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.

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.

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.

Lithium extraction from hard rock lithium ores(spodumene,lepidolite,zinnwaldite,petalite):Technology,resources,environment and cost

Lithium production in China mainly depends on hard rock lithium ores,which has a defect in resources,environment,and economy compared with extracting lithium from brine.This paper focuses on the research progress of extracting lithium from spodumene,lepidolite,petalite,and zinnwaldite by acid,alkali,salt roasting,and chlorination methods,and analyzes the resource intensity,environmental impact,and production cost of industrial lithium extraction from spodumene and lepidolite.It is found that the sulfuric acid method has a high lithium recovery rate,but with a complicated process and high energy consumption;alkali and chlorination methods can directly react with lithium ores,reducing energy consumption,but need to optimize reaction conditions and safety of equipment and operation;the salt roasting method has large material flux and high energy consumption,so require adjustment of sulfate ratio to increase the lithium yield and reduce production cost.Compared with extracting lithium from brine,extracting lithium from ores,calcination,roasting,purity,and other processes consume more resources and energy;and its environmental impact mainly comes from the pollutants discharged by fossil energy,9.3-60.4 times that of lithium extracted from brine.The processing cost of lithium extraction from lepidolite by sulfate roasting method is higher than that from spodumene by sulfuric acid due to the consumption of high-value sulfate.However,the production costs of both are mainly affected by the price of lithium ores,which is less competitive than that of extracting lithium from brine.Thus,the process of extracting lithium from ores should develop appropriate technology,shorten the process flow,save resources and energy,and increase the recovery rate of related elements to reduce environmental impact and improve the added value of by-products and the economy of the process.

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.

Leaching of phosphorus from incinerated sewage sludge ash by means of acid extraction followed by adsorption on orange waste gel

Ashes from sewage sludge incineration have a high phosphorus content, approximately 8% （W/W）, which indicates a potential resource of the limiting nutrient. Incineration of sewage sludge with subsequent recovery of phosphorus is a relatively new sludge treatment technique. In this article, the leaching of phosphorus by using sulfuric acid as well as hydrochloric acid by means of several batch experiments was presented. At the same time a selective recovery of phosphorus by adsorption was also discussed. The effects of acid concentration, temperature and time on extraction were studied. The phosphorus leaching increased with the increase in acid concentration and temperature. Kinetic studies showed that the complete leaching of phosphorus took place in less than 4 h. Selective adsorption of phosphorus by using orange waste gel provided a hint for recovery of this natural resource, which eventually could meet the ever-increasing requirement for phosphorus. The overall results indicated that the incinerated sewage sludge ash can be treated with acid to efficiently recover phosphorus and thus can be considered a potentially renewable source of phosphorus.

Extraction of vanadium from vanadium slag by high pressure oxidative acid leaching

To extract vanadium in an environment friendly manner, this study focuses on the process of leaching vanadium from vanadium slag by high pressure oxidative acid leaching. Characterizations of the raw slag, mineralogy transformation, and the form of leach residues were made by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy. The result shows that the vana-dium slag is composed of major phases of fayalite, titanomagnetite, and spinel. During the high pressure oxidative acid leaching process, the fayalite and spinel phases are gradually decomposed by sulfuric acid, causing the release of vanadium and iron in the solution. Meanwhile, unreacted silicon and titanium are enriched in the leach residues. With the initial concentration of sulfuric acid at 250 g·L^-1, a leaching tem-perature of 140℃, a leaching time of 50 min, a liquid-solid ratio of 10：1 mL·g^-1, and oxygen pressure at 0.2 MPa, the leaching rate of vana-dium reaches 97.69%.

Solvent extraction of vanadium from sulfuric acid solution

The behaviour of vanadium（V） extracted from sulfuric acid solution was investigated using Cyanex 923 as an extractant. The effects of the concentration of Cyanex 923 and the pH of the solution were studied. The extraction of vanadium（V） increases with the increase of Cyanex 923 concentration and shaking time. Cyanex 923 can extract vanadium（V） from sulfuric acid solution at low pH conditions, and the best pH conditions for extraction of vanadium（V） are at pH 1.0-2.0. The species extracted into the organic phase is VO2HSO4 with one molecule of Cyanex 923. Equilibrium studies were used to assess the extraction efficiency of vanadium（V） recovery from the sulfuric acid solution.

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.

Optimization of an innovative approach involving mechanical activation and acid digestion for the extraction of lithium from lepidolite

The recovery of lithium from hard rock minerals has received increased attention given the high demand for this element. There- fore, this study optimized an innovative process, which does not require a high-temperature calcination step, for lithium extraction from le- pidolite. Mechanical activation and acid digestion were suggested as crucial process parameters, and experimental design and re- sponse-surface methodology were applied to model and optimize the proposed lithium extraction process. The promoting effect of amorphi- zation and the formation of lithium sulfate hydrate on lithium extraction yield were assessed. Several factor combinations led to extraction yields that exceeded 90%, indicating that the proposed process is an effective approach for lithium recovery.

Process design and economic analysis of methacrylic acid extraction for three organic solvents

In this work,a techno-economic study for the solvent based extraction of methacrylic acid from an aqueous solution is presented.The involved phase equilibrium calculations in process design are verified by measured experimental data.First,experiments are conducted with different solvent candidates to measure LLE(liquid–liquid equilibrium)data and to establish the effects of extraction temperature and dosage of solvent.Next,the binary interaction parameters for the UNIQUAC model to be used for equilibrium calculations are fine-tuned with measured data.Then,a process for the solvent based extraction of methacrylic acid recovery is designed and verified through simulation with the regressed UNIQUAC model parameters.The optimal configuration of the process flowsheet is determined by minimizing the total annualized cost.Among the three solvent candidates considered-cyclohexane,hexane and toluene-the highest efficiency and the lowest total annualized cost is found with toluene as the solvent.

Extraction Separation of Germanium with Hydroxamic Acid HGS98

The extraction separation of germanium from indium raffinate in hydrometallurgical zinc process was discussed. The conditions and mechanism of the extraction with hydroxamic acid HGS98 have been investigated in detail. The results show that u sing 2% (mass fraction) hydroxamic acid HGS98 and 5% D 2EHPA as synergist, germanium is extracted (1 stage) over 99% in 5 min at phase ratio ( V o∶ V a) of 1∶5 from indium raffinate with original acidity. Then, using 2 mol·L -1 NH 4F as strip liquor, the stripping recovery is over 98% in 15 min at phase ratio of 1∶1. This process has the following advantages:easy to operate, high recovery and selectivity, and lower investment cost. It provides a new way to recover rare metal-germanium from metallurgical spent residues.

Extraction process of chlorogenic acid in flos lonicerae by enzymatic treatment

A new method of extracting chlorogenic acid from flos lonicerae, and treating the materials with enzyme before being extracted by ethanol is developed, and the optimum conditions are also investigated in detail. Three important factors, enzyme dosage, treatment time and treatment temperature are adapted to optimize the extraction process. The experimental results show that the extract yield of flos lonicerae and chlorogenic acid can be obviously increased by the cellulase treatment, 61.5 mg chlorogenic acid is obtained from 1.00 g flos lonicerae at most. The optimal temperature of enzymatic treatment is 40 50 ℃. Compared with the use of single cellulase, the combined treatment of cellulase and pectinase increase the extract yield obviously but fail to improve that of chlorogenic acid.

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.

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.