 Procedure for the biological treatment of waste contaminated with hydrocarbons (Machine-translation
专利摘要:
Procedure for the biological treatment of waste contaminated with hydrocarbons. Procedure for the biological treatment of waste with high hydrocarbon content through composting processes, in combination with phytoremediation and vermicomposting processes. During composting the sediment of the residue obtained in the cleaning of hydrocarbon storage tanks is mixed with an organic waste that has a fat content higher than 15% of an organic content higher than 75%, and a recirculated vegetable structurant is added to mix. The mixture deposited in piles reaches a temperature higher than 60ºc, for more than 15 days and, after a minimum of 4 months, a composted material with an important reduction of hydrocarbons is obtained. The product obtained has a high content of stable organic matter that allows the growth of various plant and animal species, reducing, to a greater extent, the concentration of hydrocarbons. (Machine-translation by Google Translate, not legally binding) 公开号:ES2632633A1 申请号:ES201630289 申请日:2016-03-14 公开日:2017-09-14 发明作者:Celsa Del Carmen PRADO PORTELA；David ALVES COMESAÑA；Iria VILLAR COMESAÑA；Domingo PEREZ DIAZ；Salustiano Mato De La Iglesia 申请人:Codisoil SA； IPC主号:
专利说明:
image 1 image2 image3 image4 image5 A large number of articles talk about the role of plants in the remediation of contaminated soils and water and describe how these organisms, through various processes, reduce the degree of toxicity, these processes include physical and chemical modifications of the properties of contaminated soil . Sangabriel et al. (Sangabriel, W .; Ferrera, R .; Trejos, A .; Mensoza, M., Cruz, J., Alarcón, A., 2006. Tolerance and phytoremediation capacity of fuel oil in the soil by six plant species. International Magazine Environmental Pollution National Autonomous University of Mexico 22 (2), 63-73) evaluated the tolerance and ability to bioremediate fuels in the soil by grasses and legumes, concluding that the former were more tolerant; Phillips et al. (Phillips, L .; Greer, C., Germida, J., 2006. Culture-based and culture-independent assessment of the impact of mixed and single plant treatments on rhizosphere microbial communities in hydrocarbon contaminated flare-pit Soil Biology Biochemistry 38, 2823-2833) investigated the phytoremediation of hydrocarbons in soils with 6 different species of grasses and the combined effect of them; after 4.5 months it was found that the greatest decreases in the concentration of hydrocarbons (50%) occurred in the individual treatments (Festuca rubra). Experiments were also carried out with ornamental species such as Mirabilis jalapa L. (Dondiego at night) (Peng, S, Zhou, Q., Cai, Z., Zhang, Z., 2009. Phytoremediation of petroleum contaminated soils by Mirabilis Jalapa L. in a greenhouse plot experiment, Journal of Hazardous Materials, 168, 1490–1496), measuring the ability of the Dondiego to bioremediate soils contaminated with hydrocarbons from an oilfield. After 127 days they obtained reductions between 40 and 60% of the hydrocarbons. They also concluded that Dondiego has tolerance to pollution with hydrocarbons to values close to 10,000 mg / kg. Another bioremediation technique, less studied, is vermicomposting. This process of bio-oxidation, degradation and stabilization of organic matter is mediated by the combined action of earthworms and microorganisms. Through the vermicomposting a stabilized, homogeneous and fine granulometry final product called vermicompost, lumbricompost, earthworm compost or earthworm humus is obtained. The product obtained can reach a high agronomic value since the presence of earthworms in vermicomposting accelerates and increases the nitrogen mineralization ratio (Dominguez, J., Edwards, CA, 2011. Relationships between composting and vermicomposting. In: Edwards, CA, Arancon, N., Sherman, R. (ed.), Vermiculture image6 image7 image8 Phytoremediation or vermicomposting is not possible, since it does not allow the growth and development of its own microbiota, it causes a high mortality of earthworms and the seeds of the plants have many difficulties to germinate and develop due to the physical-chemical properties of these organic compounds. To overcome these problems and the need in the state of the art for new effective bioremediation processes for the recovery of soils, sediments and waste contaminated with hydrocarbons, the authors of the present invention, after an important experimental work, have developed a new Composting process that improves the physical-chemical characteristics of the contaminated material and greatly reduces the total concentration of hydrocarbons with a low process cost. The material obtained is a material devoid