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In France, it is well known, we have more oil but we still have ideas

Preamble

The discomfort of unpleasant odors has become a social problem.
Some bad smells are, moreover, detrimental to our health like other products with little or no smell.

The odors harmful or not, that we breathe daily are decisive for our well-being and our health.

Over time, the individual manages to get used to the bad smells and these being invisible, no provision is generally taken to protect themselves from it.

 

 

 

 

 

 

Who is the inventor ?

The inventor, chemical engineer of Research & Development in pharmaceutical industry, now retired and independent researcher, is the nephew of André Bondouy, the founding President of the company SEPPIC.

The process was born from the imagination of a Normand chemist born in the mythical village who saw circulating the first car equipped with an engine designed by Édouard Delamare-Deboutteville (1856 à 1901) who had the idea in 1883 to equip a hunting wagon with a gas engine.
But the experiment ended abruptly with the explosion of the gas container.
The following year he designed and ran the first petrol car powered by an internal combustion engine.





 

How was PTC System born ?

PTC System is a totally new and innovative design technology that was patented for France in July 2018 with an international extension for 152 countries registered in August 2018.

The idea of the process is the result of the observation of the reaction of an organic molecule with a sulfur derivative very malodorous, in this case the condensation between chloroethanol and dodecylmercaptan, giving rise to a new organic molecule perfectly odorless very easily biodegradable.

This observation was the trigger to look for a simple and inexpensive reagent and if possible easily accessible.
The DAVID process is born.
Research has been undertaken for the choice of an organic molecule already marketed, affordable, easy and safe to use. Innovation is therefore based on the implementation of an original formulation, without any oxidant, which acts on the pollutant by transforming it into an odorless and bio-available organic compound.
This formulation is based on a molecule well known and used in chemistry since the 19th century for the synthesis of various specialties. The use of this molecule in the fields we are interested in is the key to the process, which represents a very important advance on the technical and economic levels.

PTC System is a technology for purifying gaseous, liquid or vesicular aerosol compositions containing pollutants that are harmful to health and the environment, or simply smelly.

  • Pollutants are Volatile Inorganic Compounds (VICs)
    • CO2, COS, NOx, halohydric acids, H2S, SO2, SOCl2, SO2Cl2, etc...
  • Pollutants are Volatile Organic Compounds (VOCs)
    • amine, amide, nitrile, aldehyde, ketone, ester, carboxylic acid, alcohol, thiol, disulfide, thioester, halogenated organic compounds, phosgene and hydrogen cyanide, etc...

The originality of the process resides on the one hand in the choice of the reagent which combines with the pollutants to be treated and on the other hand in the final natural biological destruction in the purification station not generating any new gaseous pollution.

This purification system is unique in its design and applications. It makes it stand out from the competition and to improve the productivity of the capture / treatment facilities, as long as its economic record is advantageous.
The new patent is based on the existing patent of the DAVID process (Process for the purification of gaseous or liquid effluents containing sulfur derivatives) for which it constitutes an improvement.

view history


 

Industry sector

Process for the purification of gaseous or liquid effluents containing sulfur derivatives

The present invention relates to a process for the purification of gaseous or liquid effluents containing sulfur derivatives (H2S, alkyl mercaptan, SO2).

The process has been the subject of a French, European and US patent.
An improvement is currently the subject of a new patent.

 

Hydrogen sulphide (H2S) and mercaptans (R-SH)  

H2S

Méthanethiol

Hydrogen sulphide is an extremely poisonous gas, smelly even when it is present in very small quantities, and corrosive. Its presence as well as that of alkyl mercaptans which have the same disadvantages as H2S from the olfactory point of view in the effluents (gaseous or liquid), industrial in particular, represent a considerable danger for the health of the living organisms or the plant environment.

It is therefore of utmost importance in the fight against pollution, to eliminate hydrogen sulphide as well as the alkyl mercaptans present in industrial effluents (industries related to energy, chemistry, wood, paper and viscose, food industry), waste (industry of animal by-products, manure, household waste) or in treatment plants.

Sulfur Dioxide (SO2)  

SO2

The presence of SO2 in effluents, particularly industrial ones, also represents a considerable danger for the plant environment. Indeed, its emission is responsible for an increase of acidity in the atmosphere and generates the phenomenon of acid rain.

