
H.J. HeeresUniversity of Groningen | RUG · Department of Chemical Engineering
H.J. Heeres
Prof.dr.ir
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272
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February 2003 - present
Publications
Publications (272)
The grafting of titania on SBA-15 followed by its phosphation was presented to prepare a mesoporous Lewis–Brønsted bifunctional solid acid catalyst for the tandem conversion of glucose via fructose to 5-hydroxymethylfurfural (HMF). Titania was dispersed on SBA-15 as an amorphous surface layer containing abundant coordinatively unsaturated tetrahedr...
Lignocellulosic biomass is a key feedstock for the sustainable production of biofuels, biobased chemicals and performance materials. Biomass can be efficiently converted into pyrolysis liquids (also known as bio-oils) by...
The use of a combined stirrer-torque meter allows for monitoring viscosity during polymerizations and other reactions, much faster and more continuous than off-line viscosity measurements. This method was applied in previous research about the grafting of acrylic acid onto cassava starch using Fenton’s initiator. In this article the method is used...
Efficient synthesis of furfural from xylose over the HCl catalyst in a water‐methyl isobutyl ketone biphasic system was achieved in slug flow microreactors, using NaCl as a promotor which facilitates xylose dehydration and suppresses xylose condensation. An optimized furfural yield of 93% was obtained from 1 M xylose over 0.2 M HCl with 10 wt% NaCl...
5-Hydroxymethylfurfural (HMF) synthesis from glucose over in-situ phosphated titania catalysts is presented. Phosphates were incorporated into titania framework forming a titanium phosphate surface layer, where the coordinatively unsaturated tetrahedral TiO4 units act as water-tolerant Lewis acid site (LAS) and the adjacent protonated phosphate as...
The catalytic hydrotreatment of fast pyrolysis liquids (PL) from lignocellulosic biomass is a promising technology to improve the properties of PL. Mild hydrotreatment (< 250 °C) using a suitable catalyst allows the production of stabilized oils that have for instance potential for co-processing in existing oil refinery units. Here, we report a cat...
Article published in the issue 47 of the IEA Bioenergy Agreement Task 34 Newsletter — PyNe.
Higher alcohol synthesis (HAS) from syngas is one of the most promising approaches to produce fuels and chemicals. Our recent investigation on HAS showed that potassium‐promoted cobalt‐molybdenum sulfide is an effective catalyst system. In this study, the intrinsic kinetics of the reaction were studied using this catalyst system under realistic con...
Oxidation of 5-hydroxymethylfurfural (HMF) using air or pure oxygen was performed in polytetrafluoroethylene capillary microreactors under gas-liquid slug flow, with Co/Mn/Br as the homogeneous catalyst in the acetic acid solvent. The temperature was varied from 90 to 165 °C at a pressure of 1 or 5 bar. Under atmospheric pressure conditions (at 90...
Biobased chemicals like phenols and aromatics are preferably produced from cheap biomass waste streams. In this work, we have explored the potential of a eucalyptus-derived second generation bioethanol production stillage (BPS) residue for this purpose. A comparative study between a hydrothermal liquefaction (HTL) and a catalytic hydrodeoxygenation...
The pyrolytic sugar fraction, obtained by an aqueous extraction of pyrolysis oil, is an attractive source for sugar-derived platform chemicals. However, solids (humin) formation occurs to a significant extent during hydrolysis and subsequent acid-catalyzed conversion processes. In this study, we report investigations on possible conversion routes (...
Article published in the issue 46 of the IEA Bioenergy Agreement Task 34 Newsletter — PyNe.
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was performed in perfluoroalkoxy alkane capillary microreactors packed with a carbon-supported ruthenium (Ru/C) catalyst with an average particle diameter of 0.3 or 0.45 mm. The reaction was executed under an upstream gas-liquid slug flow with 1,4-dioxane as the solvent and H2 as the...
Pyrolytic lignin (PL) is the collective name of the water-insoluble fraction of pyrolysis oils produced from the fast pyrolysis of lignocellulosic biomass. As the name suggests, PL is composed by fragments derived from lignin, which is the largest natural source of aromatic carbon. Its valorization is of major importance for the realization of econ...
Lignocellulose is a widely available carbon source and a promising feedstock for the production of advanced second‐generation biofuels. Nonetheless, lignin, one of its major components, is largely underutilized and only considered an undesired byproduct. Through catalytic hydrotreatment, the highly condensed lignin can be partially depolymerized in...
