Liquid–liquid extraction of levulinic acid from aqueous solutions using hydrophobic tri-n-octylamine/alcohol-based deep eutectic solvent

Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.

Intensified reactive extraction of 4-hydroxypyridine with di(2-ethylhexyl) phosphoric acid in 1-octanol by using tributyl phosphate

The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.

A comparison study on structure-function relationship of polysaccharides obtained from sea buckthorn berries using different methods:antioxidant and bile acid-binding capacity

In this study,the structural characters,antioxidant activities and bile acid-binding ability of sea buckthorn polysaccharides(HRPs)obtained by the commonly used hot water(HRP-W),pressurized hot water(HRP-H),ultrasonic(HRP-U),acid(HRP-C)and alkali(HRP-A)assisted extraction methods were investigated.The results demonstrated that extraction methods had significant effects on extraction yield,monosaccharide composition,molecular weight,particle size,triple-helical structure,and surface morphology of HRPs except for the major linkage bands.Thermogravimetric analysis showed that HRP-U with filamentous reticular microstructure exhibited better thermal stability.The HRP-A with the lowest molecular weight and highest arabinose content possessed the best antioxidant activities.Moreover,the rheological analysis indicated that HRPs with higher galacturonic acid content and molecular weight showed higher viscosity and stronger crosslinking network(HRP-C,HRP-W and HRP-U),which exhibited stronger bile acid binding capacity.The present findings provide scientific evidence in the preparation technology of sea buckthorn polysaccharides with good antioxidant and bile acid binding capacity which are related to the structure affected by the extraction methods.

Kinetics of cobalt(Ⅱ) extraction from sulfate aqueous solution by sodium salt of di-decylphosphinic acid (DDPA)

Kinetics of Co（II） extraction from sulfate aqueous solution by the sodium salt of di-decylphosphinic acid （Na-DDPA） was studied using a modified Lewis cell to disclose the mechanism of extraction. Parameters affecting the extraction rate, such as stirring speed, temperature, interfacial area, Na-DDPA concentration and Co（II） concentration, were investigated, respectively. The effect of diffusion resistance on extraction rate was negligible when the stirring operation was conducted in a plateau region of 95-110 r/min. Extraction rate increased with the increase in the temperature or specific interfacial area. The activation energy E was calculated to be 32.75 kJ/mol. These suggested that rate controlling mechanism of Co（II） extraction by Na-DDPA was chemical reaction regime and the rate-determining step of Co（II） extraction was chemical reaction at the interface. The initial extraction rate also increased with the increase in the concentrations of Na-DDPA and Co（II）. The extraction rate equation and mechanism of Co（II） extraction by Na-DDPA were proposed.

Effects of dietary oil sources and fat extraction methods on apparent and standardized ileal digestibility of fat and fatty acids in growing pigs

Background:There is a lack of data for the standardized ileal digestibility(SID) of fat and fatty acids in national feed databases.In addition,it is important to specify the procedures used for fat analyses.Therefore,an experiment was conducted to 1) determine the apparent ileal digestibility(AID) and SID of fat and fatty acids in ten different oil sources for growing pigs and to develop prediction equations for SID of fat based on fatty acid composition;and 2) compare the effect of the fat extraction methods on the calculated values for endogenous loss and digestibility of fat.Methods:Twenty-two barrows(initial body weight:32.1 ± 2.3 kg) were surgically fitted with a T-cannula in the distal ileum,and allotted to 1 of 11 experimental diets in a 4-period Youden Square design.A fat-free diet was formulated using cornstarch,soy protein isolate and sucrose.Ten oil-added diets were formulated by adding 6% of dietary oil sources to the fat-free diet at the expense of cornstarch.All diets contained 26% sugar beet pulp and 0.40% chromic oxide.Results:The endogenous loss of ether extract(EE) was lower than that of acid-hydrolyzed fat(AEE;P < 0.01).There were significant differences in the AID and SID of fat and saturated fatty acids across the dietary oil sources(P < 0.05).The SID of AEE for palm oil was lower than that of sunflower oil,corn oil,canola oil,rice oil and flaxseed oil(P < 0.01).The AID and SID of fat ranged from 79.65% to 86.97% and from 91.14% to 99.18%.Although the AID of EE was greater than that of AEE(P < 0.01),there was no significant difference in SID of EE and AEE except for palm oil.The ratio of unsaturated to saturated fatty acids(U/S) had a positive correlation with SID of fat(P < 0.05),whereas C16:0 and long chain saturated fatty acids(LSFA) were significant negatively correlated with SID of fat(P < 0.01).The best-fit equation to predict SID of fat was SID AEE = 102.75-0.15 × LSFA-0.74 × C18:0-0.03 × C18:1(Adjusted coefficient of determination = 0.88,P < 0.01).Conclusions:When calculating the SID of fat,the EE content of the samples can be analyzed using the direct extraction method,whereas the acid hydrolysis procedure should be used to determine the AID of fat.Fat digestibility of dietary oils was affected by their fatty acid composition,especially by the contents of C16:0,LSFA and U/S.

