A model for tribofilm growth is developed. The model is used in combination with numerical contact mechanics tools to enable evaluation of the combined effects of chemistry and contact mechanics. The model is tuned with experimental data and is thereafter applied to rough surfaces. The growth of the tribofilm is evaluated for 3 different contact cases and short-term tribofilm growth behaviour is analyzed. The results show how tribofilms grow in patches. The model is expected to be used as a tool for analysis of the interaction between rough surfaces.

In the present study, in-situ ATR-FTIR spectroscopy was used for the first time to study the competitive adsorption of phosphate and arsenate on ferrihydrite. Deuterium oxide was used as solvent to facilitate the interpretations of recorded infrared spectra.It was found that arsenate and phosphate adsorbed more strongly at lower pD values, showing similarities in the adsorption behavior as a function of pD. However, arsenate complexes were found to be more strongly adsorbed than phosphate complexes in the pD range studied. About five times higher concentration of phosphate in solution was needed to reduce the absorbance due to pre-adsorbed arsenate to the same relative level as for pre-adsorbed phosphate, which was desorbed using a solution containing equal (molar) concentrations in arsenate and phosphate. At pD 4, two phosphate complexes were adsorbed on the iron oxide, one deuterated and one de-deuterated. When phosphate was pre-adsorbed and arsenate subsequently added to the system, the deuterated phosphate complex desorbed rapidly while the de-deuterated phosphate complex was quite stable. At pD 8.5, only the de-deuterated phosphate complex was adsorbed on the iron oxide. Moreover, the arsenate adsorbed was also predominantly de-deuterated as opposite to the arsenate adsorbed at pD 4. During the substitution experiments the configuration of these complexes on the iron oxide surface did not change. To the best of our knowledge, this is the first time this difference in stability of the different phosphate complexes is reported and shows the power of employing in-situ spectroscopy for this kind of studies.

Stabilization of arsenic contaminated soils by iron oxides has been proposed as a remediation technique to prevent leaching of arsenate into the environment. Fundamental studies are needed to establish under which conditions the complexes formed are stable. In the present work, a powerful technique, viz. ATR-FTIR spectroscopy, is adapted to studies of adsorption of arsenate species on iron oxides. This technique facilitates acquisition of both quantitative and qualitative in situ adsorption data.In the present work, about 800 nm thick films of 6-lineferrihydrite were deposited on ZnSe ATR crystals. Arsenate adsorption on the ferrihydrite film was studied at pD values ranging from 4 to 12 and at an arsenate concentration of 0.03 mM in D2O solution. The amount of adsorbed arsenate decreased with increasing pD as a result of the more negatively charged iron oxide surface at higher pD values. The adsorption and desorption kinetics were also studied. Arsenate showed a higher adsorption rate within the first 70 minutes and a much lower adsorption rate from 70 up to 300 minutes. The low adsorption rate at longer reaction times was partly due to a low desorption rate of already adsorbed carbonate species adsorbed at the surface. The desorption of carbonate species was evidenced by the appearance of negative absorption bands. The desorption of adsorbed arsenate complexes was examined by flushing with D2O at pD 4 and 8.5 and it was found that the complexes were very stable at pD 4 suggesting formation of mostly inner-sphere complexes whereas a fraction of the complexes at pD 8.5 were less stable than at pD 4, possibly due to the formation of outer-sphere complexes.In summary, the ATR technique was shown to provide in situ information about the adsorption rate, desorption rate and the speciation of the complexes formed within a single experiment, which is very difficult to obtain using other techniques.

Addition of iron oxide to arsenic-contaminated soil has been proposed as a means of reducing the mobility of arsenic in the soil. Arsenic and zinc are common coexisting contaminants in soils. The presence of zinc therefore may affect the adsorption properties of arsenic on iron oxide, and may thus affect its mobility in the soil. The influence of Zn(II) on the adsorption of arsenate ions on iron oxide was studied. Batch adsorption experiments indicated that Zn(II) increased the arsenate removal from a solution by ferrihydrite at pH 8. However, ATR-FTIR spectroscopy showed that no adsorption of arsenate on a ferrihydrite film occurred at pD 8 in the presence of Zn(II). Precipitation of zinc hydroxide carbonate followed by arsenate adorption onto the precipitate was found to be a plausible mechanism explaining the arsenate removal from a solution in the presence of Zn(II) at pH/pD 8. The previously suggested mechanisms attributing the enhanced removal of arsenate from solution in the presence of Zn(II) to additional adsorption on iron oxides could not be verified under the experimental conditions studied. It was also shown that at pH/pD 4, the presence of Zn(II) in the system did not significantly affect the adsorption of arsenate on ferrihydrite.

A method was developed to enhance the arsenic adsorption capacity of porous bodies of sintered hematite. The method comprised the formation of a coating of 1 wt % iron oxide nanoparticles on the raw material. The nanoparticles showed two distinct habits: spherical habit, likely ferrihydrite, and acicular habit, likely goethite and/or akaganéite. The specific surface area of the hematite raw material increased from 0.5 to 3.75 m2/g, and the adsorption capacity increased from negligible to 0.65 mg of [As]/g as calculated from equilibrium and breakthrough adsorption data. Equilibrium adsorption data of arsenate on the adsorbent from a solution at pH 5 followed the Langmuir model, while breakthrough adsorption data for a 500 μg/L arsenate solution at pH 5 followed the Thomas model. The adsorbed arsenic could be desorbed using distilled water at pH 12. These results show the potential for the reutilization of waste products comprising coarse hematite bodies as adsorbents.

