CN114031504B - 一种制备n,n-二甲基环己胺的方法 - Google Patents
一种制备n,n-二甲基环己胺的方法 Download PDFInfo
- Publication number
- CN114031504B CN114031504B CN202111341880.5A CN202111341880A CN114031504B CN 114031504 B CN114031504 B CN 114031504B CN 202111341880 A CN202111341880 A CN 202111341880A CN 114031504 B CN114031504 B CN 114031504B
- Authority
- CN
- China
- Prior art keywords
- reactor
- dimethylcyclohexylamine
- dimethylamine
- cyclohexanone
- preparing
- 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.)
- Active
Links
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 20
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 68
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 239000007868 Raney catalyst Substances 0.000 claims abstract description 19
- 229910000564 Raney nickel Inorganic materials 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000005416 organic matter Substances 0.000 claims abstract description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005086 pumping Methods 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 6
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 6
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 claims description 6
- 229950006389 thiodiglycol Drugs 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- VTRRCXRVEQTTOE-UHFFFAOYSA-N 1-methylsulfinylethane Chemical compound CCS(C)=O VTRRCXRVEQTTOE-UHFFFAOYSA-N 0.000 claims description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 238000004817 gas chromatography Methods 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000010097 foam moulding Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 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
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
-
- 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
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0217—Mercaptans or thiols
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0218—Sulfides
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0222—Sulfur-containing compounds comprising sulfonyl groups
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
-
- 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
