5-hydroxymethylfurfural Yield Research Articles

Internal water circulation mediated synergistic co-hydrolysis of PET/cotton textile blends in gamma-valerolactone.

Recycling strategies for mixed plastics and textile blends currently aim for recycling only one of the components. Here, we demonstrate a water coupling strategy to co-hydrolyze polyester/cotton textile blends into polymer monomers and platform chemicals in gamma-valerolactone. The blends display a proclivity for achieving an augmented 5-hydroxymethylfurfural yield relative to the degradation of cotton alone. Controlled experiments and preliminary mechanistic studies underscore that the primary driver behind this heightened conversion rate lies in the internal water circulation. The swelling and dissolving effect of gamma-valerolactone on polyester enables a fast hydrolysis of polyester at much lower concentration of acid than the one in the traditional hydrolysis methods, effectively mitigating the excessive degradation of cotton-derived product and undesirable product formation. In addition, the system is also applicable to different kinds of blends and PET mixed plastics. This strategy develops an attractive path for managing end-of-life textiles in a sustainable and efficient way.

One-pot Conversion of Sago Pith Waste (SPW) into 5-Hydroxymethyl Furfural (HMF)

Hydroxymethyl furfural (HMF) is widely understood to be a robust substitute feedstock for a wide array of petroleum-derived products such as plastic and fuel. Previous research delved into the use of waste (i.e., biomass) to produce HMF. These waste products stemmed from sugarcane bagasse, algae, bread, and banana. Our study is the first to report the use of sago pith waste (SPW), a by-product of the sago starch industry, for HMF production via simultaneous conversion in one pot. The production of HMF in such a manner not only yields an industrially important product (i.e., HMF) but also confers a sustainable waste management solution to the sago starch industry. SPW primarily consists of starch and fiber, and since the density of SPW affects the feed rate of the reactor, it is necessary to optimize the reaction temperature, sample volume, and amount of activated carbon to elucidate reaction conditions with a high HMF yield. By adding activated carbon and sodium chloride into the reaction mixture with a Bronsted-Lewis acid, we obtained 50-60% mole of HMF from SPW in a simultaneous reactor system at 160°C for 8 minutes.

Efficient conversion of cellulose to 5-hydroxymethylfurfural using a bifunctional hydrophobic SBA-15 catalyst: The effects of hydrophobicity, morphology and acidity

Owing to the negative impact of water on catalyst activity, and the consequent side reactions, the hydrophobicity and acidity of the catalyst are important factors in the conversion of cellulose to 5-hydroxymethylfurfural in an aqueous solvent. In the present study, we prepared SBA-15 catalysts comprising hydrophobic methoxy groups, phosphotungstic acid as Lewis acid groups, and -SO3H Brønsted acid groups. The introduction of methoxy groups increased the contact angle of the catalyst from 57.42 to 87.80° and changed its morphology from stubby short rods to long curved sticks. The maximum 5-hydroxymethylfurfural yield (61.24%) was obtained using 2SBA-15-SO3H, which comprised 237.31 μmol·g−1 of the Brønsted acid and 14.44 μmol·g−1 of the Lewis acid and had a contact angle of 75.93°. The low yields of levulinic acid and formic acid (below 10%) confirmed the resistance of such SBA-15 catalysts to water. Furthermore, adequate hydrophobicity facilitated glucose isomerization, whereas the catalyst morphology, which tended to comprise short rods, improved the fructose dehydration rate. Density functional theory analysis of the acidity sites route revealed a 3-DG pathway for 1,4,5,6-tetrahydroxy-hexan-2-one generation with Lewis acid sites, and a free energy of 0.13 eV, paralleled by glucose isomerization to fructose through a 1,2-enediol.