Previous research has shown that alkali addition has operational advantages in entrained flow biomass gasification and allows for capture of up to 90% of the biomass sulfur in the slag phase. The resultant low-sulfur content syngas can create new possibilities for syngas cleaning processes. The aim was to assess the techno-economic performance of biofuel production via gasification of alkali impregnated biomass using a novel gas cleaning systemcomprised of (i) entrained flow catalytic gasification with in situ sulfur removal, (ii) further sulfur removal using a zinc bed, (iii) tar removal using a carbon filter, and (iv) CO2 reductionwith zeolite membranes, in comparison to the expensive acid gas removal system (Rectisol technology). The results show that alkali impregnation increases methanol productionallowing for selling prices similar to biofuel production from non-impregnated biomass. It was concluded that the methanol production using the novel cleaning system is comparable to the Rectisol technology in terms of energy efficiency, while showing an economic advantagederived from a methanol selling price reduction of 2–6 €/MWh. The results showed a high level of robustness to changes related to prices and operation. Methanol selling prices could be further reduced by choosing low sulfur content feedstocks.

The Graduate School of Space Technology

Arginine was produced via fermentation of sugars using the engineered microorganism Escherichia coli. Zeolite-Y adsorbents in the form of powder and extrudates were used to recover arginine from both a real fermentation broth and aqueous model solutions. An adsorption isotherm was determined using model solutions and zeolite-Y powder. The saturation loading was determined to be 0.2 g/g using the Sips model. Arginine adsorbed from a real fermentation broth using either zeolite-Y powder or extrudates both showed a maximum loading of 0.15 g/g at pH 11. This adsorbed loading is very close to the corresponding value obtained from the model solution showing that under the experimental conditions the presence of additional components in the broth did not have a significant effect on the adsorption of arginine. Furthermore, a breakthrough curve was determined for extrudates using a 1 wt % arginine model solution. The selectivity for arginine over ammonia and alanine from the real fermentation broth at pH 11 was 1.9 and 8.3, respectively, for powder, and 1.0, and 4.1, respectively, for extrudates. To the best of our knowledge, this is the first time recovery of arginine from real fermentation broths using any type of adsorbent has been reported.

1-Butanol and butyric acid are two interesting compounds that may be produced by acetone, butanol, and ethanol fermentation using e.g. Clostridium acetobutylicum. The main drawback, restricting the commercialization potential of this process, is the toxicity of butanol for the cell culture resulting in low concentrations of this compound in the broth. To make this process economically viable, an efficient recovery process has to be developed. In this work, a hydrophobic MFI type zeolite with high silica to alumina ratio was evaluated as adsorbent for the recovery of butanol and butyric acid from model solutions. Dual component adsorption experiments revealed that both butanol and butyric acid showed a high affinity for the hydrophobic MFI zeolite when adsorbed from aqueous model solutions. Multicomponent adsorption experiments using model solutions, mimicking real fermentation broths, revealed that the adsorbent was very selective to the target compounds. Further, the adsorption of butyric and acetic acid was found to be pH dependent with high adsorption below, and low adsorption above, the respective pKa values of the acids. Thermal desorption of butanol from MFI type zeolite was also studied and a suitable desorption temperature was identified.

Butanol, a promising biofuel, can be produced by ABE (acetone, butanol and ethanol) fermentation using e.g. Clostridium acetobutylicum. However, the butanol concentration in the resulting broth is limited to only ca. 20 g/L due to the toxicity for the microorganisms. This low product concentration demands an efficient recovery process for successful commercialization of this process. In this study, a structured adsorbent in the form of steel monolith coated with a silicalite-1 film was prepared using the in situ growth method. The adsorbent was carefully characterized by SEM and XRD. The performance of the adsorbent was evaluated by performing breakthrough experiments at room temperature using model ABE fermentation broths and the performance was compared with that of traditional adsorbents in the form of beads. The structured silicalite-1 adsorbent showed less saturation loading time as compared to commercial binder free silicalite-1 beads, reflecting the different dimensions of the columns used, set by experimental constraints. Studies of the desorption process showed that by operating at appropriate conditions, butanol with high concentration i.e. up to 95.2 wt% for butanol–water model system and 88.5 wt% for ABE fermentation broth can be obtained using the structured silicalite-1 adsorbent. Commercial silicalite-1 beads also showed good selectivity but the concentration of butanol in the desorbed product was limited to 70 % for the butanol–water model system and 69 % for ABE fermentation broth, probably as a result of entrained liquid between the beads.

A promising route for sustainable 1-butanol (butanol) production is ABE (acetone, butanol, ethanol) fermentation. However, recovery of the products is challenging because of the low concentrations obtained in the aqueous solution, thus hampering large-scale production of biobutanol. Membrane and adsorbent-based technologies using hydrophobic zeolites are interesting alternatives to traditional separation techniques (e.g., distillation) for energy-efficient separation of butanol from aqueous mixtures. To maximize the butanol over water selectivity of the material, it is important to reduce the number of hydrophilic adsorption sites. This can, for instance, be achieved by reducing the density of lattice defect sites where polar silanol groups are found. The density of silanol defects can be reduced by preparing the zeolite at neutral pH instead of using traditional synthesis solutions with high pH. In this work, binary adsorption of butanol and water in two silicalite-1 films was studied using in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy under equal experimental conditions. One of the films was prepared in fluoride medium, whereas the other one was prepared at high pH using traditional synthesis conditions. The amounts of water and butanol adsorbed from binary vapor mixtures of varying composition were determined at 35 and 50 °C, and the corresponding adsorption selectivities were also obtained. Both samples showed very high selectivities (100-23 000) toward butanol under the conditions studied. The sample having low density of defects, in general, showed ca. a factor 10 times higher butanol selectivity than the sample having a higher density of defects at the same experimental conditions. This difference was due to a much lower adsorption of water in the sample with low density of internal defects. Analysis of molecular simulation trajectories provides insights on the local selectivities in the zeolite channel network and at the film surface.