The SO2-producing industries include refineries, hydrocarbon waste processing industries, chemical industries (mineral chemistry: sulfuric acid and titanium oxide production, organic chemistry), paper industries, agro-industries food and materials industries. Various solutions have been proposed for eliminating these various sulfur compounds from the effluents (gaseous or liquid).

See the articles:: Competitive Techniques and Industrial Deodorization by Bleach.

Technical description of the DAVID process

The DAVID process is carried out in a physico-chemical deodorization process consisting of a transfer of odorous gas molecules to a liquid phase.
This process is characterized by a chemical washing of the stale air against the current, with the aid of alkaline aqueous solutions, inside series placed lathes.
These towers are lined with inert material that promotes gas-liquid contact.

Depending on the nature of the compound to be removed, a basic neutralizing agent is added to the wash water in order to accelerate the gas-liquid transfer, thereby increasing the efficiency of the treatment.


The additional addition of the specific reagent, claimed in the DAVID process, in turn contributes not only to intensifying this transfer process, but also to regenerating the washings by chemically modifying the absorbed molecules which have the property of being odorless. and biodegradable.

The DAVID process makes it possible to treat highly concentrated gaseous effluents from odorous compounds.

Highly reliable, this technique achieves purifications greater than 99% guarantee the total absence of olfactory nuisances.

The characteristics of an inert material that promotes packing (nature, specific surface, volume, height) are calculated to optimize the gas-liquid contact time and the transfer of molecules.

 

How does this original process work ?

The DAVID process is carried out in a physico-chemical process consisting of a transfer of gaseous molecules to a liquid phase.

The object of the present invention is to provide a process for the purification of gaseous or liquid effluents containing one or more sulfur derivatives, such as H2S, mercaptans or SO2, which eliminates the disadvantages of the solutions aimed at the same purpose proposed in the prior art, especially in that the method according to the present invention allows a quantitative purification efficiency of the order of 100%, does not require any particular installation (use of any gas washing column, for example), and provides a stable, biodegradable and nontoxic substitution product.
The subject of the present invention is a process for purifying effluents (gaseous or liquid) containing sulphurous derivatives (H2S, alkyl mercaptan, SO2), characterized in that it comprises:

(A) alkalinization of the effluent to be treated at a pH>9 in the presence of a base of general formula M-OH in which M represents an alkali metal, an alkaline earth metal, a condensing agent between the part organic form of a specific reagent and the sulfur derivative or a phase transfer agent and in particular a quaternary ammonium or a ligand.
(B) contacting the product obtained in (A) with a specific organic reagent.

According to an advantageous embodiment of said method, steps (A) and (B) are carried out simultaneously. This capture and depollution process also applies to the simultaneous treatment of several sulfur derivatives for very large concentrations.

(C) The final destruction of the capture products after the simultaneous process of absorption and chemical modification (A + B) The operation is carried out in a biological purification station.
The organic compounds present and formed during the condensation reaction are digested by the aerobic bio-purification process of the treatment plant.
The principle of biological treatment is based on the degradation of organic compounds by microorganisms. Organic matter present in the main liquid substrate in the presence of oxygen, nitrogen and phosphorus sources, trace elements and water is degraded to CO2, H2O, S and metabolites (reaction by-products ).

The originality of the process resides on the one hand in the choice of the reagent which combines with the pollutants to be treated and on the other hand in the final natural biological destruction in the purification station not generating any new gaseous pollution. This purification system is unique in its design and applications. It makes it stand out from the competition and to improve the productivity of the capture / treatment facilities, as long as its economic record is advantageous.
The new patent is based on the existing patent of the DAVID process (Process for the purification of gaseous or liquid effluents containing sulfur derivatives) for which it constitutes an improvement.

Equipment needed for the DAVID process

This process is feasible on a single wash tower if the ammonia/amine concentrations are less than 0.4 ppm.

GasWash module details


The process is characterized by a physicochemical washing of the gaseous flow against the current, using aqueous alkaline solutions, inside the scrubber.
The basic neutralizing agent (soda or potash) is added to the water to accelerate the gas-liquid transfer, and thus increase the effectiveness of the treatment.

