CN116283704A - Continuous preparation method of N-methylpyrrolidone - Google Patents
Continuous preparation method of N-methylpyrrolidone Download PDFInfo
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 72
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 70
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 4
- 150000002596 lactones Chemical class 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract 1
- 230000008569 process Effects 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000007036 catalytic synthesis reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
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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
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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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
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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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
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
本发明属于化工技术领域，公开了一种连续化的N‑甲基吡咯烷酮的制备方法，包括：将原料投入第一混合器中混合后，经换热器进入装填有平衡催化剂的反应I塔；生成的一甲胺、二甲胺、三甲胺从塔釜连续流入精馏I塔，脱出系统中未反应的氨，氨经精馏I塔塔顶以第一轻组分脱出，塔底馏出物为第一重组分，流入反应II塔，反应II塔中二甲胺、三甲胺发生水解反应，水解生成一甲胺；然后流入第二混合器中，与第二混合器中的γ‑丁内酯混合后流入反应III塔进行N‑甲基吡咯烷酮合成反应；待反应完成后进入精馏II塔精馏，塔釜得到第二重组分N‑甲基吡咯烷酮粗品进入精馏III塔中进一步提纯，塔顶第三轻组分为N‑甲基吡咯烷酮。
The invention belongs to the technical field of chemical industry, and discloses a continuous preparation method of N-methylpyrrolidone, comprising: putting raw materials into a first mixer for mixing, and then entering a reaction tower filled with an equilibrium catalyst through a heat exchanger; The generated monomethylamine, dimethylamine and trimethylamine continuously flow into the rectification I tower from the tower kettle to remove the unreacted ammonia in the system. The product is the first heavy component, which flows into the reaction II tower, where dimethylamine and trimethylamine undergo a hydrolysis reaction in the reaction II tower, and the hydrolysis generates monomethylamine; then flows into the second mixer, and the γ-butylene in the second mixer After the lactone is mixed, it flows into the reaction tower III to carry out the synthesis reaction of N-methylpyrrolidone; after the reaction is completed, it enters the rectification II tower for rectification, and the second heavy component N-methylpyrrolidone crude product obtained in the tower reactor enters the rectification III tower for further purification , the third light component at the top of the tower is N-methylpyrrolidone.
Description
技术领域technical field
本发明属于化工技术领域，涉及一种连续化的N-甲基吡咯烷酮的制备方法。The invention belongs to the technical field of chemical industry and relates to a continuous preparation method of N-methylpyrrolidone.
背景技术Background technique
N-甲基吡咯烷酮是一种选择性强和稳定性好的极性溶剂，广泛用于芳烃抽提、乙炔纯化、润滑油精制等，是丁二烯、异戊二烯的萃取剂，在半导体行业可用于精密仪器、线路板的清洗，也是锂离子电池的电极辅助材料。现有N-甲基吡咯烷酮的工业化生产方法主要分为三种合成路线，一是以γ-丁内酯和单甲基胺(一甲胺)为起始原料的无催化合成工艺，二是以γ-丁内酯和混合胺为起始原料的无催化合成工艺，三是以γ-丁内酯和单甲基胺为原料的催化合成和以1,4-丁二醇催化脱氢-胺化合成N-甲基吡咯烷酮的催化类合成工艺。N-Methylpyrrolidone is a polar solvent with strong selectivity and good stability. It is widely used in aromatic hydrocarbon extraction, acetylene purification, lubricating oil refinement, etc. It is an extraction agent for butadiene and isoprene. It is used in semiconductors. It can be used in the cleaning of precision instruments and circuit boards in the industry, and it is also an electrode auxiliary material for lithium-ion batteries. The industrialized production method of existing N-methylpyrrolidone mainly is divided into three kinds of synthetic routes, and the one is the non-catalyzed synthetic technique that is starting raw material with gamma-butyrolactone and monomethylamine (monomethylamine), the 2nd is with The non-catalytic synthesis process of γ-butyrolactone and mixed amines as starting materials, the third is the catalytic synthesis of γ-butyrolactone and monomethylamine as raw materials and the catalytic dehydrogenation of 1,4-butanediol-amine A catalytic synthesis process for the synthesis of N-methylpyrrolidone.
