WO2010139816A1 - Composition et utilisation d'une matière adsorbante pour le filtrage de composés toxiques dans le procédé d'incinération et/ou de distillation de la glycérine provenant de la production de biodiesel - Google Patents

Composition et utilisation d'une matière adsorbante pour le filtrage de composés toxiques dans le procédé d'incinération et/ou de distillation de la glycérine provenant de la production de biodiesel Download PDF

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Publication number
WO2010139816A1
WO2010139816A1 PCT/ES2009/070210 ES2009070210W WO2010139816A1 WO 2010139816 A1 WO2010139816 A1 WO 2010139816A1 ES 2009070210 W ES2009070210 W ES 2009070210W WO 2010139816 A1 WO2010139816 A1 WO 2010139816A1
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WO
WIPO (PCT)
Prior art keywords
composition
incineration
glycerin
adsorbent material
biodiesel
Prior art date
Application number
PCT/ES2009/070210
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English (en)
Spanish (es)
Inventor
Pedro Romera Lorca
Original Assignee
Desarrollos Tecnicos Mc, S.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Desarrollos Tecnicos Mc, S.L. filed Critical Desarrollos Tecnicos Mc, S.L.
Priority to PCT/ES2009/070210 priority Critical patent/WO2010139816A1/fr
Publication of WO2010139816A1 publication Critical patent/WO2010139816A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/11—Clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/202—Single element halogens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the object of the present invention is a composition of adsorbent material that allows the elimination of toxic emissions in the incineration and / or distillation of glycerin in order to avoid the storage of large volumes of glycerin from the production of Large-scale biodiesel, which can be incinerated without contamination of the environment due to the carcinogenic products generated from the combustion of glycerin, in particular, acrolein.
  • Biodiesel is a product obtained by a process of transesterification (formation of methyl esters) of the fatty acids in vegetable oils (soy, sunflower, rape, ). Its characteristics are similar to that of diesel, although it should be noted that biodiesel has a flash point considerably higher than diesel, which makes it much less dangerous. The percentage of sulfur is also a factor to review, since it avoids the emission of this component to the atmosphere with its corresponding environmental improvement.
  • biodiesel is a mixture of fatty acid methyl esters.
  • the raw material, fats and oils, are fundamentally triglycerides of fatty acids.
  • the fundamental raw material is rapeseed, since it is the most economical oilseed existing, being able to use other vegetable oils such as sunflower, palm, soy, etc.
  • Other possibilities are to use animal fats of low cost or used oil that was used for fried foods.
  • the transesterification reaction is a reaction characteristic of the esters, and consequently of the lipids, in which the oil or fat reacts with fatty acids, alcohols or other esters with the exchange of acyl groups.
  • a catalyst mainly sodium methylate, soda or potash, as can be seen in the following reaction:
  • Glycerin is a product of the transesterification reaction and therefore its formation in the biodiesel production process cannot be avoided.
  • the amount of glycerin that is generated is very important, representing approximately 10% of the biodiesel produced.
  • crude glycerin will be obtained, with a percentage of glycerol around 80%, or pharmaceutical grade glycerin, with a percentage of glycerol of the 99.7%
  • the substances that accompany glycerin are, mainly, water, salts and organic matter (not glycerin), formed by soaps, free fatty acids and other impurities.
  • the crude glycerin obtained in the biodiesel industry has the great disadvantage of being composed of a series of miscible components and very different chemical properties (methanol, potassium, water, free fatty acids and glycerin). For this reason glycerin is still the big problem of biodiesel plants.
  • glycerin can be separated by spliting (acidification) to obtain a purity of around 80%, this method would entail new expenses associated with those of combustion technologies, the ideal would be to use raw glycerin directly, taking advantage of the calorific value of other components such as methanol, but with an efficient system of ash withdrawals generated by inorganic minerals originated and elimination of toxic gases.
  • An area that shows an appreciable potential to consume high amounts of glycerin is the use of glycerin for energy production. Glycerin burns well, but must be burned at high temperatures so that no toxic fumes of acrolein, which is formed mainly between 200 0 C and 300 0 C are produced, and other carcinogenic pollutants.
  • the presence of salts can cause corrosion problems in the burner nozzles and in the combustion facility itself.
  • the salts are flame inhibitors, which hinders the combustion of glicehna without using it in an auxiliary fuel.
  • the present invention satisfactorily solves the process of incineration and distillation of the glycerin, since it provides an adsorbent material that can be used in the filters at the exit of the chimneys or fluid discharge tubes and which is formed mainly of graphite in the state pure or combined with activated carbon from tires or any known element, both in combination with natural silicates such as enstatite or sepiolites, attapulgites, zeolites, or the like or their mixture and plasticizing and / or polymerizable agents or a mixture thereof ,
  • the resulting mixture is capable of adding carbonates of alkaline or alkaline earth metals in substitution of the plasticizing and / or polymerizable agents, which allow to reduce in its entirety the toxic emissions in the incineration of the glycerin obtained in the biodiesel production processes due to very high adsorbent potential.
  • the object of the invention is an adsorbent material that can be used in filters at the exit of chimneys or fluid discharge tubes in order to avoid toxic emissions of various pollutants such as: CO, Dioxins, Furans, PCBs. (Polychlorobiphenyls) , NO 2 , SO 2 , Halogens, Aldehydes, CO 2 ,