The pyrolysis liquid biorefinery concept involves separation of pyrolysis liquids in various fractions followed by conversion of the fractions to value-added products. Pyrolytic lignins (PLs), the water-insoluble fractions of pyrolysis liquids, are heterogeneous, cross linked oligomers composed of substituted phenolics whose structure and physicoch...
To test and select the best column set for a GCxGC method is time consuming. Now a new experimental prediction model is proposed to simulate the contour plot of a sample on a defined column set. By simply analyzing the sample on each of the two different columns by GC-MS, it is possible to construct a simulated contour plot. The retention times (t...
Catalytic hydrotreatment is recognized as an efficient method to improve the properties of pyrolysis liquids (PO) to allow co-feeding with fossil fuels in conventional refinery units. The promising catalyst recipes identified so far are catalysts with high nickel contents (38 to 57 wt.%), promoted by Cu, Pd, Mo and/or a combination, and supported b...
Technical lignins are highly available and inexpensive feedstocks derived from current large scale biomass utilizing industries. Their valorization represents a bottleneck in the development of biorefineries, as the inherently complex lignin structure often suffers severe condensation during isolation, leading to their current application as low va...
Catalytic conversion of a furfural extract from the extraction unit of lubricating oil to valuable products was investigated over the shaped HY extrudates using bentonite as binder (HY/bentonite) and zinc and nickel promoted HY/bentonite catalyst (Zn-Ni-HY/bentonite) in a bench scale fixed bed reactor. The catalysts were characterized by XRF, XRD,...
Levoglucosan (1,6-anhydro-β-D-glucopyranose) is an anhydrosugar found in significant amounts in pyrolysis liquids obtained from lignocellulosic biomass. Levoglucosan (LG) is an attractive source for glucose (GLC), which can be used as a feedstock for biofuels (e.g. bioethanol) and biobased chemicals. Here, we report a kinetic study on the conversio...
A kinetic modeling study on long chain n-paraffin dehydrogenation using a commercial Pt-Sn-K-Mg/γ-Al 2 O 3 catalyst was carried out in a continuous flow set-up using n-dodecane as a model component at various temperatures (450-470 °C), pressures (0.17-0.30 MPa), H 2 /paraffin mole ratios (3:1-6:1) and space times (0.22-1.57 g h mol ⁻¹ ). The commer...
The pyrolysis of lignocellulosic biomass generates a liquid product, known as pyrolysis oil, that can be further processed into biofuels and value-added chemicals. During pyrolysis, cellulose and hemicelulose fractions are converted into a range of water-soluble sugar derivatives, for which several valorisation strategies exist. On the other hand,...
Kraft lignin, a side-product of the paper industry, is considered an attractive feedstock for the production of biorenewable chemicals. However, its recalcitrant nature and sulfur content render catalytic conversions challenging. This study demonstrates the efficacy of noble metal-based catalysts for the production of a lignin oil enriched in alkyl...
Biorefineries are becoming increasingly important in providing sustainable routes for chemical industry processes. The establishment of bio-economic models, based on biorefineries for the creation of innovative products with high added value, such as biochemicals and bioplastics, allows the development of “green chemistry” methods in synergy with t...
Fast pyrolysis is a promising technology to convert lignocellulosic biomass to a liquid energy carrier. The product, known as fast pyrolysis liquid (PL), has a higher energy density than solid biomass and is more easily transported and stored. The applications of PLs are limited due to a high water and oxygen content and limited storage stability....
Literature data on the rheological behavior of a reaction mixture during the graft copolymerization of acrylic acid onto gelatinized starch are scarce. Yet, such information is important for process design. In this work, continuous torque recording was found to be a suitable method to monitor the apparent viscosity. Reactions were performed in a be...
Bio-crude pyrolysis oil is obtained by a process called fast-pyrolysis, in which almost any organic-based feedstock is thermally processed at moderate temperatures, in the range of 400-600 °C, in the absence of oxygen at short residence times. After condensing the vapors in a cooling tray, a dark-brown bio-liquid is obtained. The quality of the so-...
γ-Valerolactone (GVL) is a value-added renewable chemical with great potential and can be obtained from biomass by the hydrogenation of levulinic acid (LA) using metal-based catalysts, such as Ru/TiO2. We here report an in depth study of the effect of catalyst synthesis parameters on the performance of Ru/TiO2 (anatase), varying the nature of the R...
