CN1171779A - 气相制备脂族α Ω-氨基腈 - Google Patents
气相制备脂族α Ω-氨基腈 Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 239000010948 rhodium Substances 0.000 claims abstract description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 3
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
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- 239000011591 potassium Substances 0.000 claims description 4
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- 238000010438 heat treatment Methods 0.000 claims description 3
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- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
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- 239000004411 aluminium Substances 0.000 claims description 2
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 9
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- 239000012071 phase Substances 0.000 description 4
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- 239000005995 Aluminium silicate Substances 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 2
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- 239000012018 catalyst precursor Substances 0.000 description 2
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- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 206010037544 Purging Diseases 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
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- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
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- LLEVMYXEJUDBTA-UHFFFAOYSA-N heptanedinitrile Chemical compound N#CCCCCCC#N LLEVMYXEJUDBTA-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
在升温下、在催化剂存在下、在气相中、用下述方法通过脂族α,Ω-二腈部分加氢来制备脂族α,Ω-氨基腈。该法包括,用基于至少一种选自镍、钴、钌和铑的金属的催化剂进行加氢,其前提是催化剂不是粉末。
Description
本发明涉及一种通过脂族α,Ω-二腈的部分加氢来制备脂族α,Ω-氨基腈的改进方法,该法在升温下、在催化剂存在下、在气相中进行。
分子催化杂志,61(1990),197-205描述了在碱金属掺杂的铁和镍催化剂存在下、在不含氨的条件下己二腈的气相加氢。此外,化学会志,法拉第汇刊,89(1993),3981-3986描述了己二腈在用钾掺杂的含30%(重量)镍的催化剂上的部分加氢。在170℃、常压下,在转化率为65%时,得到的产率可高达85%。但是,这些方法的缺点是,催化剂呈粉末形式,所以不适合在固定床中大规模工业应用,特别是催化剂的寿命很短。此外,使用大量过量的氢气,以及催化剂的空速为0.02公斤二腈/每升催化剂·小时也不适合商业应用。
本发明的一个目的是要提供一种通过己二腈部分加氢来制备脂族α,Ω-氨基腈的改进方法,而且这一方法没有上述的缺点。特别是,试图找到一种比目前使用的催化剂有更长寿命的催化剂。
我们已发现,这一目的可通过这样一种脂族α,Ω-二腈部分加氢、以制备脂族α,Ω-氨基腈的方法来实现,在升温下、在催化剂存在下,在气相中进行加氢,催化剂以至少一种选自镍、钴、钌和铑的金属为基础,但其条件是催化剂不是粉末状。
在新方法中,通式I的脂族α,Ω-二腈
NC-(CH2)n-CN I用作原料,式中n为1~10中的一个整数,特别是2、3、4、5或6。特别优选的化合物I是丁二腈、戊二腈、己二腈、庚二腈和辛二腈,特别优选己二腈。