of bad odors and with a high organic matter content that allows the growth of various plant species. In addition, said material allows the growth and development of earthworms. This new method of composting allows the application of low-cost biotechnological techniques, such as phytoremediation and vermicomposting, thus completing the mechanisms for the elimination of hydrocarbon contaminants still present in the product obtained by composting. Description of the figures Figure 1. Graph of evolution over time of temperatures in the different areas of the composting pile: North (), South (), East (), West (), center at 40 cm depth (), center at 80 cm depth () and ambient temperature image9 Figure 2. Graph of evolution of TPH (mg / kg) in the composting pile during the 6 months of treatment. Figure 3. Detail of copies of Pennisetum clandestinum at the end of the bioremediation process of the invention. Description of the invention Given the need in the state of the art for effective bioremediation processes for the recovery of waste contaminated with hydrocarbons, the authors of the present image10 Food sludge mixes more easily with hydrocarbon contaminated material. In addition to providing a high dose of carbon and nitrogen, essential for the growth of microorganisms, this mud, due to its origin, lacks other types of contaminants, such as heavy metals. This type of mud also allows to reach and maintain the thermophilic stage for a sufficient time, and at temperatures above 60 ° C, thus ensuring a fundamental phase in the composting process. For these reasons, the authors of the present invention have proven that food sludge is an ideal cosustrate for composting these organic pollutants. Vegetable structuring is essential in the composting of sludge because, in addition to providing porosity to the mixture, it improves the humidity conditions of the dough and provides a source of recalcitrant carbon for the microorganisms in the environment. In a preferred embodiment of the process of the present invention, the recirculated vegetable structurant used in c) is crushed wood that has been used as a structurant in previous composting processes and recovered, by sieving, for its separation from the compost. This recirculated structuring agent is characterized by presenting a microbial biomass adhered to the wood that acts as an inoculum for subsequent composting processes. The use, as cosustrates, of fresh organic sludge and crushed wood, in the defined proportions, during the composting process, improves the physical and chemical characteristics of the material and greatly reduces the total concentration of hydrocarbons with a low cost of process. In particular embodiments of the process of the present invention, in step e) the mixture is maintained at a temperature greater than 60 ° C for 30-40 days. Preferably, the temperature reached in this stage e) is between 65 and 70 ° C. The turning, carried out during stage e), consists in the mechanical action of mixing the material in the composting process. By turning the porosity is improved, image11 Table 1 shows the initial physicochemical parameters of the sludge and the residue contaminated with hydrocarbons: Table 1. Initial physical chemical parameters of the sludge and the residue contaminated with hydrocarbons. Parameters Waste contaminated with hydrocarbonsFatty mud pH 6.94 0.214.66 0.70 CE mS / cm 0.35 0.100.55 0.04 % Humidity 33.66 3.0162.29 2.25 % SSVV 41.03 4.9289.43 3.50 N-NH4 + mg / kg 123 11.10231 92.6 % Carbon 16.82 0.9951.99 1.14 % Nitrogen 0.21 0.082.32 0.32 C / N ratio 80.10 3.1222.36 2.22 Breathing mgO2 / (kgVS * h) 82 11.6956551.10 TPH g / kg 96.03 8.92Not detected Fat g / kg 4.910.51208.2822.33 Cadmium mg / kg s.m.s 4.13 0.520.850.17 Copper mg / kg s.m.s 923 848.512.57 Nickel mg / kg s.m.s 194.59 25.96.782.62 Lead mg / kg s.m.s 553 465.19 1.51 Zinc mg / kg s.m.s 1325 10319.112.35 Mercury mg / kg s.m.s 2.58 0.090.050.04 Total chrome mg / kg s.m.s 552.5 41.712.401.19 Throughout the time of composting in a pile, the analytical control was carried out by determining the humidity, organic matter, pH, conductivity, nitrogen forms, forms of carbon and respiration, as well as monitoring and control, by turning, of the temperature and the percentage of oxygen. Assembly of the battery The vegetable structuring was brought in “big bags” of a cubic meter of capacity and expanded in the reinforced concrete plate. The food sludge was then poured over the plant structurant so that it was distributed throughout its surface. Once the lower layer of vegetable structurant and the next one of sludge were formed, the residue contaminated with hydrocarbons was poured over the sludge layer. At the end of spreading the residue contaminated with hydrocarbons, the three