EP3624926A1 - Verfahren zur reinigung einer mindestens einen schadstoff enthaltenden gasförmigen, flüssigen oder aerosolzusammensetzung - Google Patents

Verfahren zur reinigung einer mindestens einen schadstoff enthaltenden gasförmigen, flüssigen oder aerosolzusammensetzung

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Publication number
EP3624926A1
EP3624926A1 EP18745284.2A EP18745284A EP3624926A1 EP 3624926 A1 EP3624926 A1 EP 3624926A1 EP 18745284 A EP18745284 A EP 18745284A EP 3624926 A1 EP3624926 A1 EP 3624926A1
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group
formula
composition
compound
pollutant
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French (fr)
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EP3624926A4 (de
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Philippe David
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    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B01D53/526—Mixtures of hydrogen sulfide and carbon dioxide
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/70—Organic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/80—Organic bases or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • 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
    • B01D2257/204—Inorganic halogen compounds
    • 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
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2045—Hydrochloric acid
    • 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
    • B01D2257/2064—Chlorine
    • 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
    • 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
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • 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
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • 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
    • B01D2257/308—Carbonoxysulfide COS
    • 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
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia
    • 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
    • B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)
    • 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
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
    • B01D2257/553—Compounds comprising hydrogen, e.g. silanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/05—Biogas
    • 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
    • B01D53/14—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 absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the invention relates to a method for purifying a gaseous, liquid or aerosol composition containing at least one pollutant consisting of a volatile inorganic compound (CIV), a siloxane, and / or a functional volatile organic compound (VOC). ).
  • CIV volatile inorganic compound
  • VOC functional volatile organic compound
  • the emission of air pollutants is regulated by law because of their negative impact, including on human health, biological resources, ecosystems and climate.
  • VOCs Volatile Organic Compounds
  • greenhouse gases may be Volatile Organic Compounds (VOCs) and / or greenhouse gases.
  • VOCs can cause eye and throat irritation, allergies, headaches, asthma attacks, nausea, etc.
  • VOCs also play an important role in the troposphere, leading to an increase in the amount of ozone in the air.
  • Ozone is produced inter alia from nitrogen dioxide under the effect of solar radiation.
  • the formed ozone then reacts with nitric oxide to produce nitrogen dioxide.
  • the previous cycle is modified by the carbon radicals (strong oxidants) which replace the ozone during the formation reaction of nitrogen dioxide, which leads to an increase in the amount of ozone.
  • the increase in the amount of ozone with its consequences for the environment and health, is therefore partly linked to VOC emissions.
  • the concentrations of greenhouse gases in the atmosphere have increased since the nineteenth century mainly for human reasons with a new record in 2014 by the World Meteorological Organization (WMO).
  • WMO World Meteorological Organization
  • the increase in the main greenhouse gases is mainly due to certain human activities, including the massive use of fossil fuels (coal, oil).
  • Greenhouse gases such as carbon dioxide (which accounts for nearly 70% of anthropogenic greenhouse gas emissions) and methane, are not necessarily dangerous for humans, biological resources and ecosystems, but their emissions are at the root of global warming, a phenomenon that has many negative consequences for humans and their environment.
  • oxidants such as bleach.
  • these oxidizing washing methods have the major disadvantage of generating in the discharges oxidation by-products themselves polluting and sometimes very strongly smelly.
  • these oxidants are unstable and their handling is dangerous.
  • biogas is a combustible gas obtained by fermentation, also known as anaerobic digestion, of organic waste of animal or vegetable origin in the absence of oxygen, which mainly comprises methane as well as carbon dioxide.
  • biogas as a source of renewable energy rather than reject it at the atmosphere.
  • Biogas is valued in different ways. It can, after a light treatment, be upgraded near the production site to provide heat, electricity or a mixture of both (the high carbon dioxide content reduces the calorific value of the biogas, increases the costs of compression and transport and consequently limits the economic value of upgrading biogas away from the production site).
  • Biogas can also be purified to allow wider use.
