• 专利附录
  • 专利说明
  • 权利要求
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  • 优先权
    • 专利摘要:
    The present invention describes a method of obtaining an activated carbon, which comprises obtaining a starting material that is wool or a textile material that contains wool in a percentage of at least 75% by weight, in a particle size of 1 mm, the determination of the ash and volatile content of said starting material, determination of a temperature at which between 70% and 80% of the volatiles of said starting material are lost from the ash and volatile content of the previous stage, and the pyrolysis of the starting material at said temperature to obtain the active carbon. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2820099A1
    申请号:ES201930921
    申请日:2019-10-17
    公开日:2021-04-19
    发明作者:Prieto Luis Fernando Calvo；Bermejo Sergio Paniagua
    申请人:Universidad de Leon；
    IPC主号:
    专利说明:

    [0002] TECHNICAL SECTOR
    [0003] The present invention belongs to the area of environmental engineering and technology, very particularly to the treatment of wastewater, with the obtaining of activated carbon that can act as a catalyst in the adsorption of pollutants.
    [0005] STATE OF THE ART
    [0006] The adsorbent properties of carbonizates can be attributed to their large internal surface area, high surface reactivity, developed porosity and favorable pore size that allows accessibility to their internal surface, thus increasing the rate of adsorption and mechanical strength.
    [0008] A typical process in the art for making chars involves heating the starting material in the absence of oxygen, or pyrolysis.
    [0010] The properties of the activated carbon obtained by a pyrolysis process will differ depending on the material or waste used, as well as the process. This process usually requires the activation of said starting material and, in addition, setting carbonization conditions, which include the heating rate and the final temperature of the activation process. This determines both the final volume of the pores and their mean diameter, as well as the total surface area.
    [0012] In the pyrolytic decomposition most of the non-carbonaceous elements of the starting material, oxygen and hydrogen, are eliminated as gaseous volatile products. The residual carbon atoms are grouped together in the form of condensed aromatic sheets or rings, resulting in a certain planar structure. The arrangement of these aromatic sheets is irregular, so that there are free interstices between them. These interstices are what will give rise to the pores that make the active carbons excellent adsorbents (Jeong Y. et al. "Three-stage air gasification of waste polyethylene: In-situ regeneration of active carbon used as a tar removal additive ”; 2019; Energy, Vol. 166, p.335-342).
    [0013] Most of the surface is associated with micropores which, according to the IUPAC definition, have effective diameters less than 2 nm, and with mesopores with diameters between 2 and 50 nm. The macropores have diameters greater than 50 nm and, although their contribution to the surface area is not very high, their function as a passageway for the adsorbate or contaminating material that it is desired to retain inside the meso and micropores is important.
    [0015] There are many patent documents related to the manufacture of activated carbons from different hydrocarbon materials.
    [0017] Thus, patent AU 617746 B2 describes obtaining carbonaceous adsorbents from pyrolyzed polysulfonated polymers, while application US 2013009152 A1 obtains them from organic fertilizers.
    [0019] All patent documents that use only physical activation set the pyrolysis temperature to a constant value to achieve complete pyrolysis. Complete pyrolysis entails, on the one hand, a higher production cost, since it is necessary to use more process energy, and on the other hand, it implies a smaller amount of material produced as the amount of volatiles lost in the process is greater. The patent CN 104874352 A uses complete pyrolysis to obtain activated carbons from industrial sludge, and the patent US 9808761 B2 also from compost and tobacco waste.
    [0021] In the textile industry, in addition to physical carbonization by temperature, chemical activation of the material is always introduced. Chemical activation is achieved with additives such as ammonium or zinc chloride, among others, and helps to achieve greater porosity in the final product and thus higher quality of the material. However, the process involves a high cost as well as being extremely polluting.
    [0023] Patent CN104071770B is based on chemical activation with a KH-550 solution of cotton-based waste material by subjecting it to a heating process under an inert atmosphere.
    [0024] On the other hand, due to a carbon and volatile content higher than 40% on a dry basis, residual wool and its textile derivatives have a great potential for transformation into adsorbent material by a thermochemical process in an inert atmosphere. Documents CN101966447A and CN106000299B use wool to obtain active carbons, always using chemical activation.
