Skip to main content
SpringerLink
Log in

The purification process and side reactions in the N-methylmorpholine-N-oxide (NMMO) recovery system

  • Original Research
  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

In the lyocell process, N-methylmorpholine-N-oxide (NMMO) with a high recovery rate is used as a solvent to directly dissolve cellulose, which is of great significance for the realization of industrialization. In this paper, the impurity removal process and side reactions in the NMMO recovery system are introduced. The NMMO recovery system is generally composed of three major processes: air flotation, ion exchange and evaporation. Air flotation and ion exchange are the processes of removing impurities. And evaporation, where side reactions occur, is the process of increasing the concentration of NMMO. In terms of conductivity and colority, organic flocculants are better than inorganic flocculants in the air flotation process which mainly removes undissolved particulate matter, part of hemicelluloses and some colored substances. The ion exchange process mainly removes ionic substances and propyl gallate (PG). Side reactions occur during evaporation, producing colored substances and black particulate matter. Through analysis, it can be known that the production of colored substances is caused by the condensation reaction of N-methylmorpholine (NMM, 1), morpholine (M, 2), 2-Amino-4-methyl-oxazole (3), furfuryl alcohol (4), Morpholinoacetonitrile (5), xylose and NMMO under alkaline and high-temperature conditions, rather than by PG. The black particles are due to thermal degradation of NMMO or NMM or M in the presence of oxygen and iron at high temperatures.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

Availability of data and materials

The data used to support the findings of this study are available from the corresponding author upon request.

References

  • Adorjan I, Potthast A, Rosenau T, Sixta H, Kosma P (2005) Discoloration of cellulose solutions in N-methylmorpholine-N-oxide (lyocell). Part 1: studies on model compounds and pulps. Cellulose 12(1):51–57

    Article  CAS  Google Scholar 

  • Bernier D, Wefelscheid UK, Woodward S (2009) Properties, preparation and synthetic uses of amine N-oxides. An Update Org Prep Proc Int 41(3):175–210

    Google Scholar 

  • Ferris JP, Gerwe RD, Gapski GR (1967) Detoxication mechanisms. II. Iron-catalyzed dealkylation of trimethylamine oxide. J Am Chem Soc 89(20):5270–5275

    Article  CAS  Google Scholar 

  • Ferris JP, Gerwe RD, Gapski GR (1968) Detoxication mechanisms. III. The scope and mechanism of the iron-catalyzed dealkylation of tertiary amine oxides. J Org Chem 33(9):3493–3498

    Article  CAS  Google Scholar 

  • Ghafari S, Aziz HA, Isa MH, Zinatizadeh AA (2009) Application of response surface methodology (RSM) to optimize coagulation–flocculation treatment of leachate using poly-aluminum chloride (PAC) and alum. J Hazard Mater 163(2–3):650–656

    Article  CAS  Google Scholar 

  • Konkin A, Wendler F, Meister F, Roth H, Aganov A, Ambacher O (2007) Degradation processes in the cellulose/N-methylmorpholine-N-oxide system studied by HPLC and ESR. Radical formation/recombination kinetics under UV photolysis at 77 K. Cellulose 14(5):457–468

    Article  CAS  Google Scholar 

  • Nelan DR, Robeson CD (1962) The oxidation product from α-tocopherol and potassium ferricyanide and its reaction with ascorbic and hydrochloric acids. J Am Chem Soc 84(15):2963–2965

    Article  CAS  Google Scholar 

  • Pieterse T (2013) N-Methylmorpholine-N-Oxide Synlett 24(16):2175–2176

    Google Scholar 

  • Potthast A, Rosenau T, Kosma P (2006) Analysis of oxidized functionalities in cellulose. Adv Polym Sci 205:1–48

    Article  CAS  Google Scholar 

  • Rosenau T, Potthast A, Kosma P, Chen CL, Gratzl JS (1999) Autocatalytic decomposition of N-methylmorpholine N-oxide induced by Mannich intermediates. J Org Chem 64(7):2166–2167

