CN114524782B - 一种有机胺和co2多相催化制甲酰胺的方法 - Google Patents
一种有机胺和co2多相催化制甲酰胺的方法 Download PDFInfo
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- CN114524782B CN114524782B CN202011321491.1A CN202011321491A CN114524782B CN 114524782 B CN114524782 B CN 114524782B CN 202011321491 A CN202011321491 A CN 202011321491A CN 114524782 B CN114524782 B CN 114524782B
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- reaction
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- organic amine
- formamide
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- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 150000001412 amines Chemical class 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 22
- 239000012263 liquid product Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 239000013110 organic ligand Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 9
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- 229920000620 organic polymer Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 claims 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 1
- 235000011054 acetic acid Nutrition 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229960001701 chloroform Drugs 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 28
- 238000004817 gas chromatography Methods 0.000 description 16
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- UOIWOHLIGKIYFE-UHFFFAOYSA-N n-methylpentan-1-amine Chemical compound CCCCCNC UOIWOHLIGKIYFE-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 4
- 238000006170 formylation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 150000003857 carboxamides Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000010640 amide synthesis reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005825 carbonyl allylation reaction Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ATHHXGZTWNVVOU-UHFFFAOYSA-N monomethyl-formamide Natural products CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 1
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 1
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
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- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/18—Bridged systems
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- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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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
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- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明属于多相催化反应工艺领域,具体涉及一种采用固体多相催化剂催化有机胺和CO2制甲酰胺的方法。一种用于有机胺和CO2制甲酰胺的方法,所述方法包括在所述固体多相催化剂存在下使有机胺和CO2在反应器中进行所述合成甲酰胺反应。该方法使用新型固体多相催化剂,反应工艺及装置简单,催化剂具有优异的反应活性及稳定性,降低了催化剂同反应物和产物的分离成本,有效提高了有机胺和CO2制甲酰胺反应过程的经济效益,具有重要的实际应用前景和研究意义。
Description
技术领域
本发明属于多相催化反应工艺领域,具体涉及一种采用固体多相催化剂用于有机胺和CO2制甲酰胺反应的方法。
背景技术
胺的甲酰化反应是有机合成和医药化学重要反应之一。酰胺是有机合成重要的中间体,广泛用于合成各类药物。酰胺可以用作有机合成原料,纸张处理剂,纤维工业的柔软剂,还可以用作测定大米中氨基酸含量的分析试剂;同时酰胺也是优良的有机溶剂,可以用于分离氯硅烷、提纯油脂等;此外,酰胺具有活泼的反应性,可以作为功能团转化的试剂,羰基化合物的烯丙基化和氢硅化等反应。大量的甲酰化方法相继被报道,其中作为碳源的试剂有三氯乙醛、甲酸、甲醛、甲醇等。很多氮甲酰化试剂具有试剂昂贵,有毒,副产物多等缺点,目前甲酸是应用最广泛的氮甲酰化反应碳源,但由于其具有很强的腐蚀性,损坏仪器设备,因此人们致力于开发更清洁的碳源。
CO2作为可再生能源有着巨大的优势,储量丰富并且无毒。但由于目前CO2的化学固定技术的成本高、效率差等缺点,限制了这一技术的商业化。自上世纪初以来,人们围绕着CO2的化学利用开展了大量的研究工作并取得了一系列进展。使用CO2作为甲酰化试剂碳源、以硅烷作为还原剂进行N-甲酰化的制备也得到了实现,但是硅烷作为还原剂导致生产成本高昂、产物分离困难,难以大规模应用。H2是当前化学工业上最为清洁、廉价的还原剂,以CO2为甲酰化碳源、H2为还原剂进行N-甲酰化胺类化合物制备无疑具有更为优良的经济性和环境友好性。因此,以工业化应用为目的,对开发以CO2为甲酰化碳源、H2为还原剂的N-甲酰化胺类化合物的制备方法具有强烈需求。
综上所述,对于实际工业应用的氮甲酰化反应,研发高效可回收利用的催化剂,从而开发绿色清洁适用于大规模生产的反应工艺,是本领域的主要研究方向。
发明内容
针对现有技术中存在的不足,本发明的目的在于提供一种能够在工业上容易实现的采用具有优异反应活性和稳定性固体多相催化剂的有机胺和CO2制甲酰胺反应工艺。
为此,本发明提供一种用于有机胺和CO2制甲酰胺反应的方法,其特征在于,所述方法采用固体多相催化剂,其由金属组分和有机配体聚合物组成,其中所述金属组分是金属Ru、Pd、Ir、Rh、Ni、Co或Fe中的一种或几种,所述有机配体聚合物是醛基和胺基官能团化含氮有机单体经溶剂热聚合生成的具有大比表面积和多级孔结构的聚合物,所述金属组分与所述有机配体聚合物骨架中的N原子形成配位键,高分散且稳定的存在于有机配体聚合物载体上,所述方法包括在所述固体多相催化剂存在下使有机胺和CO2在反应器中进行所述合成甲酰胺反应。
在一个优选实施方案中,所述有机胺选自:
其中R1和R2各自独立地选自C1-18烷基,m为1到6的整数,并且n为1到12的整数。
在一个优选实施方案中,所述有机胺原料与所述CO2原料的摩尔比为1:1-1:300,所述CO2原料与所述H2原料的摩尔比为1:0.1-1:100。