上述方法一虽然能使产品精制纯化简单，但该工艺路线所用原料单甲基胺的获得需要胺分离装置(混合甲胺需要五塔分离，分别为脱氨、萃取、脱水、分离、环保处理)，导致投资和运行成本增加，工业化生产导致收益减少；上述方法二采用混胺，无需混合胺分离装置，投资低、消耗低，但是二甲胺和三甲胺的占比太大，降低了γ-丁内酯的转化率，合成效率低；上述方法三中多需要加入金属氧化物催化剂使γ-丁内酯直接引入单甲基胺进行脱水反应生成N-甲基吡咯烷酮，舍去纯化γ-丁内酯的过程，易于分离和纯化，且反应中的中间产物易于分离，但是催化剂使用和回收成本较高，此外，其他脱氢催化剂如Cr催化剂虽然能提高N-甲基吡咯烷酮产率，但是会对环境和人体造成较大的危害，废水处理成本高。Although the above method 1 can make the product refining and purification simple, the acquisition of the raw material monomethylamine used in this process route requires an amine separation device (mixing methylamine requires five towers for separation, respectively deamination, extraction, dehydration, separation, and environmental protection treatment) , leading to an increase in investment and operating costs, and a reduction in income due to industrial production; the second method above uses mixed amines without a mixed amine separation device, which has low investment and low consumption, but the proportion of dimethylamine and trimethylamine is too large, which reduces the γ- The conversion rate of butyrolactone is low in synthesis efficiency; in the above method three, it is necessary to add a metal oxide catalyst to directly introduce γ-butyrolactone into monomethylamine for dehydration reaction to generate N-methylpyrrolidone, and the purification of γ-butyrolactone is omitted. The process of lactone is easy to separate and purify, and the intermediate product in the reaction is easy to separate, but catalyst use and recovery cost are higher, in addition, although other dehydrogenation catalysts such as Cr catalyst can improve N-methylpyrrolidone productive rate, but will It causes great harm to the environment and human body, and the cost of wastewater treatment is high.
发明内容Contents of the invention
本发明的目的是针对现有技术存在的上述问题，提出了一种环保、程序简洁、高产率、节能的连续化的N-甲基吡咯烷酮的制备方法。The purpose of the present invention is to solve the above-mentioned problems in the prior art, and propose a continuous N-methylpyrrolidone preparation method with environmental protection, simple procedure, high yield and energy saving.
本发明的目的可通过下列技术方案来实现：The purpose of the present invention can be achieved through the following technical solutions:
一种连续化的N-甲基吡咯烷酮的制备方法，所述制备方法包括：A preparation method of continuous N-methylpyrrolidone, the preparation method comprising:
将原料(甲醇、液氨)投入第一混合器中混合后，经换热器进入装填有平衡催化剂的反应I塔；生成的一甲胺(MMA)、二甲胺(DMA)、三甲胺(TMA)从塔釜连续流入精馏I塔，脱出系统中未反应的氨，氨经精馏I塔塔顶以第一轻组分脱出，塔底馏出物为第一重组分，流入反应II塔，反应II塔中二甲胺、三甲胺发生水解反应，水解生成一甲胺；然后流入第二混合器中，与第二混合器中的γ-丁内酯(GBL)混合后流入反应III塔进行N-甲基吡咯烷酮(NMP)合成反应；待反应完成后进入精馏II塔精馏，塔釜得到第二重组分N-甲基吡咯烷酮(NMP)粗品进入精馏III塔中进一步提纯，塔顶第三轻组分为N-甲基吡咯烷酮(NMP)。After the raw materials (methanol, liquid ammonia) are dropped into the first mixer and mixed, they enter the reaction I tower filled with an equilibrium catalyst through a heat exchanger; the monomethylamine (MMA), dimethylamine (DMA) and trimethylamine ( TMA) continuously flows into the rectification I tower from the bottom of the tower to remove the unreacted ammonia in the system. The ammonia is removed from the top of the rectification I tower as the first light component, and the distillate at the bottom of the tower is the first heavy component, which flows into the reaction II Tower, reaction II In the tower, dimethylamine and trimethylamine undergo hydrolysis reaction, and hydrolysis generates monomethylamine; then flow into the second mixer, mix with γ-butyrolactone (GBL) in the second mixer and flow into reaction III The tower carries out the synthetic reaction of N-methylpyrrolidone (NMP); after the reaction is completed, it enters the rectification II tower for rectification, and the second heavy component N-methylpyrrolidone (NMP) crude product obtained in the tower reactor enters the rectification III tower for further purification. The third light component at the top of the tower is N-methylpyrrolidone (NMP).