在新方法中,上述二腈I在催化剂存在下被部分加氢,得到通式II的α,Ω-氨基腈
NC-(CH2)n-CH2-NH2 II式中,n有上述含义。特别优选的氨基腈II是其中n为2、3、4、5或6,特别是4的那些氨基腈,即4-氨基丁腈、5-氨基戊腈、6-氨基己腈、7-氨基庚腈和8-氨基辛腈,最优选6-氨基己腈。
反应通常在100~250、优选150~220、特别优选160~200℃下进行:压力通常选择在0.01~3、优选0.07~1、特别优选0.09~0.5兆帕范围内。
在进口气体中,氢的浓度主要由二腈的浓度决定。通常,氢与二腈的摩尔比选择在2∶1至300∶1、优选10∶1至200∶1范围内。
在一优选的实施方案中,还使用氨或胺、特别优选氨。特别是当使用氨时,对数据分析表明,催化剂的寿命提高。按使用的二腈计,氨或胺的数量通常为5~50、优选10~30%(重量)。
根据本发明,使用的催化剂是以至少一种选自镍、钴、钌和铑的金属为基础的那些催化剂,优选以镍为基础的催化剂。
催化剂可以未负载的催化剂或负载催化剂的形式使用,适合的载体例如为氧化铝、氧化硅、硅酸铝、二氧化硅、二氧化锆和氧化镁、优选氧化铝、氧化硅和硅酸铝、特别优选氧化铝。
在一优选的实施方案中,催化剂可用以选自锂、钠、钾、铷、铯、镁、钙、锶、钡、钪、钇、镧、银、镉、铝、锡和锌的金属为基础的改性剂进行改性,优选用其氧化物改性。碱金属氧化物如氧化锂、氧化钠、氧化钾、氧化铷和氧化铯,以及氧化锌是特别优选的,氧化铯是最优选的。
通过这样选择催化剂的数量,以致催化剂的空速为0.03~10、优选0.05~3公斤二腈/公斤催化剂/小时。
当使用负载型催佛剂时,按载体计,催化剂的金属含量通常选择在0.1~80、优选0.2~70、特别优选0.5~50%(重量)范围内。
根据本发明,不使用粉末形式的催化剂,而使用模制品催化剂,如挤条形、小片丸和球形,它取决于用途。
优选使用固定床催化剂的固定床连续进行反应,例如用液相或滴流床方式进行。通过改变停留时间,可控制转化率,从而可控制选择性。
催化剂的制备方法是已知的(参见多相催化作用应用,(1987),106-122;催化作用,4(1981),1-30;DE-A2260978)。通常通过以下步骤进行制备:在载体存在下或无载体存在的条件下,使相应金属的水溶性盐如硝酸盐、硫酸盐、氯化物、甲酸盐或乙酸盐沉淀;如果需要,将生成的催化剂前体加工成挤条物或小片丸;干燥产物;然后焙烧产物。负载型催化剂通常也可用以下步骤制得:用相应金属的盐溶液浸渍载体,如果需要,在上述改性剂、特别是铯化合物存在下浸渍;或者将相应的金属盐溶液喷雾到载体上。
通常通过加入沉淀剂或通过改变pH值或温度来进行沉淀。
如此制得的预制催化剂材料通常在80~150、优选80~120℃下干燥。通常在150~700、优选200~600℃下,在含有氢和氮的混合气中进行焙烧。
在新方法中,所用的催化剂、特别是负载型催化剂比先有的催化剂有更高的活性和更长的寿命。得到高产率的α,Ω-氨基腈,有很好的选择性。α,Ω-氨基腈是制备环状内酰胺的重要原料,特别是6-氨基胺是制备己内酰胺的重要原料。
实施例
实施例1
将67毫升硝酸镍水溶液(按金属镍计,镍含量为16.22克)加到225克氧化铝挤条物(直径4毫米,BET表面积1米2/克)中,然后将混合物在室温下反复搅拌下静置2小时。然后在120℃下将生成的催化剂前体干燥16小时,在350℃下焙烧4小时。然后重复整个过程。
冷却后,将挤条物放入还原设备中,用20升/小时氮气吹扫2小时。此后,以2℃/分钟的升温速率将挤条物加热到300℃,同时通入20升/小时氢气,并在此温度下保持20小时。在氮气流中、冷却后,用空气/氮气混合物钝化催化剂,温度上升不超过20℃。
制得的催化剂挤条物含有13%(重量)镍(基于氧化铝并按金属计算)。
实施例2
重复实施例1,不同的是,在用硝酸镍浸渍以前,用硝酸锂(32毫升3.4%(重量)溶液)进行浸渍。
制得的催化剂挤条物含有13%(重量)镍和0.1%(重量)锂。在每一情况下的百分数都基于氧化铝并按金属计算。
实施例3
重复实施例1,不同的是,在用硝酸镍浸渍以前,用硝酸钾(32毫升1.4%(重量)溶液)进行浸渍。
制得的催化剂挤条物含13%(重量)镍和0.1%(重量)钠。在每一情况下的百分数都基于氧化铝并按金属计算。
实施例4
重复实施例1,不同的是,在用硝酸镍浸渍以前,用硝酸钾(32毫升1.0%(重量)溶液)进行浸渍。
制得的催化剂挤条物含13%(重量)镍和0.1%(重量)钾。在每一种情况下,百分数都基于氧化铝并按金属计算。
实施例5
重复实施例1,不同的是,在用硝酸镍浸渍以前,用硝酸铯(32毫升0.5%(重量)溶液)进行浸渍。
制得的催化剂挤条物含13%(重量)镍和0.1%(重量)铯。在每一情况下的百分数都基于氧化铝并按金属计算。
实施例6
重复实施例5,氧化铝的BET表面积为5.5米2/克(SCS9(Pechiney))。
制得的催化剂挤条物含13%(重量)镍和0.1%(重量)铯。在每一情况下的百分数都基于氧化铝并按金属计算。
实施例7
重复实施例5,氧化铝的BET表面积为7.7米2/克(SPH512B(Rhone-Poulenc))。
制得的催化剂挤条物含13%(重量)镍和0.1%(重量)铯。在每一情况下的百分数都基于氧化铝并按金属计算(。
实施例8
3~20克/小时己二腈通过汽化器,从汽化器出来并与100~200升/小时氢一起,以滴流床方式通过100毫升催化剂。在冷阱中冷凝气体反应混合物,并用气相色谱法分析。其他反应参数和结果列入下表。
表
催化剂 | 温度(℃) | H2/ADN-摩尔比 | 催化剂空速[克ADN/克催化剂·小时] | ACN产率% | HMD产率% | ACN选择性% | 转化率% |