  • the biogas can be subjected to a purification which consists of removing unwanted substances and traces of pollutants (ammonia, sulfur compounds, VOCs including organochlorines, siloxanes) from crude biogas and increasing its methane content (in particular by removing CO 2 ) to produce a gas comparable to natural gas.
  • pollutants ammonia, sulfur compounds, VOCs including organochlorines, siloxanes
  • the biogas thus purified and enriched is called biomethane, and has a calorific value equivalent to that of natural gas.
  • the purified biogas is also the precursor of the biohydrogen obtained by steam-cracking.
  • the purification of biogas is generally carried out according to the following methods:
  • PSA Pressure swing adsorption
  • this water washing process involves a washing tower with pressurized water, a degassing tower and a desorption tower;
  • this process is similar to that of washing with water, the solvent being in this case an organic fluid, especially glycols, amino-alcohols or amines. However, this process requires the regeneration of the solvent;
  • membrane separation functions as a filter.
  • this process is complicated by the need to work under pressure, and to the disadvantage of releasing CO2 into the atmosphere at the end of the treatment cycle.
  • This method also offers several advantages.
  • the process according to the invention allows the "one-pot" treatment of any pollutant, alone or in a multi-pollutant mixture, chosen from volatile inorganic compounds (carbon dioxide, nitrogen monoxide, nitrogen dioxide, hydrohalic acid, thionyl chloride, sulfuryl chloride, ammonia, halogens, hydrogen sulfide, oxysulphide carbon and sulfur dioxide), siloxanes and functional volatile organic compounds, especially on a single scrubber.
  • volatile inorganic compounds carbon dioxide, nitrogen monoxide, nitrogen dioxide, hydrohalic acid, thionyl chloride, sulfuryl chloride, ammonia, halogens, hydrogen sulfide, oxysulphide carbon and sulfur dioxide
  • siloxanes siloxanes and functional volatile organic compounds
  • the process allows, in a single operation, the capture of C0 2 but also all of the aforementioned pollutants, when they are present in the biogas.
  • the C0 2 thus treated can be advantageously recovered, especially in the form of carbonate, which can be valorised, particularly in cement plants.
  • the method according to the invention is simple to implement, and easily integrates with existing systems, for example without the need to modify the existing washing towers.
  • the process according to the invention is economically competitive, especially for the production of biomethane.
  • the invention relates to a process for purifying a gaseous, liquid or aerosol composition containing at least one pollutant consisting of:
  • CIV volatile inorganic compound selected from carbon dioxide, nitrogen monoxide, nitrogen dioxide, halohydric acids, thionyl chloride, sulfuryl chloride, ammonia, halogens, hydrogen sulphide, carbon oxysulfide and sulfur dioxide, and / or
  • VOC functional volatile organic compound
  • said method comprising the following steps:
  • R represents:
  • X represents:
  • R 1 represents:
  • R represents a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium group, or
  • n 1, 2, 3 or 4;
  • said pollutant does not consist exclusively of hydrogen sulfide, sulfur dioxide, or a volatile organic compound bearing a thiol group.
  • inert gaseous compounds such as methane, butane, propane, nitrogen, oxygen
  • the process according to the present invention thus makes it possible to purify gaseous flows comprising mainly said inert gaseous compounds, alone or in mixtures.
  • the pollutant does not consist exclusively of hydrogen sulfide, a functional volatile organic compound bearing a thiol group, or mixtures thereof.
  • the pollutant does not consist exclusively of hydrogen sulphide, carbon disulfide, sulfur dioxide, thionyl chloride, sulfuryl chloride, a volatile organic compound bearing a thiol, disulfide or thioester, or mixtures thereof.
  • the pollutant does not consist exclusively of hydrogen sulfide, carbon oxysulfide, sulfur dioxide, thionyl chloride, sulphuryl chloride, a volatile organic compound bearing a thiol group, disulfide or thioester, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, or mixtures thereof.