本申请对现有的N-甲基吡咯烷酮制备方法进行改进，将生成的混合甲胺中的二甲胺、三甲胺先转化为一甲胺，再与γ-丁内酯反应，提高N-甲基吡咯烷酮的产率，同时避免甲胺的单独分离程序；相比于直接采用一甲胺溶液，降低原料成本及处理成本；相比于采用混合甲胺直接与γ-丁内酯反应，能更好地提高GBL的转化率。The present application improves the existing preparation method of N-methylpyrrolidone, and converts dimethylamine and trimethylamine in the generated mixed methylamine into monomethylamine, and then reacts with γ-butyrolactone to increase N-methylpyrrolidone. The productive rate of pyrrolidone is improved, and the separate separation procedure of methylamine is avoided simultaneously; Compared with directly adopting monomethylamine solution, raw material cost and processing cost are reduced; Compared with adopting mixed methylamine to directly react with γ-butyrolactone, it can be more Improve the conversion rate of GBL well.
作为优选，所述第一混合器中原料包括甲醇、液氨。Preferably, the raw materials in the first mixer include methanol and liquid ammonia.
进一步优选，所述氨和甲醇的摩尔比，N/C为(1.0～5.0):1。More preferably, the molar ratio of ammonia to methanol, N/C, is (1.0-5.0):1.
更进一步优选，所述氨和甲醇的摩尔比，N/C为(1.5～3.5):1。More preferably, the molar ratio of ammonia to methanol, N/C, is (1.5-3.5):1.
作为优选，所述反应I塔的催化剂床层中装填的平衡催化剂为沸石分子筛。Preferably, the equilibrium catalyst packed in the catalyst bed of the reaction I tower is a zeolite molecular sieve.
进一步优选，所述反应I塔中平衡催化剂填充到反应器中部，装填量40％～60％。Further preferably, the equilibrium catalyst in the reaction I tower is filled in the middle of the reactor, and the filling amount is 40% to 60%.
作为优选，所述反应I塔中生成的一甲胺、二甲胺、三甲胺的含量比为(30～55):(25～35):(10～45)。Preferably, the content ratio of monomethylamine, dimethylamine and trimethylamine generated in the reaction I tower is (30-55):(25-35):(10-45).
作为优选，所述反应I塔中温度为415～430℃，反应空速为2～5h-1，压力为1.7～3.5MPa。Preferably, the temperature in the reaction I tower is 415-430°C, the reaction space velocity is 2-5h -1 , and the pressure is 1.7-3.5MPa.
作为优选，所述精馏I塔中第一重组分包括混合甲胺、水、少量未反应的甲醇。As a preference, the first heavy component in the rectifying column I includes mixed methylamine, water, and a small amount of unreacted methanol.
作为优选，所述精馏I塔塔顶出口温度为30～50℃，绝对压力为1～3MPa。Preferably, the outlet temperature at the top of the rectification I column is 30-50° C., and the absolute pressure is 1-3 MPa.
作为优选，所述反应后，反应II塔中二甲胺的含量为0～2wt％，三甲胺的含量为0～4wt％，水含量为30～50％。Preferably, after the reaction, the content of dimethylamine in the reaction II tower is 0-2wt%, the content of trimethylamine is 0-4wt%, and the water content is 30-50%.
作为优选，所述反应II塔的温度为220～300℃，时间为4～8h。Preferably, the temperature of the reaction II tower is 220-300° C., and the time is 4-8 hours.
作为优选，所述反应II塔中水的加入量为第一重组分的35～55％。As a preference, the amount of water added in the reaction II tower is 35-55% of the first heavy component.
作为优选，所述第二混合器中的一甲胺、γ-丁内酯的质量比为(1～3)：1。Preferably, the mass ratio of monomethylamine and γ-butyrolactone in the second mixer is (1-3):1.
作为优选，所述反应III塔温度为250～300℃，压力为6～14Mpa。Preferably, the temperature of the reaction III tower is 250-300°C, and the pressure is 6-14Mpa.
作为优选，所述精馏II塔中塔顶采出第二轻组分，包括未反应的一甲胺、二甲胺、三甲胺，和反应产生的水、甲醇，套回反应II塔中，继续进行水解反应。As preferably, the second light component is extracted from the top of the rectification II tower, including unreacted monomethylamine, dimethylamine, trimethylamine, and water and methanol produced by the reaction, which are put back into the reaction II tower, The hydrolysis reaction is continued.