实施例1 | a180b200 | 6060 | 0.070.07 | 5456 | 413 | 7559 | 7295 |
实施例2 | 180 | 45 | 0.08 | 22 | 0.3 | 85 | 26 |
实施例3 | 180 | 45 | 0.08 | 5 | 0 | 71 | 7 |
实施例4 | 180 | 45 | 0.08 | 16 | 0.2 | 89 | 18 |
实施例5 | a180b200 | 4545 | 0.080.08 | 4960 | 14 | 8879 | 5676 |
实施例6 | a180b180c200d180 | 456045150 | 0.10.10.10.05 | 25212946.4 | 0.50.30.41.4 | 89918592 | 28233450.7 |
实施例7 | a180b180c180d180 | 45905060 | 0.10.10.20.2 | 71543428 | 3210.5 | 91939293 | 78583730 |
Claims (5)
1.一种在升温下、在催化剂存在下、在气相中通过脂族α,Ω-二腈的部分氢化来制备脂族α,Ω-氨基腈的方法,该法包括,用基于至少一种选自镍、钴、钌和铑的金属的催化剂进行加氢,其前提是催化剂不是粉末状。
2.根据权利要求1的方法,其中催化剂用至少一种基于选自锂、钠、钾、铷、铯、镁、钙、锶、钡、钪、钇、镧、银、镉、铝、锡和锌的金属的改性剂进行改性。
3.根据权利要求1或2的方法,其中在100~250℃下进行加氢。
4.根据权利要求1~3中任一项的方法,其中在0.01~3兆帕下进行加氢。
5.根据权利要求1~4中任一项的方法,其中己二腈用作脂族α,Ω-二腈,并制得6-氨基己腈。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19500040A DE19500040A1 (de) | 1995-01-03 | 1995-01-03 | Verfahren zur Herstellung von aliphatischen alpha,omega-Aminonitrilen in der Gasphase |
DE19500040.4 | 1995-01-03 |
Publications (2)
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CN1171779A true CN1171779A (zh) | 1998-01-28 |
CN1072207C CN1072207C (zh) | 2001-10-03 |
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CN95197240A Expired - Fee Related CN1072207C (zh) | 1995-01-03 | 1995-12-22 | 气相制备脂族α,Ω-氨基腈 |
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US (1) | US5508465A (zh) |
EP (1) | EP0801641B1 (zh) |
JP (1) | JPH10511669A (zh) |
KR (1) | KR100424833B1 (zh) |
CN (1) | CN1072207C (zh) |
AU (1) | AU4347296A (zh) |
DE (2) | DE19500040A1 (zh) |
MY (1) | MY112950A (zh) |
RU (1) | RU2154631C2 (zh) |
TW (1) | TW316262B (zh) |
WO (1) | WO1996020916A1 (zh) |
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FR2771091B1 (fr) * | 1997-11-20 | 2000-01-14 | Rhone Poulenc Fibres | Procede d'hydrogenation de dinitriles |
EP1415981A1 (en) * | 1998-03-20 | 2004-05-06 | E.I. Du Pont De Nemours And Company | Aminonitrile production |
AU2001257006A1 (en) | 2000-04-11 | 2001-10-23 | Du Pont Pharmaceuticals Company | Substituted lactams as inhibitors of abeta protein production |
KR20230001792U (ko) | 2022-03-03 | 2023-09-12 | 전대성 | 파도타기 야외 운동장치 |
KR20230130445A (ko) | 2022-03-03 | 2023-09-12 | 전대성 | 좌우파도타기 |
KR102479547B1 (ko) | 2022-04-18 | 2022-12-20 | 주식회사 지아이 | 전신파도타기 |
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GB534939A (en) * | 1938-09-24 | 1941-03-24 | Ici Ltd | Improvements in or relating to the manufacture of aminonitriles |