Pure silica zeolites are potentially hydrophobic and have therefore been considered to be interesting candidates for separating alcohols, e.g., 1-butanol, from water. Zeolites are traditionally synthesized at high pH, leading to the formation of intracrystalline defects in the form of silanol defects in the framework. These silanol groups introduce polar adsorption sites into the framework, potentially reducing the adsorption selectivity toward alcohols in alcohol/water mixtures. In contrast, zeolites prepared at neutral pH using the fluoride route contain significantly fewer defects. Such crystals should show a much higher butanol/water selectivity than crystals prepared in traditional hydroxide (OH−) media. Moreover, silanol groups are present at the external surface of the zeolite crystals; therefore, minimizing the external surface of the studied adsorbent is important. In this work, we determine adsorption isotherms of 1-butanol and water in silicalite-1 films prepared in a fluoride (F−) medium using in situ attenuated total reflectance−Fourier transform infrared (ATR−FTIR) spectroscopy. This film was composed of well intergrown, plate-shaped b-oriented crystals, resulting in a low external area. Single-component adsorption isotherms of 1-butanol and water were determined in the temperature range of 35− 80 °C. The 1-butanol isotherms were typical for an adsorbate showing a high affinity for a microporous material and a large increase in the amount adsorbed at low partial pressures of 1-butanol. The Langmuir−Freundlich model was successfully fitted to the 1-butanol isotherms, and the heat of adsorption was determined. Water showed a very low affinity for the adsorbent, and the amounts adsorbed were very similar to previous reports for large silicalite-1 crystals prepared in a fluoride medium. The sample also adsorbed much less water than did a reference silicalite-1(OH−) film containing a high density of internal defects.The results show that silicalite-1 films prepared in a F− medium with a low density of defects and external area are very promising for the selective recovery of 1-butanol from aqueous solutions.

Biobutanol produced by, e.g., acetone–butanol–ethanol (ABE) fermentation is a promising alternative to petroleum-based chemicals as, e.g., solvent and fuel. Recovery of butanol from dilute fermentation broths by hydrophobic membranes and adsorbents has been identified as a promising route. In this work, the adsorption of water and butanol vapor in a silicalite-1 film was studied using in situ attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy to better understand the adsorption properties of silicalite-1 membranes and adsorbents. Single-component adsorption isotherms were determined in the temperature range of 35–120 °C, and the Langmuir model was successfully fitted to the experimental data. The adsorption of butanol is very favorable compared to that of water. When the silicalite-1 film was exposed to a butanol/water vapor mixture with 15 mol % butanol (which is the vapor composition of an aqueous solution containing 2 wt % butanol, a typical concentration in an ABE fermentation broth, i.e., the composition of the gas obtained from gas stripping of an ABE broth) at 35 °C, the adsorption selectivity toward butanol was as high as 107. These results confirm that silicalite-1 quite selectively adsorbs hydrocarbons from vapor mixtures. To the best of our knowledge, this is the first comprehensive study on the adsorption of water and butanol in silicalite-1 from vapor phase.

Self-diffusion of D 2O in partially filled silicalite-1 crystals was studied at 25°C by 2H nuclear magnetic resonance (NMR) with bipolar field gradient pulses and longitudinal Eddy-current-delay. For the first time, reliable experimental diffusion data for this system were obtained. Analysis of NMR diffusion decays revealed the presence of a continuous distribution of apparent self-diffusion coefficients (SDCs) of water, ranging from 10 -7 to ~10 -10 m 2/s, which include values much higher and lower than that of bulk water (~10 -9 m 2/s) in liquid phase. The observed distribution of SDC changes with variation of the diffusion time in the range of 10-200 ms. A two-site Kärger exchange model was successfully fitted to the data. Finally, the water distribution and exchange in silicalite-1 pores were described by taking into account (a) a gas-like phase in the zeolite pores, a gas-like phase in mesopores and an intercrystalline gas-like phase and (b) intercrystalline liquid droplets with intermediate exchange rate with the other phases. The other phases experience fast exchange on the NMR diffusion time scale. Diffusion coefficients and mean residence times of water in some of these states were estimated

Thin zeolite films have great potential in several novel application areas such as structured catalysts, membranes and sensors. To fully exploit the advantages of these films it is of great importance to determine the adsorption properties of the films. A powerful technique for studies of phenomena at surfaces or in thin films is FTIR/ATR-spectroscopy (Fourier Transform Infra Red / Attenuated Total Reflection). In this work, MFI zeolite films were prepared on ATR elements using two methods. One method produced 200 nm thick films with small crystals (<200nm). The other method was used for preparing b-oriented ZSM-5 films. These films were discontinuous and ca 420 nm thick and consisted of well intergrown, and substantially larger crystals, ca 1.1 ìm in diameter. Silicalite-1 coated elements were evaluated as gas sensors and the sensitivity for a hydrocarbon for zeolite-coated elements was compared with a standard 10 cm gas cell. The sensitivity was approximately 85 times higher for the coated elements at low hydrocarbon concentration. The response time was investigated by exposing the coated element to a step increase of an analyte and recording the response as a function of time. The response was relatively fast, equilibrium was achieved after approximately 250 s, but already after a few seconds, a strong signal could be detected. The coated elements were also used for determining single gas adsorption isotherms. The studied systems were n-hexane/silicalite-1, p-xylene/silicalite-1 and p-xylene/ZSM-5. The observed isotherms for temperatures between 323 and 423 K were typical for microporous materials with a fast increase of the amount adsorbed at low partial pressures. p-Xylene isotherms of type I were observed as opposed to the type IV isotherms reported in literature for powders. This difference was assigned to strain in the films and/or to reduced flexibility of the MFI framework when attached to a support. Further, some capillary condensation occurred at higher pressures in the films consisting of smaller crystals, which was assigned to condensation in open grain boundaries. Henry's constants and heats of adsorption determined from low-pressure data agreed well with previous reports. Measurements with polarized radiation revealed that p- xylene molecules are mainly oriented with their long axis in the b- direction of the crystals and it was also observed that some kind of rearrangement of n-hexane occurs with increasing loading, both of these findings were in agreement with previously reported results.