在一个优选实施方案中,所述有机胺原料采用高压泵输送进入反应系统,液时空速为0.01-10h-1;CO2和H2原料以气体形式直接进料,气体空速为500-20000h-1。
在一个优选实施方案中,所述反应器是滴流床或釜式反应器。
在一个优选实施方案中,所述有机胺和CO2制甲酰胺反应以连续方式或间歇方式进行。
在一个优选实施方案中,所述有机胺和CO2制甲酰胺反应的反应温度为333-573K,反应压力为0.05-20MPa。
在一个优选实施方案中,所述金属组分在所述固体多相催化剂总重量中占0.01-40.0%。
在一个优选实施方案中,所述有机配体聚合物的比表面积为100-2000m2/g,孔容为0.1-2.0cm3/g,孔径分布在0.1-200.0nm。
惰性气体气氛氩气,氦气,氮气,氖气中的一种或二种以上。
在一个优选实施方案中,当所述反应器是滴流床时,所述有机胺和CO2制甲酰胺反应在所述固体多相催化剂上连续地进行,生成的液体产物持续流出所述反应器并通过产品收集罐在-20-25℃的温度进行收集;当所述反应器是釜式反应器时,所述有机胺和CO2制甲酰胺反应间歇地进行,生成的液体产物经过过滤与所述固体多相催化剂分离获得,并且所得到的液体产物通过精馏或闪蒸进一步处理而获得高纯度的甲酰胺类产品。
本发明产生的有益效果包括但不限于以下方面:本发明的有机胺和CO2制甲酰胺反应技术与现有技术相比,该方法使用新型固体多相催化剂,反应工艺及装置简单,催化剂具有优异的反应活性及稳定性,降低了催化剂同反应物和产物的分离成本,有效提高了有机胺和CO2制甲酰胺反应过程的经济效益,具有广阔的工业应用前景。
附图说明
图1是根据本发明的一种连续进行的有机胺和CO2制甲酰胺反应的反应工艺流程图。
具体实施方式
为了更好的说明催化剂的制备方法及其在有机胺和CO2制甲酰胺反应中的应用,下面举出一些催化剂样品的制备及其在反应工艺中应用的实施例,但本发明不限于所列举的实施例。除非另有具体说明,本申请中的含量和百分比均按“质量”计算。
实施例1
在298K和氩气保护氛围下,将1.0克2,6-二氨基吡啶和1.3克2,6-二醛基吡啶溶于60ml邻氯二苯和二甲基亚砜的混合溶剂中(邻氯二苯:二甲基亚砜=1:2),向上述溶剂中加入15ml浓度为6mol/L的乙酸水溶液,搅拌0.5小时。将搅拌好的溶液移至水热高压釜中,于393K和氩气保护氛围下溶剂热法聚合24h。待上述聚合后冷却至室温,333K温度条件下真空抽除溶剂,即得到含氮多孔有机聚合物。在298K和氩气保护氛围下,称取0.0203克醋酸钯溶于40ml四氢呋喃溶剂中,加入1.0克上述制备的含氮多孔有机聚合物,搅拌24小时。随后,333K温度条件下真空抽除溶剂,即获得由有机配体聚合物负载金属组分的固体多相催化剂。所获得的固体多相催化剂Pd负载量为1%,比表面积为597.8m2/g,孔容为0.336cm3/g,孔径分布主要分布在1-5nm。
将上述制备的固体多相催化剂加入到滴流床反应器中,通入CO2和H2混合气(CO2:H2=1:1),有机胺吗啉原料经高压计量泵泵入反应器中开始反应,吗啉和CO2制甲酰胺反应温度100℃,反应压力6MPa,吗啉液时空速0.1h-1,CO2/吗啉摩尔比50。液体产物N-甲酰吗啉收集于冷阱收集罐内。液体产物使用配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析,采用甲苯作内标。反应尾气使用配有Porapak-QS柱和TCD检测器的HP-7890N气相色谱进行在线分析。本发明的一种连续进行的有机胺和CO2制甲酰胺反应的反应工艺流程见图1。反应评价结果见表1。
实施例2
催化剂的制备过程参见实施例1,除了在催化剂制备中采用0.0克0.0261克三水合三氯化钌替代0.0203克醋酸钯,催化剂制备其他过程与实施例1相同。
催化剂评价反应工艺过程与实施例1相同,反应评价结果见表1。
实施例3
催化剂的制备过程与实施例1相同。
将上述制备的固体多相催化剂加入到滴流床反应器中,通入CO2和H2混合气(CO2:H2=1:1),有机胺吗啉原料经高压计量泵泵入反应器中开始反应,吗啉和CO2制甲酰胺反应温度120℃,反应压力8MPa,吗啉液时空速0.15h-1,CO2/吗啉摩尔比75。液体产物N-甲酰吗啉收集于冷阱收集罐内。液体产物使用配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析,采用甲苯作内标。反应尾气使用配有Porapak-QS柱和TCD检测器的HP-7890N气相色谱进行在线分析,反应评价结果见表1。
实施例4
催化剂的制备过程与实施例1相同。
