Skip to main content

Advertisement

SpringerLink
Log in

Life cycle assessment of N-methyl-2-pyrrolidone reduction strategies in the manufacture of resin precursors

  • Original Paper
  • Published:
Clean Technologies and Environmental Policy Aims and scope Submit manuscript

Abstract

A case study has been conducted on the reduction of N-methyl-2-pyrrolidone (NMP) solvent waste in the manufacture of polyimide and polybenzoxazole precursors. The evaluation includes the environmental and economic life cycle assessment of solvent recovery and solvent substitution strategies. A two-step distillation process proved effective in recovering 95 % of the NMP at a purity of 99.97 % from an aqueous waste stream comprised 17 % NMP, 0.5 % hydroxyethyl methacrylate, 0.5 % trifluoroacetic acid, and 0.5 % hydrochloric acid. Yearly operating costs were reduced by 83 %, with the greatest impact on the reduction in virgin NMP purchase and hazardous waste disposal cost. Even if a capital acquisition was needed, the recovery option would still result in a net present value at 10 years of 3.12 MM $US. The environmental life cycle assessment (LCA) showed that a 44 % reduction of total emissions is possible with the solvent recovery process, impacting the virgin NMP and hazardous waste disposal life cycle emissions the most. The efficiency in the reduction in life cycle emissions is limited by the thermodynamics of the system, in particular the large composition of water in the waste stream which requires significant energy to distill, thus generating significant life cycle emissions. Solvent substitutes dimethyl sulfoxide and sulfolane reduce life cycle emissions by 44 and 47 %, respectively, when they replace NMP in the process, even without a recovery operation, due to their greener manufacturing profile. Although, when the recovery systems for the solvent substitutes are incorporated into the design, no further reductions in the environmental impact are seen. This demonstrates the need for a complete analysis of all the aspects of a greener design (including the recovery step), since the thermodynamic characteristics of the solvents are important when performing an LCA. Water reuse was also considered for the overall process, but not recommended due to the cost of recovering it from the waste stream to ultrapure water standards.

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
Fig. 5

Similar content being viewed by others

References

  • Alcalde R, Aparicio S, Davila MJ, Garcia B, Leal JM (2008) Liquid–liquid equilibria of lactam containing binary systems. Fluid Phase Equilibr 266:90–100

    Article  CAS  Google Scholar 

  • Alfonsi K, Colberg J, Dunn PJ, Fevig T, Jennings S, Johnson TA, Kleine HP, Knight C, Nagy MA, Perry DA, Stefaniak M (2007) Green chemistry tools to influence a medicinal chemistry and research chemistry based organisation. Green Chem 10:31–36

    Article  Google Scholar 

  • Ashcroft CP, Dunn PJ, Hayler JD, Wells AS (2015) Survey of solvent usage in papers published in Organic Process Research and Development 1997–2012. Org Process Res Dev 19:740–747

  • Chapman PD, Oliveira T, Livingston AG, Li K (2008) Membranes for the dehydration of solvents by pervaporation. J Membr Sci 318:5–37

    Article  CAS  Google Scholar 

  • Constable DJ, Dunn PJ, Hayler JD, Humphrey GR, Leazer JL, Linderman RJ, Lorenz K, Manley J, Pearlman BA, Wells A, Zaks A, Zhang TY (2007a) Key Green Chemistry Research Areas—a perspective from pharmaceutical manufacturers. Green Chem 9:411–420

    Article  CAS  Google Scholar 

  • Constable DJ, Jimenez-Gonzalez C, Henderson RK (2007b) Perspective on solvent use in the pharmaceutical industry. Org Process Res Dev 11:133–137

    Article  CAS  Google Scholar 

  • Dahlgren PE (1995) Solvent recycling for reuse in semiconductor manufacturing. 1995 International Symposium on Semiconductor Manufacturing, Austin, TX, September 1995, pp 205–209

  • Dow Water Solutions (2015) DOWEX MONOSPHERE MR-450 UPW. Available: http://www.dow.com/en-us/water-and-process-solutions. Accessed June 2015

  • Figoli A, Marino T, Simone S, Di Nicolo E, Li XM, He T, Tornaghi S, Drioli E (2014) Towards non-toxic solvents for membrane preparation: a review. Green Chem 16:4034–4059

    Article  CAS  Google Scholar 

  • GE Power and Water (2015) AG Series: Standard Brackish Water RO Elements. Available www.gewater.com. Accessed June 2015

  • Ghosh M (1996) Polyimides: fundamentals and applications. Marcel Dekker, New York

    Google Scholar 

  • Ghosh UK, Pradhan NC, Adhikari B (2006) Pervaporation recovery of N-methyl-2-pyrrolidone from dilute aqueous solution by using polyurethaneurea membranes. J Membr Sci 285:249–257

    Article  CAS  Google Scholar 

  • Gilles DG, Loehr RC (1994) Waste generation and minimization in semiconductor industry. J Environ Eng 120:72–86