    Article  CAS  Google Scholar 

  • Rosenau T, Potthast A, Sixta H, Kosma P (2001) The chemistry of side reactions and byproduct formation in the system NMMO/cellulose (lyocell process). Progr Polym Sci 26(9):1763–1837

    Article  CAS  Google Scholar 

  • Rosenau T, Potthast A, Adorjan I, Hofinger A, Sixta H, Firgo H, Kosma P (2002a) Cellulose solutions in N-methylmorpholine-N-oxide (NMMO)–degradation processes and stabilizers. Cellulose 9(3–4):283–291

    Article  CAS  Google Scholar 

  • Rosenau T, Potthast A, Hofinger A, Sixta H, Kosma P (2002b) Instabilities in the system NMMO/water/cellulose (lyocell process) caused by Polonowski type reactions. Holzforschung 56(2):199–208

    Article  CAS  Google Scholar 

  • Rosenau T, Hofinger A, Potthast A, Kosma P (2003) On the conformation of the cellulose solvent N-methylmorpholine-N-oxide (NMMO) in solution. POLYMER-LONDON- 44(20):6153–6158

    Article  CAS  Google Scholar 

  • Rosenau T, Potthast A, Milacher W, Adorjan I, Hofinger A, Kosma P (2005) Discoloration of cellulose solutions in N-methylmorpholine-N-oxide (lyocell). Part 2: isolation and identification of chromophores. Cellulose 12(2):197–208

    Article  CAS  Google Scholar 

  • Shiba R, Takahashi M, Ebisuno T, Takimoto M (1993) Reaction of N″-cyanoguanidine with formaldehyde (VII). Preparation of new flocculants for anionic colloidal particles. Bull Chem Soc Jpn 66(8):2452–2453

    Article  CAS  Google Scholar 

  • Sohn OS, Fiala ES, Conaway CC, Weisburger JH (1982) Separation of morpholine and some of its metabolites by high-performance liquid chromatography. J Chromatogr A 242(2):374–380

    Article  CAS  Google Scholar 

  • Xie W, Gong Y, Yu K (2017) Determination of total sugar content in lignocellulosic hydrolysates by using a reaction headspace gas chromatographic technique. Cellulose 24(11):4591–4597

    Article  CAS  Google Scholar 

  • Zeng T, Ke X, Li L, Cheng X, Ni Y, Ouyang X, Zhang X, Chen L, Huang L, Hu H (2020) Quantification of N-methylmorpholine N-oxide in biorefinery process solution by headspace gas chromatography. Cellulose 27:6861–6870

    Article  CAS  Google Scholar 

  • Zhang S, Ke X, Zeng T, Ni Y, Luo X, Hu H, Chen L, Huang L (2020) Determination of N-Methyl morpholine in biomass pretreatment solutions by the ammonia-assisted headspace gas chromatography. Renew Energy 145:2380–2386

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge financial support from the National Key Research and Development Program of China (Grant No. 2017YFB0309502).

Funding

This work was supported by the National Key Research and Development Program of China (No. 2017YFB0309502).

Author information

Authors and Affiliations

  1. State Key Laboratory of Bio-Based Fiber Manufacturing Technology, China Textile Academy, Beijing, 100025, China

    Yaoxian Guo, Jian Cai, Tianqi Sun, Liqiang Xing, Chunzu Cheng, Kedong Chi, Jigang Xu & Ting Li

Authors
  1. Yaoxian Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jian Cai
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Tianqi Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Liqiang Xing
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Chunzu Cheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Kedong Chi
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jigang Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Ting Li
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by YG, JC, TS, LX, CC, KC, JX and TL. The first draft of the manuscript was written by YG and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

Corresponding author

Correspondence to Jigang Xu.

Ethics declarations

Conflict of interest

All authors certify that they have no affiliations with or involvement in any organization or entity with any financial interest or non-financial interest in the subject matter or materials discussed in this manuscript.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Guo, Y., Cai, J., Sun, T. et al. The purification process and side reactions in the N-methylmorpholine-N-oxide (NMMO) recovery system. Cellulose 28, 7609–7617 (2021). https://doi.org/10.1007/s10570-021-03929-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-021-03929-0

Keywords

Search

Navigation