  • the at least one pollutant consists of:
  • CIV volatile inorganic compound selected from carbon dioxide, nitrogen monoxide, nitrogen dioxide, ammonia, halogens, and / or
  • At least one functional volatile organic compound chosen from volatile organic compounds (VOCs) carrying an amine, amide, nitrile, aldehyde, ketone, ester, carboxylic acid, alcohol, halogenated volatile organic compounds, phosgene and hydrogen cyanide group; .
  • VOCs volatile organic compounds
  • said composition is liquid or in the form of a natural aerosol.
  • said composition when it is liquid, is transformed into an aerosol prior to step (i).
  • This transformation is in particular made according to techniques well known to those skilled in the art.
  • said composition contains carbon dioxide and at least one other pollutant consisting of:
  • At least one volatile inorganic compound selected from nitrogen monoxide, nitrogen dioxide, halohydric acids, thionyl chloride, sulfuryl chloride, ammonia, halogens, hydrogen sulfide, oxysulphide, carbon and sulfur dioxide, and / or
  • said method comprising the following steps:
  • the at least one other pollutant consists of:
  • At least one volatile inorganic compound selected from carbon dioxide, nitrogen monoxide, nitrogen dioxide, ammonia, halogens, and / or
  • At least one siloxane and / or At least one functional volatile organic compound chosen from volatile organic compounds bearing an amine, amide, nitrile, aldehyde, ketone, ester, carboxylic acid, alcohol, halogenated volatile organic compounds, phosgene and hydrocyanic acid group.
  • said composition is a biogas.
  • Said biogas comes in particular from the methanisation of industrial or agricultural waste, household waste, sewage sludge or products of natural hydraulic fracturing and more generally from a biomass heat treatment.
  • said capture product consists of a first capture product resulting from the reaction of carbon dioxide with the base, and a second capture product resulting from the reaction of the at least one other polluting with the base and / or the compound of formula (I).
  • the first capture product is separated from the second capture product at the end of step (iii).
  • said composition is a natural gas, obtained in particular by hydraulic fracturing.
  • Hydraulic fracturing is a technique that releases the gas trapped in underground rocks. This is called hydrofracturing or "fracking".
  • It can also be natural hydraulic fracturing (or cryoclastic), which can be terrestrial or marine.
  • the process according to the invention has the advantage of converting CO2 into carbonates.
  • These carbonates are precursors of the cement production chain, either dry or wet.
  • the first capture product is brought into contact with calcium chloride to form calcium carbonate.
  • the first capture product mainly corresponds to sodium carbonate.
  • the sodium carbonate can then be advantageously displaced by calcium chloride to obtain calcium carbonate practically insoluble according to the reaction:
  • said composition is an effluent.
  • bioenergy biogas, biomethane and biohydrogen
  • steps (i) and (ii) are performed simultaneously.
  • steps (i) and (ii) are carried out in a washing tower, in particular in a single washing tower.
  • the method according to the invention easily integrates with the systems in place, in particular without it being necessary to modify the existing washing towers.
  • steps (i) and (ii) can be performed in a single wash tower. It is then a batch process, called "batch".
  • the tower can then be emptied, and the liquid effluent discharged to an industrial water receiving basin.
  • the tower can then be reloaded for another operation.
  • the composition to be treated can be sent to a treatment unit generally comprising two to three laps of washing.
  • each tower is equipped with at least one recycling pump.
  • the foot of each tower serves as retention volume and suction cover of the bath recirculation pump.
  • air is introduced from the bottom up and the washing solutions sprayed countercurrent, from top to bottom. This type of 2 or 3 stage installation is suitable for continuous treatment.
  • Plastic, ceramic or stainless steel materials are most often recommended to avoid or limit corrosion problems.
  • M represents Na or K.
  • R is chlorine, R 1 represents an OR 2 group, X represents hydrogen and n represents 1.
  • OR is an OH or ONa group.
  • R represents chlorine
  • R 1 represents an OH group
  • X represents hydrogen
  • n represents 1
  • the compound of formula (I) then represents monochloroacetic acid (CAS No. 79-11-8).