Thin zeolite films have great potential in several novel application areas such as: structured catalysts, membranes and sensors. To fully exploit the advantages of these films it is of great importance to determine the properties of the films. A powerful technique for studies of phenomena at surfaces or in thin films is FTIR/ATR-spectroscopy (Fourier Transform Infra Red / Attenuated Total Reflection). Furthermore, thin zeolite films may be utilized for enhanced selectivity and sensitivity for this technique. In this work films with a thickness of 200 nm of the zeolites ZSM-5 and silicalite-1 were grown on ZnSe, ZnS, ZrO2, Si and Ge ATR elements using a method that had been developed previously. The coated elements were evaluated in a gas sensor application by comparing the sensitivity for a hydrocarbon of zeolite-coated elements versus a standard 10 cm gas cell. The sensitivity was approximately 85 times higher for the coated elements compared to the gas cell at low hydrocarbon concentration. The response time was investigated by exposing the coated element to a step increase of an analyte and recording the response as a function of time. The response was relatively fast, equilibrium was achieved after approximately 250 s, but already after a few seconds a strong signal could be detected. The coated elements were also used to determine single gas adsorption isotherms. The systems studied were n-hexane/silicalite-1 and p-xylene/silicalite-1. Adsorption isotherms determined at varying temperatures were typical for microporous materials. Capillary condensation was observed at higher concentration of the adsorbent. Henry constants and heats of adsorption determined from low-pressure data agreed well with previously reported data in the literature.

This work presents the synthesis of nearly defect-free ZSM-5 nanosized crystals, prepared in fluoride medium by seeding with silicalite-1. This material was carefully characterized and its catalytic performances in the methanol to hydrocarbons (MTH) reaction were assessed. Such fluoride-based material was compared to a reference ZSM-5, produced through a conventional alkaline synthesis but from the same seeding. Despite both the materials show closely identical morphology and they have a comparable acid site population, the catalyst prepared using the fluoride route showed significantly longer lifetime in MTH compared to the catalyst prepared using conventional synthesis at high pH. The slower deactivation for the samples prepared using the fluoride route was ascribed, thanks to a thorough in situ IR spectroscopy study, to its lower density of internal defects. According to the UV-Raman characterization of coke on the spent catalyst, the fluoride-based ZSM-5 catalyst produces less molecular coke species, most probably because of the absence of enlarged cavities/channels as due to the presence of internal defects. On the basis of these observations, the deactivation mechanism in the ZSM-5 synthesized by fluoride medium could be mostly related to the deposition of an external layer of bulk coke, whereas in the alkali-synthesized catalyst an additional effect from molecular coke accumulating within the porous network accelerates the deactivation process.

In this work, a Maxwell-Stefan model for high flux tubular silicalite-1 membranes for separation of CO2 from a CO2/H2 mixture was developed. The model concerns tubular membranes operating in a counter flow module and includes transport through flow-through defects in the silicalite-1 film and pressure drop over the graded alumina support. Adsorption and diffusion parameters for perfect silicalite-1 crystals were taken from literature. The flux and selectivity predicted by the model were in reasonably good agreement with experimentally observed data for a ZSM-5 membrane without any fitting of the model. However, the CO2 flux and selectivity measured experimentally for the ZSM-5 membrane were higher than that predicted by the model for a silicalite-1 membrane.The model was used to investigate a case with a 20 000 Nm3/d feed comprised of a 50/50 mixture of CO2/H2 at pressure of 25 bar and a membrane temperature of 296 K. The permeate pressure was 1 bar and 90% of the CO2 permeated the membrane. In this case, the membrane permselectivity and CO2 flux varied along the length of the tubes between 20–26 and 950–396 kg/(m2 h), respectively. Further, both defects and pressure drop over the support were shown to have an adverse effect on the selectivity, which indicates that membrane selectivity can be improved by reducing the flow-through defects and/or by preparing supports with less flow resistance. For a one-stage process, the required membrane area is as small as ca 0.85 m2 and the hydrogen loss through the membrane was 12.4%. For a two-stage process the required membrane area almost doubled to 1.6 m2, however the hydrogen loss through the second membrane is reduced to as little as 2.5%. In summary, this work shows that high flux zeolite membranes may be an interesting option for CO2 removal from synthesis gas.

Adsorption isotherms for p-xylene and n-hexane in silicalite-1 films with a thickness of 200 nm were determined at 323, 343, 368, 393, and 423 K using Fourier transform infrared/attenuated total reflection (FTIR/ATR) spectroscopy. For both adsorbates, the low-pressure data agreed with literature data for MFI powder and the estimated Henry's constant and adsorption enthalpy were close to previously reported results. The upper region of the n-hexane isotherm (p > 2 kPa at 323 K) was likely influenced by micropores in open grain boundaries, as expected for a polycrystalline film of small (<200 nm) crystals. As for n-hexane, the first part (0 ≤ p ≤ 65 Pa at 323 K) of the p-xylene isotherm agreed with data for powder. However, the saturation capacity was only about half of that previously reported for powders, which indicates that p-xylene molecules do not adsorb in the sinusoidal channels in the film. We speculate that the small crystals used in the present work may behave differently from the larger crystals in previous works. Another explanation for the lower saturation capacity may be the bonding of crystals to the supports, which are known to induce strain in the attached crystals.

FTIR spectroscopy in combination with polarized light and an ATR probe coated with a b-oriented ZSM-5 film was for the first time used to determine the orientation of adsorbed molecules in the ZSM-5 structure. Two adsorbates were studied, n-hexane and p-xylene and the results agreed with previously reported results obtained by other experimental techniques.

