Valdis Kampars

Bio-oil from thermo-chemical hydro-liquefaction of wet sewage sludge.

The present work demonstrates the influence of experimental conditions such as weight ratio of sewage sludge to water (1/0-1/15), reaction temperature (200-350°C), initial H2 pressure (2.0-11.0MPa), residence time (10-100min) and type of catalysts (Na2CO3, Raney nickel, FeSO4, MoS2) on hydro-liquefaction process of sewage sludge. High amount of water improves the hydro-liquefaction process of sewage sludge by increasing the yield of bio-oil and the total conversion. The highest yield of bio-oil (47.79 wt.%) from sewage sludge was obtained with initial H2 pressure 5.0MPa, reaction temperature 300°C, and residence time 40min. Under these experimental conditions, using weight ratio of sewage sludge to water 1/5, catalyst (FeSO4) - 5 wt.% of dry SS, mixing speed 350rpm the obtained bio-oil had the highest energy recovery (69.84%), total conversion (70.64%) and its calorific value was 35.22MJ/kg.

Catalytic pyrolysis of wheat bran for hydrocarbons production in the presence of zeolites and noble-metals by using TGA-FTIR method.

Pyrolysis of wheat bran with or without catalysts was investigated using TGA-FTIR method in order to determine the influence of zeolite and noble metal catalysts on the evolution profile and relative yield of the volatile compounds. The addition of all catalysts decreased the volatile matter of wheat bran from 76.3% to 75.9%, 73.9%, 73.5%, 69.7% and increased the solid residue from 18.0% to 18.4%, 20.4%, 20.8%, 24.6% under the catalyst of ZSM-5, 5% Pd/C, MCM-41, and 5% Pt/C. Noble-metal catalysts had higher activity for deoxygenation of compounds containing carbonyl, carboxyl, and hydroxyl groups than zeolites. Degradation of nitrogen containing compounds atom proceeded better in presence of zeolites. Noble-metal catalysts promoted formation of aromatics and changed the profiles of evolved compounds whereas zeolites advanced formation of aliphatics and olefins.

Novel second-order nonlinear optical polymer materials containing indandione derivativatives as a chromophore

Second order non linear optical (NLO) properties of sPMMA based host-guest systems containing eight dimethylaminobenzylidene -1, 3 - indandione (DMABI) related chromophores have been investigated by means of quantum chemical calculations and SHG experimental characterization. Ab initio calculations with basis set 6-31G were used for molecular geometry determination as well as in the calculations of molecular hyperpolarizability by FF approach. Influence of the chromophore concentration on the host-guest film NLO performance was obtained by SHG Maker fringe experiments. The highest value of d53233 =80 pm/V (frequency corrected value d033 =12 pm/V) at chromophore concentration 15 %wt have been recorded for tret-butyl substituted DMABI chromophore.

Hydrotreating of wheat straw in toluene and ethanol.

In the present work, wheat straw was hydroliquefied at a temperature of 300°C for 4h in ethanol or toluene in order to obtain bio-components which are useful for fuel purposes. The experiments were performed in a 100mL batch reactor under hydrogen pressure of 70 bar. Typically, 2g of straw and 0.1g of catalyst (66%Ni/SiO2-Al2O3) were dispersed in 15 g of solvent. The main compounds of the oil produced during the liquefaction of hemicellulose, cellulose and lignin of wheat straw in both solvents are: tetrahydrofuran-2-methanol, 1,2-butanediol and butyrolactone. Besides the mentioned compounds, ethanol favoured the decomposition of bigger molecules to short-chain alcohols such as 1-butanol, 1,2-propanediol and 1,2-ethanediol. Toluene contributes to the production of furans and other cyclic compounds. The light fractions distilled together with the solvent also contain the following: 1-propanol, 2-methyl-cyclopentanone, acetic acid and ethyl acetate.

Isolation and characterization of the phenolic fractions of wood pyrolytic oil

Abstract A fraction of pyrolytic oils (PyO) – obtained by fast pyrolysis of alder (Alnus incana), ash-tree (Fraxinus excelsior) and aspen (Populus tremula) in a laboratory scale reactor – was precipitated in water. This hydrophobic moiety of PyO is called pyrolytic lignin (PyL). The composition of the volatile monomeric compounds of PyO and the PyL fraction was determined by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). It has been found that PyL has a high content of phenolic products (between 75% and 83%), which varies depending on the wood species. The antioxidant properties of the PyL fraction were studied and it was demonstrated that the antioxidant activity determined in different tests exceeded the corresponding activity of alkali lignin. The antioxidant properties of PyL are on the same level as those of the widely used antioxidants, such as rutin, trolox, curcumine, and tert-butylhydroquinone (TBHQ). A new method was developed for the extraction of a monomeric phenol fraction (Py-monPh) from PyO by means of the organic solvent methyl tert-butyl ether (MTBE). The Py-monPh can be considered as a promising source of antioxidants.

