TWI534131B - 氫化4,4’-二胺基二苯甲烷的觸媒與方法 - Google Patents
氫化4,4’-二胺基二苯甲烷的觸媒與方法 Download PDFInfo
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- TWI534131B TWI534131B TW103141126A TW103141126A TWI534131B TW I534131 B TWI534131 B TW I534131B TW 103141126 A TW103141126 A TW 103141126A TW 103141126 A TW103141126 A TW 103141126A TW I534131 B TWI534131 B TW I534131B
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- catalyst
- diaminodiphenylmethane
- hydrogenating
- pacm
- hydrogenation
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- 239000003054 catalyst Substances 0.000 title claims description 53
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 31
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 15
- GSWGDDYIUCWADU-UHFFFAOYSA-N aluminum magnesium oxygen(2-) Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims description 12
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 51
- 239000000843 powder Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 10
- 229910052703 rhodium Inorganic materials 0.000 description 10
- 239000000543 intermediate Substances 0.000 description 8
- 125000002950 monocyclic group Chemical group 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- YBVAXJOZZAJCLA-UHFFFAOYSA-N nitric acid nitrous acid Chemical compound ON=O.O[N+]([O-])=O YBVAXJOZZAJCLA-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- -1 alicyclic diamine Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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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
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B01J35/397—
-
- B01J35/615—
-
- 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
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- B01J35/40—
-
- 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
Description
本發明係關於4,4’-二胺基二苯甲烷的氫化反應,更特別關於其應用之觸媒。
雙胺類化合物為重要化工原料,其可與雙酸酐類製成聚醯亞胺(PI)、與雙酸類製成聚醯胺(PA)如尼龍、或與光氣反應形成異酸氰酯(diisocyanate),再與多元醇製成聚氨酯(PU)。二胺基二環己基甲烷(簡稱PACM)為重要之脂環族二胺,常以4,4’-二胺基二苯甲烷(4,4’-methylenedianiline,簡稱MDA)為原料,經氫化反應將分子中的苯環完全氫化而得。經氫化反應產生的PACM包含了順,順((cis,cis),又稱(c,c))、順,反((cis,trans),又稱(c,t))、與反,反((trans,trans),又稱(t,t))三種異構物。而PACM之(t,t)異構物的莫耳比例,將影響PACM的物性。當PACM之(t,t)莫耳比例接近50莫耳%(平衡組成)時,一般稱為PACM-50,其熔點較高,在常溫常壓下為固體。若PACM之(t,t)莫耳比例只佔產物組成的約20%左右,一般稱為PACM-20,其熔點較低,在室溫下為液體。早期PACM最主要的運用為製備尼龍,高(t,t)莫耳比例之PACM可製得清澈透明之Nylon,因此PACM-50的生產為主流。然而近年來,由於PU
產業的快速發展,可用於生產液態之異酸氰酯之PACM-20轉為主流。
由PACM為原料所製得之異氰酸酯具有良好的光學穩定性(抗黃變)、耐候性及機械性能,可用於製備透明聚醯胺樹脂、環氧樹脂的固化劑,也可做為強電絕緣體材料、磁性黏結劑的原料,用做染料、醫藥中間體等用途,廣泛運用於光學、電子及醫藥等產業,市場需求持續擴增。
MDA氫化合成PACM的氫化製程已開發多年,亦有許多相關文獻報導,除了高反應性與選擇性之外,控制產品之異構物莫耳比例亦為研發重點。而觸媒的設計與開發是此氫化技術的關鍵,近年來,仍不斷有新的觸媒專利出現,表示用於此氫化反應之觸媒仍有改善的空間。舉例來說,目前仍需高轉化率之氫化MDA方法,生產低(t,t)莫耳比例之液態PACM產品。
本發明一實施例提供氫化4,4’-二胺基二苯甲烷的觸媒,包括:載體;氧化鎂鋁層,披覆於載體上;銠-釕活性層,負載於氧化鎂鋁層上,其中銠-釕活性層中的銠與釕之重量比介於40:60至10:90之間。
本發明一實施例提供氫化4,4’-二胺基二苯甲烷的方法,包括:以上述氫化4,4’-二胺基二苯甲烷的觸媒搭配氫氣,氫化4,4’-二胺基二苯甲烷以形成二胺基二環己基甲烷。
本發明一實施例提供氫化4,4’-二胺基二苯甲烷的觸媒,包括載體與披覆其上的氧化鎂鋁層。在本發明一實施例中,載體可為氧化矽、氧化鋁、或其他常見多孔性載體。在本發明一實施例中,載體之比表面積介於100m2/g至300m2/g之間。一般來說,較大的比表面積較有利於反應。在本發明一實施例中,氧化鎂鋁層與載體之重量比介於1:1至1:4之間。上述氧化鎂鋁層中鎂與鋁的重量比可介於2:1至1:2之間。鎂的含量與載體的特性(酸鹼度)有一定的關係。一般來說,載體鹼度隨著鎂含量上升而增加,適當比例的鎂含量可得較佳的反應性與產品選擇率。在本發明一實施例中,氧化鎂鋁層的形成方法可為先將鎂鹽與鋁鹽溶於鹼性溶液中,形成鎂鋁溶膠凝膠。接著混合鎂鋁溶膠凝膠與載體,過濾後燒結烘乾粉碎即可得表面披覆有氧化鎂鋁層之載體。
上述氫化4,4’-二胺基二苯甲烷的觸媒還包含銠-釕活性層負載於氧化鎂鋁層上。在本發明一實施例中,銠-釕活性層中的銠與釕之重量比介於40:60至10:90之間。若活性層中的釕比例過高,則需較高的反應溫度與反應壓力,增加設備與工安成本。若活性層中的銠比例過高,則會提高觸媒成本而不利商業化。在本發明一實施例中,銠-釕活性層與該載體之重量比介於1:24至1:16之間。若銠-釕活性層之比例過高,則會增加觸媒成本。若銠-釕活性層之比例過低,則無法有效氫化4,4’-二胺基二苯甲烷。
本發明一實施例將上述觸媒搭配氫氣以氫化4,4’-
二胺基二苯甲烷(MDA),形成低(反,反)異構物莫耳比例之二胺基二環己基甲烷(PACM),如式1所示:
在本發明一實施例中,式1中PACM的反,反-異構物莫耳比例介於25莫耳%至0莫耳%之間。若PACM的反,反-異構物含量過高,則產物偏向固態而非液態,不利於後續應用。在上述氫化製程中,氫氣之壓力可介於60bar至70bar之間。一般來說,氫化速率隨著氫氣壓力增加而上升,然而若氫氣壓力過高,則增加設備與工安成本。在本發明一實施例中,上述氫化製程的溫度介於120℃至160℃之間。氫化速率隨著溫度上升而增加,然而若氫化製程的溫度過高,可能會增加產物中反,反-異構物的含量與副產物的比例。
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉數實施例配合所附圖示,作詳細說明
如下:
A觸媒之製備方法(同時含浸法)如下。首先將含硝酸鎂256g與硝酸鋁357g之1L去離子水溶液加入含氫氧化鈉208g與碳酸鈉152g之1L去離子水溶液,於室溫攪拌並熟化18小時,形成鎂鋁溶膠凝膠(sol-gel)。之後將200g氧化鋁載體加入鎂鋁溶膠凝膠中,並持續攪拌1小時之後過濾,所得濾餅經水洗三次後於110℃烘乾,烘乾之濾餅粉碎至100mesh以下,即得表面披覆有氧化鎂鋁層之氧化鋁載體的粉體。秤取15g至20g之上述粉體,加入60g至80g之含浸溶液後攪拌40分鐘。上述含浸溶液包含硝酸亞硝釕(Ru(NO)(NO3)3)與硝酸銠(Rh(NO3)3)的去離子水溶液,其濃度依後述實施例之比例配製。含浸後之觸媒經過濾烘乾後,於450℃下鍛燒4小時即得A觸媒。
B觸媒之製備方法(依序含浸法)如下。同A觸媒之表面披覆有氧化鎂鋁層之氧化鋁載體的粉體,差別在於含浸溶液分為硝酸亞硝釕(Ru(NO)(NO3)3)溶液以及硝酸銠(Rh(NO3)3)溶液,其濃度依後述實施例之比例配製。首先將粉體加入硝酸亞硝釕含浸溶液進行攪拌40分鐘,之後於110℃下烘乾後再加入硝酸銠溶液進行攪拌40分鐘。含浸後之粉體進行過濾烘乾後,於450℃下鍛燒4小時,即得B觸媒。