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种制备N,N‑二甲基环己胺的方法。将湿润的雷尼镍加入反应器中,用氮气排除反应器内空气,将二甲胺打入反应器，充入氢气，开启搅拌,升温至45～90℃，将环己酮和助催化剂含硫有机物混合液滴加打入反应器，反应后得到N,N‑二甲基环己胺。本发明采用非贵金属催化剂雷尼镍和含硫有机物为助催化剂与传统的贵金属催化剂相比极大地降低了生产成本，N,N‑二甲基环己胺收率最高可达96%。
Description
技术领域
本发明属于合成化学工程技术领域，尤其涉及一种制备N,N-二甲基环己胺的方法。
背景技术
N,N-二甲基环己胺是一种低粘度的中等活性胺类催化剂，主要用于硬质聚氨酯泡沫催化剂，该催化剂对凝胶和发泡均有催化作用，是泡沫反应的强初始催化剂，除用于硬泡外，也用于模塑软泡及半硬泡等辅助催化剂。目前产业化的N,N-二甲基环己胺的制备方法有环己酮法、环己胺法和N,N-二甲基苯胺加氢法。
CN1092061 公开了一种以环己酮和40%二甲胺水溶液为原料，钯炭为催化剂制备N,N-二甲基环已胺的方法，在氢气压力2.5～3.5MPa和100～140℃条件下，反应3～8h，反应液经分液精馏得到成品，收率为98%，该方法的缺点是采用了贵金属钯为催化剂，钯价格高，反应过程钯易流失，生产成本较高。
CN101208319A 公开了一种环己酮和二甲胺为原料，胺：酮摩尔比1.2，钯炭为催化剂，在14bar氢气压力和120℃条件下，反应6h，环己酮转化率94%，N,N-二甲基环已胺选择性98%，该方法同样采用贵金属钯为催化剂，生产成本较高。
CN104892429A公开了一种以环己酮、氨、氢气和甲醛为原料制备N,N-二甲基环已胺的方法，催化剂采用掺杂铜和铬的负载型镍系催化剂，载体为γ-氧化铝、二氧化硅和分子筛，镍的负载量为0.1%～50%，反应在两段串联固定床反应器中进行，反应压力6MPa，第一段反应温度120℃，第二段反应温度130℃，N,N-二甲基环已胺收率84.2%，N-甲基二环己胺收率10.3%，该方法的缺点在于主产品收率低，两个产品总收率仅为94.5%，设备投资大。
CN111333520A 公开了一种以环己胺、溶剂和甲醛水溶液为原料，钯炭为催化剂制备N,N-二甲基环已胺的方法，在氢气压力2～4MPa，110～130℃条件下，滴加甲醛水溶液，甲醛滴加时间6h，N,N-二甲基环已胺收率大于99%，该方法同样采用贵金属钯为催化剂，生产成本较高。
发明人认为现有相关技术存在以下缺陷：
（1）现有主流N,N-二甲基环已胺产业化工艺，环己酮和环己胺工艺均使用贵金属钯为催化剂，近年来钯价格大幅上涨，极大地增加了N,N-二甲基环已胺的生产成本，而单纯的用雷尼镍为催化剂，N,N-二甲基环已胺收率非常低，主要生成副产物环己醇。
（2）采用非贵金属催化剂制备N,N-二甲基环已胺的方法，使用负载型催化剂和固定床反应器，收率低，设备投资大而且对催化剂稳定性要求高，使用寿命差的催化剂难以产业化。
发明内容
本发明针对现有相关技术存在的缺陷，提供了一种制备N,N-二甲基环己胺的方法。
本发明采用的技术方案，一种制备N,N-二甲基环己胺的方法包括以下过程：S1：将湿润的雷尼镍加入反应器中，拧紧反应器；S2：室温下用高纯氮气吹扫，排除反应器内空气；S3:将液体二甲胺或二甲胺水溶液打入反应器，充入氢气，开启搅拌；S4：升温至45～90℃，将环己酮和助催化剂含硫有机物混合液滴加打入反应器，滴加时间为20～600min，反应温度45～135℃，反应压力1～5MPa；S5:滴加结束后，继续反应30～200min，得到N,N-二甲基环己胺；上述环己酮和助催化剂含硫有机物的质量比为(10～150):1，环己酮与雷尼镍的质量比为(3～100):1，二甲胺与环己酮的物质的量比为(1～2):1。
上述中环己酮和助催化剂含硫有机物混合液滴加时间优选为65～120℃，1.5～3MPa。
上述二甲胺水溶液二甲胺质量含量为35～42%。
上述液体二甲胺为质量含量大于98%的二甲胺。
上述助催化剂含硫有机物为硫二甘醇、正十二烷基硫醇、叔十二烷基硫醇、二甲基亚砜、乙基甲基亚砜、二乙基亚砜、噻吩、4,4'-二羟基二苯硫醚、苯甲硫醚、二甲硫醚中的一种。
上述催化剂雷尼镍，镍质量含量为85～96%，铝或钼或铁或铬质量含量为4～15%。
上述反应器采用釜式搅拌反应器。
上述反应器采用回路反应器。
本发明具有如下有益效果：
（1）使用非贵金属催化剂雷尼镍和助催化剂含硫有机物，以环己酮和二甲胺为原料，合成N,N-二甲基环己胺，收率可达96%，雷尼镍可多次循环使用，极大的降低了N,N-二甲基环己胺的生产成本，而单纯的使用雷尼镍，N,N-二甲基环己胺收率仅18%。
（2）反应器可采用釜式搅拌反应器或回路反应器，设备投资较低。
具体实施方式
下面结合实施例对本发明进行进一步说明，但本发明并不限于所列出的实施例。
以下实施例气相色谱分析条件为：HP-5色谱柱，气化室温度260℃，FID检测器温度280℃，柱箱升温程序为80℃保持2min，10℃min升温至260℃保持5min。
实施例1
制备N,N-二甲基环己胺的方法：
将5g湿润的雷尼镍加入300mL反应釜，镍含量大于90%，铝含量小于8%，拧紧反应釜，室温下用高纯氮气吹扫5min，排除反应釜内空气，用柱塞泵将液体二甲胺30g打入反应釜，充入1MPa氢气，开启搅拌，升温至55～60℃，补充氢气至2.5MPa，用平流泵将60g环己酮滴入反应釜，滴加时间300min，反应温度75～85℃，氢气压力2～3MPa，环己酮滴加毕，继续反应120min，将反应釜冷却降温，过滤催化剂，反应产物经气相色谱分析，环己酮转化率100%，N,N-二甲基环己胺气相色谱收率18.6%，副产物环己醇气相色谱收率80.3%。