    Article  CAS  Google Scholar 

  • Goedkoop M, Heijungs R, Huijbregts M, De Schryver A, Struijs J, van Zelm R (2009) ReCiPe 2008: a life cycle impact assessment method which comprises harmonised category indicators at the midpoint and the endpoint level. Report I: Characterisation, 1st ed

  • Griffin D, Anchukaits KJ (2014) How unusual is the 2012–2014 California drought? Geophys Res Lett 41:9017–9023

    Article  Google Scholar 

  • Henderson RK, Jimenez-Gonzalez C, Constable DJ, Alston SR, Inglish GGA, Fisher G, Sherwood J, Binks SP, Curzons AD (2011) Expanding GSK’s solvent selection guide—embedding sustainability into solvent selection starting at medicinal chemistry. Green Chem 13:854–862

    Article  CAS  Google Scholar 

  • Hergenrother PM (2003) The use, design, synthesis, and properties of high performance/high temperature polymers: an overview. High Perform Polym 15:3–45

    CAS  Google Scholar 

  • Higgins (1995) Pollution prevention handbook. CRC Press, New York

    Google Scholar 

  • ICIS (2008) Indicative Chemical Prices A-Z. http://www.icis.com/chemicals/channel-info-chemicals-a-z/. Accessed June 2015

  • Jessop PG (2011) Searching for green solvents. Green Chem 13:1391–1398

    Article  CAS  Google Scholar 

  • Ji P, Atherton J, Page MI (2011) Liquid ammonia as a dipolar aprotic solvent for aliphatic nucleophilic substitution reactions. J Org Chem 76:1425–1435

    Article  CAS  Google Scholar 

  • Jimenez-Gonzalez C, Constable DJ (2011) Green chemistry and engineering: a practical design approach. Wiley, New Jersey

    Google Scholar 

  • Jouyban A, Fakhree MAA, Shayanfar A (2010) Review of pharmaceutical applications of N-methyl-2-pyrrolidone. J Pharm Pharm Sci 13:524–535

    Article  CAS  Google Scholar 

  • Kirby AJ (1992) Polyimides: materials, processing, and applications. Pergamon Press, New York

    Google Scholar 

  • Li L, Quinlivan PA, Knappe DR (2002) Effects of activated carbon surface chemistry and pore structure on the adsorption of organic contaminants from aqueous solution. Carbon 40:2085–2100

    Article  CAS  Google Scholar 

  • Liaw DJ, Liaw BY (1997) Synthesis and properties of polyamides derived from 1,4-bis(4-aminophenoxy)-2-tert-butylbenzene. Macromol Sy 122:343–348

    Article  CAS  Google Scholar 

  • Liaw DJ, Wang KL, Huang YC, Lee KR, Lai JY, Ha CS (2012) Advanced polyimide materials: syntheses, physical properties and applications. Prog Polym Sci 13:907–974

    Article  Google Scholar 

  • Liou GS, Hsiao SH, Ishida M, Kakimoto M, Imai Y (2002) Synthesis and characterization of novel soluble triphenylamine-containing aromatic polyamides based on N, N’-bis(4-aminophenyl)-N, N’-diphenyl-1,4-phenylenediamine. J Polym Sci A 40:2810–2818

    Article  CAS  Google Scholar 

  • Madbouly SA, Otaigbe JU (2009) Recent advances in synthesis, characterization and rheological properties of polyurethanes and POSS/polyurethane nanocomposites dispersions and films. Progr Polym Sci 34:1283–1332

    Article  CAS  Google Scholar 

  • Minges ML (1989) Electronic materials handbook: packaging, vol 1. ASM International, Materials Park

    Google Scholar 

  • Pande S, Sharma DK (2002) Ethylenediamine-assisted solvent extraction of coal in N-methyl-2-pyrrolidone: synergistic effect of ethylenediamine on extraction of coal in N-methyl-2-pyrrolidone. Energ Fuel 16:194–204

    Article  CAS  Google Scholar 

  • Pollet P, Eckert CA, Liotta CL (2011) Switchable solvents. Chem Sci 2:609–614

    Article  CAS  Google Scholar 

  • Prat D, Hayler J, Wells A (2014) A survey of solvent selection guides. Green Chem 16:4546–4551

    Article  CAS  Google Scholar 

  • Ramzan N, Degenkolbe S, Witt W (2008) Evaluating and improving environmental performance of HC’s recovery system: a case study of distillation unit. Chem Eng J 140:201–203

    Article  CAS  Google Scholar 

  • Raymond MJ, Slater CS, Savelski MJ (2010) LCA approach to the analysis of solvent waste issues in the pharmaceutical industry. Green Chem 12:1826–1834

    Article  CAS  Google Scholar 

  • Razali M, Kim JF, Attfield M, Budd PM, Drioli E, Lee YM, Szekely G (2015) Sustainable wastewater treatment and recycling in membrane manufacturing. Green Chem

  • Reisch M (2008) Solvent users look to replace NMP. Chem Eng News 86:32

    CAS  Google Scholar 

  • Renganathan K, Zondlo JW, Mintz EA, Kneisl P, Stiller AH (1988) Preparation of an ultra-low wash coal extract under mild conditions. Fuel Process Technol 18:273–278

