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WO2025027151A1 - Procédé discontinu pour la fabrication d'une solution de formaldéhyde méthanolique par dépolymérisation de paraformaldéhyde - Google Patents

Procédé discontinu pour la fabrication d'une solution de formaldéhyde méthanolique par dépolymérisation de paraformaldéhyde Download PDF

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Publication number
WO2025027151A1
WO2025027151A1 PCT/EP2024/071864 EP2024071864W WO2025027151A1 WO 2025027151 A1 WO2025027151 A1 WO 2025027151A1 EP 2024071864 W EP2024071864 W EP 2024071864W WO 2025027151 A1 WO2025027151 A1 WO 2025027151A1
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Prior art keywords
formaldehyde
bar
mixture
paraformaldehyde
methanol
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Inventor
Moritz BALKENHOHL
Eugen Risto
Joerg Pastre
Sven FUERSTENBERG
Stephanie JAEGLI
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/55—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of oligo- or polymeric oxo-compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings

Definitions

  • the invention concerns a batch process for the preparation of a methanolic formaldehyde solution by depolymerization of paraformaldehyde in the presence of methanol and water.
  • the invention further concerns a process for preparing N-methylmorpholine, a process for preparing N-methylmorpholine oxide and a process for preparing pentamethyl diethylenetriamine.
  • Formaldehyde is manufactured by subjecting methanol to selective oxidation on a large scale. It is available as aqueous solution, methanolic solution or paraformaldehyde. Since paraformaldehyde is a solid, it cannot be easily used in any continuous process. Aqueous and methanolic formaldehyde can be used in both batch and continuous processes. The usage of methanolic formaldehyde can have certain advantages over aqueous formaldehyde. For instance, it has been recently found that in the NMM production yellowing can be avoided when methanolic formaldehyde is used. Another advantage resides in the fact that the separation of methanol from the reaction product is less energy demanding than the separation of water.
  • Paraformaldehyde can be synthesized from an aqueous formaldehyde solution via polymerization of the formaldehyde. It typically forms as a white precipitate. Its chemical formula is OH(CH2O) n H with n typically being in the range from 8 to 100.
  • Formaldehyde is used for instance for the preparation of N-methylmorpholine (NMM) and pentamethyl diethylentriamine (PMDETA) by reductive amination of formaldehyde with morpholine (MO) and diethylentriamine (DETA), respectively, in the presence of hydrogen and a hydrogenation catalyst.
  • NMM and PMDETA are used as catalysts in polyurethane production. It was found that it is advantageous to employ formaldehyde as a methanolic formaldehyde solution.
  • CN 110627654 A teaches a batch process for the methylation of amines being selected from ethylenediamine, cyclohexylamine, aniline or benzylamine using paraformaldehyde.
  • CN 111675677 B teaches a batch process for the manufacture of N-methylmorpholine using paraformaldehyde but no metal catalyst or reducing agent.
  • CN 106957232 A teaches a batch process for the manufacture of an N-monomethylamine compound using paraformaldehyde.
  • an aqueous solution of formaldehyde is distilled to form formaldehyde vapor which contains water.
  • the formaldehyde vapor is mixed with alcohol vapor, for example methanol vapor, which absorbs the water and is condensed with it in the first stage, while part of the formaldehyde vapor is only later condensed with further methanol in a second stage to form a product which has a high formaldehyde concentration, namely from 70% or more.
  • alcohol vapor for example methanol vapor
  • the object is solved by a batch process for the preparation of a methanolic formaldehyde solution by depolymerization of paraformaldehyde in the presence of methanol and water, the process comprising the steps of:
  • step (b) subjecting the mixture obtained in step (a) to a first heating step, wherein the mixture is kept in a temperature range of from 50 to 90°C for a period of 5 to 300 minutes,
  • step (c) subjecting the mixture obtained in step (b) to a second heating step, wherein the mixture is kept in a temperature range of from 100 to 130 °C for a period of 0.1 to 48 hours.
  • the inventors have found that the application of the two heating steps (b) and (c) results in an improved process for the manufacture of a methanolic formaldehyde solution.
  • heating means the supply of thermal energy in the form of heat. For instance, one can supply so much heat, that the temperature of the mixture increases. One can also supply heat in an amount required to compensate the heat dissipated to the environment and/or to a respective condenser with which a suitable batch reactor is typically equipped.