MICROWAVE-ASSISTED EXTRACTION OF GLYCYRRHIZIC ACID FROM LICORICE ROOT-EFFECT OF THE PROPERTY OF SOLUTION ON EXTRACTION OF GA

The property of extraction solution is an important factor influencing the extraction efficiency. In the present work, the effect of the property of solution on extraction of GA was studied, which including the concentration of ethanol, ammonia and cation (M+), pH of extraction solution, different kinds of organic solvent etc. The results show that 50%-60%(v/v) ethanol can reach high percentage extraction of GA. If 1% (v/v) ammonia solution was added into 60%(v/v) ethanol, the percentage extraction can be increased from 2.0% to 2.31%. Without ammonia, 50mmol/L [M+] (M+ = K+, NH4+) was added into 60%(v/v) ethanol, percentage extraction of GA can reach about 2.26%. If pH of solution (60% ethanol) was adjust to pH=4.0, it can reach high percentage extraction. If pH of solution (60% ethanol + 50mmol [M+], pH=6.1) was adjust tO PH=4.0, especially M+ is K+ or NH4+, it can reach almost same extraction efficiency as that of 1% ammonia solution + 60% ethanol, and the operation environment can be greatly improved.

Extracting vanadium from stone-coal by oxygen pressure acid leaching and solvent extraction

Vanadium extraction from stone-coal was investigated by oxygen pressure acid leaching and solvent extraction.The mineralogy of the stone-coal from Tongren City of Guizhou Province,China,was investigated by various determination methods. The effects of leaching time,leaching temperature,leaching agent concentration,leaching L/S ratio,granularity of material,additive consumption were investigated based on the mineralogy.The results show that under the conditions of leaching time of 3-4 h, temperature of 150℃,sulfuric acid consumption of 25%?30%,ratio of liquid to solid of 1.2:1,the granularity less than 0.074 mm, additive consumption of 3%-5%,and oxygen pressure of 1.2 MPa,and the vanadium leaching rate can be more than 92%by the method of two-step pressurized acid leaching.The powdery V2O5 product with 99.52%in V2O5 content is obtained by the flowsheet of acid recovery,removing iron by reduction process,solvent extraction,precipitating vanadium with ammonium water,and pyrolysis from the stone-coal oxygen pressure acid-leaching solution.The total recovery efficiency of vanadium is above 85%,which is more than 20%higher than that obtained in the conventional process.Furthermore,the new process does not cause air pollution since no HCl or Cl2 is released by calcination of the raw material.