C觸媒之製備方法(初濕法)如下。同A觸媒之表面披覆有氧化鎂鋁層之氧化鋁載體的粉體,且金屬前驅物亦為硝
酸亞硝釕(Ru(NO)(NO3)3)與硝酸銠(Rh(NO3)3),唯C觸媒利用初濕法製備。初濕法為取適量之金屬前驅物溶液,慢慢滴入粉體中,於滴入同時進行攪拌。當金屬前驅物溶液全部滴入粉體中,使粉體表面成微濕狀態之溶液量為適當之溶液量。將濕潤的粉體進行烘乾,接著於450℃下鍛燒4小時即得C觸媒。
取7ml上述20-30mesh之A觸媒,其含有4.5wt%Ru與0.5wt%Rh。將此觸媒置於固定床反應器中,以連續式滴流床(trickle-bed)模式進行試驗,對85%二胺基二苯甲烷(購自双邦實業公司之MDA85,內含約15%高環寡聚物)進行氫化反應。反應條件:溶劑為THF,MDA85濃度為25wt%,液體之空間流速(Weight hourly space velocity,WHSV)為0.26hr-1,反應溫度為140℃,反應壓力為70kg/cm2,且氫氣與MDA莫耳比為69。以氣相層析分析儀(GC)分析氫化結果如下:MDA轉化率為100%且無單環氫化中間產物H6MDA,PACM選擇率為92.6%,且(t,t)-PACM莫耳比例為22.3%。
取7ml 20-30mesh之A觸媒,其含有3wt%Ru與2wt%Rh。將此觸媒置於固定床反應器中,以連續式滴流床(trickle-bed)模式進行試驗,對MDA85進行氫化反應。反應條件:溶劑為THF,MDA85濃度為25wt%,液體之空間流速(WHSV)為0.25hr-1,反應溫度為130℃,反應壓力為70kg/cm2,且氫氣與MDA莫耳比為60。以GC分析結果如下:MDA轉化率為100%且無單環氫化中間產物H6MDA,PACM選擇率為94.0%,(t,t)-PACM莫耳比例
為15.9%。
取7ml 20-30mesh之A觸媒,其含有4wt%Ru與1wt%Rh。將此觸媒置於固定床反應器中,以連續式滴流床(trickle-bed)模式進行試驗,對MDA85進行氫化反應。反應條件:溶劑為THF,MDA85濃度為30wt%,液體之空間流速(WHSV)為0.43hr-1,反應溫度為140℃,反應壓力為70kg/cm2,且氫氣與MDA莫耳比為34。以GC分析結果如下,MDA轉化率為100%且無單環氫化中間產物H6MDA,PACM選擇率為94.9%,且(t,t)-PACM莫耳比例為18.8%。上述氫化反應進行約1000小時後(WHSV=0.28hr-1至0.43hr-1,且氫氣與MDA莫耳比為34-52),出現1-3% H6MDA,即觸媒活性下降。
取7ml 20-30mesh之B觸媒,其含有4wt%Ru與1wt%Rh。將此觸媒置於固定床反應器中,以連續式滴流床(trickle-bed)模式進行試驗,對MDA85進行氫化反應。反應條件:溶劑為THF,MDA85濃度為25wt%,液體之空間流速(WHSV)為0.27hr-1,反應溫度為140℃,反應壓力為70kg/cm2,且氫氣與MDA莫耳比為53。以GC分析結果如下:MDA轉化率為100%且無單環氫化中間產物H6MDA,PACM選擇率為93.3%,且(t,t)-PACM莫耳比例為22.8%。
取7ml 20-30mesh之B觸媒,其含有4wt%Ru與1wt%Rh。將此觸媒置於固定床反應器中,以連續式滴流床(trickle-bed)模
式進行試驗,對二胺基二苯甲烷(購自双邦實業公司之MDA100)進行氫化反應。反應條件如下:溶劑為THF,MDA100濃度為25wt%,液體之空間流速(WHSV)為0.35hr-1,反應溫度為130℃,反應壓力為70kg/cm2,且氫氣與MDA莫耳比為42。以GC分析結果如下,MDA轉化率為100%且無單環氫化中間產物H6MDA,PACM選擇率為93.5%,且(t,t)-PACM莫耳比例為17.0%。
取13.5ml 20-30mesh之C觸媒,其含有4wt%Ru與1wt%Rh。將此觸媒置於固定床反應器中,以連續式滴流床(trickle-bed)模式進行試驗,對MDA85進行氫化反應。反應條件如下:溶劑為THF,MDA85濃度為25wt%,液體之空間流速(WHSV)為0.27hr-1,反應溫度為140℃,反應壓力為70kg/cm2,且氫氣與MDA莫耳比為51。以GC分析結果如下:MDA轉化率為100%且無單環氫化中間產物H6MDA,PACM選擇率為92.0%,且(t,t)-PACM莫耳比例為20.3%。
取2.5克含5wt%Rh粉狀之A觸媒、50克MDA85、與75克THF於高壓釜反應器中進行氫化反應。反應條件如下:反應溫度為160℃,反應壓力為60kg/cm2,待氫氣壓力不再變化停止反應,反應時間為210分鐘。以GC分析結果如下:MDA轉化率為100%且無單環氫化中間產物H6MDA,PACM選擇率為93.7%,且(t,t)-PACM莫耳比例為25.0%。由上述可知,具有氧化鎂鋁層披覆於氧化鋁表面的Rh觸媒,其反應活性可被調控,以同時達到