  • step (b) keeping the mixture in a temperature range of from 50 to 90°C for a period of 5 to 300 minutes as per step (b) results in the formation of a solution comprising the hemiacetal of formaldehyde with methanol and/or higher polyoxymethylene homologues thereof, which are higher boiling compounds than methanol itself.
  • the depolymerization of paraformaldehyde is incomplete in this temperature range. Full depolymerization is achieved in the higher temperature range of from 100 to 130 °C according to step (c).
  • hemiacetal of formaldehyde and methanol
  • methanol evaporation is very much reduced in the higher temperature range.
  • hemiacetal formaldehyde and methanol
  • methanol is constantly evaporating. This requires a very high condenser load which is needed to ensure a significant amount of methanol (solvent) in the reactor.
  • a high condenser load means that a large amount of thermal energy is removed per unit of time and, thus, is energetically inefficient.
  • the mixture is first kept in a temperature range of from 50 to 90°C. It is believed that in such temperature range the hemiacetal formation and/or formation of higher polyoxymethylene homologues thereof occurs at a significant rate. To ensure that enough hemiacetal and/or higher polyoxymethylene homologues thereof are formed, the mixture needs to be kept in such temperature range for at least 5 minutes.
  • One way to realize step (b) is to directly heat the mixture to a specific temperature in the range of from 50 to 90°C (for instance 80°C) and keep it at that temperature for a certain period (for instance 150 minutes) in accordance with step (b).
  • Another way to realize step (b) is to gently heat the mixture so that temperature slowly rises.
  • heating can also be interrupted, although this is not preferred.
  • step (c) The above equally applies to step (c).
  • the mixture is stirred in step (b) as well as in step (c).
  • Steps (b) and (c) can be carried out for instance with an average heating rate of from 2 to 200 °C/h, preferably with an average heating rate of from 5 to 100 °C/h, more preferably with an average heating rate of from 10 to 50 °C/h
  • the absolute pressure is in general in the range of 0.5 to 20 bar, preferably 0.5 to 10 bar, more preferably 0.5 to 5 bar, particularly preferably 0.8 to 3 bar, especially 0.9 to 2 bar, for example 1 .0 to 1.5 bar.
  • the mixture provided in step (a) in general comprises 20 to 69 wt.-% paraformaldehyde, 30 to 69 wt.-% methanol, and 1 to 20 wt.-% water.
  • the mixture provided in step (a) comprises paraformaldehyde in the range of from 35 to 65 wt.-%, methanol in the range of from 30 to 45 wt.-% and water in the range of from 5 to 20 wt.-%.
  • the mixture provided in step (a) comprises paraformaldehyde in the range of from 40 to 60 wt.-%, methanol in the range of from 30 to 45 wt.-% and water in the range of from 5 to 15 wt.-%.
  • the mixture provided in step (a) in general exists at ambient temperature. This depends on the location of the respective production facility. Typically, it has a temperature in the range of from 1 to 49 °C, preferably from 5 to 45°C.
  • the temperature range according to step (b) is in general of from 60 to 90 °C, preferably 70 to 90 °C, more preferably 75 to 85 °C.
  • a higher temperature range is preferred because it provides for a higher formation rate of the hemiacetal and higher polyoxymethylene homologues thereof. As a result, the period in which such temperature range is realized can be shorter.
  • the period according to step (b) is in general 30 to 250 minutes, preferably 60 to 200 minutes, more preferably 90 to 200 minutes, even more preferably 120 to 200 minutes.
  • the temperature range according to step (c) is in general of from 110 to 130 °C, preferably 110 to 125°C, more preferably 110 to 120 °C.
  • the period according to step (c) is in general 0.5 to 36 hours, preferably 1 to 24 hours, more preferably 1 to 12 hours, even more preferably 2 to 12 hours.
  • the reaction is preferably performed in a reactor, typically a STR (stirred tank reactor, also referred to as agitated vessel). It is typically performed under air or under nitrogen atmosphere, wherein a nitrogen atmosphere is preferred.
  • the reactor is operated in a batch mode, meaning that all components of the mixture are added to the vessel and the agitation is started.
  • a respective stirrer having a suitable geometry to achieve thorough mixing can be easily selected by the person having ordinary skill in the art.
  • Such reactor is preferably equipped with a condenser.
  • a condenser is a device that is used to condense vapor into liquid using a cooling agent that may be selected from water, air or brine. Suitable condensers can be easily selected by the person having ordinary skill in the art.