作为优选，所述精馏II塔的压力为常压，塔顶温度为40～130℃，塔釜温度为120～170℃。Preferably, the pressure of the rectification II column is normal pressure, the temperature at the top of the column is 40-130°C, and the temperature at the bottom of the column is 120-170°C.
进一步优选，所述精馏II塔中回流时间为0.1～2h。Further preferably, the reflux time in the rectification II column is 0.1-2 hours.
作为优选，所述精馏III塔的压力为减压，高真空度10mmHg；塔顶温度为80～84℃，塔釜温度为100～160℃。Preferably, the pressure of the rectification III tower is reduced pressure, and the high vacuum degree is 10mmHg; the temperature at the top of the tower is 80-84°C, and the temperature at the bottom of the tower is 100-160°C.
进一步优选，所述精馏III塔中塔釜重组分做废液处理。Further preferably, the heavy components in the bottom of the rectification column III are treated as waste liquid.
作为优选，所述整个过程的反应停留时间为4～16h。Preferably, the reaction residence time of the whole process is 4-16h.
进一步优选，所述整个过程的反应停留时间为5～10h。Further preferably, the reaction residence time of the whole process is 5-10 h.
作为优选，所述N-甲基吡咯烷酮(NMP)的收率为99.6～99.9％。Preferably, the yield of N-methylpyrrolidone (NMP) is 99.6-99.9%.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、本发明的连续化的N-甲基吡咯烷酮的制备方法中减少低转化率的二甲胺(DMA)、三甲胺(TMA)参与NMP合成，提升γ-丁内酯的转化率，降低生产成本，提高综合效益。1, in the preparation method of the continuous N-methylpyrrolidone of the present invention, reduce the dimethylamine (DMA) of low transformation rate, trimethylamine (TMA) to participate in NMP synthesis, promote the conversion rate of γ-butyrolactone, reduce production cost and improve overall benefits.
2、本发明的连续化的N-甲基吡咯烷酮的制备方法中无需单独的分离氨的精馏过程，减少了分离氨的精馏成本，且将胺化反应得到的混甲胺直接进行水解反应，程序节约。2. In the continuous preparation method of N-methylpyrrolidone of the present invention, there is no need for a separate rectification process for separating ammonia, which reduces the cost of rectification for separating ammonia, and the mixed methylamine obtained by the amination reaction is directly hydrolyzed , program savings.
3、本发明的连续化的N-甲基吡咯烷酮的制备方法中调整精馏II塔中二甲胺(DMA)、三甲胺(TMA)至反应II塔的的回流比，降低混合胺分离成本，提高γ-丁内酯转化率，降低工艺能耗。3. In the preparation method of the continuous N-methylpyrrolidone of the present invention, adjust the reflux ratio of dimethylamine (DMA) and trimethylamine (TMA) in the rectification II tower to the reaction II tower to reduce the separation cost of mixed amines, Improve the conversion rate of γ-butyrolactone and reduce process energy consumption.
4、本发明的连续化的N-甲基吡咯烷酮的制备方法为连续化生产，避免传统间歇生产反应周期长等问题，使得反应过程更加平稳、安全。4. The preparation method of the continuous N-methylpyrrolidone of the present invention is continuous production, which avoids problems such as long reaction period of traditional intermittent production, and makes the reaction process more stable and safe.
5、本发明的连续化的N-甲基吡咯烷酮的制备方法更加易于实现密闭化、自动化，减少人工成本，提高反应收率、提升产品质量。5. The continuous N-methylpyrrolidone preparation method of the present invention is easier to realize sealing and automation, reduces labor costs, improves reaction yield, and improves product quality.
附图说明Description of drawings
图1为本发明的连续化的N-甲基吡咯烷酮的制备工艺流程图。Fig. 1 is the process flow diagram for the preparation of continuous N-methylpyrrolidone of the present invention.