Hydroxymethylfurfural (HMF) Synthesis from Starch with Zeolite Based Catalysts

AbstractIn the study, it is aimed to use effective zeolite‐based catalysts for the synthesis of hydroxymethylfurfural (HMF) from starch in different solvent environments. Al, Zn, and heteropolyacid (HPW) loaded USY zeolites are prepared and characterized using XRD, BET method, Inductive Coupling Plasma Mass Spectrometry (ICP‐MS), Pyridine‐DRIFTS, and X‐ray Photoelectron Spectroscopy (XPS). The efficiency of the prepared catalysts is investigated in 1‐Butyl‐3‐Methylimidazolium Chloride (BMIMCI) ionic liquid, DMSO, and THF solvents at different temperatures and reaction times for HMF synthesis. 24.5% HMF yield using Zn‐USY zeolite and 50.3% HMF yield using USY H‐zeolite is obtained in BMIMCI ionic liquid at 130 °C for 3 h. HMF yield of 47% is obtained using Zn‐USY zeolite catalyst at 160 °C in 4 h, at 170 °C in 2 h, and at 180 °C in 1 h in DMSO. In a two‐phase reaction medium with THF and H2O, the HMF yield is 46.8% at 160 °C in 4 h, 52.2% at 170 °C in 30 min, and 38.1% at 180 °C in 2 h with Zn‐USY zeolite catalyst. The reusability of the Zn‐USY zeolite has been tested and the efficiency of catalyst does not decrease in reuse for five times.

Hydrothermal reaction of cellulose in ionic liquid catalyzed by Er(OTf)3

This research explores the potential of ionic liquid to improve lactic acid yield of the hydrothermal reaction of cellulose. The research premise was that ionic liquid dissolved cellulose and water into liquid phase, which would facilitate the formation of glucose and lactic acid using water-tolerant catalyst Erbium (III) trifluoromethanesulfonate (Er(OTf)3). Contrary to the research premise, the experiment revealed that dissolving cellulose in ionic liquid prior to hydrothermal reaction lowered lactic acid yield while increasing hydroxymethylfurfural (HMF) yield. The phenomenon could be attributed to dissociation of water and ionic liquid to give hydronium ion and chloride ion, which subsequently formed hydrochloric acid (HCl). HCl catalyzed cellulose into HMF, in addition to lactic acid. Pressure and pressurized gas had minimal impact on the yield of lactic acid, while the hydrothermal reaction was affected by type of cation and anion of ionic liquid. The highest lactic acid yield of 54.26% was achieved by using 1-butyl-3 methylimidazolium chloride ionic liquid, with 190 °C, 30-min, 10 bar CO2 initial pressure, and Er(OTf)3 50 wt% cellulose. Meanwhile, the highest HMF yield of 66.06% was realized with 1-butyl-3-methylimidazolium hydrogen sulfate in the absence of Er(OTf)3.

A Hybrid Process for Valorization of d-Fructose to 2,5-Bis(hydroxymethyl)furan by Bridging Chemocatalysis and Biocatalysis in a Betaine:Benzenesulfonic Acid System

Biobased 2,5-bis(hydroxymethyl)furan is a versatile building block for the production of drugs, polymers, crown ethers, bioactive compounds, and value-added intermediates. To explore a more efficient route to synthesize 2,5-bis(hydroxymethyl)furan, a tandem transformation by quick dehydration with a deep eutectic solvent betaine:benzenesulfonic acid (Bet:BSA) and mild bioreduction with recombinant Escherichia coli (E. coli) DCF was developed for converting d-fructose into 2,5-bis(hydroxymethyl)furan. The 5-hydroxymethylfurfural yield reached 62.3 ± 1.6% (based on d-fructose) in Bet:BSA at 120 °C after a short time (2 min). d-Fructose-valorized 5-hydroxymethylfurfural was biologically transformed to 2,5-bis(hydroxymethyl)furan by newly constructed recombinant E. coli DCF containing reductase and formate dehydrogenase at 40 °C and pH 7.5 after 48 h, with a yield of 99.6 ± 0.1% (based on 5-hydroxymethylfurfural) in Bet:BSA-water containing the cosubstrate HCOONa (5-HMF-to-HCOONa molar ratio, 1:2.5). Meanwhile, 150 mM commercial 5-hydroxymethylfurfural was transformed into 2,5-bis(hydroxymethyl)furan in a yield of 94.4 ± 0.9%. An efficient hybrid process was constructed to valorize d-fructose to 2,5-bis(hydroxymethyl)furan in Bet:BSA-water, which has good industrial application potential.

