Property Data Estimation for Hemiformals, Methylene Glycols and Polyoxymethylene Dimethyl Ethers and Process Optimization in Formaldehyde Synthesis

Abstract

<jats:p>Polyoxymethylene dimethyl ethers (OMEn) are frequently discussed as alternative diesel fuels, with various synthesis routes considered. OME3–5 syntheses demand significant amounts of thermal energy due to the complex separation processes that they entail. Therefore, innovative process designs are needed. An important tool for the development of new processes is process simulation software. To ensure sound process simulations, reliable physico-chemical models and component property data are necessary. Herein we present the implementation of a state-of-the-art thermodynamic model to describe the component systems of formaldehyde-water and formaldehyde-methanol using Microsoft® Excel (2010, Microsoft Corp, Redmond, WA, USA) and Aspen Plus®, (V8.8, Aspen Tech, Bedford, MA, USA) determine the deviation between the calculated results and experimental literature data, and minimize the deviation by means of parameter fitting. To improve the accuracy of the estimation of the missing property data of hemiformals and methylene glycols formed from formaldehyde using group contribution methods, the normal boiling points were estimated based on molecular analogies. The boiling points of OME6-10 are determined through parameter regression in accordance with the vapor pressure equation. As an application example, an optimization of the product separation of the state-of-the-art formaldehyde synthesis is presented that helps decrease the losses of methanol and formaldehyde in flue gas and wastewater.</jats:p>

Synthesis of tailored oxymethylene ether (OME) fuels via transacetalization reactions

“…Current models for the prediction of physical properties and especially fuel properties are very sophisticated, relying on large databases and complex calculation methods. 36,37,[39][40][41][42][43][44][45][46][47] A common type of predictive model described in literature is the group contribution method. It describes the investigated compound as a set of molecular groups.…”

“…35 Furthermore, systematic investigations on physico-chemical properties, including various OMDAE compounds, have been published recently. 36,37 Within this work, symmetric as well as asymmetric OMDAEs have been investigated with a strong focus on physico-chemical and fuel properties. Regarding the symmetric compounds, diethoxymethane (DEM), dipropoxymethane (DPM), dibutoxymethane (DBM) and di(2-ethylhexyloxy)methane (D(2-EH)M) have been purchased and extensively characterized.…”

An Overview of Promising Alternative Fuels for Road, Rail, Air, and Inland Waterway Transport in Germany

“…Gasification of farmed TRL 8 [5] Renewable electricity via alkaline electrolysis TRL 9 [5] Renewable electricity via polymer electrolyte membrane electrolysis TRL 9 [57] Renewable electricity via solid oxide electrolysis cell TRL 6-7 [57] HVO Conventional (biomass) TRL 9 [5,76] FAME Conventional (biomass) TRL 9 [5,76] Syndiesel BtL, lignocellulose pyrolysis-based TRL 6 [5,76] lignocellulose gasification TRL 8 [5] lignocellulose hydrothermal liquefaction (HTL) and upgrading TRL 4 [5] FT diesel from CO 2 and H 2 TRL 6 [4] Diesel via methanol from CO 2 and H 2 TRL 9 [5] Synthetic gasoline lignocellulose pyrolysis-based TRL 6 [5] MtG TRL 9 [4] Methanol Lignocellulose TRL 8 [5] From CO 2 and H 2 TRL 9 [4,5] Ethanol Conventional (biomass) TRL 9 [5,76] Lignocellulose TRL 7 [76], TRL 8 [5] From CO 2 and H 2 TRL 4 [4] Butanol(1/2) Conventional (biomass) TRL 7 [5] From CO 2 and H 2 TRL 4 [4] DME Lignocellulose TRL 8 [5] From CO 2 and H 2 TRL 9 [4,5] OME 1 Lignocellulose TRL 5 [5] From CO 2 and H 2 TRL 5 [4] OME 3-5 Lignocellulose TRL 5 [5] From CO 2 and H 2 TRL 4-5 [4,79] Iso-octanol From CO 2 and H 2 TRL 4 [4] Octanol TRL 1 [78] From lignocellulose TRL 3 based on Leitner et al [77] Table A1. Cont.…”

“…For longer ether-chains, the technical maturity is lower. Synthetic OME 3-5 from CO 2 and H 2 can be produced through different pathways with varying technical maturity levels in the range of a TRL of 4-5 [4,79], whereas OME 1 production is determined to have a TRL of 5 [4]. The production of OME 1 and OME 3-5 from lignocellulose as advanced biofuel is assessed as TRL 5 by Prussi et al [5].…”

Techno-Economic Analysis of Large Scale Production of Poly(oxymethylene) Dimethyl Ether Fuels from Methanol in Water-Tolerant Processes

“…For instance, the FA reactor could be trimmed toward hydrogen recovery. There is also the possibility to use methanol or wastewater as an absorbent in the FA absorber, which could lower the water content of FA solutions [52]. Although these options were not considered in the present work, major cost reductions seem unlikely as the levelized product cost is determined mainly by the methanol cost.…”