Estimation of production cost and sensitivity analysis for small scale production of rubber seed oil and biodiesel was studied. The production unit is projected to be built in the ex-Mega Rice Project area south of Palangkaraya, Indonesia which has a serious land degradation and deforestation problem. The valorization of rubber seed to produce biop...
In this work, the synthesis of biodegradable and yet renewable thermoplastics materials through a transesterification reaction of sago starch and waste palm cooking oil (WPO) in densified CO2 as the solvent is reported. The aim of this research is to investigate the potential used of sago starch and WPO as raw materials in the thermoplastics starch...
Biodiesel or fatty acid methyl ester (FAME) synthesis from sunflower oil and methanol using an immobilized lipase, an example of a liquid-liquid solid reaction, was studied in batch and various continuous reactor set-ups including the use of a centrifugal contactor separator (CCCS). The latter is an example of a highly intensified device, integrati...
Supporting Information of 'Biobased alkylphenols from lignins via a two-step pyrolysis - hydrodeoxygenation approach'.
A catalyst screening study is reported on the liquefaction of humins, the solid byproducts from C6 sugar biorefineries for levulinic acid and 5-hydroxymethylfurfural production. Experiments were carried out in a batch reactor using an artificial model of humin derived from glucose with isopropanol (IPA) as the solvent at 400 °C for a 3 h batchtime....
Five technical lignins (three organosolv, Kraft and soda lignin) were depolymerised to produce monomeric biobased aromatics, particularly alkylphenols, by a new two-stage thermochemical approach consisting of dedicated pyrolysis followed by catalytic hydrodeoxygenation (HDO) of the resulting pyrolysis oils. Pyrolysis yielded a mixture of guaiacols,...
Background Rubber seed oil (RSO) derived from rubber seeds is considered a promising plant oil. However, subsequent biodiesel synthesis from RSO was reported to be difficult due to the high acidity of the oil. Detailed studies on the effects of storage time of rubber seeds on relevant product properties such as acid value are not yet available. The...
A systematic study on the expression of rubber seed oil from dehulled rubber seeds in a hydraulic press was performed in the presence and absence of ethanol. The effect of seed moisture content (0–6 wt%, w.b.), temperature (35–105 °C), pressure (15–25 MPa) and ethanol to seed ratio (0–21%v/w) on the oil recovery was investigated. An optimum oil rec...
Jatropha curcas L. is a tropical plant that grows well on poor soils in arid regions and produces oil-rich, unedible seeds. The oil from these seeds can be used in the production of biodiesel. In addition, the press-cake waste that is left after oil extraction contains approximately 40% of protein. The use of Jatropha press-cake as substrate for fu...
We here report the catalytic hydrotreatment of three different Alcell lignin fractions using a Ru/C catalyst in a batch reactor set-up (400 °C, 4 h, 100 bar H2 intake, 5 wt% catalyst on lignin). The fractions, obtained by a solvent fractionation scheme from Alcell lignin, differ in composition and molecular weight. The resulting product oils were c...
The aim of this research was to evaluate the potential for the stabilization of biomass-derived pyrolysis oils by using acid-catalyzed (Amberlyst 70) reactions with alcohol (T=140–170 °C, P≈20 bar (1 bar=105 Pa)). The alcohol-stabilized oils were further upgraded by catalytic hydrotreatment (T=400 °C, non-sulfided NiMo/Al2O3 catalyst) to give a bio...
γ-Valerolactone (GVL) has been identified as a sustainable platform chemical for the production of carbon-based chemicals. Here we report a screening study on the hydrogenation of levulinic acid (LA) to GVL in water using a wide range of ruthenium supported catalysts in a batch set-up (1 wt. % Ru, 90 °C, 45 bar of H2, 2 wt. % catalyst on LA). Eight...
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The analysis of this complex multicomponent lignin oil was performed by 2-D comprehensive Gas Chromatography (GCxGC) by two different column sets. For the GCxGC analysis a non-polar/polar and a polar/non-polar column system was tested to find out the best profiles for...
γ-Valerolactone (GVL) is considered a very interesting green, bio-based platform chemical with high application potential for the production of both biofuels and biobased chemicals. In this contribution, we report a kinetic study on the hydrogenation of levulinic acid (LA) to 4-hydroxypentanoic acid (4-HPA) and the subsequent intramolecular esterif...
The acid-catalysed dehydration of the four 2-ketohexoses (fructose, sorbose, tagatose and psicose) to furanics was studied in methanol (65 g L(-1) substrate concentration, 17 and 34 mm sulfuric acid, 100 °C) with Avantium high-throughput technology. Significant differences in the reactivities of the hexoses and yields of 5-hydroxymethylfurfural (HM...
The kinetics of sunflower oil transesterification with 1-butanol using a homogeneous lipase (Rhizomucor miehei) in an aqueous-organic biphasic system were studied in a stirred batch reactor set-up. An initial screening study was performed to optimize relevant process conditions (enzyme concentration, stirring speed, 1-butanol to oil ratio). A kinet...
Sorbitol is an important commercially available chemical with a broad application range and is typically made by the catalytic hydrogenation of glucose. Here we report a high yield synthesis of sorbitol from levoglucosan (1,6-anhydro-β-D-glucopyranose) and cellobiose, two sugars present in pyrolysis liquids, using a mesoporous carbon supported Ru c...
In this paper, an experimental study on the hydrotreatment of fast pyrolysis liquids is reported in both batch and continuous set-ups using a novel bimetallic Ni-Cu based catalyst with a high Ni loading (up to 50%) made by a sol-gel method. The experiments were carried out in a wide temperature range (80 - 410 oC) and at a hydrogen pressure between...
The catalytic hydrotreatment of humins, the solid byproducts from the conversion of C6 sugars (glucose, fructose) to 5-hydroxymethylfurfural (HMF) and levulinic acid (LA), using supported Ru catalysts has been investigated. Reactions were carried out in a batch setup at elevated temperatures (400°C) using a hydrogen donor (formic acid (FA) in isopr...
The Cover picture shows how humins, byproducts from sugar conversion in biorefineries, can be broken down to valuable humin oil. Biomass and residue valorization to high-added-value chemicals is high on the global research agenda. The current routes to synthesize the platform chemicals 5-hydroxymethylfurfural (HMF) and levulinic acid (LA) inevitabl...
gamma-Valerolactone (GVL) has been identified as a sustainable platform chemical for the production of carbon-based chemicals. We here report an experimental study on the catalytic hydrogenation of levulinic acid (LA) in water to GVL in a packed bed reactor using supported Ru catalysts (carbon, alumina, and titania) with particle sizes in the milli...
Capillary microreactors operated under the slug flow regime were investigated for the separation of lactic acid from the aqueous phase using liquid-liquid reactive extraction. The experiments were performed at 1 to 1 flow ratio of the aqueous to organic phase in a setup consisting of an inlet Y-type mixer connected with a poly(tetrafluoroethylene)...
The catalytic hydrotreatment of humins, which are the solid byproducts from the conversion of C6 sugars (glucose, fructose) into 5-hydroxymethylfurfural (HMF) and levulinic acid (LA), by using supported ruthenium catalysts has been investigated. Reactions were carried out in a batch setup at elevated temperatures (400 °C) by using a hydrogen donor...
Inulin is considered an attractive feed for the synthesis of 5-hydroxymethylfurfural (HMF), an important biobased platform chemical with high application potential. We here report a systematic study to optimize the HMF yield from inulin a batch reactor for reactions in water using sulphuric acid as the catalyst. The latter was selected on the basis...
With the awareness of the need for optimal and sustainable use of natural resources, hydrothermal treatment
of biomass and biomass waste for energy and resource recovery has received increasing attention. The
hydrothermal carbonization (HTC) of a biomass is achieved using water as the reaction medium and applying
mild temperatures (180–250 ° C) und...
Catalytic hydrotreatment is an attractive technology to convert fast pyrolysis oil to stabilized oil products for co processing in conventional crude oil refinery units. We report here the use of novel bimetallic NiCu- and NiPd-based (Picula) catalysts characterized by a high Ni content (29-58 wt %) and prepared using a sol gel method with SiO2, La...
The catalytic conversion of Alcell® lignin in iso-propanol/formic acid mixtures (1:1 mass ratio) was explored in a batch set-up using Ru/C as the catalyst (673 K, 4 h, 28% mass lignin intake on solvent). Lignin oils were obtained in good yields (71% mass yields on lignin input) and shown to consist of a mixture of mainly aromatics (10.5% mass yield...
Efficient catalytic hydrotreatment of Kraft lignin to yield aromatic monomers was demonstrated in supercritical methanol using a variety of NiW and NiMo catalysts on acidic, basic and neutral supports. It was found that NiW catalysts on neutral or basic supports are highly suitable for depolymerization of Kraft lignin to methanol soluble organics i...
The depolymerization of lignin model compounds and soda lignin by super Lewis acidic metal triflates has been investigated in a mixture of ethanol and water at 400. °C. The strong Lewis acids convert representative model compounds for the structure-forming linkages in lignin, namely α-O-4, 5-O-4 (C-O-C ether bridge), and α-1 (methylene bridge). Onl...
The conversion of benzyl phenyl ether, diphenyl ether, diphenyl methane and biphenyl as representative model compounds for α-O4, 5-O4, α 1 (methylene bridges) and 5-5′ lignin linkages was investigated. We compared the use of metal chlorides and acetates. The reactions were studied in sub- and supercritical water and supercritical ethanol between 30...
The catalytic hydrotreatment of Kraft lignin using sulfided NiMo and CoMo catalysts on different acidic and basic supports (Al2O3, ZSM-5, activated carbon (AC) and MgO-La2O3) was studied in the absence of a solvent. Experiments were carried out in a batch set-up at a reaction temperature of 350 °C, 4 h and 100 bar initial H2 pressure. The catalysts...
A catalyst screening study on the catalytic hydrotreatment of Alcell lignin in a batch setup was performed using supported Ru (C, Al2O3,TiO2), Pd (C, Al2O3), and a Cu/ZrO2 catalyst with the objective to determine the best catalyst for high yields of biobased aromatics and alkylphenolics. Experiments were performed at 400 °C, 4 h reaction time and a...
Continuous synthesis and refining of biodiesel (FAME) using a laboratory scale bench scale unit was explored. The unit consists of three major parts: (i) a continuous centrifugal contactor separator (CCCS) to perform the reaction between sunflower oil and methanol; (ii) a washing unit for the crude FAME with water/acetic acid consisting of a mixer...
A series of epoxidized oils were prepared from rubber seed, soybean, jatropha, palm, and coconut oils. The epoxy content varied from 0.03 to 7.4 wt %, in accordance with the degree of unsaturation of the oils (lowest for coconut, highest for rubber seed oil). Bulk polymerization/curing of the epoxidized oils with triethylenetetramine (in the absenc...
5-Hydroxymethylfurfural (HMF), an important biobased platform chemical, is accessible by the acid catalysed conversion of biopolymers containing hexoses (cellulose, starch, inulin) and monomeric sugars derived thereof. We here report an experimental study on the uncatalysed, thermal conversion of inulin to HMF in aqueous solutions in a batch set-up...
The use of metal acetates, metal chlorides and metal triflates as Lewis acid catalysts for the depolymerization of soda lignin under supercritical conditions was investigated. The reactions were carried out at 400 °C in water and ethanol. Lignin conversion in supercritical water led to formation of insoluble char and resulted in low yields of monom...
De biobased economie biedt Indonesie veel kansen, maar leidt tot ontbossing , verlies aan biodiversiteit, en klimaatverandering. Onderzoekers tonen aan datniet grote bedrijven, maar kleine boeren dehoofdrolpselers zijn geworden. En dat zij veel slimmer gebruik moeten gaan maken van afval van land.
Noble-metal-free copper-zinc nanoalloy (<150 nm) is found to be uniquely suited for the highly selective catalytic conversion of 5-hydroxymethylfurfural (HMF) to potential biofuels or chemical building blocks. Clean mixtures of 2,5-dimethylfuran (DMF) and 2,5-dimethyltetrahydrofuran (DMTHF) with combined product yields up to 97 % were obtained at 2...
The valorization of the humin byproducts that are formed during hydrothermal, acid-catalyzed dehydration of carbohydrates is hampered by the insolubility of these byproducts. Here, we report on an alkaline pretreatment method that allows for the insolubility of this highly recalcitrant and structurally complex feed to be overcome. The reactive solu...
Polymerization of biomass-based diol precursors such as N,N’-1,2-ethanediylbis-(4-hydroxy-pentanamide) and 4-hydroxy-N-(2-hydroxyethyl)-pentanamide with aliphatic (hexamethylene diisocyanate, HDI) and aromatic di-isocyanates (1,4-phenylene-di-isocyanate, PDI and 2,4-toluene-di-isocyanate,TDI) resulted in some novel polyurethanes. The diol precursor...
An unprecedented catalytic pathway for oxa-Michael addition reactions of alcohols to unsaturated nitriles has been revealed using a PNN pincer ruthenium catalyst with a dearomatized pyridine backbone. The isolation of a catalytically competent Ru-dieneamido complex from the reaction between the Ru catalyst and pentenenitrile in combination with DFT...