Modeling and prediction of methanol air release from bleached chemi-thermo mechanical pulp board.

This paper reports on the modeling, prediction and evaluation approaches of methanol release from bleached chemi-thermo mechanical pulp (BCTMP) board during storage. A pseudo-first order desorption kinetics model of methanol release was established for describing the desorption behavior of methanol from BCTMP, i.e., , in which the desorption constant (K) and rate constant (k des) were well described by van't Hoff and Arrhenius equations. Based on the simulation experiments at various temperatures, the desorption activation energy of methanol and its adsorption enthalpy is calculated and is 53.7 and -86.2 kJ mol-1 K-1, respectively. With the developed model, the risk of methanol release for the storage of BCTMP board can be examined by either the time-dependent kinetics model or a two-step thermodynamic approach using the equilibrium concentration of methanol in indoor air. This paper provides a valuable tool to assess the risk of methanol release for the paper industry and related warehouse departments.

Determination of total acid content in biomass hydrolysates by solvent-assisted and reaction based headspace gas chromatography.

This work reports on a novel method for the determination of total acid (TA) in biomass hydrolysates by a solvent-assisted and reaction-based headspace gas chromatography (HS-GC). The neutralization reaction between the acids in hydrolysates and bicarbonate in an ethanol (50%) aqueous solution was performed in a closed headspace sample vial, from which the carbon dioxide generated from the reaction was detected by HS-GC. It was found that the addition of ethanol can effectively eliminate the precipitation of some organic acids in the biomass hydrolysates. The results showed that the reaction and headspace equilibration can be achieved within 45min at 70°C; the method has a good precision (RSD<3.27%) and accuracy (recovery of 97.4-105%); the limit of quantification is 1.36µmol. The present method is quite suitable to batch analysis of TA content in hydrolysate for the biorefinery related research.

Rapid method for determination of carbonyl groups in lignin compounds by headspace gas chromatography.

The paper reports on a novel method for rapid determination of carbonyl in lignins by headspace gas chromatography (HS-GC). The method involves the quantitative carbonyl reduction for aldehydes in 2min at room temperature or for acetones in 30min at 80°C by sodium borohydride solution in a closed headspace sample vial. After the reaction, the solution was acidified by injecting sulfuric acid solution and the hydrogen released to the headspace was determined by GC using thermal-conductivity detector. The results showed that with the addition of SiO2 powder, the reduction reaction of carbonyl groups can be greatly facilitated. The method has a good measurement precision (RSD<7.74%) and accuracy (relative error <10% compared with a reference method) in the carbonyl quantification. It is suitable to be used for rapid determination of carbonyl content in lignin and related materials.

A novel method for rapid determination of total solid content in viscous liquids by multiple headspace extraction gas chromatography.

This work demonstrates a novel method for rapid determination of total solid content in viscous liquid (polymer-enriched) samples. The method is based multiple headspace extraction gas chromatography (MHE-GC) on a headspace vial at a temperature above boiling point of water. Thus, the trend of water loss from the tested liquid due to evaporation can be followed. With the limited MHE-GC testing (e.g., 5 extractions) and a one-point calibration procedure (i.e., recording the weight difference before and after analysis), the total amount of water in the sample can be determined, from which the total solid contents in the liquid can be calculated. A number of black liquors were analyzed by the new method which yielded results that closely matched those of the reference method; i.e., the results of these two methods differed by no more than 2.3%. Compared with the reference method, the MHE-GC method is much simpler and more practical. Therefore, it is suitable for the rapid determination of the solid content in many polymer-containing liquid samples.

Increasing the sensitivity of headspace analysis of low volatility solutes through water removal by hydrate formation.

This paper reports on the development of a new headspace analytical technique that is based on water removal by hydrate formation (WRHF). By adding anhydrous salt, the liquid water in an aqueous sample will be removed leaving behind volatile analytes that are fully vaporized at temperatures well below their boiling points. With WRHF, the amount of sample in the headspace can be significantly increased, thereby dramatically improving the detection sensitivity. The technique reduces the risk of possible column damage in gas chromatography (GC) systems. The technique was applied to the determination of phenol at different stages of a coking wastewater treatment plant. The results showed that up to mL-levels of sample solution can be used in WRHF HS-GC analysis when 5g of CaCl2 were used as the anhydrous salt. The detection sensitivity for phenol content was 500 times greater than that in earlier HS-GC work that did not incorporate hydrate formation. The proposed WRHF headspace analysis technique is simple and practical, making it a useful tool for quantifying low concentrations of volatile analytes in aqueous samples.