The additional addition of a specific reagent in turn not only helps to intensify this transfer process, but also to regenerate the washings by chemically modifying the absorbed molecules which have the property of being odorless and biodegradable.

In the tower, air is introduced from the bottom up and the washing solutions sprayed countercurrent, from top to bottom.
These towers are lined with inert material that promotes gas-liquid contact.
The tower is equipped with a recycling pump.
The foot of the tower serves as a retention volume and as a suction cover for the recirculating bath pump.


Operating mode:

An Excel spreadsheet allows you to determine the amounts of reagent and soda depending on the gas flow and to compare the cost of treatment with bleach and other oxidants.
For that it is important to know and to inform precisely in the blue boxes:

  •           The hourly flow rate in m3
  •           The daily treatment time
  •           The concentration of the compounds to be collected in mg/m3

In the suction tank is charged in the order the calculated amounts of alkaline solution of soda or potash, then the 40% solution of the reagent. The additional water determined in the spreadsheet corresponding to 20 volumes of the pure reagent is charged. The reaction medium 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 process adapts to any type of installation already existing

- In the case of an installation with only one tower, it is a unit operation (batch):

The tower is emptied, the liquid effluent is discharged to the industrial water receiving basin.
The tower can be reloaded for another operation.

Such an installation can also operate continuously with dosing pumps and simultaneous evacuation of the washing juices.

 

 

- In the case of an installation equipped with several towers, it allows a continuous operation:

This type of installation with 2 or 3 floors, or more, will be suitable for continuous treatment.

Once the arrival one turn era saturation controlled by pH-metry (pH <9), the flow is switched to the 2 nd round. Meanwhile, the 1 st tower is reloaded and so on ...

 

The method according to the invention therefore does not require specific specific equipment.

 

Biological treatment of liquid effluents in wastewater treatment plants:

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-neutralization pond or a water treatment basin of a treatment plant, moreover, acidification does not regenerate mercaptan, SO2 or hydrogen sulphide.
Biological treatment in wastewater treatment plants does not create any new nuisance either at the station itself or at the level of the sewerage network.
The BOD (Biological Oxygen Demand) and COD (Chemical Oxygen Demand) measurements are consistent with rejection standards and improved compared to conventional oxidative destruction processes.



 

Sustainable Development Sector

Process for the purification of gaseous, liquid or vesicular aerosol compositions containing pollutants which are harmful to health and the environment or which are simply odor-causing.

This first experience in the field of odors has led this Engineer to reflect and guide his research in other areas of industry and the environment.

The research quickly led to innovative improvements and a complete overhaul of the DAVID process towards Sustainable Development with the invention of the PTC system (Pollution Trap Concept).
This brand new system is currently the subject of an international patent application.

Today, the PTC system is mainly in the field of waste methanation (biogas purification), a particularly advanced field.

According to Ademe, the sector could provide more than 14% of French gas consumption in 2030.
In its document "Contribution to the development of energy visions 2030-2050", the agency estimates that with 600 biogas plants per year (ie almost half as much as in Germany), the accessible deposit would be 6 Mtep primary in 2030 (ie 20% of the estimated gas consumption for this period).

Whatever the nature of the biogas, the PTC system separates the biogas from its impurities (CO2, H2S, VOC, Siloxanes). The methane content of biogas then goes from 45% to 98% and can be directly injected into the national gas distribution network. The advantage of our PTC process is that it uses reliable, robust, widely proven technology that comes directly from industry. This system adapts according to the variation of the methane richness according to the composition of the incoming raw biogas.

The main sources of biogas

Beyond the new public support mechanisms expected by market players, it is above all "the structuring of the sector that is required as a necessity. Inputs, the most common sources of biogas (containing biomethane), come from voluntary or involuntary organic material stores that originate from:

Livestock effluents (manure)

  • Slurry (composed of liquid and solid excrement of animals)
  • Manure (mixing manure with animal litter: straw, hay ...).
    They represent the major part of the effluents.

Livestock effluents are derived from livestock activities, particularly cattle and pigs, and are located in livestock buildings.

Energy crops
These are crops grown primarily for energy production purposes. They can be used as inputs in biogas plants that will use the energy power of these plants.

