CN112194582A - 一种催化加氢制备环己二胺的方法 - Google Patents
一种催化加氢制备环己二胺的方法 Download PDFInfo
- Publication number
- CN112194582A CN112194582A CN201910617532.2A CN201910617532A CN112194582A CN 112194582 A CN112194582 A CN 112194582A CN 201910617532 A CN201910617532 A CN 201910617532A CN 112194582 A CN112194582 A CN 112194582A
- Authority
- CN
- China
- Prior art keywords
- cyclohexanediamine
- phenylenediamine
- catalytic hydrogenation
- reaction
- hydrogen
- 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.)
- Pending
Links
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 13
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 22
- 239000010941 cobalt Substances 0.000 claims abstract description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical class OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 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 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000162 poly(ureaurethane) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种由苯二胺催化加氢制备环己二胺的方法，属于催化加氢技术领域。将苯二胺溶解于1，4‑二氧六环溶剂中，配制成反应液，将反应液通入装有担载型金属钴催化剂的固定床反应器中，用氢气将苯二胺催化加氢为环己二胺。在100～180℃、2.0～7.0MPa氢气气氛下进行固定床催化加氢反应，在优化的反应条件下，苯二胺的加氢转化率可达100％，环己二胺的选择性可达90％以上。
Description
技术领域
本发明涉及一种苯二胺催化加氢制备环己二胺的方法，属于催化加氢技术领域。
技术背景
环己二胺属于脂肪多胺，根据两个胺基位置的不同，环己二胺可以为1，2-环己二胺、1，3-环己二胺和1，4-环己二胺。其中，1，2-环己二胺和1，4-环己二胺是用途十分广泛的化工原料中间体，如作为医药中间体及制造聚酰胺、聚酰亚胺、聚脲及聚氨酯的单体等。
环己二胺的制造方法已有很多文献报道。例如，可以利用脂肪环上二醇的羟基胺化来制备，如专利WO0029236披露了一种由环己二醇在氨气气氛下胺化制备环己二胺的方法。更常用的方法是利用苯二胺(1，2或1，4-苯二胺)在催化剂的存在下与氢气反应制备环己二胺。例如，美国专利US2606924、US3644552、US3697449都使用钌催化剂催化苯二胺的加氢反应来制备相应的环己二胺。
中国专利CN102688757公开了一种在临氨条件下苯二胺加氢制备环己二胺的方法，所用的催化剂由主活性组分、助剂和载体三部分组成。主活性组分为贵金属钌或钯，助剂为铼、钴、镍和铁等的金属氧化物中的一种或几种，载体选用活性炭或氧化铝或二氧化硅等。在浆态床反应器中，苯二胺和氢气可高活性、高选择性地转化为以环己二胺为主要产物的多种胺产品。
中国专利CN106994344公开了一种甲苯二胺催化加氢制备甲基环己二胺的催化剂，该催化剂由活性组分钌和助剂组成，助剂包括铈、锰、钡、钙、镁和镧中的一种或几种。可以获得很高的转化率和目标产物选择性。
马小丹等(化学世界，2012年增刊，第6页)报道了在超临界状态下，使用骨架镍催化剂将对苯二胺催化加氢为1，4-环己二胺的结果，在优化的条件下，可以获得99.8％的转化率，但没有提供选择性数据。
中国专利CN102911063公开了一种在列管式连续反应器中，将邻苯二胺连续加氢为1，2-环己二胺的方法。该方法使用1，4-二氧六环为溶剂，催化剂为三氧化二铝负载的钯催化剂，氢气压力3-7Mpa。与间歇式高压加氢工艺相比，该工艺可以提高1，2-环己二胺的收率和产能，节约原料氢气。同时，得到的1，2-环己二胺产品的顺反比为2∶8左右，降低了后期单一产品的分离难度。