materials were mixed using a mechanical shovel. The process of forming and mixing the battery lasted about an hour, until leaving the three materials distributed in the most homogeneous way possible. Finally, the battery was configured with a conical shape so that the interior volume was greater than in the plateau form, to achieve higher temperature and, thus, a greater intensity of degradation and reduction of TPH. In order to avoid odors and minimize the emission of hydrocarbons into the atmosphere, the battery was covered with a plastic mesh. This mesh allowed the passage of air through it avoiding anoxia of the material, also allowed the retention of steam, produced by high temperatures, preventing the loss of moisture from the mass. The final dimensions of the stack after assembly were: 1.60 meters high and about 11 meters perimeter. Temperature evolution The evolution of the temperature indicated that the battery reached 45 ° C of the thermophilic phase a day after its assembly (figure 1), and that it was in this stage about 40 days, after which the cooling phase began. The battery reduced the temperature until reaching values close to ambient temperatures during material maturation. The entire process lasted about 6 months during which temperatures were reached above 70 ° C. The number of turns was four and the frequency was established based on the needs of the process. The first turn was made a week after assembly in order to destroy the mud aggregates that are formed in this type of materials. The second turn was carried out in the third week of the process in order to homogenize the material and for the microorganisms to have the entire mass accessible, avoiding the formation of anaerobic areas. After the second turn the battery did not turn again until after 3 weeks since it was the most active period and where the highest temperatures were reached. In a common composting process it is interesting to have the material without exceeding 65ºC in temperature but in the bioremediation processes alkanes of high molecular weight are treated, so that a greater activity of the microorganisms is interested in order to achieve a greater biodegradation of the contaminants. Once the temperature decrease was observed, the fourth turn was performed to reactivate the battery. If the material does not reactivate, the cooling phase begins. During these three weeks the battery gradually lost temperature until it turned for the fourth time to begin the ripening phase. In Figure 1 we observe how the temperature was very similar in all areas of the battery without influencing the placement of the battery. A small difference is observed in the area of the center of the pile at a depth of about 80 centimeters, this area comprises the lower part of the mass, just below the "heart" of the pile. In addition to homogenizing and moisturizing the material, the flips served to collect a representative sample with which to perform the analytics and observe the parameters of maturity and stability necessary to determine the quality of the final compost. During the turning of the material, a great quantity of gases were released, such as: water, carbon dioxide and the most volatile alkanes. Therefore, during the mechanical aeration of the mixing there was a reduction in the concentration of hydrocarbons. Evolution of composting parameters The evolution in the composting parameters of the stack is shown in Table 2. Sampling was carried out during the turns of the stack in order to collect a representative fraction of the mass. Table 2. Evolution of composting parameters in samples taken during flips. Parameters Initial1st flip2nd flip3rd flip4th flip5th flipFinal compost pH 6.61 ± 0.067.81 ± 0.098.48 ± 0.038.87 ± 0.038.83 ± 0.038.37 ± 0.118.18 ± 0.10 CE (mS / cm) 1.42 ± 0.092.18 ± 0.162.18 ± 0.151.75 ± 0.171.58 ± 0.121.66 ± 0.130.97 ± 0.05 Humidity (%) 44.06 ± 0.1042.01 ± 1.2135.01 ± 1.8434.40 ± 1.6336.96 ± 0.5640.39 ± 1.0442.50 ± 0.94 SSVV (%) 39.94 ± 0.1736.44 ± 2.2732.87 ± 3.3133.29 ± 2.7732.05 ± 1.9728.36 ± 1.2527.38 ± 1.40 Breathing rate (mgO2 / kgVS / h) 4991 ± 2641081 ± 112721 ± 73381 ± 84322 ± 52202 ± 6180 ± 5 AT4 mgO2 / gTS 89.37 ± 1.7537.83 ± 3.9223.06 ± 2.3412.16 ± 2.716.81 ± 0.185.50 ± 0.175.02 ± 0.16 NH4 + (mg / kg) 1217 ± 1393221 ± 2042900 ± 3032007 ± 2601044 ± 6166 ± 1138 ± 6 NO3 - (mg / kg) 52.80 ± 7.26104.19 ± 11.27103.15 ± 14.35108.70 ± 15.98167.61 ± 18.91240.77 ± 22.31172.09 ± 29.49 NH4 + / NO3 ratio - 21.75 ± 3.1830.98 ± 1.3928.29 ± 1.1217.63 ± 0.116.25 ± 1.210.30 ± 0.020.21 ± 0.01 Total Carbon (%) 19.31 ± 0.8917.55 ± 0.1415.95 ± 1.5915.70 ± 1.3815.61 ± 1.2015.43 ± 1.2913.01 ± 1.84 image12 image13 Hydrocarbon concentration is mainly due to the high temperatures produced by the microorganisms present in the cell within 40 days of the thermophilic phase. From the third turn, in the cooling stage followed by the maturation of the material, the bioremediation of TPH stabilizes until the end of the process. 