1、第一混合器，2、反应I塔，3、精馏I塔，4、反应II塔，5、第二混合器，6、反应III塔，7、精馏II塔，8、精馏III塔，9、换热器，10、进料泵，11、冷凝器，12、储罐；A、甲醇，B、液氨，C、一甲胺，D、二甲胺，E、三甲胺，F、水，G、γ-丁内酯，H、N-甲基吡咯烷酮粗品，I、N-甲基吡咯烷酮，J、废液。1. First mixer, 2. Reaction I tower, 3. Rectification I tower, 4. Reaction II tower, 5. Second mixer, 6. Reaction III tower, 7. Rectification II tower, 8. Rectification III tower, 9, heat exchanger, 10, feed pump, 11, condenser, 12, storage tank; A, methanol, B, liquid ammonia, C, monomethylamine, D, dimethylamine, E, trimethylamine , F, water, G, γ-butyrolactone, H, crude N-methylpyrrolidone, I, N-methylpyrrolidone, J, waste liquid.
具体实施方式Detailed ways
以下是本发明的具体实施例，对本发明的技术方案作进一步的描述，但本发明并不限于这些实施例。The following are specific examples of the present invention to further describe the technical solution of the present invention, but the present invention is not limited to these examples.
本发明的连续化的N-甲基吡咯烷酮的工艺流程图如图1所示，具体包括：The process flow chart of the continuous N-methylpyrrolidone of the present invention is as shown in Figure 1, specifically comprises:
将N/C摩尔比为(1.5～3.5):1的甲醇A、液氨B投入第一混合器1中混合后，经换热器9进入装填有平衡催化剂(沸石分子筛)的反应I塔2；反应I塔2中温度为415～430℃，反应时间0.5h，压力为1.7～3.5Mpa，空速为2～5h-1；生成的一甲胺(MMA)C、二甲胺(DMA)D、三甲胺(TMA)E从塔釜经进料泵10连续流入精馏I塔3。Put methanol A and liquefied ammonia B with an N/C molar ratio of (1.5-3.5):1 into the first mixer 1 for mixing, and then enter the reaction tower 2 filled with an equilibrium catalyst (zeolite molecular sieve) through a heat exchanger 9 ; The temperature in the reaction I tower 2 is 415～430 ℃, the reaction time is 0.5h, the pressure is 1.7～3.5Mpa, and the space velocity is 2～5h −1 ; the monomethylamine (MMA) C and dimethylamine (DMA) generated D, trimethylamine (TMA) E continuously flows into the rectifying tower 3 through the
包括如下反应方程式：Include the following reaction equations:
精馏I塔3反应后脱出系统中未反应的氨B，氨B经精馏I塔3塔顶以第一轻组分脱出，塔顶温度为30～50℃，绝对压力为1～3MPa，塔顶组分经冷凝器11冷却，液氨B回到混合器1中，冷凝后的其他组分储存在储罐12中，返回精馏I塔3；第一重组分(一甲胺C、二甲胺D、三甲胺E、水F、少量未反应的甲醇A)作为塔底馏出物经进料泵10进入反应II塔4。The unreacted ammonia B in the system is released after the reaction in the rectification I tower 3, and the ammonia B is released as the first light component through the top of the rectification I tower 3. Tower top component is cooled by
反应II塔4中加水F，与二甲胺D、三甲胺E发生水解反应，温度为220～300℃，常压条件下水解生成转化率较高的一甲胺C，其中第一重组分、水F的质量比为1:(0.35～0.55)，反应后的混合胺溶液中二甲胺的含量为0～7wt％，三甲胺的含量为0～6wt％，水含量为30～50％。Water F is added to Reaction II tower 4 to undergo hydrolysis reaction with dimethylamine D and trimethylamine E at a temperature of 220-300°C. Under normal pressure, the hydrolysis produces monomethylamine C with a relatively high conversion rate, wherein the first heavy component, The mass ratio of water F is 1:(0.35-0.55), the content of dimethylamine in the mixed amine solution after reaction is 0-7wt%, the content of trimethylamine is 0-6wt%, and the water content is 30-50%.