Biodiesel Production from Rhynchophorus ferrugineus Larvae Oil: Physichochemical Properties and Acid Composition of Oil as Affected by Oil Extraction Protocol

Biodiesel, a renewable energy source made from natural oils and fats, can be produced using white raffia larvae as a raw material. These larvae have a high lipid content and a short life cycle, making them suitable for this purpose. One crucial step in biodiesel production is oil extraction, and this study aimed to investigate how the extraction protocol affects the fuel properties of the oil. To study the impact of solvent type, solvent volume, and residence time on oil yield, 200 grams of Rhynchophorus ferrugineus were used in a Soxhlet extractor. The researchers examined the physicochemical properties and fatty acid composition of the crude grease using the European biodiesel standard (EN14214) and gas chromatography methods, respectively. The study found that hexane as a solvent produced the highest oil yield (64.44%) during a four-hour extraction period with a solvent ratio of 300 ml. Furthermore, the hexane-extracted oil had the highest iodine number (3.02 g/100 g) and cetane number (55.69). These values indicate favorable properties for biodiesel production. The Rhynchophorus ferrugineus larvae oil proved to be a rich source of monounsaturated fatty acids (76%), which were found to be significantly affected by the solvent type. Based on quality assessment, Rhynchophorus ferrugineus can be suitable for biodiesel production. In summary, under the given operational conditions, hexane is the most suitable solvent for Rhynchophorus ferrugineus oil extraction for biodiesel production. Further research in optimizing the extraction process can contribute to the efficient utilization of renewable energy sources like white raffia larvae for biodiesel production.

Centrifugal extraction of rare earths from wet-process phosphoric acid

Phosphorite ore is a potential resource of rare earths （RE） as well as phosphate; therefore, the recovery of RE from wet-process phosphoric acid （WPA） is promising. This study investigated the influence of rotational speed, extractant concentration, flow ratio and phase contact time on the centrifugal extraction of RE from WPA and the separation of RE from impurities. The results indicate that higher rotational speed, higher extractant concentration and larger flow ratio are beneficial to the extraction of RE and impurities from phosphoric acid. It is found that the phase contact time for efficiently extracting RE and that for iron are of great difference, which provides an effective method for separating RE from iron using the non-equilibrium extraction process in centrifugal contactors. Compared with equilibrium extraction, the separation factor βRE/Fe is enhanced from 0.07 to 17.6.

Synergistic extraction of cerium from sulfuric acid medium using mixture of 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester and Di-(2-ethyl hexyl) phosphoric acid as extractant

Synergistic extraction of cerium（IV） from sulfuric acid medium using mixture of 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester（HEH/EHP, HL） and Di-（2-ethyl hexyl） phosphoric acid（HDEHP, HA） as extractant was investigated.The results indicated that the maximum synergistic enhancement coefficients were obtained at the mole fraction of HEH/EHP=0.6, and cerium（IV） was extracted into organic phase in the form of Ce（SO4）0.5HL2A2.A cation exchange mechanism was proposed for the synergistic extraction of Ce（IV）.The equilibrium constants and thermodynamic functions such as △G, △H, and △S were determined in the extraction of Ce（IV） from sulfuric medium using mixture of HEH/EHP and HDEHP.

Extraction of Zr(IV) from hydrochloric acid with tri-octyl amine and Cyanex 921 in kerosene

This article reports the extraction of zirconium （IV） from aqueous HC1 solution by tri-octyl amine （TOA）, Cyanex 921, and their binary mixture using kerosene as the diluent. The effect of some parameters on the extraction of Zr（IV） was investigated such as equilibration time, aqueous phase acidity, extractant molarity, chloride ion concentration, nature of diluents, and temperature. The extraction of Zr（IV） was found to be 99% from 7.5 M HC1 using the mixture of extractants containing 0.1 M TOA and 0.02 M Cyanex 921 in kerosene. Kerosene was found to be the effective diluent for the extraction of Zr（IV） with the binary mixture of TOA and Cyanex 921. The positive enthalpy change and positive entropy change in the binary extraction system show the endothermic process with an increase in entropy. Stripping of Zr（IV） from the loaded organic phase containing the mixture of TOA （0.1 M） and Cyanex 921 （0.02 M） indicates that HNO3 and Na2CO3 are the best stripping agents.