ZnS ATR elements were coated with well-defined b-oriented ZSM-5 films by in situ growth. Both adsorption isotherms, as well as molecular orientation of p-xylene adsorbed in the films, were measured at 323 and 373 K by FTIR/ATR spectroscopy. The observed isotherms for the b-oriented ZSM-5 films in the present work were very similar to previously reported isotherms of supported MFI films, albeit the crystals in the latter films were aluminum free (silicalite-1) and orientated differently relative to the support surface than the crystals in the films studied in the present work. The novel technique facilitated, for the first time, the examination of how the tilt angle varies with loading and temperature. The data obtained in the present work showed that the p-xylene molecules were mainly oriented with their long axis parallel to the b-direction of the MFI crystals in concert with previously reported results based on FTIR microscopy, Monte Carlo simulations, NMR, and XRD data. At high concentrations, the tilt angle was in good agreement with observations by FTIR microscopy. It was also found that the orientation of the molecules changed with loading, this might be due to different adsorption geometries in the channel intersection as reported previously. The observed tilt angles may also be influenced from competitive adsorption on silanol groups, as was also indicated in the spectra. The results also indicate that the adsorption properties of zeolite films and powders may differ. Hence, adsorption parameters determined for zeolite powders may not necessarily be applicable to films.

The effect of ZDDP on fretting wear was investigated in a ball on flat machine. The results confirm previous work that anti-wear agents may reduce friction and wear in fretting contacts. It was further found that temperature, adsorption time and base oil polarity were all important parameters affecting the ability of ZDDP to protect the surfaces against fretting wear.

The effect of ZDDP on fretting wear was investigated in a ball on flat machine. The results confirm previous work that anti-wear agents may reduce friction and wear in fretting contacts. It was further found that temperature, adsorption time, base oil polarity as well as the presence of other surface active additives in the oil were all important parameters affecting the ability of ZDDP to protect the surfaces against fretting wear.

A novel sensitive chemical sensor probe has been fabricated. The sensor principle is based on silicalite-1 coated ATR (attenuated total reflection) elements and FTIR spectroscopy. The microporous silicalite-1 film enriches the analyte to the probe surface, thus increasing the sensitivity. At a relative pressure of n-hexane in helium of 6 × 10−5 the sensitivity of the probe is approximately 85 times higher for the silicalite-1 coated element compared to a 10 cm transmission gas cell and ca. 180 times higher compared to an uncoated element. The performance of the probe is illustrated by determination of an adsorption isotherm for n-hexane in silicalite-1.

In the present work, the mass transport of helium through zeolite is experimentally determined by measuring the flow of helium through a zeolite membrane. By using a mathematical model, the mass transport through defects was accounted for to arrive at mass transport through zeolite pores. For the first time, we could thereby experimentally show that the mass transport of helium in zeolite pores is strongly controlled by the amount and location of hydrocarbons in the zeolite pores and varies several orders of magnitude. The mass transport of helium in ZSM-5 zeolite pores is first reduced gradually more than one order of magnitude when the loading of n-hexane is increased from 0 to 47% of saturation. As the loading of n-hexane is further increased to 54% of saturation, the mass transport of helium in the zeolite pores is further reduced abruptly by more than two orders of magnitude. This gradual decrease followed by an abrupt decrease of mass transport is caused by adsorption of n-hexane in the zeolite pores. In a similar yet different fashion, the mass transport of helium in the zeolite pores is reduced abruptly by almost two orders of magnitude when the loading of benzene is increased from 0 to 19% of saturation due to adsorption of benzene in the pore intersections. Effective medium approximation percolation models with parameters estimated using density functional theory employing the local density approximation, i.e. models with no adjustable parameters and the most sophisticated theory yet applied to this system, can adequately describe the experimental observations.

A systematic investigation of two sets of defect free and defective ZSM-5 crystals with controlled thickness (T) between 30 and 400 nm and of their performances in methanol conversion was reported for the first time in the present work. The defect free ZSM-5 crystals with a thickness of 35 nm are by far the smallest ever reported and displayed superior activity, stability and selectivity to slower diffusing compounds, which resulted in high yield of e.g. gasoline and the 1,2,4-trimethylbenzene isomer with high octane number, as compared to the other studied catalysts. Almost only products forming in the zeolite pores were detected and consequently, the external surface must be nearly inactive. Strong correlations between T and deactivation rate were observed. Thick crystals deactivated much faster than thin crystals, probably due to formation of carbon species in the zeolite pores, which results in pronounced percolation effects and faster deactivation of the former. At comparable thickness, crystals with defects deactivated much faster than defect free crystals, due to formation of additional small molecular coke species in the former. Strong correlations between T and selectivity were also observed and assigned to control of diffusion resistance by crystal thickness.

Intelligent control of friction is an attractive but challenging topic and it has rarely been investigated for full size engineering applications. In this work, it is instigated if it would be possible to adjust friction by controlling viscosity in a lubricated contact. By exploiting the ability to adjust the viscosity of the switchable ionic liquids, 1,8-Diazabicyclo (5.4.0) undec-7-ene (DBU)/ glycerol mixture via the addition of CO2, the friction could be controlled in the elastohydrodynamic lubrication (EHL) regime. The friction decreased with increasing the amount of CO2 to the lubricant and increased after partial releasing CO2. As CO2 was absorbed by the liquid, the viscosity of the liquid increased which resulted in that the film thickness increased. At the same time the pressure-viscosity coefficient decreased with the addition of CO2. When CO2 was released again the friction increased and it was thus possible to control friction by adding or removing CO2.