现有的苯二胺加氢为环己二胺工艺中使用的加氢催化剂主要活性组分为贵金属钌或钯，由于钌或钯价格较高，增加了生产成本。本申请经过研究发现，贱金属钴也具有很高的催化活性，可以将苯二胺高效地加氢为环己二胺。
发明内容
本发明申请提供一种在固定床反应器中使用担载的金属钴为催化剂，将苯二胺加氢为环己二胺的方法，在优化的反应条件下，可以将苯二胺高效地加氢为环己二胺。
本发明的技术方案如下：
一种催化加氢制备环己二胺的方法，其特征在于：将苯二胺溶解于1，4-二氧六环溶剂中，配制成反应液，将反应液通入装有担载型金属钴催化剂的固定床反应器中，用氢气将苯二胺催化加氢为环己二胺。
上述担载型金属钴催化剂中钴的含量(以金属钴质量计)为15～60％；载体为氧化铝和氧化镁的混合物，其中镁与铝的比例，以氧化物质量计为7∶1～1∶7；担载型金属钴催化剂可使用可溶性的钴盐、镁盐和铝盐的混合溶液通过共沉淀法制备，也可以将溶解有可溶性钴盐的溶液浸渍于成型氧化铝/氧化镁混合氧化物载体上制备。
上述担载型金属钴催化剂中钴元素需经氢气高温还原为金属钴才具有加氢活性。
上述的苯二胺催化加氢为环己二胺的反应条件为：反应温度为100～180℃，反应压力为2.0-7.0MPa；氢气与苯二胺的物质的量的比7～20∶1。
具体实施方式
下面用具体实施例对本发明作进一步说明。
实施例1
将15.2g的Co(NO3)2·6H2O和3.8g的Al(NO3)3·9H2O以及9.1g Mg(NO3)2·6H2O溶解于200ml的蒸馏水中，得到溶液A，将12.6g无水Na2CO3溶解于200ml的蒸馏水中，得到溶液B。在搅拌条件下，将溶液A和溶液B同时逐滴加入盛有200ml蒸馏水中的烧杯中，形成沉淀料浆。沉淀经去离子水洗涤后在120℃下烘干，即可得氧化铝/氧化镁混合氧化物担载的钴催化剂的前体。将所得前体压片、破碎，筛取20～40目催化剂颗粒。
实施例2
取2g实施例1中的担载的钴催化剂的前体颗粒，装填到固定床反应管中，催化剂床层上下用20～40目的石英砂装填，在40ml/min的氢气流速下，升温至500℃还原3h，然后降至室温。将氢气压力升至4.0MPa，反应温度升至140℃，通入反应液。反应液的质量组成为，对苯二胺：1，4-二氧六环＝1∶20。反应液流速18mL/h，氢气与对苯二胺的物质的量的比为10∶1。收集反应后的溶液，用气相色谱分析其组成。得到对苯二胺的转化率为100％，1，4-环己二胺的选择性92％。
实施例3
取2g实施例1中的担载的钴催化剂的前体颗粒，装填到固定床反应管中，催化剂床层上下用20～40目的石英砂装填，在40ml/min的氢气流速下，升温至500℃还原3h，然后降至室温。将氢气压力升至5.0MPa，反应温度升至160℃，通入反应液。反应液的质量组成为，邻苯二胺：1，4-二氧六环＝1∶20。反应液流速18mL/h，氢气与邻苯二胺的物质的量的比为10∶1。收集反应后的溶液，用气相色谱分析其组成。得到邻苯二胺的转化率100％，1，2-环己二胺的选择性83％。
Claims (4)
1.一种催化加氢制备环己二胺的方法，其特征在于：将苯二胺溶解于1，4-二氧六环溶剂中，配制成反应液，将反应液通入装有担载型金属钴催化剂的固定床反应器中，用氢气将苯二胺催化加氢为环己二胺。
2.根据权利要求1，所述的担载型金属钴催化剂中钴的含量(以金属钴质量计)为15～60％；载体为氧化铝和氧化镁的混合物，其中镁与铝的比例，以氧化物质量计为7∶1～1∶7。
3.根据权利要求1，所述的担载型金属钴催化剂中钴元素需经氢气高温还原为金属钴才具有加氢活性。
4.根据权利要求1，所述的苯二胺催化加氢为环己二胺的反应条件为：反应温度为100～180℃，反应压力为2.0-7.0MPa；氢气与苯二胺的物质的量的比7～20∶1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910617532.2A CN112194582A (zh) | 2019-07-08 | 2019-07-08 | 一种催化加氢制备环己二胺的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910617532.2A CN112194582A (zh) | 2019-07-08 | 2019-07-08 | 一种催化加氢制备环己二胺的方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112194582A true CN112194582A (zh) | 2021-01-08 |
Family
ID=74004529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910617532.2A Pending CN112194582A (zh) | 2019-07-08 | 2019-07-08 | 一种催化加氢制备环己二胺的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112194582A (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911063A (zh) * | 2012-10-18 | 2013-02-06 | 江苏康恒化工有限公司 | 一种邻苯二胺连续化高压制备1,2-环己二胺的方法 |