5 Results With the final material the determination of its granulometry was made. For this purpose, around 2 kilos of representative sample of the different points of the stack were taken, subsequently, the sample was allowed to air dry, screened using a 0.5 light sieve 10 centimeters in diameter and, finally, the different separated fractions were weighed (table 3). Table 3. Granulometry of composted material. Fractions Weights (grams)Percentages (%) Less than 0.5cm 1174.5657.82 Greater than 0.5cm 841.7241.44 Impropios 14.180.70 Earthworms 0.930.05 TOTAL 2031.39100.00 From the data provided by the granulometry of the material, it was obtained that 57.82% of the final product corresponds to the final material recovered and 41.44% can be recycled for use in another composting cycle. The analysis of these data highlights the presence of improprieties such as fabrics, rags or cigarette butts that cannot be degraded by microorganisms and persist in the material larger than 5mm. Another interesting fact is the colonization by animals such as earthworms 20 earth, which opens the door to the use of other biological techniques to treat the material. Conclusions In the composting tests, a material with a high decrease in the total hydrocarbon concentration (reduction of TPH = 75%) was obtained. The conclusion of the test was that the composting of the residue contaminated with hydrocarbons, using as co-substrates a fresh organic sludge and crushed wood, in the established proportions, improves the physical-chemical characteristics of the material and greatly reduces the total concentration of hydrocarbons with a low process cost. In addition, the final composted material, obtained after 6 months from the beginning of the assembly of the pile, is a material devoid of bad odors and with a high content of organic matter that allows the growth of various plant species. EXAMPLE 2. TEST WITH PLANTS AND Worms In order to treat and assess the effects of composted material on the growth and development of plants and soil decomposers, a test treatment was performed. For this, the material obtained in the previous test was screened by a 5 mm sieve to facilitate rooting of the plants. The plant used in the phytoremediation test was Pennisetum clandestinum, (var. Whittet) common name kikuyo, which is a tropical perennial species of the Poaceae family. This species, under favorable conditions, acquires rapid growth, which allows it to dominate the other species that are sown with it. It reproduces vegetatively through powerful rhizomes and stolons. The choice of this species for the performance of the test was conditioned by the rapid and continuous growth of the root system. P. clandestinum has a great capacity to adapt to environmental conditions and an enormous facility for vegetative dispersion in a soil. In turn, this species has low light, water and temperature requirements to maintain its activity during the hardest months of the year. As a representative of the decomposing mesofauna, the worm species Eisenia andrei was used, because it has an enormous capacity to feed and live in different organic waste, in addition to presenting a high reproductive rate. image14 image15 Table 5. Evolution of the parameters and measures at the beginning and end of the test. Parameters Starting initialsControlE. andreiP. clandestinumE. andrei + P. clandistinum pH 8.18 ± 0.108.09 ± 0.098.12 ± 0.118.13 ± 0.068.06 ± 0.08 CE (mS / cm) 0.97 ± 0.050.82 ± 0.101.05 ± 0.111.12 ± 0.090.99 ± 0.08 Germination (%) ---75.55 ± 1.3274.71 ± 1.03 Total plant biomass (g MS) ---8.28 ± 0.757.92 ± 0.66 Earthworm Survival (%) --91.02 ± 0.78-90.31 ± 0.66 Total weight worms (g / box) 10.41 ± 0.1-14.08 ± 0.65-13.22 ± 0.91 TPH (mg / kg) 2311 ± 112298 ± 492302 ± 372095 ± 421960 ± 39 Evolution of hydrocarbons 5 A decrease in the concentration of TPH was detected in the presence of the P. clandestinum species after three months of process, the reduction in treatment with E. Andrei. The joint action of earthworms and root biomass of plants allows the decrease in the total concentration of hydrocarbons. This effect may be due to the stimulation or creation of favorable conditions for the growth of 10 microbial communities responsible for the degradation of hydrocarbons. The worms and the roots modify the conditions of the substrate, when increasing the porosity and aeration, and increase the availability and the type of nutrients due to the passage of the material through the intestinal tract of the worms and to the exudates of the roots.
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