实施例2
制备N,N-二甲基环己胺的方法：
将5g湿润的雷尼镍加入300mL反应釜，镍含量大于90%，铝含量小于8%，拧紧反应釜，室温下用高纯氮气吹扫5min，排除反应釜内空气，用柱塞泵将液体二甲胺30g打入反应釜，充入1MPa氢气，开启搅拌，升温至55～60℃，补充氢气至2.5MPa，将60g环己酮与0.8g二甲基亚砜混合均匀，用平流泵将环己酮与二甲基亚砜混合液滴入反应釜，滴加时间300min，反应温度75～85℃，氢气压力2～3MPa，环己酮滴加毕，继续反应120min，将反应釜冷却降温，过滤催化剂，反应产物经气相色谱分析，环己酮转化率100%，N,N-二甲基环己胺气相色谱收率82.8%，副产物环己醇气相色谱收率16.6%。
实施例3
制备N,N-二甲基环己胺的方法：
将5g湿润的雷尼镍加入300mL反应釜，镍含量大于90%，铝含量小于8%，拧紧反应釜，室温下用高纯氮气吹扫5min，排除反应釜内空气，用柱塞泵将液体二甲胺35g打入反应釜，充入1MPa氢气，开启搅拌，升温至55～60℃，补充氢气至2.5MPa，将60g环己酮与1.5g二甲基亚砜混合均匀，用平流泵将环己酮与二甲基亚砜混合液滴入反应釜，滴加时间300min，反应温度70～80℃，氢气压力2～3MPa，环己酮滴加毕，继续反应120min，将反应釜冷却降温，过滤催化剂，反应产物经气相色谱分析，环己酮转化率100%，N,N-二甲基环己胺气相色谱收率93.2%，副产物环己醇气相色谱收率6.6%。
实施例4
制备N,N-二甲基环己胺的方法：
将5g湿润的雷尼镍加入300mL反应釜，镍含量大于90%，铝含量小于8%，拧紧反应釜，室温下用高纯氮气吹扫5min，排除反应釜内空气，用柱塞泵将液体二甲胺35g打入反应釜，充入1MPa氢气，开启搅拌，升温至55～60℃，补充氢气至2.5MPa，将60g环己酮与0.8g硫二甘醇混合均匀，用平流泵将环己酮与硫二甘醇混合液滴入反应釜，滴加时间300min，反应温度70～80℃，氢气压力2～3MPa，环己酮滴加毕，继续反应120min，将反应釜冷却降温，过滤催化剂，反应产物经气相色谱分析，环己酮转化率99.9%，N,N-二甲基环己胺气相色谱收率96.1%，副产物环己醇气相色谱收率3.7%。
实施例5
制备N,N-二甲基环己胺的方法：
将实施例4中回收的雷尼镍和0.3g新鲜的雷尼镍加入300mL反应釜，拧紧反应釜，室温下用高纯氮气吹扫5min，排除反应釜内空气，用柱塞泵将液体二甲胺35g打入反应釜，充入1MPa氢气，开启搅拌，升温至55～60℃，补充氢气至2.5MPa，将60g环己酮与0.8g硫二甘醇混合均匀，用平流泵将环己酮与硫二甘醇混合液滴入反应釜，滴加时间300min，反应温度70～80℃，氢气压力2～3MPa，环己酮滴加毕，继续反应120min，将反应釜冷却降温，过滤催化剂，反应产物经气相色谱分析，环己酮转化率99.9%，N,N-二甲基环己胺气相色谱收率96.4%，副产物环己醇气相色谱收率3.3%，原料转化率、主、副产物色谱收率与实施例4相近。
实施例6
制备N,N-二甲基环己胺的方法：
将5g湿润的雷尼镍加入300mL反应釜，镍含量大于90%，铝含量小于8%，拧紧反应釜，室温下用高纯氮气吹扫5min，排除反应釜内空气，用柱塞泵将液体二甲胺35g打入反应釜，充入1MPa氢气，开启搅拌，升温至55～60℃，补充氢气至2.5MPa，将60g环己酮与1g正十二烷基硫醇混合均匀，用平流泵将环己酮与正十二烷基硫醇混合液滴入反应釜，滴加时间300min，反应温度70～80℃，氢气压力2～3MPa，环己酮滴加毕，继续反应120min，将反应釜冷却降温，过滤催化剂，反应产物经气相色谱分析，环己酮转化率99.9%，N,N-二甲基环己胺气相色谱收率94.1%，副产物环己醇气相色谱收率5.7%。
Claims (6)
1.一种制备N,N-二甲基环己胺的方法，其特征在于包括以下过程：
S1：将湿润的雷尼镍加入反应器中，拧紧反应器；
S2：室温下用高纯氮气吹扫，排除反应器内空气；
S3:将液体二甲胺或二甲胺水溶液打入反应器，充入氢气，开启搅拌；
S4：升温至45～90℃，将环己酮和助催化剂含硫有机物混合液滴加打入反应器，滴加时间为20～600min，反应温度45～135℃，反应压力1～5MPa；
S5：滴加结束后，继续反应30～200min，得到N,N-二甲基环己胺；
上述环己酮和助催化剂含硫有机物的质量比为(10～150):1，环己酮与雷尼镍的质量比为(3～100):1，二甲胺与环己酮的物质的量比为(1～2):1；
上述助催化剂含硫有机物为硫二甘醇、正十二烷基硫醇、叔十二烷基硫醇、二甲基亚砜、乙基甲基亚砜、二乙基亚砜、噻吩、4,4'-二羟基二苯硫醚、苯甲硫醚、二甲硫醚中的一种。
2.按照权利要求1所述的一种制备N,N-二甲基环己胺的方法，其特征在于上述二甲胺水溶液二甲胺质量含量为35～42％。
3.按照权利要求1所述的一种制备N,N-二甲基环己胺的方法，其特征在于上述液体二甲胺为质量含量大于98％的二甲胺。
4.按照权利要求1所述的一种制备N,N-二甲基环己胺的方法，其特征在于上述催化剂雷尼镍，镍质量含量为85～96％，铝或钼或铁或铬质量含量为4～15％。