将上述制备的固体多相催化剂加入到滴流床反应器中,通入CO2和H2混合气(CO2:H2=1:1),有机胺吗啉原料经高压计量泵泵入反应器中开始反应,吗啉和CO2制甲酰胺反应温度140℃,反应压力8MPa,吗啉液时空速0.2h-1,CO2/吗啉摩尔比75。液体产物N-甲酰吗啉收集于冷阱收集罐内。液体产物使用配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析,采用甲苯作内标。反应尾气使用配有Porapak-QS柱和TCD检测器的HP-7890N气相色谱进行在线分析,反应评价结果见表1。
实施例5
催化剂的制备过程与实施例1相同。
将上述制备的固体多相催化剂加入到滴流床反应器中,通入CO2和H2混合气(CO2:H2=1:1),六亚甲基亚胺原料经高压计量泵泵入反应器中开始反应,六亚甲基亚胺和CO2制甲酰胺反应温度120℃,反应压力6MPa,六亚甲基亚胺液时空速0.1h-1,CO2/六亚甲基亚胺摩尔比50。液体产物收集于冷阱收集罐内。液体产物使用配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析,采用甲苯作内标。反应尾气使用配有Porapak-QS柱和TCD检测器的HP-7890N气相色谱进行在线分析,反应评价结果见表1。
实施例6
催化剂的制备过程与实施例1相同。
将上述制备的固体多相催化剂加入到滴流床反应器中,通入CO2和H2混合气(CO2:H2=1:1),四氢吡咯原料经高压计量泵泵入反应器中开始反应,四氢吡咯和CO2制甲酰胺反应温度120℃,反应压力6MPa,四氢吡咯液时空速0.1h-1,CO2/四氢吡咯摩尔比50。液体产物收集于冷阱收集罐内。液体产物使用配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析,采用甲苯作内标。反应尾气使用配有Porapak-QS柱和TCD检测器的HP-7890N气相色谱进行在线分析,反应评价结果见表1。
实施例7
催化剂的制备过程与实施例1相同。
将上述制备的固体多相催化剂加入到滴流床反应器中,通入CO2和H2混合气(CO2:H2=1:1),β-苯乙胺原料经高压计量泵泵入反应器中开始反应,β-苯乙胺和CO2制甲酰胺反应温度120℃,反应压力6MPa,β-苯乙胺液时空速0.1h-1,CO2/β-苯乙胺摩尔比50。液体产物收集于冷阱收集罐内。液体产物使用配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析,采用甲苯作内标。反应尾气使用配有Porapak-QS柱和TCD检测器的HP-7890N气相色谱进行在线分析,反应评价结果见表1。
实施例8
催化剂的制备过程与实施例1相同。
将上述制备的固体多相催化剂加入到滴流床反应器中,通入CO2和H2混合气(CO2:H2=1:1),N-甲基正戊胺原料经高压计量泵泵入反应器中开始反应,N-甲基正戊胺和CO2制甲酰胺反应温度120℃,反应压力8MPa,N-甲基正戊胺液时空速0.1h-1,CO2/N-甲基正戊胺摩尔比50。液体产物收集于冷阱收集罐内。液体产物使用配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析,采用甲苯作内标。反应尾气使用配有Porapak-QS柱和TCD检测器的HP-7890N气相色谱进行在线分析,反应评价结果见表1。
实施例9
催化剂的制备过程与实施例1相同。
将上述实施例1制备的固体多相催化剂0.093克装入高压釜式反应器中,依次加入1mmol吗啉和4ml溶剂1,3-二甲基-2-咪唑啉酮,密闭反应釜,充入CO2/H2混合气(CO2:H2=1:1),高压釜系统压力升至6MPa,由温度控制仪控制温度缓慢升至100℃,反应24h。反应结束后,将反应釜冷却至室温,缓慢放出过量的反应气,过滤分离出催化剂,将所得的产品加入甲苯作为内标,进入配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析,反应评价结果见表1。
实施例10
催化剂的制备过程与实施例1相同。
将上述实施例1制备的固体多相催化剂0.0186克装入高压釜式反应器中,依次加入4mmol吗啉和4ml溶剂1,3-二甲基-2-咪唑啉酮,密闭反应釜,充入CO2/H2混合气(CO2:H2=1:1),高压釜系统压力升至8MPa,由温度控制仪控制温度缓慢升至120℃,反应48h。反应结束后,将反应釜冷却至室温,缓慢放出过量的反应气,过滤分离出催化剂,将所得的产品加入甲苯作为内标,进入配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析,反应评价结果见表1。
