JP2011148768A - 3級アミンの製造方法 - Google Patents
3級アミンの製造方法 Download PDFInfo
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- JP2011148768A JP2011148768A JP2010273331A JP2010273331A JP2011148768A JP 2011148768 A JP2011148768 A JP 2011148768A JP 2010273331 A JP2010273331 A JP 2010273331A JP 2010273331 A JP2010273331 A JP 2010273331A JP 2011148768 A JP2011148768 A JP 2011148768A
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- Prior art keywords
- alcohol
- reaction
- catalyst
- amine
- tertiary amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000003512 tertiary amines Chemical class 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 105
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 51
- 150000003141 primary amines Chemical class 0.000 claims abstract description 42
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 45
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical group NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 28
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 21
- 239000007858 starting material Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 32
- 239000002994 raw material Substances 0.000 description 31
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 239000010949 copper Substances 0.000 description 14
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical group CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 230000009467 reduction Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- -1 Aliphatic amines Chemical class 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- ATBNMWWDBWBAHM-UHFFFAOYSA-N n-decyl-n-methyldecan-1-amine Chemical compound CCCCCCCCCCN(C)CCCCCCCCCC ATBNMWWDBWBAHM-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000003622 immobilized catalyst Substances 0.000 description 4
- OMEMQVZNTDHENJ-UHFFFAOYSA-N n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCNC OMEMQVZNTDHENJ-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- COFKFSSWMQHKMD-UHFFFAOYSA-N n,n-didecyldecan-1-amine Chemical compound CCCCCCCCCCN(CCCCCCCCCC)CCCCCCCCCC COFKFSSWMQHKMD-UHFFFAOYSA-N 0.000 description 2
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- B01J29/072—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J2229/30—After treatment, characterised by the means used
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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
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
【解決手段】アルコールと1級アミンを触媒の存在下で反応させて3級アミンを製造した後、当該反応に用いた当該触媒の存在下にアルコールと2級アミンを反応させる、3級アミンの製造方法。
【選択図】なし
Description
フェノール樹脂をバインダーとして粉末状触媒を固定化した、フィルム型触媒Aを以下のように調製した。
製造例1で得たフィルム型触媒Aを、内径28.4mmの反応器1の内部に装填した。フィルム型触媒の装填された部分の体積は0.25Lで、反応器1の軸方向に連通した、断面積0.1cm2程度の複数の流路がフィルム型触媒によって形成された。
ラウリルアルコール(花王(株)製カルコール2098)600gを緩衝槽2に仕込み、水素ガスを標準状態体積換算で16.5L/Hrの流量で供給しながら、緩衝槽2と反応器1との間で液を5.92L/Hrで循環させた。この状態で反応器1内部の温度を130℃まで昇温した後6時間保持して、触媒の還元処理を行った。その後全系を冷却してから、液を全量抜き出した。
デシルアルコール(花王(株)製カルコール1098)660gを緩衝槽2に仕込み、水素ガスを標準状態体積換算で9.9L/Hrの流量で供給しながら、緩衝槽2と反応器1との間で液を5.92L/Hrで循環させた。反応器1内部の温度を165℃まで昇温してからモノメチルアミンを反応器1に供給し、さらに反応器1内部の温度を192℃まで昇温して反応を開始した。モノメチルアミン供給量は反応の進行に合わせて調整し、反応時間平均で17g/Hrであった。反応開始から7時間後にモノメチルアミンの供給を停止し、全系を冷却して緩衝槽2及び反応器1内部の液全量を抜き出した。ガスクロマトグラフにて分析を行い、面積百分率法にて定量した結果、未反応のデシルアルコールは2.6%、生成したN,N−ジデシル−N−メチルアミンは89.6%、N−デシル−N,N−ジメチルアミンは0.7%、N,N,N−トリデシルアミンは0.8%であった。