Determination of maximal amount of minor gases adsorbed in a shale sample by headspace gas chromatography.

In this paper, we present a novel method for determining the maximal amount of ethane, a minor gas species, adsorbed in a shale sample. The method is based on the time-dependent release of ethane from shale samples measured by headspace gas chromatography (HS-GC). The study includes a mathematical model for fitting the experimental data, calculating the maximal amount gas adsorbed, and predicting results at other temperatures. The method is a more efficient alternative to the isothermal adsorption method that is in widespread use today.

[A triple-wavelength visible spectroscopic method for determination of iron content in lignocellulosic materials].

The present paper described a triple-wavelength visible spectroscopic method for the determination of iron content in lignocellulosic materials. After the sample was pretreated with acidic hydrolysis method under selected conditions, the color agent, 1, 10-phenanthroline monohydrate, was added in the filtrate and then measured by a triple-wavelength spectroscopic method at wavelengths of 416, 510 and 700 nm, from which the iron contents of the sample can be calculated. The results showed that this method can efficiently deduct the influences of acidic soluble lignin and furfural compounds generated during the sample pretreatment and baseline drift caused by the tiny particles in the filtrates. It not only has a good measurement precision but also is accurate, in which the relative differences of the results obtained by the present method and ICP-OES method is less than 5%. The method is simple and practical, and suitable for industrial applications.

A novel method for the determination of black liquor viscosity by multiple headspace extraction gas chromatography.

This work demonstrates a novel method for the determination of viscosity in the concentrated black liquors from pulp mill recovery process. The method is based on the kinetic release of methanol (a vapor tracer) to the headspace in a sample closed vial by a multiple headspace extraction gas chromatographic technique. Both theoretical and empirical models were proposed for establishing the correlation with the reference method. The results showed that the correlation using either of the models is excellent for the tested black liquor samples (at 110°C). The presented method is simple and practical and can be a valuable tool for black liquor viscosity related research and applications.

A new headspace gas chromatographic method for the determination of methanol content in paper materials used for food and drink packaging.

This study reports on a method for determination of methanol in paper products by headspace gas chromatography (HS-GC). The method is based on the hydrolysis of the pulp or paper matrix, using a phosphoric acid solution (42.5%) as the medium at 120 °C in 5 h (excluding air contact) in order to release matrix-entrapped methanol, which is then determined by HS-GC. Data show that, under the given conditions of hydrolysis, no methanol was formed from the methoxyl groups in the material. Reproducibility tests of the method generated a relative standard deviation of <3.5%, with recovery in the range of 93.4-102%. The present method is reliable, accurate, and suitable for use in batch testing of the methanol content in paper-related materials. The method can play an important role in addressing food safety concerns that may be raised regarding the use of paper materials in food and beverage packaging.

A novel method for the determination of adsorption partition coefficients of minor gases in a shale sample by headspace gas chromatography.

A novel method has been developed for the determination of adsorption partition coefficient (Kd) of minor gases in shale. The method uses samples of two different sizes (masses) of the same material, from which the partition coefficient of the gas can be determined from two independent headspace gas chromatographic (HS-GC) measurements. The equilibrium for the model gas (ethane) was achieved in 5h at 120°C. The method also involves establishing an equation based on the Kd at higher equilibrium temperature, from which the Kd at lower temperature can be calculated. Although the HS-GC method requires some time and effort, it is simpler and quicker than the isothermal adsorption method that is in widespread use today. As a result, the method is simple and practical and can be a valuable tool for shale gas-related research and applications.

A new method for the determination of biological oxygen demand in domestic wastewater by headspace gas chromatography.

A headspace gas chromatographic method (HS-GC) has been developed for the determination of biological oxygen demand (BOD) in the water samples from domestic wastewater treatment plants. The method is based on measuring the remaining oxygen in the headspace of the sample (that has been seeded with microorganisms) in a closed container after a period of incubation. The relative standard deviation of the method in replicate testing was <4.9%. Further, the results differed by less than 6% when compared with the widely used reference method (the ISO standard) for determining BOD5. The limit of quantification in BODn testing was about 1.8 mg/L. The new method is simple and suitable for use in the batch sample testing for BODn measurement.