Continuous synthesis of 5‐hydroxymethylfurfural from biomass in on‐farm biorefinery

Abstract5‐hydroxymethylfurfural (HMF) is the object of extensive research in recent times. The challenge in the industrial production of HMF is the choice of cheap, hexose feedstock. This study compares continuous HMF synthesis from hexoses—fructose and glucose, and biomass—Miscanthus × giganteus and chicory roots. The experiments were conducted in technical‐scale biorefinery (TRL 6/7). In the first stage, optimal conditions for the production of HMF from hexoses were selected using sulfuric acid as a catalyst in an aqueous medium. The following conditions were chosen for fructose: temperature of 200°C, the reaction time of 18 min, and pH = 2, and for glucose: 210°C, 18 min, and pH = 3. Under these conditions, the HMF yield was 56.5 mol% (39.6 wt.%) from fructose and 18.1 mol% (12.6 wt.%) from glucose. From the biomass, the HMF yields were 36.7 and 16.2 wt.% for miscanthus and chicory roots, respectively. Some results from the conversion of biomass solutions are unexpected and show a need for further investigations. This work has demonstrated the capacity to produce HMF from biomass as part of an environmentally friendly process in a biorefinery. Further research in this field and process optimization will be a step forward in the sustainable production of bioplastics.

Low-temperature hydrothermal liquefaction of pomelo peel for production of 5-hydroxymethylfurfural-rich bio-oil using ionic liquid loaded ZSM-5

Ionic liquid loaded ZSM-5 with high stability and catalytic performance was used for hydrothermal liquefaction (HTL) of pomelo peel for the first time. Bio-oil obtained at 200 °C had the highest yield (29.21 wt%) and high heating value (21.41 MJ/kg), with main constituents of 5-hydroxymethylfurfural (5-HMF, 50.10%), 3-Pyridinol (19.8%) and pentanoic acid (5.35%). The higher 5-hydroxymethylfurfural yield obtained using ionic liquid loaded ZSM-5 was further compared to other studies (0–50%). In comparison to high-temperature HTL, catalytic HTL with ionic liquid loaded ZSM-5 led to lower activation energy requirements (31.93 kJ·mol−1) for the conversion of glucose into 5-HMF. Additionally, the catalysts showed excellent recyclability, with 19.68 wt% of bio-oil containing 59.6% of light oil obtained after 5 cycles. Hence, this study presents a novel approach for the catalytic conversion of lignocellulosic biomass into 5-HMF-rich bio-oil for energy and green chemistry applications.

Continuous‐Flow Synthesis of 5‐Hydroxymethylfurfural, Furfural from Monosaccharides: A Simple, Fast, and Practical Method

Abstract5‐Hydroxymethylfurfural (HMF), a versatile intermediate from biomass, can be applied to prepare a wide range of valuable compounds in the petroleum and chemical industries. Thus, simple, fast, and practical methods to convert carbohydrates into HMF have been capturing increasing attention. We reported herein a method of using p‐toluenesulfonic acid (p‐TsOH) and Brønsted acidic ionic liquid as catalysts for the dehydration of fructose in dimethyl sulfoxide (DMSO) under a continuous flow process. The effect of the various reaction conditions on HMF formation was investigated, and the HMF yields were determined by the HPLC method. The results showed that p‐TsOH and Brønsted acidic ionic liquid are effective catalysts within short residence times. This study provides a simple and safe procedure that can be potentially performed on a large scale to synthesize HMF from fructose.

Engineering the Distinct Structure Interface of Subnano-alumina Domains on Silica for Acidic Amorphous Silica-Alumina toward Biorefining.

Amorphous silica–aluminas (ASAs) are important solid catalysts and supports for many industrially essential and sustainable processes, such as hydrocarbon transformation and biorefining. However, the wide distribution of acid strength on ASAs often results in undesired side reactions, lowering the product selectivity. Here we developed a strategy for the synthesis of a unique class of ASAs with unvarying strength of Brønsted acid sites (BAS) and Lewis acid sites (LAS) using double-flame-spray pyrolysis. Structural characterization using high-resolution transmission electron microscopy (TEM) and solid-state nuclear magnetic resonance (NMR) spectroscopy showed that the uniform acidity is due to a distinct nanostructure, characterized by a uniform interface of silica–alumina and homogeneously dispersed alumina domains. The BAS population density of as-prepared ASAs is up to 6 times higher than that obtained by classical methods. The BAS/LAS ratio, as well as the population densities of BAS and LAS of these ASAs, could be tuned in a broad range. In cyclohexanol dehydration, the uniform Brønsted acid strength provides a high selectivity to cyclohexene and a nearly linear correlation between acid site densities and cyclohexanol conversion. Moreover, the concerted action of these BAS and LAS leads to an excellent bifunctional Brønsted–Lewis acid catalyst for glucose dehydration, affording a superior 5-hydroxymethylfurfural yield.