  • R represents chlorine
  • R 1 represents an ONa group
  • X represents hydrogen
  • n represents 1
  • the compound of formula (I) then represents sodium monochloroacetate (CAS No. 3926-62-3).
  • the functional volatile organic compound is chosen from volatile organic compounds bearing an amine, amide, nitrile, aldehyde, ketone, ester, carboxylic acid, alcohol, thiol, disulfide or thioester group, halogenated volatile organic compounds. , phosgene and hydrogen cyanide.
  • Volatile aldehydes especially in gaseous form, are, for example, formaldehyde.
  • Volatile aldehydes especially in the form of vesicular aerosols, are, for example, acetaldehyde, butanal, pentanal, hexanal and leptanal.
  • the volatile ketones are, for example, acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • the volatile carboxylic acids are, for example, formic acid, acetic acid and acrylic acid.
  • halogenated volatile organic compounds are, for example, methyl chloride, dichloromethane, chloroform, carbon tetrachloride, their C 2 or C 3 analogs, chlorofluorocarbons, vinyl chloride, dichlorethylene, trichlorethylene, tetrachlorethylene, dichloroacetylene and allyl chloride.
  • the volatile alcohols are, for example, methanol, ethanol, propanol, butanol and ethylene glycol.
  • Volatile thiols are for example methanethiol, ethanethiol, 1-propanethiol, 2-propanethiol, ter-butanethiol.
  • Volatile thioesters are, for example, methylthioacetate, methylthiobutanoate and methylthiopentanoate.
  • step (iii) is followed by a step (iv) of destruction of said capture product, in particular in the form of liquid effluents, in particularly in wastewater treatment plant, more particularly in biological treatment plant, more particularly by aerobic bioépuration.
  • liquid effluents obtained at the end of the process according to the invention are odorless and colorless.
  • wastewater discharge limit values are typically as follows:
  • the method according to the invention is compatible with such a regulation, in that the sensing product makes it possible to fully respect these limit values.
  • the process according to the invention makes it possible to obtain an absolutely odorless and colorless liquid treated product which can be directly discharged to a self-neutralizing basin of a purification plant; in addition, acidification does not regenerate mercaptans or hydrogen sulfide.
  • BOD Biological Oxygen Demand
  • COD measurements are improved compared to conventional oxidative destruction processes.
  • the molar amount of pollutant in the purified composition obtained at the end of step (ii), relative to the total number of moles of said purified composition is less than 10%, in particular less than 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01, 0.005 or 0.001%.
  • the invention relates to the use of a compound of general formula (I) as described above, for purifying a gaseous, liquid or aerosol composition, containing at least one pollutant consisting of :
  • At least one volatile inorganic compound selected from carbon dioxide, nitrogen monoxide, nitrogen dioxide, halohydric acids, thionyl chloride, sulfuryl chloride, ammonia, halogens, hydrogen sulphide, carbon oxysulfide and sulfur dioxide, and / or
  • At least one functional volatile organic compound is At least one functional volatile organic compound
  • said pollutant does not consist exclusively of hydrogen sulfide, sulfur dioxide, a functional volatile organic compound bearing a thiol group.
  • the term "about” refers to an interval of values of ⁇ 10% of a specific value.
  • the term “about 120 mg” includes values of 120 mg ⁇ 10%, ie values of 108 mg to 132 mg.
  • the percentages refer to percentages by weight relative to the total weight of the formulation, unless otherwise indicated.
  • the value ranges in the form of "x-y” or “x to y” or “between x and y” include the x and y terminals as well as the integers between these terminals.
  • “1-5”, or “1 to 5" or “between 1 and 5" denote integers 1, 2, 3, 4 and 5.
  • Preferred embodiments include each integer taken individually in the value range, as well as any sub-combination of these integers.
  • preferred values for "1-5" may include integers 1, 2, 3, 4, 5, 1-2, 1-3, 1-4, 1-5, 2-3, 2 -4, 2-5, etc.
  • gaseous or liquid composition in particular a fluid (gas or liquid), for example air, nitrogen, oxygen, methane, butane, propane or their mixtures, containing at least one pollutant .