包括如下反应方程式：Include the following reaction equations:
混合液经进料泵10流入第二混合器5中，与第二混合器5中的γ-丁内酯(GBL)G混合均匀，一甲胺C、γ-丁内酯(GBL)G的质量比为(1-3):1；继续经进料泵10流入反应III塔6进行N-甲基吡咯烷酮(NMP)合成反应，温度为250～300℃，时间为1～6小时，压力为5.0～10.0Mpa。The mixed solution flows into the second mixer 5 through the
待反应完成后经进料泵10进入精馏II塔7进行精馏，塔顶温度为40～130℃，时间为1～3h，压力为常压；塔顶第二轻组分包括一甲胺C、二甲胺D、三甲胺E、水F、反应生成的甲醇A，回到反应II塔4重新进入反应系统，回流时间为0.1～2h；精馏II塔7塔釜温度为120～170℃，塔釜得到第二重组分N-甲基吡咯烷酮(NMP)粗品H。After the reaction is completed, enter the rectification II tower 7 through the
包括如下反应方程式：Include the following reaction equations:
N-甲基吡咯烷酮(NMP)粗品H经进料泵10进入精馏III塔8中进一步提纯，精馏III塔8中压力10mmHg，塔顶温度为80～84℃，塔顶第三轻组分为N-甲基吡咯烷酮(NMP)I，塔釜温度为100～160℃，塔釜第三重组分为废液J。The crude product H of N-methylpyrrolidone (NMP) enters the rectification III tower 8 through the
实施例1Example 1
将N/C摩尔比为3:1的甲醇A、液氨B投入第一混合器1中混合后，经换热器9进入装填有平衡催化剂(沸石分子筛HZSM-5)的反应I塔2；反应I塔2中温度为420℃，停留时间为0.5h，压力为2.3Mpa，反应空速为2.3h-1；生成的一甲胺(MMA)C、二甲胺(DMA)D、三甲胺(TMA)E从塔釜经进料泵10连续流入精馏I塔3。After methanol A and liquefied ammonia B with an N/C molar ratio of 3:1 are put into the first mixer 1 and mixed, they enter the reaction tower 2 filled with an equilibrium catalyst (zeolite molecular sieve HZSM-5) through a heat exchanger 9; The temperature in reaction I tower 2 is 420°C, the residence time is 0.5h, the pressure is 2.3Mpa, and the reaction space velocity is 2.3h -1 ; the generated monomethylamine (MMA) C, dimethylamine (DMA) D, trimethylamine (TMA)E continuously flows into the rectification I tower 3 from the tower kettle through the
精馏I塔3反应后脱出系统中未反应的氨B，氨B经精馏I塔3塔顶以第一轻组分脱出，塔顶温度为40℃，绝对压力为2MPa，塔顶组分经冷凝器11冷却，液氨B回到混合器1中，冷凝后的其他组分储存在储罐12中，返回精馏I塔3；第一重组分(一甲胺C、二甲胺D、三甲胺E、水F、少量未反应的甲醇A)作为塔底馏出物经进料泵10进入反应II塔4。The unreacted ammonia B in the system is released after the reaction in the rectification I tower 3, and the ammonia B is released as the first light component through the top of the rectification I tower 3. The temperature at the top of the tower is 40°C, and the absolute pressure is 2MPa. Cooled by
反应II塔4中加水F，与二甲胺D、三甲胺E发生水解反应，温度为270℃，时间为6h，常压下水解生成转化率较高的一甲胺C，其中第一重组分、水F的质量比为1:0.4，反应后的混合液中一甲胺C、二甲胺D、三甲胺E质量比为97:0.9:2.1。Add water F to reaction II tower 4, and undergo hydrolysis reaction with dimethylamine D and trimethylamine E. The temperature is 270°C, the time is 6 hours, and hydrolysis under normal pressure produces monomethylamine C with a higher conversion rate. The first heavy component , The mass ratio of water F is 1:0.4, and the mass ratio of monomethylamine C, dimethylamine D, and trimethylamine E in the reacted mixed solution is 97:0.9:2.1.
混合液经进料泵10流入第二混合器5中，与第二混合器5中的γ-丁内酯(GBL)G混合均匀，一甲胺C、γ-丁内酯(GBL)G的摩尔比为1.6:1；继续经进料泵10流入反应III塔6进行N-甲基吡咯烷酮(NMP)合成反应，温度为270℃，时间为3小时，压力为7Mpa。The mixed solution flows into the second mixer 5 through the
待反应完成后经进料泵10进入精馏II塔7进行精馏，塔顶温度为90℃，压力为常压；塔顶第二轻组分包括一甲胺C、二甲胺D、三甲胺E、水F、反应生成的甲醇A，回流时间为0.5h后开始套用第二轻组分到反应II塔4重新进入反应系统，精馏II塔7塔釜温度为150℃，塔釜得到第二重组分N-甲基吡咯烷酮(NMP)粗品H。After the reaction is completed, enter the rectification II tower 7 through the
N-甲基吡咯烷酮(NMP)粗品H经进料泵10进入精馏III塔8中进一步提纯，精馏III塔8中压力10mmHg，塔顶温度为82℃，塔顶第三轻组分为N-甲基吡咯烷酮(NMP)I，塔釜温度为140℃，塔釜第三重组分为废液J。N-methylpyrrolidone (NMP) crude product H enters rectification III tower 8 through
N-甲基吡咯烷酮(NMP)I的纯度为99.99％，收率为99.9％。The purity of N-methylpyrrolidone (NMP) I was 99.99%, and the yield was 99.9%.