  • Acrolein, etc. in the process of incineration of non-pharmaceutical grade glycerin that is produced as a secondary product in the biodiesel production process, that is, a material that has an adsorption capacity superior to pure activated carbon and the same present time special mechanical qualities, also high surface performance, resistant to breakage and abrasion and easily conformable, by integrating the properties of natural silicates of clay or plasticizing and / or polymerizable agents or carbonates of alkali or alkaline earth metal carbonates to structures such as graphite and / or activated carbon.
  • the surface available for adsorption depends on the size of the adsorbate molecule and the pore diameter of the adsorbent material; if it is intended to adsorb large molecules it is of greater interest to have adsorbents with adequate pore diameter.
  • the intimate mixing of the aforementioned components produces several effects: a) it results in materials that have a significant increase in specific surface area and a greater volume of meso and macropores when compared with the values that would correspond to the starting products taking into account their percentages in the mixture; b) the graphite and / or activated carbon integrated in the mass limits the reduction in volume that normally occurs when a wet piece can be made of silicate, algae or carbonates is subjected to drying and subsequent heat treatment: c) the graphite also allows increase the adsorption capacity and avoid the attack of other chemical agents, since by means of the activation process of said graphite, it is possible to obtain a material formed by unions of elementary graffiti microcrystals, usually blocked by tars and carbonization residues that are the cause of the decrease in the adsorbent capacity of this graphite in its pure state.
  • any natural silicate from clays or other components can be used in the mixture, in particular bentonite, enstatite or ⁇ -sepiolite, attapulgite, zeolites, in the pure state or forming mixtures, the aggregate increases its mechanical capabilities.
  • the mixture adds one or more plasticizing and / or polymerizable agents independent of its origin or extraction procedure with a disaggregated particle size between 2 to 100 microns, the resulting porous texture of this material having an average surface area of 6 m 2 g "1 with a texture development with a tendency to macroporosity, so that they are treated at temperatures above 500 ° C in order to improve their mechanical and abrasion conditions, at that temperature carbon dioxide is released with formation of calcium and magnesium oxides whereby the specific surface of the material is reduced.
  • alkaline or alkaline earth metal carbonates may be added in substitution of the plasticizing and / or polymerizable agents which produce similar results.
  • the weight ratio between graphite, activated carbon, clay silicates and the agents plasticizers and / or polymerizable can vary between 1: 0: 2: 2 to 1: 1: 2: 1, in case of not using plasticizers and / or polymerizable agents, it is possible to use alkaline or alkaline earth metal carbonates as previously stated, but the results are significantly lower in their adsorption capacity, now an increase in the aggregate of graphite or activated carbon increases the adsorbent power but to the detriment of the mechanical qualities of the pieces obtained after drying and activation.
  • the adsorbent material graphite, activated carbon, clay fibrous silicates and the plasticizing and / or polymerizing agent in the range of the proportions specified above are mixed dry and homogeneously, preferably kneaded with water preferably deionized for approximately 5 hours ,
  • the resulting paste is molded or extruded, to obtain the desired shapes, which can be shaped as granules, pellets, spheres, hollow cylinders, plates or in parallel channel structures along the longitudinal axis
  • the composition has a structure of parallel channels along the longitudinal axis of between 5 and 100 channels per square centimeter of its cross section being preferably formed as hollow cylinders, of the smooth, striated, straight, curved "macaroni" type, of regular or irregular cut, in any shape and size in the form of hollow cylinders, spheres or the like, these may have an approximate length 0.4 cm to approximately 10 cm and the thickness of the wall can be between 0.03 to 0.5 cm in order to allow its application for large
  • the molded elements are dried at room temperature for at least 2 hours, then the product is heat treated in an inert atmosphere oven at a temperature ranging from 500 to 1000 0 C.
  • the resulting product has a unique composition and tested for use.
  • large-scale contaminant gas adsorption filters allowing the elimination of CO, Dioxins, Furans, PCBs (NO 2 , SO 2 , Halogens, Aldehydes, CO 2 , Acrolein, etc.) emissions in incineration processes , combustion and / or distillation of the glycerin, solving the problem of storage of said glycerin in the Biodiesel production plants, the filtering product can be used in the fixed bed and mobile bed filters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention a pour objet une composition d'une matière adsorbante permettant l'élimination d'émissions toxiques dans l'incinération et/ou la distillation de la glycérine, en vue d'éviter l'accumulation de grands volumes de glycérine provenant de la production de biodiesel à grande échelle, la glycérine pouvant être incinérée sans contamination du milieu par les produits cancérigènes issus de sa combustion, notamment l'acroléine. Pour préparer la matière adsorbante, on mélange, par voie sèche et de façon homogène, du graphite, du charbon actif, des silicates fibreux d'argile et des agents plastifiants et/ou polymérisables.
PCT/ES2009/070210 2009-06-05 2009-06-05 Composition et utilisation d'une matière adsorbante pour le filtrage de composés toxiques dans le procédé d'incinération et/ou de distillation de la glycérine provenant de la production de biodiesel WO2010139816A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/ES2009/070210 WO2010139816A1 (fr) 2009-06-05 2009-06-05 Composition et utilisation d'une matière adsorbante pour le filtrage de composés toxiques dans le procédé d'incinération et/ou de distillation de la glycérine provenant de la production de biodiesel