Subcritical water hydrolysis of Phragmites for sugar extraction and catalytic conversion to platform chemicals

Phragmites karka, also known as common reed, is a perennial grass and a highly invasive crop species, which creates ecological problems by competing with native biodiversity and vegetation. This study involves subcritical water hydrolysis of Phragmites to produce monomeric sugars followed by the catalytic conversion of the sugar-rich hydrolysate to furfural and levulinic acid. Subcritical water hydrolysis was performed by the Central Composite Design method at variable temperatures (150–230 °C), reaction time (15–60 min) and feed concentration (2–5 wt%). The temperature was found to be the most prominent factor affecting biomass hydrolysis. The yield of total reducing sugars from biomass hydrolysis was in the range of 2.1–18.1% where the highest yield was obtained at the optimal temperature (190 °C), reaction time (37.5 min) and feed concentration (2 wt%). During subcritical water hydrolysis of Phragmites, two main degradation products obtained at a higher temperature (230 °C) and reaction time (37.5 min) were furfural (8.2%) and 5-hydroxymethylfurfural (11.7%). However, at 230 °C and a longer reaction time of 60 min, 5-hydroxymethylfurfural yield reduced to 5.1% owing to its conversion to humin while furfural yield elevated to 9.9%. Catalysts such as ZrO2, TiO2, Zr0.5Ti0.5O2, WO3–ZrO2, WO3–TiO2 and WO3–Zr0.5Ti0.5O2 were involved in the conversion of the sugar-rich hydrolysate obtained from subcritical water hydrolysis of Phragmites. The highest sugar conversion was found to be 92% with WO3–ZrO2 resulting in the yields of furfural (51%) and levulinic acid (34%). The activity of particular catalysts (e.g. WO3–ZrO2, WO3–TiO2 and WO3–Zr0.5Ti0.5O2) relied on the synergistic effects of Lewis and Brønsted acid sites.

Fast Synthesis of Hydroxymethylfurfural from Levoglucosenone by Mixing with Sulphuric Acid and Heating in a Microtube Reactor

Hydroxymethylfurfural (HMF) is a promising platform chemical in future bio-based chemical industry for synthesis of a variety of furan derivatives. Studies on the HMF synthesis have focused mainly on saccharides as the feedstock. Recently, levoglucosenone (LGO), anhydrosugar available from cellulose pyrolysis, has been identified as an alternative feedstock, which can be converted to HMF under milder conditions only with acid and water as catalyst and solvent, respectively. To further explore the potential of this reaction, in this study, we demonstrated the HMF synthesis below 100°C within a few minutes at high yields. The employment of microtube reactor and high concentration sulfuric acid as catalyst was effective, leading to the highest HMF yield of 61.5%-C with the reaction selectivity over 80%. Kinetic analysis revealed that rapid heating after mixing LGO with the catalytic aqueous solution was essential to supress side reaction that generates degradation products from LGO. The reaction with glucose or fructose as feedstock under same conditions resulted in poor HMF yield.

In Situ Synthesis of Sn-Beta Zeolite Nanocrystals for Glucose to Hydroxymethylfurfural (HMF)

The Sn substituted Beta nanocrystals have been successfully synthesized by in-situ hydrothermal process with the aid of cyclic diquaternary ammonium (CDM) as the structure-directing agent (SDA). This catalyst exhibits a bifunctional catalytic capability for the conversion of glucose to hydroxymethylfurfural (HMF). The incorporated Sn acting as Lewis acid sites can catalyze the isomerization of glucose to fructose. Subsequently, the Brønsted acid function can convert fructose to HMF via dehydration. The effects of Sn amount, zeolite type, reaction time, reaction temperature, and solvent on the catalytic performances of glucose to HMF, were also investigated in the detail. Interestingly, the conversion of glucose and the HMF yield over 0.4 wt% Sn-Beta zeolite nanocrystals using dioxane/water as a solvent at 120 °C for 24 h are 98.4% and 42.0%, respectively. This example illustrates the benefit of the in-situ synthesized Sn-Beta zeolite nanocrystals in the potential application in the field of biomass conversion.