上記の反応器1内部に装填されたフィルム型触媒はそのままで、ラウリルアルコール(花王(株)製カルコール2098)600gを緩衝槽2に仕込み、水素ガスを標準状態体積換算で16.5L/Hrの流量で供給しながら、緩衝槽2と反応器1との間で液を5.92L/Hrで循環させた。反応器1内部の温度を185℃まで昇温してからジメチルアミンを反応器に供給し、さらに反応器1内部の温度を220℃まで昇温して、反応を開始した。ジメチルアミン供給量は反応の進行に合わせて調整し、反応時間平均で51g/Hrであった。反応開始から2.6時間後にジメチルアミンの供給を停止し、全系を冷却して緩衝槽2及び反応器1内部の液全量を抜き出した。ガスクロマトグラフにて分析を行い、面積百分率法にて定量した結果、未反応のラウリルアルコールは0.8%、生成したN−ドデシル−N,N−ジメチルアミンは91.2%、N,N−ジドデシル−N−メチルアミンは4.7%であった。N,N,N−トリドデシルアミンは検出されなかった。
実施例1と同じく、製造例1で得たフィルム型触媒Aを反応器1の内部に装填し、実施例1と同様の操作にて触媒の還元処理を行った。
ラウリルアルコール(花王(株)製カルコール2098)600gを緩衝槽2に仕込み、水素ガスを標準状態体積換算で16.5L/Hrの流量で供給しながら、緩衝槽2と反応器1との間で液を5.92L/Hrで循環させた。反応器1内部の温度を185℃まで昇温してからジメチルアミンを反応器に供給し、さらに反応器1内部の温度を220℃まで昇温して、反応を開始した。ジメチルアミン供給量は反応の進行に合わせて調整し、反応時間平均で42g/Hrであった。反応開始から3.3時間後にジメチルアミンの供給を停止し、全系を冷却して緩衝槽2及び反応器1内部の液全量を抜き出した。ガスクロマトグラフにて分析を行い、面積百分率法にて定量した結果、未反応のラウリルアルコールは0.5%、生成したN−ドデシル−N,N−ジメチルアミンは78.9%、N,N−ジドデシル−N−メチルアミンは17.2%であった。N,N,N−トリドデシルアミンは検出されなかった。
粉末状触媒Bを以下のように調製した。
《触媒の還元処理》
デシルアルコール(花王(株)製カルコール1098)1200gを攪拌槽21に仕込み、さらに製造例2で得た粉末状触媒Bを6.0g仕込んで、水素ガスを標準状態体積換算で18L/Hrの流量で供給しながら、攪拌槽21内部を攪拌翼23によって1000rpmで攪拌混合した。この状態で攪拌槽21内部の温度を180℃まで昇温した後1時間保持して、触媒の還元処理を行った。
上記の粉末状触媒Bの還元処理に引き続いて、水素ガスを標準状態体積換算で18L/Hrの流量で攪拌槽21に供給しながら、さらにモノメチルアミンを供給し、攪拌槽21内部の温度を192℃まで昇温して反応を開始した。モノメチルアミン供給量は反応の進行に合わせて調整し、反応時間平均で26g/Hrであった。反応開始から3.9時間後にモノメチルアミンの供給を停止し、全系を冷却して攪拌槽21内部の液及び触媒全量を抜き出し、触媒を濾過分離した。濾過した液についてガスクロマトグラフにて分析を行い、面積百分率法にて定量した結果、未反応のデシルアルコールは3.2%、生成したN,N−ジデシル−N−メチルアミンは93.1%、N−デシル−N,N−ジメチルアミンは0.3%、N,N,N−トリデシルアミンは0.5%であった。
上記のN,N−ジデシル−N−メチルアミンの製造に使用して濾過分離した粉末状触媒の2/3量(4.0g相当量)と、新たにラウリルアルコール(花王(株)製カルコール2098)1200gを攪拌槽21に仕込み、水素ガスを標準状態体積換算で13L/Hrの流量で供給しながら、攪拌槽21内部を攪拌翼23によって1000rpmで攪拌混合した。攪拌槽21内部の温度を190℃まで昇温してからジメチルアミンを反応器に供給して反応を開始し、さらに攪拌槽21内部の温度を220℃まで昇温しながら水素ガスの流量を標準状態体積換算で27L/Hrまで増加した。ジメチルアミン供給量は反応の進行に合わせて調整し、反応時間平均で93g/Hrであった。反応開始から2.3時間後に攪拌槽21内部の液をサンプリングしてガスクロマトグラフにて分析を行い、面積百分率法にて定量した結果、未反応のラウリルアルコールは1.7%、生成したN−ドデシル−N,N−ジメチルアミンは93.3%、N,N−ジドデシル−N−メチルアミンは3.7%であった。N−ドデシル−N−メチルアミン及びN,N,N−トリドデシルアミンは検出されなかった。さらに反応を継続して反応開始から2.6時間後にジメチルアミンの供給を停止し、全系を冷却して攪拌槽21内部の液全量を抜き出し、触媒を濾過分離した。濾過した液についてガスクロマトグラフにて分析を行い、面積百分率法にて定量した結果、未反応のラウリルアルコールは1.0%、生成したN−ドデシル−N,N−ジメチルアミンは93.8%、N,N−ジドデシル−N−メチルアミンは3.8%であった。N−ドデシル−N−メチルアミン及びN,N,N−トリドデシルアミンは検出されなかった。
《触媒の還元処理》
実施例2と同じく、製造例2で得た粉末状触媒Bを4.0g攪拌槽21に仕込み、実施例2と同様の操作にて触媒の還元処理を行った。
ラウリルアルコール(花王(株)製カルコール20)1200gを攪拌槽21に仕込み、さらに上記還元処理した粉末状触媒Bの全量を仕込んで、水素ガスを標準状態体積換算で13L/Hrの流量で供給しながら、攪拌槽21内部を攪拌翼23によって1000rpmで攪拌混合した。攪拌槽21内部の温度を190℃まで昇温してからジメチルアミンを反応器に供給して反応を開始し、さらに攪拌槽21内部の温度を220℃まで昇温しながら水素ガスの流量を標準状態体積換算で27L/Hrまで増加した。ジメチルアミン供給量は反応の進行に合わせて調整し、反応時間平均で98g/Hrであった。反応開始から2.3時間後にジメチルアミンの供給を停止し、全系を冷却して攪拌槽21内部の液全量を抜き出し、触媒を濾過分離した。濾過した液についてガスクロマトグラフにて分析を行い、面積百分率法にて定量した結果、未反応のラウリルアルコールは1.0%、生成したN−ドデシル−N,N−ジメチルアミンは93.1%、N,N−ジドデシル−N−メチルアミンは5.5%であった。N−ドデシル−N−メチルアミン及びN,N,N−トリドデシルアミンは検出されなかった。
2:緩衝槽
3:外部循環用ポンプ
4:外部循環用導管
5:充填塔用導管
6:充填塔
21:攪拌槽
22:攪拌機
23:攪拌翼
24:ガス吹込み管
25:充填塔用導管
26:充填塔
Claims (3)
- アルコールと1級アミンを触媒の存在下で反応させて3級アミンを製造した後、当該反応に用いた当該触媒の存在下にアルコールと2級アミンを反応させる、3級アミンの製造方法。
- 触媒がCu及び/又はNiを含む、請求項1記載の製造方法。
- 1級アミンがモノメチルアミン又はモノエチルアミン、2級アミンがジメチルアミン又はジエチルアミンである、請求項1又は2記載の製造方法。
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