5.按照权利要求1所述的一种制备N,N-二甲基环己胺的方法，其特征在于上述反应器采用釜式搅拌反应器。
6.按照权利要求1所述的一种制备N,N-二甲基环己胺的方法，其特征在于上述反应器采用回路反应器。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111341880.5A CN114031504B (zh) | 2021-11-12 | 2021-11-12 | 一种制备n,n-二甲基环己胺的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111341880.5A CN114031504B (zh) | 2021-11-12 | 2021-11-12 | 一种制备n,n-二甲基环己胺的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114031504A CN114031504A (zh) | 2022-02-11 |
| CN114031504B true CN114031504B (zh) | 2023-09-22 |
Family
ID=80137468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111341880.5A Active CN114031504B (zh) | 2021-11-12 | 2021-11-12 | 一种制备n,n-二甲基环己胺的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114031504B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429294A (zh) * | 2021-07-12 | 2021-09-24 | 浙江捷达科技有限公司 | 一种n,n-二甲基正丁胺的间歇式合成方法 |
| CN115947660A (zh) * | 2022-12-19 | 2023-04-11 | 江苏万盛大伟化学有限公司 | 一种高纯度二甲基环己胺的制备方法 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4190601A (en) * | 1978-05-31 | 1980-02-26 | Union Carbide Corporation | Production of tertiary amines by reductive alkylation |
| EP0014985A1 (en) * | 1979-02-21 | 1980-09-03 | Uniroyal, Inc. | Trialkylamine preparation by reductive alkylation of dialkylamines with ketones |
| EP0355351A2 (de) * | 1988-07-20 | 1990-02-28 | Bayer Ag | Verfahren zur Herstellung von Aminen |
| US4914239A (en) * | 1987-06-24 | 1990-04-03 | New Japan Chemical Co., Ltd. | Method for production of cyclohexylamines |
| DE3834848A1 (de) * | 1988-10-13 | 1990-05-03 | Bayer Ag | Verfahren zur herstellung von aminen |
| US4954654A (en) * | 1988-08-29 | 1990-09-04 | Phillips Petroleum Company | Process for the preparation of secondary and tertiary amines |
| HU9901547D0 (en) * | 1999-05-10 | 1999-07-28 | Process for producing n,n-dimethyl-cyclohexyl-amine | |
| JPH11343269A (ja) * | 1998-05-29 | 1999-12-14 | Kuraray Co Ltd | 一級アミンの製造法 |
| CN111333520A (zh) * | 2020-03-09 | 2020-06-26 | 万华化学集团股份有限公司 | 一种制备n,n-二甲基环己胺的方法 |
-
2021
- 2021-11-12 CN CN202111341880.5A patent/CN114031504B/zh active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4190601A (en) * | 1978-05-31 | 1980-02-26 | Union Carbide Corporation | Production of tertiary amines by reductive alkylation |