表1有机胺和CO2制酰胺反应评价结果
以上已对本发明进行了详细描述,但本发明并不局限于本文所描述具体实施方式。本领域技术人员理解,在不背离本发明范围的情况下,可以作出其他更改和变形。本发明的范围由所附权利要求限定。
Claims (10)
1.一种有机胺和CO2制甲酰胺反应的方法,其特征在于:在氢气存在下,采用固体多相催化剂催化反应,所采用的固体多相催化剂由Pd和有机配体聚合物组成,所述有机配体聚合物是2,6-二氨基吡啶和2,6-二醛基吡啶经溶剂热聚合生成的聚合物,Pd与所述有机配体聚合物骨架中的N原子形成配位键,存在于有机配体聚合物载体上;
所述有机胺选自下述中的一种或二种以上: ,
其中R1和R2各自独立地分别选自C1-18烷基,m为1到6的整数,并且n为1到12的整数;
所述金属组分在所述固体多相催化剂总重量中占0.5-5.0%;
有机配体聚合物的溶剂热聚合过程:
a)在0-50℃,惰性气体气氛下,在有机溶剂中,加入2,6-二氨基吡啶和2,6-二醛基吡啶、再加入聚合催化剂,混合后,将混合物搅拌0.1~100小时;
b)将步骤a)制得的混合溶液转移至合成高压釜中,60-200℃,惰性气体气氛下,采用溶剂热聚合法,搅拌1~100小时进行聚合反应,得到一种含氮多孔有机聚合物;
c)将步骤b)得到的聚合物,在室温条件下真空抽除溶剂,即得到具有多级孔结构的含有裸露N原子的有机聚合物,即所述多相催化剂的载体;
步骤a)中所述的有机溶剂为苯、甲苯、四氢呋喃、甲醇、乙醇、二氯甲烷、二甲基亚砜、邻氯二苯或三氯甲烷中一种或两种以上;所述的聚合催化剂为甲酸,乙酸,丙酸,磷酸,硫酸或磷钨酸的一种或两种以上;
步骤a)中所述的2,6-二氨基吡啶和2,6-二醛基吡啶之和与聚合催化剂的摩尔比为300:1~10:1,聚合成有机聚合物前,2,6-二氨基吡啶在有机溶剂中的浓度范围为0.01-1000g/L;2,6-二氨基吡啶和2,6-二醛基吡啶的摩尔比为1:1。
2.根据权利要求1所述的方法,其特征在于,所述有机胺原料与所述CO2原料的摩尔比为1:1-1:300,所述CO2原料与所述H2原料的摩尔比为1:0.1-1:100。
3.根据权利要求1-2任一所述的方法,其特征在于,有机胺原料输送进入反应器,液时空速为0.01-10 h-1;CO2和H2混合气原料以气体形式直接进料,气体空速为500-20000 h-1。
4.根据权利要求1-2任一所述的方法,其特征在于,所述有机胺和CO2制甲酰胺反应的反应温度为333-573 K,反应压力为0.05-20 MPa。
5.根据权利要求4所述的方法,其特征在于,所述反应器是有机胺和CO2制甲酰胺反应以连续方式于滴流床或间歇方式于釜式反应器进行;
当所述反应器是滴流床时,所述有机胺和CO2制甲酰胺反应在所述固体多相催化剂上连续地进行,生成的液体产物持续流出所述反应器并通过产品收集罐在-20-25℃的温度进行收集;
当所述反应器是釜式反应器时,所述有机胺和CO2制甲酰胺反应间歇地进行,生成的液体产物经过过滤与所述固体多相催化剂分离获得,并且所得到的液体产物通过精馏或闪蒸进一步处理而获得高纯度的甲酰胺类产品。
6.根据权利要求1所述的方法,其特征在于,
步骤a)在20-50℃,惰性气体气氛下,在有机溶剂中,加入2,6-二氨基吡啶和2,6-二醛基吡啶、再加入聚合催化剂,混合后,将混合物搅拌0.1~1小时;
步骤b)将步骤a)制得的混合溶液转移至合成高压釜中, 100-180℃,惰性气体气氛下,采用溶剂热聚合法,搅拌6-48小时进行聚合反应,得到一种含氮多孔有机聚合物;
步骤a)中所述的2,6-二氨基吡啶和2,6-二醛基吡啶之和与聚合催化剂的摩尔比为100:1-10:1,聚合成有机聚合物前,2,6-二氨基吡啶在有机溶剂中的浓度范围为10-200 g/L。
7.根据权利要求1所述的方法,其特征在于,所述有机胺原料与所述CO2原料的摩尔比为1:10-1:200,所述CO2原料与所述H2原料的摩尔比为1:0.5-1:10。
8.根据权利要求1所述的方法,其特征在于,有机胺原料输送进入反应器,液时空速为0.5-5 h-1;CO2和H2混合气原料以气体形式直接进料,气体空速为1000-8000 h-1。
9.根据权利要求1所述的方法,其特征在于,所述有机胺和CO2制甲酰胺反应的反应温度为353-473 K,反应压力为4-10 MPa。
10.根据权利要求1所述的方法,其特征在于,所述有机配体聚合物的比表面积为100-2000 m2/g,孔容为0.1-2.0cm3/g,孔径分布在0.1-200.0nm。
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