Multi-layered nanocellulose membranes were prepared using vacuum-filtration of cellulose nanofibers (CNF) suspensions followed by dip coating with cellulose nanocrystals having sulphate (CNCSL) or carboxyl surface groups (CNCBE). It was possible to tailor the specific surface area, pore structure, water flux and wet strength of the membranes based on drying conditions and acetone treatment. CNF coated with CNCBE showed the highest a tensile strength (95 MPa), which decreased in wet conditions (≈3.7 MPa) and with acetone (2.7 MPa) treatment. The water dried membranes showed pore sizes in nanofiltration range (74 Å) from liquid nitrogen adsorption/desorption data and the acetone treatment increased the average pore sizes to tight ultrafiltration range (194Å) with a concomitant increase (7000%) of the BET surface area. The water flux, also increased from zero to 25 Lm-2h-1 at a pressure differential of 0.45 MPa, for acetone treated ones. The membranes irrespective of the surface functionality showed exceptional capability (≈100%) to remove Ag+, Cu2+ and Fe3+ ions from mirror industry effluents. Surface adsorption followed by microprecipitation was considered as the possible mechanism of ion removal, which opens up a new generation of ultrafiltration membranes with high selectivity towards ions and low-pressure demands.

Biobased nanocomposite membranes were prepared using chitosan as te matrix and cellulose nano whisker as the reinforcing phase. Cellulosee production. Atomic force microscopy of the nanowhiskers showed diameters of 10 -20nm and lengths of 250 - 350nm. Nanocomposites were prepared in 1:1, 1:2 and 1:3 ratios to investigate the effect of nanoadditive concentration on the membrane properties. The nanocomposites were prepared by solution mixing followed by freeze-drying, to obtain porous structures with high degree of internal surface area. These nanocomposites were further treated with ammonia vapours to prepare the crosslinked nanocomposites and thereby stabilize it towards moisture and pH variations. The morphology, surface area, crystallinity, porosity, and mechanical properties of prepared membranes were studied. The effect of the nanocomposite composition, crosslinking and the pore size distribution on the water transport through the membranes was also evaluated.

Fully biobased composite membranes for water purification were fabricated with cellulose nanocrystals (CNCs) as functional entities in chitosan matrix via freeze-drying process followed by compacting. The chitosan (10 wt%) bound the CNCs in a stable and nanoporous membrane structure with thickness of 250-270 μm, which was further stabilized by cross-linking with gluteraldehyde vapors. Scanning electron microscopy (SEM) studies revealed well-individualized CNCs embedded in a matrix of chitosan. Brunauer, Emmett and Teller (BET) measurements showed that the membranes were nanoporous with pores in the range of 13-10 nm. In spite of the low water flux (64 L m-2 h-1), the membranes successfully removed 98%, 84% and 70% respectively of positively charged dyes like Victoria Blue 2B, Methyl Violet 2B and Rhodamine 6G, after a contact time of 24 h. The removal of dyes was expected to be driven by the electrostatic attraction between negatively charged CNCs and the positively charged dyes.

Fully biobased affinity membrane processing and its application in the removal of heavy metal ions from mirror industry effluents were successfully demonstrated; indicating the potential use of these membranes in point-of-use or point-of-entry water cleaning products that are cheap, environmentally friendly and efficient. Layered cellulose nanocomposite membranes were fabricated using cellulose microfiber sludge as a support layer and cellulose nanocrystals (CNCSL, CNCBE or PCNCSL) in a gelatin matrix as the functional layer. Scanning electron microscopy (SEM) studies revealed the bi-layered morphology of the membrane and well-individualized nanocelluloses in the functional layer. Bubble point measurements confirmed the membrane pore structure in the microfiltration range (5.0-6.1 μm), which provided very high water permeability (900-4000 L h-1 m-2) at <1.5 bars. A tensile strength of 16 MPa in dry conditions and a wet strength of 0.2 MPa, was considered sufficient for use of these membranes in spiral wound modules. Mirror industry effluent laden with metal ions (Ag+ and Cu2+/Fe3+/Fe2+) when treated with cellulose nanocomposite membranes, showed high ion removal capacity, being 100% for PCNCSL followed by CNCBE than CNCSL. The removal of metal ions was expected to be driven by interactions between negatively charged nanocellulose and the positively charged metal ions.

Biobased nanoparticles viz cellulose nanocrystals (CNCs) and cellulose nanofiber (CNFs) isolated by mechanical process (grinding) were used to fabricate of fully biobased nanocomposite membranes. Biobased nanofibers were used as support layer via a very simple process of vacuum filtration was used for the fabrication of CNF support layer. In order to coat CNCs or CNCbio on the two sides to CNF layer, the membrane was dipped in a solution of cellulose nanocrystals. Scanning electron microscopy (SEM) confirmed the infusion of functional layer within supportive layer. Tensile strength was measured in dry as well as in wet conditions, illustrated mechanical performances compareble to commercially available membranes. To increase the flux, membranes were treated with acetone for 24 and 72 h. The drastic increase in the flux for acetone treated membranes confirmed the discontinuities of hydrogen . The membranes succefully removed two metal ions Ag+ and As3- from real wastewater, from mirror making and mining industries respectively, within Europe. Complete removal of Ag+ was reported after 24 h of incubation. The study concludes that, the developed membranes having good mechanical stability in wet conditions, high water flux and adsorption efficiency are potential candidates for heavy metal ion remediation of industrial effluents.