实施例2～47Examples 2-47
与实施例1相比，区别在于按照表1中的参数进行制备，具体收率见表1。Compared with Example 1, the difference is that the preparation is carried out according to the parameters in Table 1, and the specific yield is shown in Table 1.
对比例1Comparative example 1
与实施例1相比，区别在于直接将精馏I塔中得到的混合甲胺与γ-丁内酯混合后在反应III塔中进行反应，后续步骤相同。Compared with Example 1, the difference is that the mixed methylamine obtained in the rectification tower I is directly mixed with γ-butyrolactone and then reacted in the reaction tower III, and the subsequent steps are the same.
N-甲基吡咯烷酮(NMP)I的纯度为99.99％，收率为94.5％。The purity of N-methylpyrrolidone (NMP) I was 99.99%, and the yield was 94.5%.
对比例2Comparative example 2
与实施例1相比，区别在于采用常规的工艺制得混甲胺，一甲胺、二甲胺、三甲胺的含量比为27：23：50；将该混合甲胺直接与γ-丁内酯混合后在反应III塔中进行反应，后续步骤相同。Compared with Example 1, the difference is that mixed methylamine is prepared by conventional technology, and the content ratio of monomethylamine, dimethylamine and trimethylamine is 27:23:50; the mixed methylamine is directly mixed with γ-butyrol After the esters are mixed, the reaction is carried out in the reaction III tower, and the subsequent steps are the same.
N-甲基吡咯烷酮(NMP)I的纯度为99.99％，收率为93.1％。The purity of N-methylpyrrolidone (NMP) I was 99.99%, and the yield was 93.1%.
表1、制备过程参数及产品收率数据表Table 1. Preparation process parameters and product yield data table
综上所述，本发明的连续化的N-甲基吡咯烷酮的制备方法中减少低转化率的二甲胺(DMA)、三甲胺(TMA)参与NMP合成，提升γ-丁内酯的转化率，降低生产成本，提高综合效益。In summary, in the preparation method of continuous N-methylpyrrolidone of the present invention, dimethylamine (DMA) and trimethylamine (TMA) with low conversion rate are reduced to participate in NMP synthesis, and the conversion rate of gamma-butyrolactone is improved , reduce production costs and improve comprehensive benefits.
本文中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which the present invention belongs can make various modifications or supplements to the described specific embodiments or adopt similar methods to replace them, but they will not deviate from the spirit of the present invention or go beyond the definition of the appended claims range.
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| US6987191B1 (en) * | 1999-10-27 | 2006-01-17 | Basf Aktiengesellschaft | Process for the production of N-methyl pyrrolidone using gamma butyrolactone and mixed methylamines as starting materials |
| CN106278983A (en) * | 2015-06-05 | 2017-01-04 | 中国石化仪征化纤有限责任公司 | A kind of N-Methyl pyrrolidone continuous preparation method |
| JP2020083789A (en) * | 2018-11-19 | 2020-06-04 | 昭和電工株式会社 | Method for producing N-methyl cyclic amide |
| CN219631278U (en) * | 2023-01-17 | 2023-09-05 | 联盛化学(沧州)有限公司 | N-methyl pyrrolidone's reaction system |
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| US6987191B1 (en) * | 1999-10-27 | 2006-01-17 | Basf Aktiengesellschaft | Process for the production of N-methyl pyrrolidone using gamma butyrolactone and mixed methylamines as starting materials |
| CN106278983A (en) * | 2015-06-05 | 2017-01-04 | 中国石化仪征化纤有限责任公司 | A kind of N-Methyl pyrrolidone continuous preparation method |
| JP2020083789A (en) * | 2018-11-19 | 2020-06-04 | 昭和電工株式会社 | Method for producing N-methyl cyclic amide |
| CN219631278U (en) * | 2023-01-17 | 2023-09-05 | 联盛化学(沧州)有限公司 | N-methyl pyrrolidone's reaction system |
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