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Application Number Priority Date Filing Date Title
PCT/ES2009/070210 WO2010139816A1 (fr) 2009-06-05 2009-06-05 Composition et utilisation d'une matière adsorbante pour le filtrage de composés toxiques dans le procédé d'incinération et/ou de distillation de la glycérine provenant de la production de biodiesel

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WO2010139816A1 true WO2010139816A1 (fr) 2010-12-09

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103506095A (zh) * 2012-06-29 2014-01-15 中原工学院 一种罗布麻纤维/膨胀石墨复合纤维吸附材料的制备方法
CN103506082A (zh) * 2012-06-29 2014-01-15 中原工学院 一种亚麻纤维/膨胀石墨复合纤维吸附材料的制备方法
CN103506085A (zh) * 2012-06-29 2014-01-15 中原工学院 棉纤维/膨胀石墨复合纤维超过滤水吸附材料的制备方法
CN105327673A (zh) * 2015-11-03 2016-02-17 李明顺 一种去除污水处理后余量氨氮的复合吸附剂的制备及其应用

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WO1998039093A1 (fr) * 1997-03-05 1998-09-11 Blanco Alvarez Jesus Silicates naturels a structure fibreuse
CN1486940A (zh) * 2003-08-13 2004-04-07 涉 张 用于污水处理生物膜工艺的复合填料
JP2005177576A (ja) * 2003-12-17 2005-07-07 Yahashi Kogyo Kk ハロゲン系ガス及び酸性ガスの除害剤
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WO2007085672A1 (fr) * 2006-01-27 2007-08-02 Bionatur Biotechnologies S.L. Composition absorbante à base d'enstatite, procédé d'obtention et application
CN101310854A (zh) * 2008-02-22 2008-11-26 周奇迪 一种过滤介质及制备方法、使用该过滤介质的滤芯、净水装置和饮水机
CN101417193A (zh) * 2008-11-07 2009-04-29 江苏正本净化节水科技实业有限公司 纳米微晶复合滤料及其制造方法的补充
WO2009103831A1 (fr) * 2008-02-19 2009-08-27 Bionatur Biotechnologies S.L. Composition d'un matériau à structure poreuse, ses procédés de préparation de ce matériau et applications correspondantes

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EP0776696A2 (fr) * 1995-12-01 1997-06-04 Kawata Mfg Co., Ltd. Céramique en nid d'abeilles et sa méthode de production
WO1998039093A1 (fr) * 1997-03-05 1998-09-11 Blanco Alvarez Jesus Silicates naturels a structure fibreuse
CN1486940A (zh) * 2003-08-13 2004-04-07 涉 张 用于污水处理生物膜工艺的复合填料
JP2005177576A (ja) * 2003-12-17 2005-07-07 Yahashi Kogyo Kk ハロゲン系ガス及び酸性ガスの除害剤
WO2007085672A1 (fr) * 2006-01-27 2007-08-02 Bionatur Biotechnologies S.L. Composition absorbante à base d'enstatite, procédé d'obtention et application
CN1872401A (zh) * 2006-04-28 2006-12-06 夏先明 中药纯化微滤膜
WO2009103831A1 (fr) * 2008-02-19 2009-08-27 Bionatur Biotechnologies S.L. Composition d'un matériau à structure poreuse, ses procédés de préparation de ce matériau et applications correspondantes
CN101310854A (zh) * 2008-02-22 2008-11-26 周奇迪 一种过滤介质及制备方法、使用该过滤介质的滤芯、净水装置和饮水机
CN101417193A (zh) * 2008-11-07 2009-04-29 江苏正本净化节水科技实业有限公司 纳米微晶复合滤料及其制造方法的补充

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103506095A (zh) * 2012-06-29 2014-01-15 中原工学院 一种罗布麻纤维/膨胀石墨复合纤维吸附材料的制备方法
CN103506082A (zh) * 2012-06-29 2014-01-15 中原工学院 一种亚麻纤维/膨胀石墨复合纤维吸附材料的制备方法
CN103506085A (zh) * 2012-06-29 2014-01-15 中原工学院 棉纤维/膨胀石墨复合纤维超过滤水吸附材料的制备方法
CN103506085B (zh) * 2012-06-29 2015-04-29 中原工学院 棉纤维/膨胀石墨复合纤维超过滤水吸附材料的制备方法
CN105327673A (zh) * 2015-11-03 2016-02-17 李明顺 一种去除污水处理后余量氨氮的复合吸附剂的制备及其应用

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