高反應性、高選擇率以及低(t,t)-PACM莫耳比例。
取2.5克市售之5wt%Rh/Al2O3粉狀觸媒(購自Alfa Aesar公司)、50克MDA85、75克THF、與0.125克LiOH於高壓釜反應器中進行氫化反應。反應條件如下:反應溫度為160℃,反應壓力:60kg/cm2,待氫氣壓力不再變化停止反應,反應時間為60-120分鐘。以GC分析結果如下:MDA轉化率為100%且無單環氫化中間產物H6MDA,PACM選擇率為65%,且(t,t)-PACM莫耳比例為39.0%。由上述可知,缺乏氧化鎂鋁層披覆於氧化鋁表面的Rh觸媒,其選擇率偏低且(t,t)-PACM莫耳比例偏高。
取2.5克市售之5wt%Ru/Al2O3粉狀觸媒(購自Alfa Aesar公司),50克MDA85、75克THF、與0.125克LiOH於高壓釜反應器中進行氫化反應。反應條件如下:反應溫度為160℃,反應壓力為60kg/cm2,待氫氣壓力不再變化停止反應,反應時間為420分鐘。以GC分析結果如下,MDA轉化率接近100%,PACM選擇率為91.1%,且(t,t)-PACM莫耳比例為43.5%。由上述可知,商用Ru觸媒,其反應活性較低,反應時間較長,且(t,t)-PACM莫耳比例偏高(>25%)。
取2.5克5wt%Rh/LiAl5O8粉狀觸媒(利用初濕法自製,載體為根據US Patent 5885917中Example7方法製備)、50克MDA85、75克THF、與0.125克LiOH於高壓釜反應器中進行氫化反應。反應條件如下:反應溫度為160℃,反應壓力為
60kg/cm2,待氫氣壓力不再變化停止反應,反應時間為210分鐘。以GC分析結果如下:MDA轉化率接近100%,PACM選擇率為89.4%,且(t,t)-PACM莫耳比例為48.0%。由上述可知,利用Li金屬修飾氧化鋁載體之Rh觸媒,其對選擇率的提升與(t,t)-PACM莫耳比例的降低,效果不如氧化鎂鋁層披覆於氧化鋁表面之Rh觸媒。
取7ml 4wt%Ru-1wt%Rh/Al2O3觸媒(利用初濕法自製,載體購自UOP公司)。將此觸媒置於固定床反應器中,以連續式滴流床(trickle-bed)模式進行試驗,對MDA85進行氫化反應。反應條件如下:溶劑為THF,MDA85濃度為25wt%,液體之空間流速(WHSV)為0.22hr-1,反應溫度為140℃,反應壓力為70kg/cm2,且氫氣與MDA莫耳比為41。上述氫化反應約140小時後,開始出現H6MDA。由上述可知,缺乏氧化鎂鋁層披覆於氧化鋁表面的觸媒,觸媒活性易下降。
雖然本發明已以數個實施例揭露如上,然其並非用以限定本發明,任何本技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作任意之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
Claims (10)
- 一種氫化4,4’-二胺基二苯甲烷的觸媒,包括:一載體;一氧化鎂鋁層,披覆於該載體上;一銠-釕活性層,負載於該氧化鎂鋁層上,其中該銠-釕活性層中的銠與釕之重量比介於40:60至10:90之間。
- 如申請專利範圍第1項所述之氫化4,4’-二胺基二苯甲烷的觸媒,其中該載體包括氧化矽或氧化鋁。
- 如申請專利範圍第1項所述之氫化4,4’-二胺基二苯甲烷的觸媒,其中該載體之比表面積介於100m2/g至300m2/g之間。
- 如申請專利範圍第1項所述之氫化4,4’-二胺基二苯甲烷的觸媒,其中該氧化鎂鋁層與該載體之重量比介於1:1至1:4之間。
- 如申請專利範圍第1項所述之氫化4,4’-二胺基二苯甲烷的觸媒,其中該氧化鎂鋁層中鎂與鋁的重量比介於2:1至1:2之間。
- 如申請專利範圍第1項所述之氫化4,4’-二胺基二苯甲烷的觸媒,其中該銠-釕活性層與該載體之重量比介於1:24至1:16之間。
- 一種氫化4,4’-二胺基二苯甲烷的方法,包括:以申請專利範圍第1項所述之氫化4,4’-二胺基二苯甲烷的觸媒搭配氫氣,氫化4,4’-二胺基二苯甲烷以形成二胺基二環己基甲烷。
- 如申請專利範圍第7項所述之氫化4,4’-二胺基二苯甲烷的方法,其中該二胺基二環己基甲烷之反,反-異構物莫耳比例介於25莫耳%至0莫耳%之間。
- 如申請專利範圍第7項所述之氫化4,4’-二胺基二苯甲烷的方法,其中該氫氣之壓力介於60bar至70bar之間。
- 如申請專利範圍第7項所述之氫化4,4’-二胺基二苯甲烷的方法,其中氫化4,4’-二胺基二苯甲烷的溫度介於120℃至160℃之間。
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US20160152549A1 (en) | 2016-06-02 |
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