  • the formaldehyde may exist in different forms.
  • a certain amount, in general the major part, of formaldehyde exists as a hemiacetal (resulting from formaldehyde and methanol also referred to as hemiformal or 1 -methoxy-methanol) or polyoxymethylene having the formula HO-[CH2O] n -CH3 with n being an integer typically in the range from 2 to 10.
  • the weight percentages (“wt.-%”) specified herein refer to the “theoretical” amount of formaldehyde, methanol, and water, thus, neglecting any potential reactions among formaldehyde, methanol, and water.
  • the methanolic formaldehyde solution obtained according to the present invention comprises formaldehyde in the range of from 20 to 69 wt.-%, methanol in the range of from 30 to 69 wt.-% and water in the range of from 1 to 20 wt.-%.
  • the wt.-% is based on the total mass of the methanolic formaldehyde solution.
  • the methanolic formaldehyde solution comprises formaldehyde in the range of from 35 to 65 wt.-%, methanol in the range of from 30 to 45 wt.-% and water in the range of from 5 to 20 wt.-%.
  • the methanolic formaldehyde solution comprises formaldehyde in the range of from 40 to 60 wt.-%, methanol in the range of from 30 to 45 wt.-% and water in the range of from 5 to 15 wt.-%.
  • the amount of formaldehyde, methanol, and water in the methanolic formaldehyde solution is > 90 wt.-%, preferably > 95 wt.-%, more preferably > 98 wt.-%, even more preferably > 99 wt.-%, particularly preferably > 99.5 wt.-%.
  • NMM N-methylmorpholine
  • NMMO N-methylmorpholine oxide
  • pentamethyl diethylentriamine pentamethyl diethylentriamine
  • the invention also relates to a process for the preparation of N-methylmorpholine (NMM) comprising the steps of
  • step (iii) subjecting formaldehyde provided in step (i) and morpholine provided in step (ii) to a continuous reductive amination in the presence of hydrogen and a heterogenous hydrogenation catalyst, which is immobilized in the reactor, to obtain N-methylmorpholine.
  • the methanolic formaldehyde solution fed to step (i) is prepared by the process of the invention as described above and comprises formaldehyde, methanol and water in the ranges indicated above.
  • the process is preferably carried out continuously.
  • heterogenous hydrogenation catalyst is used as a fixed bed catalyst.
  • This process for the manufacture of NMM is more efficient than a process using paraformaldehyde because the amination can be conducted continuously.
  • a respective process using paraformaldehyde in the amination cannot be operated continuously (because paraformaldehyde is a solid).
  • the amination requires a heterogeneous catalyst, the latter needs to be separat- ed which is technically and economically less efficient than using an immobilized catalyst as per step (iii).
  • the space-time yield of the continuous process is superior (i.e. higher) compared to the batch process.
  • methanol is separated from N-methylmorpholine obtained in step (iii) and recycled to step (a) of the methanolic formaldehyde production process according to the present invention.
  • the combination of the process for the manufacture of methanolic formaldehyde solution and the NMM production becomes even more efficient because the methanol can be continuously reused.
  • morpholine provided in step (ii) is prepared by reacting diethylene glycol and ammonia in the presence of hydrogen and a heterogeneous hydrogenation catalyst.
  • the preparation of morpholine from diethylene glycol and ammonia is described for instance in WO2011/067199 A1 , W02008/037587 A1 , WO 2008/037589 A1 and WO 2008/037590 A1 (all BASF).
  • the continuously fed formaldehyde solution is a methanolic formaldehyde solution prepared according to the invention.
  • the reaction temperature is in the range of from 30 to 300°C, preferably from 30 to 250°C, more preferably from 30 to 200°C.
  • the reaction temperature is even more preferably from 60 to 150°C, particularly preferably from 80 to 130°C, especially from 90 to 130°C.
  • the reaction pressure is usually in the range of from 50 to 300 bar, preferably from 50 to 250 bar, more preferably from 50 to 200 bar, even more preferably from 60 bar to 150 bar, particularly preferably from 80 to 150 bar, especially from 90 to 140 bar.
  • heterogeneous catalyst designates a solid catalyst, preferably in the form of particles, which is brought into contact with the liquid reaction mixture comprising the starting materials and any intermediates and NMM already obtained.
  • Any heterogeneous catalyst that has sufficient hydrogenation activity can be used for the manufacture of NMM in accordance with the present invention. It may be a supported or an unsupported catalyst. An unsupported catalyst is preferred.