Synergistic extraction of rare earth by mixtures of 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester and di-(2-ethylhexyl) phosphoric acid from sulfuric acid medium

The extraction of Nd^3＋ and Sm^3＋, including the extraction and stripping capability as well as the separation effect of Nd^3＋ or Sm^3＋, from a sulfuric acid medium, by mixtures of di-（2-ethylhexyl） phosphoric acid （HDEHP, H2A2（0）） and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester （HEH/EHP, H2L2（0）） were studied. The distribution ratios and synergistic coefficients of Nd^3＋ and Sm^3＋ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3＋ or Nd^3＋. The chemical compositions of the extracted complex were determined as Nd.（HA2）2-HL2 and Sm.（HA2）2-HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.

Efficient Extraction of Astaxanthin from Phaffia rhodozyma with Polar and Non-polar Solvents after Acid Washing

method of extracting astaxanthin from Phaffia rhodozyma with various solvents after acid washing was investigated. The extraction efficiency was distinctly increased after acid washing of P. rhodozyma cells. When the concentration of HCl was 0.4 mol.L^-1, the highest extraction efficiency of astaxanthin was achieved which was about three times higher than the control. Acetone or benzene as single polar or non-polar solvent was the most ef- fective solvent in our research. With a combination of isopropanol and n-hexane （volume ratio of 2 ： 1）, the maxi- mal extraction efficiency was achieved, approximately 60% higher than that obtained with a single solvent. The liquid-solid ratio and the extracting time were also optimized. Under the optimum extraction conditions, the extraction yield of astaxanthin exceeded 98%.

Recovery of oxalic acid from mother-liquor containing hydrochloric acid and cobalt by solvent extraction with P350

The solvent of P350 was applied to extract and separate the oxalic acid from the mother-liquor originated from the precipitation of cobalt by oxalic acid,and its extraction mechanism was deduced.Some factors,including the concentration of P350, the concentration of hydrochloric acid and the concentration of oxalic acid were investigated to determine the best distribution coefficient of the oxalic acid.In the case of phase ratio(O/A)at 2.0,the extraction of the oxalic acid was more than 95%and its concentration in the extraction raffinate was lower than 0.004 0 mol/L after six-stage counter-current extraction.While the phase ratio(O/A)of the stripping was at 1.0,the recovery of oxalic acid attained more than 95%after ten-stage counter-current stripping.

Extraction of metals from a zinc smelting slag using two-step procedure combining acid and ethylene diaminetetraacetic acid disodium

A two-step leaching method in combination of acid and ethylene diaminetetraacetic acid disodium （EDTA-Na2） was applied to extract metals such as Cd, Cu, Fe, Pb and Zn from a zinc smelting slag. The results show that the extraction rates of Cd, Cu, Fe and Zn in slag reach 88.3%, 54.1%, 69.6% and 54.7%, respectively, while the extraction rate of Pb is only 0.05% leached with 1.25 mol/L sulfuric acid under the conditions of the ratio of slag to liquid of 100 g/L, 65 ℃ and 120 r/min for 2 h. However, Pb extraction rate from 1.25 mol/L sulfuric acid leached residue reaches as high as 66.5% by using 0.1 mol/L EDTA-Na2 solution. The results indicate that two-step sequential extraction procedure combining 1.25 mol/L sulfuric acid and 0.1 mol/L EDTA-Na2 solution can extensively extract Cd, Cu, Fe, Pb and Zn from zinc smelting slag.

Kinetics of Forward Extraction of Boric Acid from Salt Lake Brine by2-Ethyl-1,3-hexanediol in Toluene Using Single Drop Technique

The kinetics of forward extraction of boric acid from salt lake brine by 2-ethyl-1,3-hexanediol in toluene was investigated using the single drop technique. The factors affecting the extraction rate include interfacial area between aqueous phase and organic phase, initial concentration of boric acid in aqueous phase, initial concentration of 2-ethyl-1,3-hexanediol in organic phase, and extraction temperature. The experimental results show that the extraction rate increases with the increase of the initial concentration of boric acid and2-ethyl-1,3-hexanediol, interfacial area of two phases, and temperature. With the temperature-dependence study, it is showed that the extraction is a diffusion-controlled process. The kinetic equation is presented for pH 1.0 in the aqueous phase and temperature of 318 K.