Permporometry was used for the first time to characterize flow-through micropore defects down to 0.7 nm in size in MFI zeolite membranes. Helium was used as the non-adsorbing gas and n-hexane or benzene was used as the adsorbate. The helium flow through zeolite pores was estimated using percolation theory and the remaining flow was assigned to flow-through defects. The area distribution of flow-through defects was estimated from the data using a simple model and similar results were obtained using both adsorbates. The total area of defects determined using n-hexane as the adsorbate was as low as about 0.7% of the membrane area and defects with a width below 1 nm constituted 97% of the total defect area for the best membrane. The permporometry results were supported by n-hexane/1,3,5-trimethylbenzene separation experiments. The permporometry data were also consistent with HR-SEM observations indicating the presence of narrow open grain boundaries, and absence of large cracks and pinholes

Separation of CO2 and CO is of great importance for many industrial applications. Today, CO2 is removed from CO mainly by adsorption or physical or chemical absorption systems that are energy-intensive and expensive. Membranes are listed among the most promising sustainable and energy-efficient alternatives for CO2 separation. Here, we study CO2/CO separation by novel sub-micron b-oriented MFI zeolite membranes in a temperature range of 258-303 K and at a feed pressure of 9 bar. Under all experimental conditions studied, the membranes were CO2-selective and displayed high CO2 permeance ranging from 17 000 to 23 000 gpu. With decreasing temperature, the CO2/CO selectivity was increasing, reaching a maximum of 26 at 258 K. We also developed a mathematical model to describe the membrane process, and it indicated that the membrane separation performance was a result of selective adsorption of CO2 on the polar zeolite. The heat of adsorption of CO2 on the zeolite is more negative due to the high quadrupole moment and polarisability of the molecule as compared to CO. At the same time, diffusional coupling (correlation effects) at high adsorbed loadings was found to favour the overall CO2/CO selectivity of the membranes by reducing the diffusivity of the lighter CO molecule in the ca. 0.55 nm pores in the zeolite. The model also indicated that the separation performance was limited by the mass transfer resistance in the support and concentration polarisation on the feed side of the membrane.

MFI membranes with a thickness of 0.5 μm prepared on a graded α-alumina support were evaluated for separation of feed mixtures of 3 wt.% n-butanol/water and 10 wt.% ethanol/water by pervaporation. The membranes were selective to n-butanol and ethanol. The flux observed in the present work was about 100 times higher than that previously reported for n-butanol/water separation by pervaporation and about 5 times higher than that for ethanol/water separation by pervaporation. At 60 °C, the observed n-butanol/water flux was about 4 kg m−2 h−1 and the n-butanol/water separation factor was about 10 for the best membrane. At the same temperature, the membrane displayed an ethanol/water flux of ca. 9 kg m−2 h−1 and an ethanol/water separation factor of ca. 5. A mathematical model indicated significant mass transfer resistance in the support, which reduced the flux and the selectivity of the membranes.

Novel structured adsorbents in the form of thin zeolite films grown on substrates designed for low pressure drop have a great potential to improve pressure swing adsorption (PSA) processes. In the present work, template free films of NaX zeolite were grown on the walls of ceramic cordierite supports using a seeding technique. The supports had 400 parallel channels per square inch. Films were grown both from a gel and a clear synthesis solution. The materials were analyzed by scanning electron microscopy, X-ray diffraction, N2 adsorption/desorption measurements, Hg-porosimetry as well as CO2 breakthrough experiments. When a gel was used for film growth, a film consisting of well intergrown crystals with a thickness of about 1 μm was obtained. However, a large amount of sediments were deposited on top of the film, which resulted in a dispersed CO2 adsorption breakthrough front. Zeolite films grown in one longer hydrothermal treatment in a clear solution were less intergrown and consisted of both NaX and hydroxysodalite crystals and, in addition, some sediments were deposited on top of the film, which again resulted in a dispersed breakthrough front. By using a multiple-step synthesis procedure and a clear synthesis solution, well intergrown NaX films, free from sediments and with only a very small fraction of hydroxysodalite crystals could be prepared. The CO2 breakthrough front for the latter adsorbent was sharper than the front for an empty adsorption column and only shifted in time. This indicates that the flow distribution in the adsorbent is even and that the mass transfer resistance in the film is very low due to the small film thickness and high effective diffusivity for CO2 in the NaX film and still, the adsorption capacity is considerable. The even flow distribution, very low mass transfer resistance and low pressure drop in combination with considerable adsorption capacity in this adsorbent indicates that it is a promising adsorbent for PSA applications. The findings from the present work will be important for the development of structured adsorbents to use as a competitive alternative to traditionally used adsorbents in PSA.

Ethylene glycol (EG)-based lubricant was prepared with dissolved organosolv lignin from birch wood (BL) and softwood (SL) biomass. The effects of different lignin types on the rheological, thermal, and tribological properties of the lignin/EG lubricants were comprehensively investigated by various characterization techniques. Dissolving organosolv lignin in EG results in outstanding lubricating properties. Specifically, the wear volume of the disc by EG-44BL is only 8.9% of that lubricated by pure EG. The enhanced anti-wear property of the EG/lignin system could be attributed to the formation of a robust lubrication film and the strong adhesion of the lubricant on the contacting metal surface due to the presence of a dense hydrogen bonding (H-bonding) network. The lubricating performance of EG-BL outperforms EG-SL, which could be attributed to the denser H-bonding sites in BL and its broader molecular weight distribution. The disc wear loss of EG-44BL is only 45.7% of that lubricated by EG-44SL. Overall, H-bonding is the major contributor to the different tribological properties of BL and SL in EG-based lubricants.

ZSM-5 zeolite crystals with carefully controlled thicknesses in the range 20–110 nm, i.e. in the colloidal domain, were synthesized in fluoride and hydroxide media. The crystals were treated in steam at high temperature to evaluate the stability and evaluated by SEM, XRD, NMR and NH3-TPD. The results showed that the framework of crystals synthesized in fluoride media was more stable than the framework of crystals synthesized in hydroxide media. This should be an effect of lower concentration of structural defects and silanol groups in the former zeolites as reported by other groups. However, independently of the synthesis conditions, all crystals dealuminated rapidly when treated with steam at the conditions investigated in the present work.