  • the heterogeneous hydrogenation catalyst is devoid or substantially devoid of any palladium.
  • the amount of palladium is preferably less than 0.5 wt.-%, preferably less than 0.05 wt.-%, more preferably less than 0.01 wt.-%, based on the total weight of the heterogeneous hydrogenation catalyst.
  • the heterogeneous hydrogenation catalyst is installed in the reactor, preferably as fixed bed.
  • the heterogeneous hydrogenation catalyst may comprise cobalt.
  • it comprises cobalt and/or copper, more preferably cobalt, copper and/or manganese, even more preferably cobalt, copper, manganese and/or molybdenum, particularly preferably cobalt, copper, manganese, molybdenum, and/or phosphorus.
  • cobalt and/or copper more preferably cobalt, copper and/or manganese, even more preferably cobalt, copper, manganese and/or molybdenum, particularly preferably cobalt, copper, manganese, molybdenum, and/or phosphorus.
  • the heterogeneous hydrogenation catalyst can for instance be prepared by applying precipitation or impregnation methods. Suitable heterogeneous hydrogenation catalysts and respective methods for their production are for instance taught in EP 2043996 B1 , WO 2011/067200 A1 , WO 2011/067199 A1 and EP 2780109 B1 (all BASF).
  • the heterogeneous hydrogenation catalyst comprises
  • any “wt.-%” as specified herein with respect to the composition of the heterogeneous hydrogenation catalyst refers the heterogeneous hydrogenation catalyst after the last of any heat treatments (for instance calcination) and prior to its reduction with hydrogen.
  • the respective metals at least partially exist in an oxidized from. Nonetheless, the presence of a certain amounts of such metals in elementary form is not excluded. For instance, in the course of the preparation, one could, besides using respective metal nitrites, also apply certain amount(s) of respective metal(s) in elementary form. Usually, more than 90 wt.-%, preferably more than 95 wt.-%, more preferably more than 99 wt.-% (or even more than 99.5 wt.-%) of any respective metal exists in oxidized from. The phosphorus usually exists substantially in an oxidized form.
  • the heterogeneous hydrogenation catalyst preferably also contains oxygen.
  • the heterogeneous hydrogenation catalyst comprises oxygen and the cumulated amount of oxygen, cobalt, copper, manganese, molybdenum, phosphorus, and cobalt is > 80 wt.-%, preferably > 90 wt.-%, more preferably > 95 wt.-% even more preferably > 97 wt.-%, particularly preferably > 98 wt.-%, based on the total weight of the heterogenous hydrogenation catalyst.
  • the invention further relates to a process for preparing N-methylmorpholine oxide (NMMO), comprising the steps of:
  • step (ii) subjecting the N-methylmorpholine obtained in step (i) to an oxidation reaction to obtain N-methylmorpholine oxide.
  • Oxidation step (ii) comprises reacting N-methylmorpholine with a less than stoichiometric amount of aqueous hydrogen peroxide in an aqueous medium in the presence of carbon dioxide as promotor.
  • oxidation step (ii) comprises reacting N-methylmorpholine with a less than stoichiometric amount of aqueous hydrogen peroxide in an aqueous medium while imposing on the aqueous medium a vapor space having a carbon dioxide partial pressure p (CO2) of less than 0.75 bar absolute, preferably less than 0.20 bar absolute.
  • CO2 carbon dioxide partial pressure
  • the initial concentration of N-methylmorpholine in the aqueous medium is in the range of from 40 to 95 vol.-%, preferably 60 to 85 vol.-%. Any aqueous hydrogen peroxide can be used. In view of practical considerations, the concentration of hydrogen peroxide in the aqueous hydrogen peroxide that is added to the aqueous medium is in the range of from 10 to 70 wt.-%, preferably 29 to 51 wt.-%.
  • the process is preferably carried out continuously.
  • the invention further relates to a process for the preparation of pentamethyl diethylentriamine (PMDETA) comprising the steps of
  • step (ii) providing diethylentriamine, (iii) subjecting formaldehyde provided in step (i) and diethylentriamine (DETA) provided in step (ii) to reductive amination in the presence of hydrogen and a hydrogenation catalyst to obtain pentamethyl diethylentriamine.
  • DETA diethylentriamine
  • the methanolic formaldehyde solution fed to step (i) is prepared by the process of the invention as described above and comprises formaldehyde, methanol and water in the ranges indicated above.