  • composition in aerosol form is meant in particular a set of liquid particles consisting of or containing at least one pollutant, suspended in a gas, for example air, nitrogen, oxygen, methane, butane, propane or their mixtures.
  • purified composition in particular a composition obtained at the end of stage (ii), in which the quantity in moles of the said at least one pollutant is less than 10% relative to the total number of moles of the said purified composition.
  • volatile organic compound is meant any chemical compound having carbon and hydrogen, which may be replaced by other atoms such as halogens, oxygen, phosphorus, sulfur, silicon or silicon. nitrogen, and having a saturation vapor pressure above 10 Pa under normal conditions of temperature and pressure, with the exception of carbon oxides and inorganic carbonates and bicarbonates.
  • ком ⁇ онент any VOC carrying at least one functional group.
  • the functional volatile organic compound is chosen from volatile organic compounds bearing an amine, amide, nitrile or aldehyde group. ketone, ester, carboxylic acid, alcohol, thiol, disulfide, thioester, halogenated volatile organic compounds, phosgene and hydrogen cyanide.
  • Capture product means the product of reaction of the at least one pollutant with said base and / or said compound of formula (I), this product not being a gas, a volatile inorganic compound (CIV), a VOC, or a siloxane. It is in particular liquid effluents.
  • the composition can not contain hydrogen sulfide as the only pollutant , sulfur dioxide, or a functional volatile organic compound bearing a thiol group.
  • biogas is meant a gas produced by the fermentation of organic matter in the absence of oxygen.
  • siloxane is meant a saturated silicon-oxygen hydride with unbranched or branched chains alternating between silicon and oxygen (each silicon atom is separated from its nearest neighbor silicon atoms by single oxygen atoms).
  • the general structure of unbranched siloxanes is H Si [OSiH 2 ] "OSiH 3 .
  • H 3 Si [OSiH 2 ] "OSiH [OSiH 2 OSiH 3 ] 2 is an example of a branched siloxane.
  • the hydrocarbyl derivatives, wherein one or more hydrogen atoms are substituted by an aryl, in particular phenyl, or a straight or branched chain allyl QC O, especially methyl, are also included.
  • hydrohalic acid is meant hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid.
  • optionally substituted is meant in particular a group optionally substituted with at least one group chosen from linear or branched C1 to C6 alkyls and halogens.
  • FIG. 1 represents the diagram of an installation capable of implementing the method that is the subject of example 3.
  • F e and F s correspond respectively to the gas flow at the inlet and the gas flow at the outlet.
  • R 1 corresponds to the base.
  • R 2 corresponds to the aqueous solution of the compound of formula (I).
  • the 100 m biogas from the methanisation of sewage sludge is treated (absorption and destruction of the polluting compounds of the methanation).
  • the 100 m 3 of biogas consists of:
  • the material used is as follows:
  • Fluid circulation pump adjustable from 0 to 25 m 3 / H;
  • the compound of formula (I) is in particular monochloroacetic acid or sodium monochloroacetate.
  • Methyl mercaptan 0 0.00 0.00 Potash 30% 0.31
  • the treatment with bleach is 5 times more expensive than the process according to the invention.
  • Treatments C10 2 or H 2 0 2 are even more expensive, returning 10 times more expensive than the method of the invention.
  • the reaction medium then displays a pH value> 11.
  • the circulation pump is activated then the gas flow valve is gradually released and controlled at the desired flow rate.
  • the end of the reaction is determined and controlled by pH ⁇ 9.
  • the precipitate of sodium carbonate is then separated and is recyclable for example in cement plant.
  • the process according to the invention made it possible to purify 100 m 3 of biogas which provided 70 m 3 of pure biomethane, but also to capture and eliminate 30 m 3 of carbon dioxide and to eliminate 0.4 kg of H2S.
  • the cost of the treatment according to the process of the invention is as follows: treatment of 100 m 3 of biogas: 0.36 € per m 3 ;
  • the cost price of the biomethane completely purified according to the process of the invention is 0.054 € / kW / h.