| EP0014985A1 (en) * | 1979-02-21 | 1980-09-03 | Uniroyal, Inc. | Trialkylamine preparation by reductive alkylation of dialkylamines with ketones |
| US4914239A (en) * | 1987-06-24 | 1990-04-03 | New Japan Chemical Co., Ltd. | Method for production of cyclohexylamines |
| EP0355351A2 (de) * | 1988-07-20 | 1990-02-28 | Bayer Ag | Verfahren zur Herstellung von Aminen |
| US4954654A (en) * | 1988-08-29 | 1990-09-04 | Phillips Petroleum Company | Process for the preparation of secondary and tertiary amines |
| DE3834848A1 (de) * | 1988-10-13 | 1990-05-03 | Bayer Ag | Verfahren zur herstellung von aminen |
| JPH11343269A (ja) * | 1998-05-29 | 1999-12-14 | Kuraray Co Ltd | 一級アミンの製造法 |
| HU9901547D0 (en) * | 1999-05-10 | 1999-07-28 | Process for producing n,n-dimethyl-cyclohexyl-amine | |
| CN111333520A (zh) * | 2020-03-09 | 2020-06-26 | 万华化学集团股份有限公司 | 一种制备n,n-二甲基环己胺的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114031504A (zh) | 2022-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114031504B (zh) | 一种制备n,n-二甲基环己胺的方法 | |
| US3959374A (en) | Process for the preparation of mixed isomeric methylene-bridged polycyclohexylpolyamines | |
| WO2018121042A1 (zh) | 一种高品质精己二胺的生产方法 | |
| CN109456200B (zh) | 一种间苯二甲胺的制备方法 | |
| CN110551278B (zh) | 一种负载催化剂及其制备方法和应用 | |
| CN109851508B (zh) | 合成低反反异构体含量和低焦油含量h12mda的方法 | |
| CN113620813A (zh) | 一种n，n-二甲基-1，3-丙二胺的制备方法 | |
| CN104557564B (zh) | 苯甲胺的制备方法 | |
| CN101497572A (zh) | 一种基于反应-分离耦合生产叔丁胺的方法 | |
| CN110627650A (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 | |
| CN110372516B (zh) | 一种制备环己胺的方法 | |
| CN113200870A (zh) | 一种使用微混合与固定床反应器连续制备n,n-二甲基-1，3-丙二胺的工艺 | |
| CN104193578A (zh) | 一种萘加氢生产十氢化萘和四氢化萘的方法 | |
| CN115433067B (zh) | 一种β-异佛尔酮的制备方法 | |
| CN114380698B (zh) | 连续法二氨基甲苯选择性加氢合成甲基环己二胺的方法 | |
| CN108516939B (zh) | 一种高反反体含量4,4’-二氨基二环己基甲烷的制备方法 | |
| CN107628957A (zh) | 一种环己烯直接氨化合成环己胺的新方法研究 | |
| CZ46697A3 (cs) | Způsob výroby směsi cyklohexylaminu a dicyklohexylaminu | |
| JPH10259167A (ja) | ビス（アミノメチル）シクロヘキサンの異性化方法 | |
| CN105315133A (zh) | 一种百里香酚合成工艺 | |
| CN113620841A (zh) | 一种制备2,6-二氟苯腈的方法 | |
| CN115197048A (zh) | 一种氢化双酚a的制备方法 | |
| CN114632543A (zh) | 一种乙醇氨化脱氢制备乙腈催化剂及其制备方法、应用 | |
| WO2019120064A1 (zh) | 一种异佛尔酮腈亚胺加氢还原制备异佛尔酮二胺的方法 | |
| CN113492012A (zh) | 一种非贵金属Ni基催化剂及其制备方法和环戊二烯加氢制备环戊烷的方法 |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |