Crop Management Impacts Biofuel Quality: Influence of Switchgrass Harvest Time on Yield, Nitrogen and Ash of Fast Pyrolysis Products

Although upgrading bio-oil from fast pyrolysis of biomass is an attractive pathway for biofuel production, nitrogen (N) and mineral matter carried over from the feedstock to the bio-oil represents a serious contaminant in the process. Reducing the N and ash content of biomass feedstocks would improve process reliability and reduce production costs of pyrolytic biofuels. This study investigated: (1) How does switchgrass harvest date influence the yield, N concentration ([N]), and ash concentration of biomass and fast pyrolysis products? and (2) Is there a predictive relationship between [N] of switchgrass biomass and [N] of fast pyrolysis products? Switchgrass from five harvest dates and varying [N] from central Iowa were pyrolyzed using a free-fall reactor. Harvestable biomass peaked in August (8.6 Mg ha^?1), dropping significantly by November (6.7 Mg ha^?1, P?=?0.0027). Production of bio-oil per unit area mirrored that of harvested biomass at each harvest date; however, bio-oil yield per unit dry biomass increased from 46.6 % to 56.7 % during the season (P?=?0.0018). Allowing switchgrass to senesce lowered biomass [N] dramatically, by as much as 68 % from June to November (P?<?0.0001). Concurrently, bio-oil [N] declined from 0.51 % in June to 0.17 % by November (P?<?0.0001). Significant reductions in ash concentration were also observed in biomass and char. Finally, we show for the first time that the [N] of switchgrass biomass is a strong predictor of the [N] of bio-oil, char, and non-condensable gas with R ² values of 0.89, 0.94, and 0.88, respectively.     

Sources of Biomass Feedstock Variability and the Potential Impact on Biofuels Production

Terrestrial lignocellulosic biomass has the potential to be a carbon neutral and domestic source of fuels and chemicals. However, the innate variability of biomass resources, such as herbaceous and woody materials, and the inconsistency within a single resource due to disparate growth and harvesting conditions, presents challenges for downstream processes which often require materials that are physically and chemically consistent. Intrinsic biomass characteristics, including moisture content, carbohydrate and ash compositions, bulk density, and particle size/shape distributions are highly variable and can impact the economics of transforming biomass into value-added products. For instance, ash content increases by an order of magnitude between woody and herbaceous feedstocks (from ～0.5 to 5 %, respectively) while lignin content drops by a factor of two (from ～30 to 15 %, respectively). This increase in ash and reduction in lignin leads to biofuel conversion consequences, such as reduced pyrolysis oil yields for herbaceous products as compared to woody material. In this review, the sources of variability for key biomass characteristics are presented for multiple types of biomass. Additionally, this review investigates the major impacts of the variability in biomass composition on four conversion processes: fermentation, hydrothermal liquefaction, pyrolysis, and direct combustion. Finally, future research processes aimed at reducing the detrimental impacts of biomass variability on conversion to fuels and chemicals are proposed.© 2015 Battelle Energy Alliance, LLC, contract manager for Idaho National Laboratory.     

Fermentative hydrogen production from Laminaria japonica and optimization of thermal pretreatment conditions

As a sustainable biofuel feedstock, marine algae have superior aspects to terrestrial biomass such as less energy and water requirement for cultivation, higher CO₂ capture capacity, and negligible lignin content. In this study, various marine algae were tested for fermentative hydrogen production (FHP). Among them, Laminaria japonica exhibited the best performance, showing the highest H₂ yield of 69.1 mL H₂/g COD_added. It was attributed to its high carbohydrate content and main constituents of polysaccharides, laminarin and alginate, which were found to posses higher H₂ production potential than agar and carrageenan. To enhance the H₂ production from L. japonica, thermal pretreatment was applied at various conditions. At 170 °C and 20 min, H₂ yield was maximized to 109.6 mL H₂/g COD_added. The experimental results suggested that marine algae, especially L. japonica, could be used for FHP, and future works would be focused on gaining more energy from the H₂ fermentation effluent.     

Growth medium standardization and thermotolerance study of the freshwater microalga <Emphasis Type="Italic">Acutodesmus dimorphus—</Emphasis>a potential strain for biofuel production

Microalgal biomass seems to be one of the potential alternative feedstocks for the production of various types of biofuel. In the present study, first of all, suitable growth media and harvesting time were determined for the freshwater chlorophyte microalga Acutodesmus dimorphus. Cultivation of A. dimorphus in BG-11 medium for 15 days resulted in the highest biomass productivity with 24.60 % lipid and 22.78 % carbohydrate contents. Further, thermotolerance property of A. dimorphus was evaluated by heat stressing the cells at 45 °C and 50 °C up to 24 h and determining the cell mortality and pigment composition along with lipid and carbohydrate contents. Chlorophyll and carotenoid contents of cells significantly increased after heat stress at 45 °C. Increasing the heat stress from 8 to 24 h increased the dead cells by 3–4 % at both temperatures, which shows the thermotolerance of A. dimorphus. Lipid content of 27 % and carbohydrate content of 26–28 % even after 24 h of heat stress at 45 and 50 °C suggest A. dimorphus as a potential feedstock for biofuel production.     

Subcritical Water Hydrolysis of Microalgal Biomass for Protein and Pyrolytic Bio-oil Recovery

Microalgae are a promising source of protein and biofuels. This study involved the extraction of soluble proteins from raw microalgae using subcritical water hydrolysis followed by pyrolysis of the resulting spent microalgal biomass for bio-oil production. The extraction process produced solubilized protein in amounts up to 10 wt% of the dry biomass. The effects of hydrolysis temperature (150–220 °C), process time (90–180 min), and initial pH (2–12) on the chemical compositions and reactivity of the spent biomass as biofuel intermediates were investigated. It was found that when the temperature and time increased, the protein and carbohydrate fractions of the spent biomass were reduced, while their lipid fraction increased. A low initial pH led to lower protein content in the spent biomass. Compared with the raw microalgae, the spent biomass gave a higher yield of pyrolytic bio-oil that contained much less of the N-containing compounds and higher amounts of long-chain fatty acids (C₁₆) and C₁₄–C₂₀ long-chain hydrocarbons. In addition, enhanced energy recovery and a reduction in the energy consumption of the pyrolysis process were the other benefits acquired from the protein extraction. Therefore, subcritical water hydrolysis was considered to be an effective process to recover solubilized proteins, enhance the properties of the spent biomass, improve the energy balance of the subsequent pyrolysis process, and raise the quality of the bio-oil.     

Carbohydrates Production and Bio-flocculation Characteristics in Cultures of Arthrospira (Spirulina) platensis: Improvements Through Phosphorus Limitation Process

Carbohydrates are a desirable biomass compound for the generation of several biofuels. Phosphorus nutrient limitation causes a significant increase in the carbohydrate content of the cyanobacterium Arthrospira (Spirulina) platensis. Carbohydrates accumulated up to a content of 63.09?±?3.43?% (±SD) in both batch and semi-continuous cultures. In order the production of carbohydrate-rich biomass through nutrient limitation to be maximized, it is suggested that the limited nutrients have to be supplied in amounts that they on one hand can support the biomass production while on the other hand they alter the composition of the biomass. In this study, phosphorus of 1.82?±?0.16?mg g^?1 of dry biomass was the optimized amount for the maximization of carbohydrates production by A. platensis. Regarding the need to decrease the application amounts of nutrients for biomass production, this study demonstrates that the phosphorus supply could be decreased an order of magnitude with no significant decrease in biomass production. In addition, it was observed that biomass rich in carbohydrates bio-flocculates, during settling without the addition of any flocculation agent or any other intervention. The bio-flocculation efficiency appears to be related with the carbohydrate content of the biomass. In maximum carbohydrate content (60?%), the biomass bio-flocculated at 68.49?±?7.73?% the first 15?min and reached 80.25?±?5.58?% 60?min after settling. The produced carbohydrates might be used as feedstock for biofuel generation, while the bio-flocculation and the overall settling characteristics of the carbohydrate-rich biomass could make its harvesting process much easier.     

含氮类培养基对海洋微藻Isochrysis zhanjiangensis 油脂与碳水化合物积累的影响

考察了8种含氮培养基对湛江等鞭金藻(I. zhanjiangensis)生长、PSⅡ活性、油脂及碳水化合物积累的影响。结果显示,当培养基中氮浓度为1.5 g/L,藻细胞的总脂肪含量和产量分别达到最高值为39.8 %和 0.92 g/L, 碳水化合物的含量为最低11.6 %;而当培养基中氮浓度为 0.016 g/L,藻细胞的总脂肪含量和产量分别达到最低值为21.1 %和0.16 g/L。而此时总碳水化合物含量最高达到44.4 %。同时线性拟合方程的结果表明培养基中NO₃^-的浓度与藻细胞的总脂含量呈较好的正相关性。因此,通过研究不同含氮水平的培养基实现了脂肪或碳水化合物产量的调控。     

Compositional and Thermal Evaluation of Lignocellulosic and Poultry Litter Chars via High and Low Temperature Pyrolysis

Inorganic elements in biomass feedstocks can influence thermochemical reactions as well as the resultant char’s elemental, compositional, and thermal characteristics. Chars were produced using slow pyrolysis under low (≤400°C) and high (≥500°C) temperature regimes from sugarcane bagasse, peanut hulls, pecan shell, pine chips, poultry litter, and switchgrass. The chars and raw feedstocks were characterized for their elemental, structural, and thermal properties to ascertain the implications of feedstock selection and pyrolysis temperatures on these properties. Char mass yields from the six feedstocks ranged between 28% and 78% by weight while carbon yields ranged between 44% and 89%. In both instances, lower yields were obtained with increasing pyrolysis temperature. Higher pyrolysis temperatures (≥500°C) resulted in more neutral to alkaline chars possessing greater ash contents and increased aromatic character with narrow O/C and H/C ratios. A significant exponential curve response (r ²?=?0.87, P?<?0.001) was revealed between char mass yields vs. pyrolysis temperature. All raw feedstocks and chars contained mixed amounts of macro-, micro-, and trace element concentrations. The higher heating values (HHV) tended to increase with heightened pyrolysis temperature with some chars producing >30 MJ kg^?1. The chars’ HHV values inversely correlated to their total ash and Cl content. Lignocelluloses chars had better thermal characteristics and lower ash quality concerns implying suitable service in thermal energy production. In contrast, poultry litter char had greater ash contents, medium HHV values, and contained corrosive inorganic elements, which rendered it problematic as a feedstock for thermal energy generation.     

Fast Pyrolysis of Biomass Residues in a Twin-screw Mixing Reactor

Fast pyrolysis is being increasingly applied in commercial plants worldwide. They run exclusively on woody biomass, which has favorable properties for conversion with fast pyrolysis. In order to increase the synergies of food production and the energetic and/or material use of biomass, it is desirable to utilize residues from agricultural production, e.g., straw. The presented method is suitable for converting such a material on an industrial scale. The main features are presented and an example of mass balances from the conversion of several biomass residues is given. After conversion, fractionated condensation is applied in order to retrieve two condensates — an organic-rich and an aqueous-rich one. This design prevents the production of fast pyrolysis bio-oil that exhibits phase separation. A two phase bio-oil is to be expected because of the typically high ash content of straw biomass, which promotes the production of water of reaction during conversion.Both fractionated condensation and the use of biomass with high ash content demand a careful approach for establishing balances. Not all kind of balances are both meaningful and comparable to other results from the literature. Different balancing methods are presented, and the information that can be derived from them is discussed.     

Seasonal variation in light utilisation,biomass production and nutrient removal by wastewater microalgae in a full-scale high-rate algal pond

There has been renewed interest in the combined use of high-rate algal ponds (HRAP) for wastewater treatment and biofuel production. Successful wastewater treatment requires year-round efficient nutrient removal while high microalgal biomass yields are required to make biofuel production cost-effective. This paper investigates the year-round performance of microalgae in a 5-ha demonstration HRAP system treating primary settled wastewater in Christchurch, New Zealand. Microalgal performance was measured in terms of biomass production, nutrient removal efficiency, light absorption and photosynthetic potential on seasonal timescales. Retention time-corrected microalgal biomass (chlorophyll a) varied seasonally, being lowest in autumn and winter (287 and 364 mg m^?3day^?1, respectively) and highest in summer (703 mg m^?3day^?1), while the conversion efficiency of light to biomass was greatest in winter (0.39 mg Chl- a per μmol) and lowest in early summer (0.08 mg Chl- a per μmol). The percentage of ammonium (NH₄–N) removed was highest in spring (79 %) and summer (77 %) and lowest in autumn (47 %) and winter (53 %), while the efficiency of NH₄–N removal per unit biomass was highest in autumn and summer and lowest in winter and spring. Chlorophyll-specific light absorption per unit biomass decreased as total chlorophyll increased, partially due to the package effect, particularly in summer. The proportional increase in the maximum electron transport rate from winter to summer was significantly lower than the proportional increase in the mean light intensity of the water column. We concluded that microalgal growth and nutrient assimilation was constrained in spring and summer and carbon limitation may be the likely cause.     

Seasonal variation in Laminaria digitata and its impact on biochemical conversion routes to biofuels

Laminaria digitata is a highly prevalent kelp growing off the coast of the UK but has rarely been considered as a source of biomass to date. This study shows it can be used as a feedstock in both ethanol fermentation and anaerobic digestion for methane production. The study optimised several parameters in the fermentation of L. digitata and investigated the suitability of the macroalgae through the year using samples harvested every month. For both methane and ethanol production, minimum yields were seen in material harvested in March when the carbohydrates laminarin and mannitol were lowest. July material contained the highest combined laminarin and mannitol content and maximum yields of 167 mL ethanol and 0.219 m³ kg⁻¹L. digitata.     

Molecular Identification and Comparative Evaluation of Tropical Marine Microalgae for Biodiesel Production

Marine microalgae have emerged as important feedstock for liquid biofuel production. The identification of lipid-rich native microalgal species with high growth rate and optimal fatty acid profile and biodiesel properties is the most challenging step in microalgae-based biodiesel production. In this study, attempts have been made to bio-prospect the biodiesel production potential of marine and brackish water microalgal isolates from the west coast of India. A total of 14 microalgal species were isolated, identified using specific molecular markers and based on the lipid content; seven species with total lipid content above 20% of dry cell weight were selected for assessing biodiesel production potential in terms of lipid and biomass productivities, nile red fluorescence, fatty acid profile and biodiesel properties. On comparative analysis, the diatoms were proven to be promising based on the overall desirable properties for biodiesel production. The most potential strain Navicula phyllepta MACC8 with a total lipid content of 26.54 % of dry weight of biomass, the highest growth rate (0.58 day^?1) and lipid and biomass productivities of 114 and 431 mgL^?1 day^?1, respectively, was rich in fatty acids mainly of C16:0, C16:1 and C18:0 in the neutral lipid fraction, the most favoured fatty acids for ideal biodiesel properties. The biodiesel properties met the requirements of fuel quality standards based on empirical estimation. The marine diatoms hold a great promise as feedstock for large-scale biodiesel production along with valuable by-products in a biorefinery perspective, after augmenting lipid and biomass production through biochemical and genetic engineering approaches.     

Harvest management affects biomass composition responses of C4 perennial bioenergy grasses in the humid subtropical USA

Elephantgrass (Pennisetum purpureum Schum.) and energycane (Saccharum spp. hybrid) are high‐yielding C4 grasses that are attractive biofuel feedstocks in the humid subtropics. Determining appropriate harvest management practices for optimal feedstock chemical composition is an important precursor to their successful use in production systems. In this research, we have investigated the effects of harvest timing and frequency on biomass nutrient, carbohydrate and lignin composition of UF1 and cv. Merkeron elephantgrasses and cv. L 79‐1002 energycane. Biomass properties under increased harvest frequency (twice per year) and delayed harvest (once per year after frost) were compared with a control (once per year prior to frost). There were no differences between elephantgrass entries in structural carbohydrates; however, elephantgrasses had greater structural hexose concentration than energycane for single‐harvest treatments (avg. 398 vs. 366 mg g^?1), a trait that is preferred for biofuel production. Delayed harvest of energycane decreased structural hexose compared with the control (374 vs. 357 mg g^?1) because nonstructural components accumulated in energycane stem as harvest was delayed. Frequent defoliation (2X) increased N, P, and ash concentrations (75% for N and P and 58% for ash) in harvested biomass compared with single‐harvest treatments. We conclude that multiple harvests per year increase the harvest period during which feedstock is available for processing, but they do not result in optimal feedstock composition. In contrast, extending the period of feedstock supply by delaying a single harvest to after first freeze did not negatively affect cell wall constituent properties, while it increased length of the harvest period by ~30 days in the southeast USA.     

Simulating the effects of harvest and biofuel production on the forest system carbon balance of the Midwest,USA

Forests of the Midwestern United States are an important source of fiber for the wood and paper products industries. Scientists, land managers, and policy makers are interested in using woody biomass and/or harvest residue for biofuel feedstocks. However, the effects of increased biomass removal for biofuel production on forest production and forest system carbon balance remain uncertain. We modeled the carbon (C) cycle of the forest system by dividing it into two distinct components: (1) biological (net ecosystem production, net primary production, autotrophic and heterotrophic respiration, vegetation, and soil C content) and (2) industrial (harvest operations and transportation, production, use, and disposal of major wood products including biofuel and associated C emissions). We modeled available woody biomass feedstock and whole‐system carbon balance of 220 000 km² of temperate forests in the Upper Midwest, USA by coupling an ecosystem process model to a collection of greenhouse gas life‐cycle inventory models and simulating seven forest harvest scenarios in the biological ecosystem and three biofuel production scenarios in the industrial system for 50 years. The forest system was a carbon sink (118 g C m^?2 yr^?1) under current management practices and forest product production rates. However, the system became a C source when harvest area was doubled and biofuel production replaced traditional forest products. Total carbon stores in the vegetation and soil increased by 5–10% under low‐intensity management scenarios and current management, but decreased up to 3% under high‐intensity harvest regimes. Increasing harvest residue removal during harvest had more modest effects on forest system C balance and total biomass removal than increasing the rate of clear‐cut harvests or area harvested. Net forest system C balance was significantly, and negatively correlated (R² = 0.67) with biomass harvested, illustrating the trade‐offs between increased C uptake by forests and utilization of woody biomass for biofuel feedstock.     

Co-Cultivation of Fungal and Microalgal Cells as an Efficient System for Harvesting Microalgal Cells,Lipid Production and Wastewater Treatment

The challenges which the large scale microalgal industry is facing are associated with the high cost of key operations such as harvesting, nutrient supply and oil extraction. The high-energy input for harvesting makes current commercial microalgal biodiesel production economically unfeasible and can account for up to 50% of the total cost of biofuel production. Co-cultivation of fungal and microalgal cells is getting increasing attention because of high efficiency of bio-flocculation of microalgal cells with no requirement for added chemicals and low energy inputs. Moreover, some fungal and microalgal strains are well known for their exceptional ability to purify wastewater, generating biomass that represents a renewable and sustainable feedstock for biofuel production. We have screened the flocculation efficiency of the filamentous fungus A. fumigatus against 11 microalgae representing freshwater, marine, small (5 µm), large (over 300 µm), heterotrophic, photoautotrophic, motile and non-motile strains. Some of the strains are commercially used for biofuel production. Lipid production and composition were analysed in fungal-algal pellets grown on media containing alternative carbon, nitrogen and phosphorus sources contained in wheat straw and swine wastewater, respectively. Co-cultivation of algae and A. fumigatus cells showed additive and synergistic effects on biomass production, lipid yield and wastewater bioremediation efficiency. Analysis of fungal-algal pellet''s fatty acids composition suggested that it can be tailored and optimised through co-cultivating different algae and fungi without the need for genetic modification.     

Characterization of cell growth and starch production in the marine green microalga Tetraselmis subcordiformis under extracellular phosphorus-deprived and sequentially phosphorus-replete conditions

Microalgal starch is a potential feedstock for biofuel production. Nutrient stress is widely used to stimulate starch accumulation in microalgae. Cell growth and starch accumulation in the marine green microalga Tetraselmis subcordiformis were evaluated under extracellular phosphorus deprivation with initial cell densities (ICD) of 1.5, 3.0, 6.0, and 9.0?×?10⁶ cells mL^?1. The intracellular stored phosphorus supported cell growth when extracellular phosphorus was absent. The maximum starch content of 44.1 % was achieved in the lowest ICD culture, while the maximum biomass productivity of 0.71 g L^?1 day^?1, starch concentration of 1.6 g L^?1, and starch productivity of 0.30 g L^?1 day^?1 were all obtained in the culture with the ICD of 3.0?×?10⁶ cells mL^?1. Appropriate ICD could be used to regulate the intracellular phosphorus concentration and maintain adequate photosynthetic activity to achieve the highest starch productivity, along with biomass and starch concentration. The recovery of phosphorus-deprived T. subcordiformis in medium containing 0.5, 1.0, or 6.0 mM KH₂PO₄ was also tested. Cell growth and starch accumulation ability could be recovered completely. A phosphorus pool in T. subcordiformis was shown to manipulate its metabolic activity under different environmental phosphorus availability. Though lower starch productivity and starch content were achieved under phosphorus deprivation compared with nitrogen- or sulfur-deprived conditions, the higher biomass and starch concentration make T. subcordiformis a good candidate for biomass and starch production under extracellular phosphorus deprivation.     

Ethanol production from marine algal hydrolysates using Escherichia coli KO11

Algae biomass is a potential raw material for the production of biofuels and other chemicals. In this study, biomass of the marine algae, Ulva lactuca, Gelidium amansii,Laminaria japonica, and Sargassum fulvellum, was treated with acid and commercially available hydrolytic enzymes. The hydrolysates contained glucose, mannose, galactose, and mannitol, among other sugars, at different ratios. The Laminaria japonica hydrolysate contained up to 30.5% mannitol and 6.98% glucose in the hydrolysate solids. Ethanogenic recombinant Escherichia coli KO11 was able to utilize both mannitol and glucose and produced 0.4 g ethanol per g of carbohydrate when cultured in L. japonica hydrolysate supplemented with Luria-Bertani medium and hydrolytic enzymes. The strategy of acid hydrolysis followed by simultaneous enzyme treatment and inoculation with E. coli KO11 could be a viable strategy to produce ethanol from marine alga biomass.     

Comparing the potential production and value of high-energy liquid fuels and protein from marine and freshwater macroalgae

The biomass production and biochemical properties of marine and freshwater species of green macroalgae (multicellular algae), cultivated in outdoor conditions, were evaluated to assess the potential conversion into high-energy liquid biofuels, specifically biocrude and biodiesel and the value of these products. Biomass productivities were typically two times higher for marine macroalgae (8.5–11.9 g m⁻² d⁻¹, dry weight) than for freshwater macroalgae (3.4–5.1 g m⁻² d⁻¹, dry weight). The biochemical compositions of the species were also distinct, with higher ash content (25.5–36.6%) in marine macroalgae and higher calorific value (15.8–16.4 MJ kg⁻¹) in freshwater macroalgae. Lipid content was highest for freshwater Oedogonium and marine Derbesia. Lipids are a critical organic component for biocrude production by hydrothermal liquefaction (HTL) and the theoretical biocrude yield was therefore highest for Oedogonium (17.7%, dry weight) and Derbesia (16.2%, dry weight). Theoretical biocrude yields were also higher than biodiesel yields for all species due to the conversion of the whole organic component of biomass, including the predominant carbohydrate fraction. However, all marine species had higher biomass productivities and therefore had higher projected biocrude productivities than freshwater species, up to 7.1 t of biocrude ha⁻¹ yr⁻¹ for Derbesia. The projected value of the six macroalgae was increased by 45–77% (up to US$7700 ha⁻¹ yr⁻¹) through the extraction of protein prior to the conversion of the residual biomass to biocrude. This study highlights the importance of optimizing biomass productivities for high-energy fuels and targeting additional coproducts to increase value.     

The mixed culture of microalgae Chlorella pyrenoidosa and yeast Yarrowia lipolytica for microbial biomass production

Microbial biomass which mostly generated from the microbial processes of bacteria, yeasts, and microalgae is an important resource. Recent concerns in microbial biomass production field, especially microbial lipid production for biofuel, have been focused towards the mixed culture of microalgae and yeast. To more comprehensive understanding of the mixed culture for microbial biomass, mono Chlorella pyrenoidosa, mono Yarrowia lipolytica and the mixed culture were investigated in the present work. Results showed that the mixed culture achieved significantly faster cell propagation of microalga and yeast, smaller individual cell size of yeast and higher relative chlorophyll content of microalga. The mixed culture facilitated the assimilation of carbon and nitrogen and drove the carbon flow to carbohydrate. Besides higher lipid yield (0.77 g/L), higher yields of carbohydrates (1.82 g/L), protein (1.99 g/L) and heating value (114.64 kJ/L) indicated the microbial biomass harvested from the mixed culture have more potential utilization in renewable energy, feedstuff, and chemical industry.