  • the process is preferably carried out continuously.
  • heterogenous hydrogenation catalyst is used as a fixed bed catalyst.
  • This process for the manufacture of PM DETA is more efficient than a process using paraformaldehyde because the amination can be conducted continuously.
  • a respective process using paraformaldehyde in the amination cannot be operated continuously (because paraformaldehyde is a solid).
  • the amination requires a heterogeneous catalyst, the latter needs to be separated which is technically and economically less efficient than using an immobilized catalyst as per step (iii).
  • the space-time yield of the continuous process is superior (i.e. higher) compared to the batch process.
  • the molar ratio of formaldehyde to DETA is in the range of from 4.5:1 to ⁇ 5.9:1.
  • PMDETA is partially recycled to the reductive amination of DETA and formaldehyde.
  • the weight ratio of recycled PMDETA to the combined amount of DETA and methanolic formaldehyde solution being fed to the one or more reactor(s) is in the range of from 1 :1 to 10:1 , preferably from 2:1 to 8:1.
  • the reaction temperature is in general in the range of from 30 to 300 °C, preferably from 30 to 250 °C, more preferably from 30 to 200 °C, even more preferably from 60 to 150 °C, particularly preferably from 80 to 130 °C, especially from 90 to 130 °C.
  • the reaction pressure is in the range of from 50 to 300 bar, preferably from 50 to 250 bar, more preferably from 50 to 200 bar, even more preferably from 60 bar to 150 bar, particularly preferably from 80 to 150 bar, especially from 90 to 140 bar.
  • the heterogeneous hydrogenation catalyst preferably comprises cobalt and/or copper.
  • Preferred heterogeneous hydrogenation catalyst are those described above in connection with the preparation of N MM.
  • a particular preferred catalyst comprises 5 to 90 wt.-%, preferably 10 to 60 wt.-%, cobalt, 1 to 40 wt.-%, preferably 2 to 30 wt.-%, copper, 0.1 to 30 wt.-%, preferably 1 to 10 wt.-%, manganese, 0.1 to 30 wt.-%, preferably 1 to 10 wt.-%, molybdenum, and 0.05 to 30 wt.-%, preferably 0.1 to 5 wt.-%, phosphorus, based on the total weight of the heterogeneous hydration catalyst.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé discontinu pour la préparation d'une solution de formaldéhyde méthanolique par dépolymérisation de paraformaldéhyde en présence de méthanol et d'eau, le procédé comprenant les étapes consistant à : (a) fournir un mélange comprenant du paraformaldéhyde, de l'eau et du méthanol, (b) soumettre le mélange obtenu à l'étape (a) à une première étape de chauffage, le mélange étant maintenu dans une plage de température de 50 à 90°C pendant une période de 5 à 300 minutes, (c) soumettre le mélange obtenu à l'étape (b) à une seconde étape de chauffage, le mélange étant maintenu dans une plage de température de 100 à 130°C pendant une période de 0,1 à 48 heures.
PCT/EP2024/071864 2023-08-03 2024-08-01 Procédé discontinu pour la fabrication d'une solution de formaldéhyde méthanolique par dépolymérisation de paraformaldéhyde Pending WO2025027151A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23189532.7 2023-08-03
EP23189532 2023-08-03

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WO2025027151A1 true WO2025027151A1 (fr) 2025-02-06

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Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB737023A (en) 1952-03-18 1955-09-21 Celanese Corp Solutions containing available formaldehyde
US3210349A (en) * 1961-11-06 1965-10-05 Jefferson Chem Co Inc Methylation of primary and secondary amines using a small stoichiometric excess of formaldehyde and adding a small stoichiometric excess of formic acid last