Aqueous Choline Chloride/γ‐Valerolactone as Ternary Green Solvent Enhance Al(III)‐Catalyzed Hydroxymethylfurfural Production from Rice Waste

A ternary green solvent γ‐valerolactone (GVL)/choline chloride (ChCl)/H2O system is used to convert rice waste to hydroxymethylfurfural (HMF) using AlCl3·6H2O as a catalyst. The effect of the reaction time, temperature, substrate, catalyst, and catalyst amount on the extraction of HMF by GVL is studied under this system. The results show that in ChCl/H2O, GVL/H2O, and GVL/ChCl/H2O systems, the HMF yield reaches the highest levels of 8.21, 12.24, and 18.60 mol% after reaction at 140 °C for 1 h, respectively. The yield of HMF obtained by reacting 0.42 mm of AlCl3·6H2O at 140 °C for 30 min is significantly higher than that of CrCl3·6H2O and FeCl3·6H2O. After reaction at 140 °C for 5 min, the extraction rate of HMF by GVL reaches more than 80%. The aqueous solution of ChCl forming the ternary system has high recyclability, and after six times, the yield loss of HMF is small.

Conversion of Glucose to 5-Hydroxymethylfurfural by Co-catalysis of p-Toluenesulfonic Acid (pTSA) and Chlorides: A Comparison Based on Kinetic Modeling

Hydroxymethylfurfural (HMF) has been considered as one of the most promising biomass derived precursors for producing bio-based materials. Lewis acids are usually used to facilitate the isomerization of glucose to fructose in order to improve the HMF yield. In this study, glucose was converted to HMF with p-toluenesulfonic acid (pTSA) and chlorides as Bronsted and Lewis acids catalysts in the DMSO medium at 120 °C under atmospheric pressure. Kinetic modeling of the process was investigated with consideration of glucose isomerization, dehydration of fructose, rehydration of HMF and formation of humin. NH4Cl was screened as the most efficient co-catalyst for glucose conversion with HMF yield of 47%. The developed model could be well used to simulate the process with satisfying goodness of fit. The activation energies for glucose isomerization, condensation, dehydration of fructose, and rehydration of HMF were determined to be 39.8, 18.1, 55.2, and 19.0 kJ/mol, respectively. However, because the fructose concentration was very low and the reaction rate of fructose dehydration was much higher than that of glucose isomerization, a pseudo-steady state assumption could be employed, by which the observed activation energy for a lumped reaction of glucose to HMF conversion (EHMF) was determined as 45.6 kJ/mol. The developed observed kinetic model could be well used to describe the kinetics of pTSA and chloride co-catalyzed conversion of HMF. Isomerization of glucose to fructose, condensation of glucose to form humin, dehydration of fructose to form HMF, and rehydration of HMF to LA were the major reactions in the system. To improve the HMF selectivity, efforts should be made to reduce the rate of glucose condensation to form humin

Environmentally friendly, hydrothermal treatment of mixed fabric wastes containing polyester, cotton, and wool fibers: Application for HMF production

Herein, a mild and efficient method for the production of 5′-hydroxymethylfurfural (HMF) from polyester/cotton mixed fiber waste is reported for the first time. This is expected to be the first step in a continuous flow process for the recovery of HMF from cotton-containing fabric wastes. It was found that under hydrothermal reaction conditions, at temperatures of 160–225 °C, and in the presence of citric acid, the hydrolysis of cotton fibers to glucose and the subsequent dehydration of glucose to HMF were enhanced. The yield of HMF reached 12.5% for 60 min at 225 °C and 3.2% for 180 min at 160 °C. According to the chemical analysis of saccharides and organic acids in the product mixture, this process is fairly selective for the production of HMF and glucose, thereby facilitating the purification of HMF from hydrothermally treated materials.