    Article  CAS  Google Scholar 

  • Sato K, Sugimoto K, Shimotsuma N, Kikuchi T, Kyotani T, Kurata T (2012) Development of practically available up-scaled high-silica CHA-type zeolite membranes for industrial purpose in dehydration of N-methyl pyrrolidone solution. J Membrane Sci 409–410:82–95

    Article  Google Scholar 

  • Shao F, Hao C, Ni L, Zhang Y, Du R, Meng J, Liu Z, Xiao C (2014) Experimental and theoretical research on N-methyl-2-pyrrolidone concentration by vacuum membrane distillation using polypropylene hollow fiber membrane. J Membrane Sci 452:157–164

    Article  CAS  Google Scholar 

  • Sheldon RA (2008) Green and sustainable chemistry: challenges and perspectives. Green Chem 10:359–360

    Article  CAS  Google Scholar 

  • Sheldon RA (2011) Fundamentals of green chemistry: efficiency in reaction design. Chem Soc Rev 41:1437–1451

    Article  Google Scholar 

  • Slater CS, Savelski MJ (2007) A method to characterize the greenness of solvents used in pharmaceutical manufacture. Environ Sci Health 42:1595–1605

    Article  CAS  Google Scholar 

  • Slater CS, Savelski MJ (2009) Towards a greener manufacturing environment. Innov Pharm Technol 29:78–83

    Google Scholar 

  • Slater CS, Savelski MJ, Hounsell G, Pilipauskas D, Urbanski F (2012a) Green design alternatives for isopropanol recovery in the celecoxib process. Clean Technol Envir 12:687–698

    Article  Google Scholar 

  • Slater CS, Savelski MJ, Moroz TM, Raymond MJ (2012b) Pervaporation as a green drying process for tetrahydrofuran recovery in pharmaceutical synthesis. Green Chem Lett Rev 5:55–64

    Article  CAS  Google Scholar 

  • Spectrum Chemical MGF Corp (2015) ACS Grade Solvents. Available: https://www.spectrumchemical.com/OA_HTML/Chemicals_Fine-Chemicals_ACS-Chemicals_ACS-Solvents.jsp?minisite=10020&respid=22372. Accessed May 2015

  • Sunitha K, Rani KY, Moulik S, Satyanarayana SV, Sridhar S (2013) Separation of NMP/water mixtures by nanocomposite PEBA membrane: part I. Membrane synthesis, characterization and pervaporation performance. Desalination 330:1–8

    Article  CAS  Google Scholar 

  • Tilstam U (2012) Sulfolane: a versatile dipolar aprotic solvent. Org Process Res Dev 16:1273–1278

    Article  CAS  Google Scholar 

  • Towler G, Sinnott R (2013) Chemical engineering design, 2nd edn. Butterworth-Heinenmann, Massachussettes

    Google Scholar 

  • Tsai HA, Chen YL, Lee KR, Lai JY (2012) Preparation of heat-treated PAN hollow fiber membranes for pervaporation of NMP/H2O mixtures. Sep Purif Technol 100:97–105

    Article  CAS  Google Scholar 

  • U.S. Energy Information Administration (2015) Electricity Data Browser. http://www.eia.gov. Accessed June 2015

  • U.S. Environmental Protection Agency, Office of Environmental Information (2015) TRI.NET. http://www.epa.gov/tri/tridotnet/index.html. Accessed March 2015

  • van Veen HM, Rietkerk MDA, Shanahan DP, van Tuel MMA, Kreiter R, Castricum HL, ten Elshof JE, Vente JF (2011) Pushing membrane stability boundaries with HybSi® pervaporation membranes. J Membrane Sci 380:124–131

    Google Scholar 

  • Wankat PC (2012) Separation process engineering, 3rd edn. Prentice Hall, New Jersey

    Google Scholar 

Download references

Acknowledgments

The authors acknowledge the support of the U.S. Environmental Protection agency through the Pollution Prevention grant program (NP96291314-0). The authors also acknowledge the Rowan Engineering Clinic students: Matt Buchanan, Ben Ficara, Joe Garrett, Steve Hertzog, Ryan Liberty, Kyle Surette, and Christian Wisniewski. The authors also appreciate the support of the DuPont Corporation and Michael Hatton Jr., Charles Richwine, Jeffery Staniszewski (ret), and Nancy Uff of DuPont.

Author information

Authors and Affiliations

  1. Department of Chemical Engineering, Rowan University, Glassboro, NJ, USA

    Brigitte M. Pastore, Mariano J. Savelski & C. Stewart Slater

  2. DuPont, Parlin, NJ, USA

    Frank A. Richetti

Authors
  1. Brigitte M. Pastore
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mariano J. Savelski
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. C. Stewart Slater
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Frank A. Richetti
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to C. Stewart Slater.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Pastore, B.M., Savelski, M.J., Slater, C.S. et al. Life cycle assessment of N-methyl-2-pyrrolidone reduction strategies in the manufacture of resin precursors. Clean Techn Environ Policy 18, 2635–2647 (2016). https://doi.org/10.1007/s10098-016-1180-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10098-016-1180-5

Keywords

Search

Navigation