Optimization of rapeseed oil fatty acid esterification with methanol in the presence of sulfuric acid

Abstract The interest in biodiesel production from low cost feedstocks is still increasing. Such feedstocks usually contain large amounts of free fatty acids, which make the currently employed base catalysts inefficient, thereby promoting the use of acid catalysts. Due to the high activity and low cost, sulfuric acid could become the most widely used acid catalyst for biodiesel production. Research undertaken so far using sulfuric acid for esterifi cation of fatty acids has shown that the products obtained fail to meet the requirements of the standard EN 14214. This paper describes a systematic study of rapeseed oil fatty acids esterification in order to obtain a product complying with the standard EN 14214. The influence of sulfuric acid concentrations (0.1-3.0%), methanol molar ratios (1:1-20:1) and reaction time (0-360 min) was evaluated. Finally, a two-stage esterification process was developed, where in optimal conditions esterification yield of 97.8% and ester content of 99.6% were achieved.

New Figure of Merit for Tailoring Optimal Structure of the Second Order NLO Chromophore for Guest-Host Polymers

Reliability to forecast SHG efficiency using two sets of non linear optical (NLO) chromophore figures of merit (FOM) was tested. One of them predicts that SHG efficiency d 33 of the poled guest-host polymer is proportional to ground state dipole ∼ μg, another to ∼ 1/μg. Correlation of maximal achieved second order NLO efficiency of the PMMA based systems containing eight dimethylaminobenzylidene-1, 3-indandione (DMABI) related chromophores with proposed FOM have been analyzed. The best correlations were obtained with second set of FOM, especially if high dipole moment (μg > 7D) chromophores are included in analysis.

Nonlinear optical properties of low molecular organic glasses formed by triphenyl modified chromophores

The series of organic molecular glasses have been studied as possible candidates for nonlinear optical (NLO) applications. Amorphous phase formation of investigated materials is ensured by the presence of bulky triphenyl substituents in molecular structure of NLO chromophores. Linear optical properties as well as NLO coefficients and thermal stability of NLO activity for the 13 molecular materials in glassy thin solid films have been determined. For the benzylidene-1,3-indandione chromophore containing compound the highest d33 value equal to 280 pm/V was measured under the 1064 nm excitation. Among the investigated compounds uppermost achieved thermal sustainability of NLO response was 108 °C. The relationship between number of triphenyl substituents and increased thermal sustainability of nonlinear response was observed.

Holographic recording of surface relief gratings in stilbene azobenzene derivatives at 633 nm

Holographic recording in stilbene azobenzene derivatives by He-Ne 633 nm laser light has been experimentally studied. It was found that surface relief gratings (SRG) can be recorded by red light. Usually shorter wavelengths are used to induce the trans-cis photo-isomerization in organic materials. SRG with 2 μm period and an amplitude of 130 nm have been recorded with 0.88 W/cm2 light in about 20 minutes in amorphous films of 3-(4-(bis(2-(trityloxy)ethyl)amino)phenyl)-2-(4-(2-bromo-4-nitrophenyl)diazenyl)phenyl)acrylonitrile spin-coated on glass substrates. Self-diffraction efficiency up to 17.4% and specific recording energy down to 114 J/(cm2%) were measured. The recorded SRG were stable as proved by subsequent AFM measurements. The photo-induced changes in absorption spectra did not reveal noticeable signs of trans-cis transformations. Rather, spectrally uniform bleaching of the films took place. We conclude that a photothermally stimulated photo-destruction of chromophores is responsible for the SRG recording. The recording of stable SRG in the stilbene azobenzene derivatives we studied is accompanied by the recording of relaxing volume-phase gratings due to the photo-orientation of chromophores by the linearly polarized recording light. It should also be noted that holographic recording efficiency in stilbene azobenzene derivatives exhibit an unusual non-monotonic sample storage-time dependence presumably caused by the peculiarities of structural relaxation of the films.

Hologram recording in azobenzene oligomers

Elementary hologram (holographic grating) recording and their coherent optical erasure have been experimentally studied in azobenzene oligomer (ABO) layers differing by their chemical composition, matrices and by the connection type of azobenzene chromophores to the matrix (dispersed or covalently bound). The best holographic parameters (7.9% diffraction efficiency and 86 J/cm2 specific recording energy) were achieved in the samples with covalent bonding to the matrix. Vector recording is also possible. Recording is unstable and reversible. The coherent optical erasure studies have shown its efficiency dependencies on the initial diffraction efficiency, erasing beam intensity and grating period which are different for three groups of ABO samples. The conclusion is made that recording is due to the photoinduced alignment of the azobenzene chromophores followed by refractive index changes. These are the first results and further studies are in progress.