  • the cost price in competing systems is around € 0.15 / kWh.
  • Example 2 Treatment of a mixture of pollutants in industry
  • the material used is as follows:
  • Fluid circulation pump adjustable from 0 to 25 m / h
  • the compound of formula (I) is in particular monochloroacetic acid or sodium monochloroacetate.
  • composition of the compound to be treated is given in the following table.
  • the treatment with bleach is 17 times more expensive than the process according to the invention.
  • Treatments with C10 2 or H 2 0 2 are even more expensive.
  • the reaction medium then displays a pH value> 11.
  • the circulation pump is activated then the gas flow valve is gradually released and controlled at the desired flow rate.
  • the flow rate of the gases is fixed at 500 m / h. and the circulation pump flow rate of the wash solution at 11 m / h.
  • the unit allowed an operating time of 10 hours during which regular checks of efficiency verified the absence of pollutants at the outlet of the installation.
  • the end of the reaction is determined and controlled by pH ⁇ 9.
  • the precipitate of sodium carbonate is then separated and is recyclable for example in cement plant.
  • the sodium carbonate can then be advantageously displaced by calcium chloride to obtain calcium carbonate, practically insoluble, according to the reaction:
  • Example 3 Continuous treatment of a biogas source containing a mixture of pollutants to obtain purified biomethane
  • the material used is composed of the following elements (figure 1):
  • a storage tank of the alkaline solution of soda or potash • A storage tank of the solution of the compound of formula (I);
  • a “reactor” turbine comprising a compressor, a vaporization / reaction chamber and a finned turbine;
  • a washing water buffer tank for control before discharge to the biological treatment plant.
  • the compound of formula (I) is in particular monochloroacetic acid or sodium monochloroacetate.
  • composition of the effluent to be treated is given below for an average flow rate of 500 m 3 / h. :
  • the alkaline solution of soda or potash is available.
  • the 40% solution of the compound of formula (I) is available.
  • the average flow rate of the measured input flow is 500 m / h. (8.333 liters / minute) and the flow rate of the metering pumps of the washing solution is adjusted as follows according to this gas input flow rate:
  • the wash water is discharged continuously to the collection buffer tank for pH correction if necessary.
  • a control of the parameters is carried out before rejection towards the biological purification station.
  • Unit a allows continuous operation during which regular checks of the efficiency check the absence of pollutants at the output of the installation.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP18745284.2A 2017-01-26 2018-01-25 Verfahren zur reinigung einer mindestens einen schadstoff enthaltenden gasförmigen, flüssigen oder aerosolzusammensetzung Withdrawn EP3624926A4 (de)

Applications Claiming Priority (2)

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FR1750652A FR3062072B1 (fr) 2017-01-26 2017-01-26 Procede de purification d'une composition gazeuse, liquide ou sous forme d'aerosol, contenant au moins un polluant
PCT/IB2018/000033 WO2018138572A1 (fr) 2017-01-26 2018-01-25 Procede de purification d'une composition gazeuse, liquide ou sous forme d'aerosol, contenant au moins un polluant

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FR2709678B1 (fr) * 1993-09-09 1995-12-08 David Philippe Marie Procédé d'épuration d'effluents gazeux ou liquides contenant des dérivés soufrés.
DE10119991A1 (de) * 2001-04-23 2002-10-24 Stephan Pieper Verfahren bzw. Vorrichtung zur Reinigung von Biogas
US8535429B2 (en) * 2011-10-18 2013-09-17 Clean Energy Renewable Fuels, Llc Caustic scrubber system and method for biogas treatment
RU2672738C2 (ru) * 2013-07-30 2018-11-19 Арктэк, Инк. Способ абсорбции и утилизации парниковых газов и способ удаления пахучих химических веществ и микроорганизмов

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US20200406187A1 (en) 2020-12-31
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FR3062072B1 (fr) 2019-07-05
EP3624926A4 (de) 2021-11-17

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