    [0026] Both due to the chemical activation and the energy expenditure of a complete pyrolysis, the manufacture of commercial activated carbon involves a high cost. This is the reason why it is not incorporated, for example, in tertiary water purification treatments for the retention of organic or inorganic pollutants that have not been retained in a conventional process.
    [0028] So the problem of the art can be posed as the need to obtain active carbons from a textile material, in a process that reduces current costs. The solution proposed by the present invention is a pyrolytic process at a temperature that involves a loss of only 75% of the volatiles of the material, instead of complete pyrolysis.
    [0030] To the best of the inventors' knowledge, obtaining active carbons from a textile material using only physical activation by temperature has not been described.
    [0032] DESCRIPTION OF THE INVENTION
    [0033] The present invention is a method for obtaining an activated carbon, which comprises several stages.
    [0035] The first is obtaining a starting material that is wool or a textile material that contains wool in a percentage of at least 75% by weight, in a particle size of up to 3 mm, preferably 1 mm, preferably also by grinding. or sieved. The original material is sized appropriately for handling in subsequent pyrolization.
    [0037] The next stage is the determination of the ash and volatile content of said starting material, preferably by thermogravimetry. From the content in Ashes and volatiles, the temperature at which between 70% and 80% of the volatiles of said starting material is lost, preferably 75%, is determined.
    [0039] Once the behavior of the sample is known under heating situations in inert atmospheres, the pyrolytic process is carried out at the temperature set by the loss of 75% of volatiles from the material to obtain activated carbon; preferably adjusting the heating ramp to 10-5 K / min, and with a residence time at the final heating temperature of 20-30 min minutes.
    [0041] The invention achieves carbonized products intended for the adsorption of pollutants in wastewater from waste wool and its textile derivatives. This material has a high content of carbon, volatiles and keratin, which facilitates the ability to retain contaminants after subjecting the indicated material to heating processes in the absence of oxygen.
    [0043] In this way, an elemental analysis of the original keratinous biomass material is first carried out, determining the carbon, volatile and ash content. Once the result is known, the final temperature of physical activation by heating under an inert atmosphere to which the material will be subjected during the active carbon manufacturing process is determined. The gravimetric profile will reflect the weight loss that occurs with increasing temperature, which is basically due to drying and devolatilization under heating in an inert atmosphere.
    [0045] The aim is to eliminate the volatile content in a non-aggressive way that ensures that the final porous residue maintains the largest number of pores with adsorbent capacity.
    [0047] The process of the present invention has the advantage of not requiring chemical additives and of not setting a process temperature at a constant and very high value a priori.
    [0049] The BET area of the coals obtained by the process of the present invention is estimated to be one third of the area values of commercial coals. But the proposed manufacturing process, by using a residual material and reducing the number of operations and the energy invested in physical activation, reduces the cost of obtaining to a quarter, making it profitable.
    [0051] In sum, the process of the present invention represents a 25% reduction in the cost of obtaining activated carbon from residual wool when compared to other active carbon manufactures that also do not use chemical activation from other materials (US 9808761 B2) , because it reduces the energy invested in the manufacturing process. With regard to savings compared to processes that use chemical activation (CN104071770B), reducing one of the stages is estimated at 40%.
    [0053] BRIEF DESCRIPTION OF THE FIGURES
    [0054] Figure 1: Thermogram 1. The weight loss is represented as a function of the temperature under inert atmosphere of the residual wool sample from Example 1. The temperature at which all the volatiles are lost (Point 2) and the defined temperature are observed. according to the invention, at which 75% of the volatiles are lost and at which the carbonization process of the material will be carried out (Point 1).
    [0056] Figure 2: Thermogram 2 in which it represents the weight loss as a function of the temperature under inert atmosphere of the residual wool sample of Example 3. The temperature at which all the volatiles are lost (Point 2) and the temperature are observed. defined according to the invention, at which 75% of the volatiles are lost and at which the carbonization process of the material will be carried out (Point 1).
    [0058] EXAMPLES
    [0059] Example 1: Manufacture of activated carbon with residual wool (material 1) from two-year-old sheep in semi-stall.
    [0060] 5 g of material 1 were taken and an elemental and immediate analysis was carried out according to regulations UNE 32-001081, UNE 32-019-84 and UNE 32-004-84 for the determination of the content of Carbon, volatiles and ashes (CHN-600 LECO and TERMOLYNE-48000 muffle furnace with automatic temperature control). Table 1 shows the result obtained.