| CN109647450A (zh) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | 用于合成环己胺的加氢催化剂 |
-
2019
- 2019-07-08 CN CN201910617532.2A patent/CN112194582A/zh active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911063A (zh) * | 2012-10-18 | 2013-02-06 | 江苏康恒化工有限公司 | 一种邻苯二胺连续化高压制备1,2-环己二胺的方法 |
| CN109647450A (zh) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | 用于合成环己胺的加氢催化剂 |
Non-Patent Citations (1)
| Title |
|---|
| 王植等: ""苯胺加氢制环己胺与二环己胺催化剂进展"", 《江苏化工》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Baiker | Utilization of carbon dioxide in heterogeneous catalytic synthesis | |
| JP4732686B2 (ja) | イソホロンジアミン（ｉｐｄａ、３−アミノメチル−３，５，５−トリメチルシクロヘキシルアミン）の製造方法 | |
| US7468342B2 (en) | Catalysts and process for producing aromatic amines | |
| CN102432565B (zh) | 一种2-羟乙基哌嗪的制备方法 | |
| US20040171884A1 (en) | Process for the manufacture of diethylenetriamine and higher polyethylenepolyamines | |
| CN101704753A (zh) | 以乙醇胺和氨为原料在临氢条件下制备为乙二胺的方法 | |
| CN112125814A (zh) | 一种制备一异丙醇胺的方法 | |
| CN112898164B (zh) | 一种由5-羟甲基糠醛制备1,6-己二胺的方法 | |
| CN112898163B (zh) | 一种环己亚胺氨化制备1,6-己二胺的方法 | |
| CN110627650B (zh) | 一种微反应器内非均相加氢连续合成苄胺类物质的装置 | |
| CN109422657B (zh) | 甲胺混合气体的分离同时联产甲酰胺类化合物的方法 | |
| CN110256198B (zh) | 一种1,4-戊二醇的生产方法 | |
| CN110372516B (zh) | 一种制备环己胺的方法 | |
| CN109678732B (zh) | 一种连续生产5-氨基-1-戊醇的方法 | |
| CN112194582A (zh) | 一种催化加氢制备环己二胺的方法 | |
| US6331624B1 (en) | Process for preparing 6-aminocaproamide | |
| CN111196761B (zh) | 一种制备3-氨基丙醇的方法以及反应装置 | |
| CN113563213B (zh) | 3,5-二氨基苯甲酸的制备方法 | |
| JP4424479B2 (ja) | キシリレンジアミンの製造方法 | |
| CN110483242A (zh) | 一种1,4-丁炔二醇加氢合成1,4-丁二醇的方法 | |
| CN114716325B (zh) | 一种连续化制备三乙胺的方法 | |
| CN111196762A (zh) | 一种含腈类化合物为原料制备胺类化合物的方法 | |
| CN112479836B (zh) | 一种由1,4-丁二醇合成环丙烷甲醛的方法 | |
| CN107570147A (zh) | 一种活性金属／金属填料催化剂在二硝基甲苯加氢合成甲苯二胺反应中的应用方法 | |
| CN113649060B (zh) | 一种用于合成1,3-丙二胺的催化剂、其制备方法及应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210108 |
|
| WD01 | Invention patent application deemed withdrawn after publication |