Rapid determination of formaldehyde in sanitary paper napkins for product quality control by headspace gas chromatography.

This study reports on a headspace gas chromatographic method (HS-GC) for the determination of formaldehyde in sanitary napkin samples. The method is based on the reaction of formaldehyde and sodium borohydride in a concentrated potassium carbonate solution (824 g/L), in which formaldehyde is quantitatively converted to methanol at 105°C in 45 min. The methanol from the conversion is determined by HS-GC. The repeatability of the method had a relative standard deviation of less than 4.5%; the limit of quantification (LOQ) was 1.17 µg, and the recovery ranged from 96.8 - 106%. The present method is simple, rapid, and accurate. It is suitable for use in the batch testing for product quality control of tissue papers during the manufacturing process and in analysis of point-of-sale samples from commercial markets.

A novel headspace gas chromatographic method for in situ monitoring of monomer conversion during polymerization in an emulsion environment.

This paper describes a novel multiple-headspace extraction/gas chromatographic (MHE-GC) technique for monitoring monomer conversion during a polymerization reaction in a water-based emulsion environment. The polymerization reaction of methyl methacrylate (MMA) in an aqueous emulsion is used as an example. The reaction was performed in a closed headspace sample vial (as a mini-reactor), with pentane as a tracer. In situ monitoring of the vapor concentration of the tracer, employing a multiple headspace extraction (sampling) scheme, coupled to a GC, makes it possible to quantitatively follow the conversion of MMA during the early stages of polymerization. Data on the integrated amount of the tracer vapor released from the monomer droplet phase during the polymerization is described by a mathematic equation from which the monomer conversion can be calculated. The present method is simple, automated and economical, and provides an efficient tool in the investigation of the reaction kinetics and effects of the reaction conditions on the early stage of polymerization.

Rapid determination of hydrogen peroxide in pulp bleaching effluents by headspace gas chromatography.

A headspace gas chromatographic (HS-GC) method has been developed for the determination of residual hydrogen peroxide in pulp bleaching effluents. The method is based on the reaction of hydrogen peroxide and permanganate in an acidic medium (0.1 mol/L), in which hydrogen peroxide is quantitatively converted to oxygen within 10 min at 60°C in a sealed headspace sample vial. The released oxygen is then determined by GC equipped with a thermal conductivity detector. The method is robust, sensitive, and accurate, with reproducibility characterized by a relative standard deviation of <0.5%, a sensitivity whose limit of quantification (LOQ) is 0.96 µmol, and a demonstrated recovery ranging from 98 to 103%. Further, the method is simple, rapid, and automated.

Determination of degree of substitution in succinic anhydride modified cellulose by headspace gas chromatography.

This paper reports on a headspace gas chromatographic method (HS-GC) for rapid determination of degree of substitution in succinic anhydride (SA) modified celluloses. The method is based on the reaction between the carboxyl groups in SA modified cellulose and bicarbonate solution in a closed headspace sample vial. The CO(2) released from the reaction was measured by HS-GC. The completion of the reaction was achieved within 25 min at 80 °C when a small sample size (<20 mg) was used. The relative standard deviation (RSD) measurement of precision was less than 4.1%, and the results were within 8.0% of those obtained with the traditional titration for determining the degree of substitution. The present method is simple, practical, automated, and suitable for use in anhydride modified cellulose research.

Determination of methanol in pulp washing filtrates by desiccated full evaporation headspace gas chromatography.

This paper reports on a desiccated full evaporation headspace gas chromatographic (FE HS-GC) technique for determination of the methanol content in dilute mill effluents. Anhydrous K(2)CO(3) was selected as the preferred salt for eliminating the water in the sample in the headspace sample vial. The results showed that the addition of 12 g K(2)CO(3) made it possible to introduce a larger sample size (up to 1 mL) into the FE HS-GC measurement, thereby increasing the sensitivity of the technique. At the given equilibration temperature (105°C), a near-complete mass transfer of methanol from the liquid phase to vapor phase (headspace) was achieved within 10 min. Replicate samples showed that the relative standard deviation of the method was less than 1.5%. Further, the limit of quantification (LOQ) was 0.12 µg and the recovery ranged from 95 to 104%. The present method greatly improves the methanol detection sensitivity in the FE HS-GC method and has the added advantage of being simple, rapid and accurate.