    [0061] Table 1. Elemental and immediate analysis of material 1
    [0066] Figure 1 shows the thermogram in which the weight loss is represented as a function of the temperature under an inert atmosphere of sample 1. The temperature at which all volatiles are lost and the temperature defined according to the invention is observed, at that 75% of the volatiles are lost and at which the carbonization process of the material will be carried out. Thermogravimetry is performed for a mass of 7.8 mg of sample.
    [0068] According to its values, the physical activation process is determined at a temperature of 357 ° C (loss temperature of 75% of the volatiles), at a ramp of 5 K / min and with a residence time at the temperature indicated of 20 minutes.
    [0070] Example 2: Characterization of the carbon obtained from material 1
    [0071] With the active carbon obtained, a BET area measurement (nitrogen adsorption at 77 K by the one-point BET method; Brunauer, Emmet and Teller (Hu d. Et al. “Active carbon supported S-promoted Bi catalysts for acetylene hyddrochlorination reaction. ”, 2018; Chinese Chemical Letters, Vo. 29, Issue 9, p. 1413-1416) obtaining a value of 421.03 m2 / g, as indicated in table 2 measured by adsorption isotherms of nitrogen.
    [0073] Table 2. BET area of the activated carbon obtained
    [0075]
    [0076] Example 3: Manufacture of activated carbon with residual wool (material 2) from a one-year-old sheep in free stall.
    [0077] 5 g of material 2 were taken and an elemental and immediate analysis was carried out according to regulations UNE 32-001081, UNE 32-019-84 and UNE 32-004-84 for the determination of the content of Carbon, volatiles and ash (CHN-600 LECO and TERMOLYNE-48000 muffle furnace with automatic temperature control). Table 3 shows the result obtained.
    [0079] Table 3. Elemental and immediate analysis of material 2
    [0084] Figure 2 shows the thermogram in which it represents the weight loss as a function of the temperature under inert atmosphere of the residual wool sample 2. It shows the temperature at which all the volatiles are lost and the temperature defined according to the invention, to which 75% of the volatiles are lost and to which the carbonization process of the material will be carried out. Thermogravimetry is performed for a 7.5 mg mass of sample.
    [0086] According to the values represented, the physical activation process is determined at a temperature of 401 ° C (loss temperature of 75% of the volatiles), at a ramp of 5 K / min and with a residence time at the indicated temperature of 20 minutes.
    [0088] Example 4: Characterization of the carbon obtained from material 2
    [0089] With the activated carbon obtained, a BET area measurement is carried out according to the procedure of Example 2, obtaining a value of 421.03 m2 / g, as indicated in Table 4, measured by nitrogen adsorption isotherms.
    [0091]
    权利要求:
    Claims (3)
    [1]
    1. Method of obtaining an activated carbon, characterized in that it comprises - obtaining a starting material that is wool or a textile material that contains wool in a percentage of at least 75% by weight, in a particle size of 1 mm ,
    - determination of the ash and volatile content of said starting material,
    - determination of a temperature at which between 70% and 80% of the volatiles of said starting material are lost, based on the ash and volatiles content of the previous stage,
    - pyrolysis of the starting material at said temperature to obtain activated carbon.
    [2]
    2. Method according to claim 1, characterized in that said volatile percentage of step b) is 75%.
    [3]
    3. Method according to claim 1 or 2, characterized in that said determination of the ash and volatile material content is carried out by thermogravimetry.

    FIGURE 2
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    同族专利:
    公开号 | 公开日
    ES2820099B2|2021-09-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CA676701A|1963-12-24|F. Abbott William|Method for carbonizing fibers and articles produced therefrom|
    WO2014162267A1|2013-04-02|2014-10-09|Israzion Ltd.|Process of converting textile or plastic solid waste into activated carbon|
    法律状态:
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    ES201930921A|ES2820099B2|2019-10-17|2019-10-17|METHOD OF OBTAINING ACTIVE CHARCOAL|ES201930921A| ES2820099B2|2019-10-17|2019-10-17|METHOD OF OBTAINING ACTIVE CHARCOAL|
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