Room temperature ionic liquids (RTILs) have several properties which make them interesting candidates as base fluids for extreme conditions. However, a lack of compatibility with tribo-improving additives combined with an often overly aggressive nature is limiting their use as base fluids. To overcome these drawbacks, hydrocarbon-imitating RTIL base fluids have recently been developed. These lubricants aim for a more balanced interaction with metal surfaces while enabling compatibility with common additives, so that the reactivity with the lubricated surface can be tuned in a manner similar to hydrocarbon base oil–additive systems. In this work, the effects of several common additives in the novel RTIL were examined by laboratory tribotesting. Surface analysis was performed in order to study the lubrication mechanisms.

Room temperature ionic liquids (RTILs) have several properties that make them interesting candidates as base fluids for extreme conditions. However, a lack of compatibility with tribo-improving additives combined with an often overly aggressive nature is limiting their use as base fluids. To overcome these drawbacks, hydrocarbon-imitating RTIL base fluids have recently been developed. In this study, the effects of several common additives in the novel RTIL (P-SiSO) were examined by laboratory tribotesting. A reciprocating steel-steel ball-on-flat setup in an air atmosphere was used, where the lubricant performance was evaluated over a range of loads and temperatures. Surface analyses after testing were carried out using optical profilometry, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). Neat P-SiSO displayed high performance in the tribotests. At an elevated load and temperature, a shift in lubrication mode was observed with an accompanying increase in friction and wear. Surface analysis revealed a boundary film rich in Si and O in the primary lubrication mode, while P was detected after a shift to the secondary lubrication mode. An amine additive was effective in reducing wear and friction under harsh conditions. The amine was determined to increase formation of the protective Si–O film, presumably by enhancing the anion activity.

Biogas and natural gas are interesting fuels with high H/C ratio. However, these gases frequently contain carbon dioxide and water which lowers the heat value of the gas and may induce corrosion. Therefore, the development of more efficient processes, such as membrane processes and improved adsorbents, for the separation of carbon dioxide and water from biogas and natural gas is of great importance. Zeolite ZSM-5 membranes are promising for this separation which is controlled by the adsorption and diffusion of the different species in the zeolite. Multicomponent adsorption data are therefore required for development of new membrane and adsorption processes. In the present work, the adsorption of water, carbon dioxide, and methane in a Na-ZSM-5 zeolite film at various temperatures was studied by in situ Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy for the first time. Adsorption isotherms were retrieved from the experimental data and the Langmuir model fitted the isotherms very well. Limiting heat of adsorption was determined from the Henrýs law regime and the values determined agreed well with previously reported data. A few experiments were conducted with multicomponent mixtures and the experimentally determined amounts adsorbed were compared with values predicted by the Ideal Adsorbed Solution Theory (IAST). It was found that for the binary mixture of carbon dioxide and methane there was good agreement between the experimental values and those predicted by the IAST. However, when water was also introduced, the IAST could not fully capture the adsorption behavior of the multicomponent mixture, probably because the adsorbed phase is not ideal. These findings are in line with previous reports for adsorption in zeolites. The multicomponent adsorption behavior of this system will be further investigated in forthcoming work.

Methane is the main component in biogas and natural gas along with contaminants such as water and carbon dioxide. Separation of methane from these contaminants is therefore an important step in the upgrading process. Zeolite adsorbents and zeolite membranes have great potential to be cost-efficient candidates for upgrading biogas and natural gas, and in both of these applications, knowing the nature of the competitive adsorption is of great importance to further develop the properties of the zeolite materials. The binary adsorption of methane and carbon dioxide in zeolites has been studied to some extent, but the influence of water has been much less studied. In the present work, in situ ATR (attenuated total reflection)–FTIR (Fourier transform infrared) spectroscopy was used to study the adsorption of water/methane and water/carbon dioxide from binary mixtures in a high-silica Na-ZSM-5 zeolite film at various gas compositions and temperatures. Adsorbed concentrations for all species were determined from the recorded IR spectra, and the experimental values were compared to values predicted using the ideal adsorbed solution theory (IAST). At lower temperatures (35, 50, and 85 °C), the IAST was able to predict the binary adsorption of water and methane, whereas the values predicted by the IAST deviated from the experimental data at the highest temperature (120 °C). For the binary adsorption of water and carbon dioxide, the IAST could not predict the adsorption values accurately. This discrepancy was assigned to the particular adsorption behavior of water in high-silica MFI forming clusters at hydrophilic sites. However, the predicted values did follow the same trend as the experimental values. The adsorption selectivity was determined, and it was found that the H2O/CH4 adsorption selectivity was decreasing with increasing water content in the gas phase at low temperatures whereas the selectivity was increasing at higher temperatures. The H2O/CO2 adsorption selectivity was increasing with increasing water content at all temperatures.

The main component in biogas and natural gas is methane but these gases also contain water and carbon dioxide that often have to be removed in order to increase the calorific value of the gas. Membrane and adsorbent-based technologies using zeolites are interesting alternatives for efficient separation of these components. To develop efficient processes, it is essential to know the adsorption properties of the zeolite. In the present work, adsorption of methane, carbon dioxide and water from ternary mixtures in high silica zeolite Na-ZSM-5 was studied using in-situ ATR (Attenuated Total Reflection) – FTIR (Fourier Transform Infrared) spectroscopy. Adsorbed concentrations were extracted from the infrared spectra and the obtained loadings were compared to values predicted by the Ideal Adsorbed Solution Theory (IAST). The IAST could not fully capture the adsorption behavior of this ternary mixture, indicating that the adsorbed phase is not behaving as an ideal mixture. The CO2/CH4 adsorption selectivities determined for the ternary mixtures were compared to selectivities determined for binary mixtures in our previous work, indicating that the presence of water slightly improves the CO2/CH4 adsorption selectivity at lower temperatures. Further, the results show that water and carbon dioxide are adsorbed preferentially over methane in high silica zeolite Na-ZSM-5.