US2257814A (en) * | 1940-05-02 | 1941-10-07 | Du Pont | Preparation of omega-amino nitriles |
US3174992A (en) * | 1962-05-21 | 1965-03-23 | Dow Chemical Co | Method for making aminonitriles |
US4389348A (en) * | 1981-10-26 | 1983-06-21 | Allied Corporation | Selective hydrogenation of dinitrile to omega-aminonitrile and supported rhodium-containing catalyst therefor |
US4362671A (en) * | 1981-10-26 | 1982-12-07 | Allied Corporation | Selective hydrogenation of dinitrile to omega-aminonitrile catalyzed by rhodium organonitrogen complex catalyst |
US4601859A (en) * | 1984-05-04 | 1986-07-22 | Allied Corporation | Selective hydrogenation of aliphatic dinitriles to omega-aminonitriles in ammonia with supported, finely dispersed rhodium-containing catalyst |
US5151543A (en) * | 1991-05-31 | 1992-09-29 | E. I. Du Pont De Nemours And Company | Selective low pressure hydrogenation of a dinitrile to an aminonitrile |
BE1007079A3 (nl) * | 1993-05-14 | 1995-03-07 | Dsm Nv | Werkwijze voor de selectieve hydrogenering van een dinitrilverbinding. |
-
1995
- 1995-01-03 DE DE19500040A patent/DE19500040A1/de not_active Withdrawn
- 1995-01-17 US US08/373,420 patent/US5508465A/en not_active Expired - Fee Related
- 1995-02-09 TW TW084101075A patent/TW316262B/zh active
- 1995-12-20 MY MYPI95003985A patent/MY112950A/en unknown
- 1995-12-22 KR KR1019970704569A patent/KR100424833B1/ko not_active IP Right Cessation
- 1995-12-22 RU RU97113759/04A patent/RU2154631C2/ru not_active IP Right Cessation
- 1995-12-22 EP EP95942195A patent/EP0801641B1/de not_active Expired - Lifetime
- 1995-12-22 JP JP8520714A patent/JPH10511669A/ja active Pending
- 1995-12-22 CN CN95197240A patent/CN1072207C/zh not_active Expired - Fee Related
- 1995-12-22 AU AU43472/96A patent/AU4347296A/en not_active Abandoned
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US5508465A (en) | 1996-04-16 |
WO1996020916A1 (de) | 1996-07-11 |
EP0801641B1 (de) | 2003-03-05 |
EP0801641A1 (de) | 1997-10-22 |
RU2154631C2 (ru) | 2000-08-20 |
DE19500040A1 (de) | 1996-07-04 |
KR980700961A (ko) | 1998-04-30 |
TW316262B (zh) | 1997-09-21 |
MY112950A (en) | 2001-10-31 |
KR100424833B1 (ko) | 2004-07-23 |
DE59510575D1 (de) | 2003-04-10 |
JPH10511669A (ja) | 1998-11-10 |
CN1072207C (zh) | 2001-10-03 |
AU4347296A (en) | 1996-07-24 |
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