Production of 5′-hydroxymethylfurfural by the hydrothermal treatment of cotton fabric wastes using a pilot-plant scale flow reactor

We developed a hydrothermal pilot-plant scale flow reactor, which enables the continuous treatment of both a glucose solution and a cotton-containing fabric waste slurry at the liter-per-hour scale. The mechanical characteristics of the pilot-plant scale flow reactor were examined using two different reactor volume sizes of 441 mL and 2685 mL. The cotton fabric wastes pretreated with cellulase were subjected to hydrothermal treatment. The hydrothermal system using the larger size flow reactor enabled for the first time the continuous treatment of cotton-containing slurry wastes to produce 5′-hydroxymethylfurfural (HMF) at 200–235 °C. The HMF yield reached 21.3% using glucose and 7.9% using cotton fabric waste, and only a limited number of byproducts were observed. This study elucidated that it is possible to scale-up a hydrothermal flow reactor to a practical scale beyond that used for laboratory experiments.

Acidic seawater improved 5-hydroxymethylfurfural yield from sugarcane bagasse under microwave hydrothermal liquefaction

5-Hydroxymethylfurfural (HMF) as value-added platform chemical can be derived from biomass. This study used microwave hydrothermal liquefaction (MHTL) to obtain HMF from sugarcane bagasse in acidic seawater conditions. The key processing parameters including temperature, reaction time, and liquid-to-solid ratio (L/S) were evaluated and optimized. The highest HMF yield of 8.1 wt% was obtained at 149 °C with a reaction time of 4 min and a L/S value of 12:1, respectively. This yield is considerable and even higher than the yield derived from sugarcane molasses under similar microwave conditions in the absence of seawater. Hence, acidic seawater was found to promote the hydrolysis of sugarcane bagasse to give HMF precursor (i.e. fructose and glucose), while simultaneously inhibiting the conversion of HMF to levulinic acid under MHTL conditions, possibly explaining the high HMF yield. This method presents a new and sustainable means of transforming waste biomass to valuable substances using seawater or brine wastewater.

Integration of Heterogeneous Acid and Base Catalysis for Clean Synthesis of Jet‐Fuel Precursor from Carbohydrates

AbstractC12 branched alkane fuel precursor was produced from carbohydrates using an efficient integrated solid acid and base catalysis approach involving: i) isomerisation‐dehydration of carbohydrates to 5‐(hydroxymethyl)furfural (HMF) over solid acid catalyst having both Lewis and Brónsted sites) in a biphasic MIBK (methylisobutylketone): water + DMSO solvent system and ii) Claisen‐Schmidt condensation of crude HMF with MIBK over solid base catalyst. Initially, high yield of jet fuel precursor, (E)‐1‐(5‐(hydroxymethyl)furan‐2‐yl)‐5‐methylhex‐1‐en‐3‐one from pure HMF and MIBK was achieved over basic CaMgAl(231) catalyst. The glucose dehydration to HMF was optimized in biphasic MIBK: H2O‐NaCl: DMSO (8:1.5:0.5; v/v/v) system, with complete glucose conversion and 42% HMF yield over Zr‐Mont possessing both Lewis and Brønsted acid sites. In an integrated dehydration + Claisen‐Schmidt condensation sequence, Zr‐Mont catalyst was filtered off and the crude HMF with MIBK underwent Claisen‐Schmidt condensation over CaMgAl(231) catalyst. The overall 32% yield of Claisen‐Schmidt condensation product was achieved from glucose. MIBK acting also as a product extractant, could be recovered upto 80%.

Comparative study of the effectiveness of protic and aprotic ionic liquids in microwave-irradiated catalytic conversion of lignocellulosic June grass to biofuel precursors

This work compares the effectiveness of protic (PIL) and aprotic (APIL) ionic liquids in microwave-irradiated transition metal-catalysed one-pot conversion of a cellulose-rich non-edible lignocellulose, namely, June grass – composed of cellulose (82.3%), hemicelluloses (1.3%), with crystallinity index of 54% – to biofuel precursors such as glucose, hydroxymethylfurfural (HMF), levulinic (LA) and formic (FA) acids. Reaction parameters such as catalyst-substrate loading, IL-substrate loading, water concentration, temperature, and time are optimized to target specific biofuel precursor molecules and regulate the product distribution. The APIL ([BMIM]Cl) gives a maximum glucose yield of 88.2% at 180 °C and 40% water concentration, while the PIL ([Et3NH][HSO4]) produces a maximum HMF yield of 34.8% at 180 °C with no added water, and maximum LA and FA yields of 19.2% and 7.6%, respectively, at 200 °C. The PIL-based conversion targeting HMF as the biofuel precursor molecule, with glucose, LA, and FA as co-products, gives a product: reactant cost ratio 194.