Microwave-assisted Micellar Extraction and Determination of Glycyrrhizic Acid and Liquiritin in Licorice Root by HPLC

The feasibility of emploving non-ionic surfactant （Triton X-100） as an alternative and effective solventfor the microwave-assisted extraction of glycyrrhizic acid （GA） and liquiritin （LQ） from licorice root was studied.The optimal extraction parameters based on the microwave-assisted micellar extraction technique were determined.Under the optimal conditions, i.e. 5% （by volume） Triton X-100, microwave-assisted extraction for 3--5min at 373K, the percentage extraction of active ingredients reached the highest value. The preconcentration tactor for GA and L＇Q （about 13.5） and the extraction efficiency for these two ingredients approached 100% showed the coupling of microwave-assisted extraction and cloud-point extraction could be employed as a new and. effective techniquefor the rapid extraction and preconcentration of pharrnacologically active ingredients from medicinal plants SUCh aslicorice root without disturbing chromatographic analysis.

Extraction Equilibria of Trimellitic and [ 1,1′-Biphenyl]-2,2′-dicarboxylic Acid with 1-Octanol, 50%TBP, and 10%TRPO in Kerosene

To explore the feasibility of extracting aromatic acid products from oxidizing coal, two aromatic acids, trimellitic and [1,1′-biphenyl]-2,2′-dicarboxylic acid, were selected as the solutes, and the extraction equilibrium of the acids were studied with 1-octanol, 50% tributyl phosphate （TBP） in kerosene, and 10% trialkylphosphine oxide （TRPO） in kerosene. The results showed that the degree of extraction of [1,1′-biphenyl]-2,2′-dicarboxylic acid was larger than that of trimellitic acid for all of the solvent, and the extraction capacity with TRPO is more effective than the one with TBP. The extraction behavior of aromatic polyacid is different from that of carboxylic acid, and the reactive extraction function of aromatic acids with TBP and TRPO is not as effective as that of carboxylic acid. 1-octanol could be used to remove [1,1′-biphenyl]-2,2′-dicarboxylic acid from the mixture of trimellitic acid and [1,1′-biphenyl]-2,2′-dicarboxylic acid. Because the weak hydrogen bond association exists between -OH in 1-octanol and -COOH in aromatic acid, the extractive selectivity of [ 1, 1′-biphenyl]-2,2′-dicarboxylic to trimellitic acid depends on the stoichiometric ratio.

Reactive Extraction of Nicotinic Acid with Trialkylamine in n-Octanol

The distributions of nicotinic acid (NA) between water and trialkylamine (N235) dissolved in n-octanol was studied. The complexes of N235 and NA were investigated by Fourier transformation infrared spectrometry to deduce the reaction mechanism. It was found that N235/n-octanol was an efficient extractant for extracting nicotinic acid. The favorable operation conditions were equilibrium aqueous pH 4.2 to 5.5 and initial N235 concentration<0.42 mol·L-1 . The reaction processes included the reaction between neutral N235 and neutral NA and the reaction between protonated N235 and anionic NA. Based on the mass action law and some assumptions, an expression for distribution coefficient D was proposed. The apparent extraction equilibrium constants were calculated by fitting the experimental data and the results were satisfactory.

Thermodynamics of Solvent Extraction of Rare and Scattered Metal-Indium with Diethylhexylmonothiophosphoric Acid

The thermodynamics of extracting In（ Ⅲ） with diethylhexylmonothiophosphoric acid as an extractant in a H2SO4 system is reported. The equilibrium molalities of In^3＋ ions were measured at a high acidity and ionic strengths varying from 0. 1 to 2.0 mol/kg in an aqueous phase containing Na2SO4 as the supporting electrolyte. The values of the standard extraction constant K^0 at various temperatures were obtained by the methods of extrapolation and polynomial approximation. The equation lgK^0 = - 51.95 - 5.93 × 10^3/T ＋ 6. 15 × 10^-2 T was also obtained and the thermodynamic quantities for the extraction process were calculated.