GB1056589A (en) * 1965-10-19 1967-01-25 Wolfen Filmfab Veb Process for the production of monochlorodimethyl ether
US3629997A (en) 1970-05-08 1971-12-28 Borden Inc Process for producing methanol-formaldehyde solution of low-water content
DE2321101A1 (de) 1973-04-26 1974-11-14 Basf Ag Kobaltkatalysator
WO2008037590A1 (fr) 2006-09-28 2008-04-03 Basf Se Procédé pour la séparation continue par distillation de mélanges contenant de la morpholine, du mono-amino-diglycol, de l'ammoniac et de l'eau
WO2008037587A1 (fr) 2006-09-28 2008-04-03 Basf Se Procédé de séparation par distillation en continu de mélanges contenant de la morpholine (mo), du monoaminodiglycol (adg), de l'ammoniac et de l'eau
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CN101659618A (zh) * 2009-09-15 2010-03-03 烟台万华聚氨酯股份有限公司 一种五甲基二乙烯三胺的制备方法
WO2011067200A1 (fr) 2009-12-03 2011-06-09 Basf Se Catalyseur et procédé de production d'une amine
WO2011067199A1 (fr) 2009-12-03 2011-06-09 Basf Se Catalyseur et procédé de production d'une amine
EP2043996B1 (fr) 2006-07-14 2012-10-17 Basf Se Procédé de production d'une amine
EP2780109B1 (fr) 2011-11-17 2016-04-13 Basf Se Procédé pour la production des catalyseurs contenant sn
CN106957232A (zh) 2017-03-14 2017-07-18 中国科学院兰州化学物理研究所 一种选择性制备n‑单甲基胺类化合物的方法
CN110256216A (zh) * 2019-07-03 2019-09-20 衡水市银河化工有限责任公司 一种含多聚甲醛粉尘甲醛的解聚方法
CN110283145A (zh) * 2019-07-22 2019-09-27 山东英利实业有限公司 一种n-甲基吗啉-n-氧化物的制备方法
CN110627654A (zh) 2019-09-28 2019-12-31 四川之江高新材料股份有限公司 胺的甲基化方法
CN111675677A (zh) 2020-07-13 2020-09-18 江苏富比亚化学品有限公司 一种n-甲基吗啉的合成工艺

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB737023A (en) 1952-03-18 1955-09-21 Celanese Corp Solutions containing available formaldehyde
US3210349A (en) * 1961-11-06 1965-10-05 Jefferson Chem Co Inc Methylation of primary and secondary amines using a small stoichiometric excess of formaldehyde and adding a small stoichiometric excess of formic acid last
GB1056589A (en) * 1965-10-19 1967-01-25 Wolfen Filmfab Veb Process for the production of monochlorodimethyl ether
US3629997A (en) 1970-05-08 1971-12-28 Borden Inc Process for producing methanol-formaldehyde solution of low-water content
DE2321101A1 (de) 1973-04-26 1974-11-14 Basf Ag Kobaltkatalysator
EP2043996B1 (fr) 2006-07-14 2012-10-17 Basf Se Procédé de production d'une amine
WO2008037590A1 (fr) 2006-09-28 2008-04-03 Basf Se Procédé pour la séparation continue par distillation de mélanges contenant de la morpholine, du mono-amino-diglycol, de l'ammoniac et de l'eau
WO2008037587A1 (fr) 2006-09-28 2008-04-03 Basf Se Procédé de séparation par distillation en continu de mélanges contenant de la morpholine (mo), du monoaminodiglycol (adg), de l'ammoniac et de l'eau
WO2008037589A1 (fr) 2006-09-28 2008-04-03 Basf Se Procédé de séparation par distillation en continu de mélanges contenant de la morpholine (mo), du monoaminodiglycol (adg), de l'ammoniac et de l'eau
CN101659618A (zh) * 2009-09-15 2010-03-03 烟台万华聚氨酯股份有限公司 一种五甲基二乙烯三胺的制备方法
WO2011067199A1 (fr) 2009-12-03 2011-06-09 Basf Se Catalyseur et procédé de production d'une amine
WO2011067200A1 (fr) 2009-12-03 2011-06-09 Basf Se Catalyseur et procédé de production d'une amine
EP2780109B1 (fr) 2011-11-17 2016-04-13 Basf Se Procédé pour la production des catalyseurs contenant sn
CN106957232A (zh) 2017-03-14 2017-07-18 中国科学院兰州化学物理研究所 一种选择性制备n‑单甲基胺类化合物的方法
CN110256216A (zh) * 2019-07-03 2019-09-20 衡水市银河化工有限责任公司 一种含多聚甲醛粉尘甲醛的解聚方法
CN110283145A (zh) * 2019-07-22 2019-09-27 山东英利实业有限公司 一种n-甲基吗啉-n-氧化物的制备方法
CN110627654A (zh) 2019-09-28 2019-12-31 四川之江高新材料股份有限公司 胺的甲基化方法
CN111675677A (zh) 2020-07-13 2020-09-18 江苏富比亚化学品有限公司 一种n-甲基吗啉的合成工艺

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