(III)、Mn(III)、及びFe(III)から選択される、請求項7に記載の方法。
- アンモニアが水酸化アンモニウム水溶液の形態である、請求項1〜8のいずれかに記載の方法。
- 40〜200℃の温度において行う、請求項1〜9のいずれかに記載の方法。
- 50〜90℃の温度において行う、請求項10に記載の方法。
- 0.5MPa(5bar)〜10MPa(100bar)の圧力において行う、請求項1〜11のいずれかに記載の方法。
- 出発物質がケトンである、請求項1〜12のいずれかに記載の方法。
- 反応生成物がオキシムである、請求項1〜13のいずれかに記載の方法。
- シクロヘキサノンをシクロヘキサノン−オキシムに転化させる、請求項14に記載の方法。
- オキシムをε−カプロラクタムに転化させる、請求項14又は15に記載の方法。
- 定性一般式(I):
M1M2AlPO−5 (I)
(式中、M1は、レドックス触媒能を有する少なくとも1種類の遷移金属原子であり;
M2は、(IV)の酸化状態の少なくとも1種類の金属であり;
M1及びM2は互いに異なり;M1M2AlPO−5タイプの構造中のリン原子の一定割合はM2原子によって置換されている)
を有するアルミノホスフェートベースのレドックス触媒。 - 式:COIIITiIVAlPO−5又はMnIIITiIVAlPO−5を有する、請求項17に記載の触媒。
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GB0900198.3 | 2009-01-07 | ||
GBGB0900198.3A GB0900198D0 (en) | 2009-01-07 | 2009-01-07 | Ammoximation process |
PCT/GB2010/000010 WO2010079324A1 (en) | 2009-01-07 | 2010-01-06 | Ammoximation process |
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EP (1) | EP2373614A1 (ja) |
JP (1) | JP2012514628A (ja) |
KR (1) | KR20110134874A (ja) |
CN (1) | CN102227404B (ja) |
BR (1) | BRPI1005523A2 (ja) |
CO (1) | CO6400134A2 (ja) |
GB (1) | GB0900198D0 (ja) |
MX (1) | MX2011004942A (ja) |
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US8772476B2 (en) | 2011-10-28 | 2014-07-08 | Honeywell International Inc. | Gas and liquid phase catalytic Beckmann rearrangement of oximes to produce lactams |
US20220040666A1 (en) * | 2020-08-10 | 2022-02-10 | Arizona Board Of Regents On Behalf Of Arizona State University | Material to separate and pump oxygen |
CN116393163B (zh) * | 2023-03-27 | 2024-05-24 | 湖北兴发化工集团股份有限公司 | 用于环己酮肟一步法合成6-氨基己腈的组合型催化剂及其制备方法 |
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US4801364A (en) | 1983-07-15 | 1989-01-31 | Uop | Separation and conversion processes using metal aluminophosphates |
US4567029A (en) * | 1983-07-15 | 1986-01-28 | Union Carbide Corporation | Crystalline metal aluminophosphates |
US4793984A (en) * | 1984-04-13 | 1988-12-27 | Union Carbide Corporation | Molecular sieve compositions |
US4917876A (en) | 1984-04-13 | 1990-04-17 | Uop | Iron-titanium-aluminum-phosphorus-oxide molecular sieve compositions |
US4956165A (en) | 1984-04-13 | 1990-09-11 | Uop | Molecular sieve compositions |
IT1222171B (it) | 1987-07-29 | 1990-09-05 | Montedipe Spa | Processo per la produzione di chetossime |
NO318680B1 (no) * | 2001-11-07 | 2005-04-25 | Polymers Holding As | Metode for a fremstille krystallinsk, mikroporost metalloaluminofosfat fra et fast legeme og anvendelse derav |
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SG123723A1 (en) | 2004-12-22 | 2006-07-26 | Sumitomo Chemical Co | Process for producing cyclohexanone oxime |
GB2450711A (en) | 2007-07-03 | 2009-01-07 | Univ Southampton | An aluminophosphate based redox catalyst |
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JPN5012007624; THOMAS, JOHN MEURIG: 'DESIGN OF A "GREEN" ONE-STEP CATALYTIC PRODUCTION OF epsilon-CAPROLACTAM (PRECURSOR OF NYLON-6)' PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA V102 N39, 2005, P13732-13736 * |
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Publication number | Publication date |
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US20110257390A1 (en) | 2011-10-20 |
SA110310039B1 (ar) | 2013-11-04 |
GB0900198D0 (en) | 2009-02-11 |
CO6400134A2 (es) | 2012-03-15 |
WO2010079324A1 (en) | 2010-07-15 |
RU2011133043A (ru) | 2013-02-20 |
US20130245322A1 (en) | 2013-09-19 |
US8444917B2 (en) | 2013-05-21 |
BRPI1005523A2 (pt) | 2019-09-24 |
MX2011004942A (es) | 2011-06-16 |
US8779124B2 (en) | 2014-07-15 |
CN102227404A (zh) | 2011-10-26 |
CN102227404B (zh) | 2014-03-26 |
KR20110134874A (ko) | 2011-12-15 |
RU2532163C2 (ru) | 2014-10-27 |
EP2373614A1 (en) | 2011-10-12 |
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