Energy Intermediate Crops (CIVE) & Intermediate Nitrate Trap Crops (CIPAN)

  • An intermediate energy culture (CIVE) is a culture implanted and harvested between two main crops in a crop rotation.
    CIVE can be harvested for use as an input into an agricultural biogas plant.
  • A nitrate trap intermediate culture (CIPAN) is a temporary crop of fast-growing plants intended to protect plots between two main crops. These cutlery are mandatory in some areas or areas because of nitrate pollution.
    By using them for their growth, the canopy plants trap the remaining nitrates at the end of the previous main crop.

Crop waste
Agricultural waste from crops (eg corn cane).

Sludge and by-products of the agro-food industries
The agri-food industries generate all sorts of co-products during the technological processes they use to develop their finished products (dairy products, meat, grain products, fruits and vegetables, etc...).
Once the product is valued, it will be called "co-product".
Sludges of agro-industrial origin come from slaughterhouses, dairies, cheese factories, biscuits, breweries, canneries, etc...

Animal by-products (SPA)
European Regulation (EC) No 1069/2009 classifies animal by-products into three categories.
It defines the manner in which the materials of each category must or may be eliminated or upgraded for certain uses in order to maintain a high level of hygiene.

Household waste
This is waste from households and assimilated waste.
Waste produced by municipal services, waste from collective sanitation, street cleaning waste, market do not fall within this scope.

Green waste (DV)
Green waste refers to vegetable waste resulting from the maintenance and renewal of public and private green spaces (parks and gardens, sports fields, etc.), local authorities, public and parapublic bodies, private companies and individuals.

Other waste (STEP sludge, etc.)
Sludge treated in urban wastewater treatment plants is the result of human activity.
Their valuation for biomethane production has been authorized since 2014.

Why methanize our waste ?

Anaerobic digestion, still underutilized, appears to be a response to the dual issue of waste management and the development of renewable energies; not to mention the fight against greenhouse gases including CO2.

The principle of anaerobic digestion consists of recovering organic waste in order to recover it in the form of biogas by anaerobic fermentation. Organic waste can come from agricultural activities (manure, manure), industrial and tertiary (including waste from LPNs) or communities (catering waste, grass clippings ...).
Biogas is composed in particular of methane in variable proportion, which gives it an energy potential.
This biogas, after purification, is used to produce electricity and / or heat. It can also be injected into the gas distribution network, or even be used in fuel gas.

To date, the purification of biogas requires a succession of operating phases.
The P.T.C. has the advantage of treating all the undesirable compounds in a single operation.

In addition to biogas, agricultural biogas allows the production of a fertilizer material, the digestate, which can be spread (as part of a spreading plan, or as a standard product after composting). The development of anaerobic digestion is fully in line with the objectives of the energy transition law for green growth promulgated on August 18, 2015.

France wants to develop by 2020 renewable energy up to 23% of the energy mix, with a strong contribution of biomass to these objectives (wood energy and biogas). Thus, the State sets a goal of 1,500 methanizers in 3 years, and methanization is at the heart of the plan Energy Methanization Nitrogen Autonomy (EMAA) of March 29, 2013 (see website http://agriculture.gouv/Plan-Energie-Methanisation).

It should be noted that in this configuration, the biogas is not purified therefore a source of olfactory nuisance due to H2S and NH3.
On the other hand, fermentation CO2 is released into the atmosphere (greenhouse gas).

The current biogas-biomethane sector

The uses of biomethane are the same as for natural gas: hot water, heating, cooking, industrial needs, etc...
One of the relevant valuations still unknown is the valuation in fuel.
The use of biomethane in transportation fuel (referred to as bioGNV) would reduce greenhouse gas emissions in this sector.
In addition, it being understood that bioGNV and NGV (natural gas for vehicles) have the same chemical composition, gas-powered vehicles and filling stations can be powered by bioGNV without technical modifications.


Diagram of the classical die

The classic purification of biogas

To date, the purification of biogas is carried out mainly for the valorization of biomethane by injection into natural gas distribution networks of fossil origin.

The diagram below shows the complexity of such a purification plant comprising several treatment units and it will be noted that the CO2, momentarily trapped, is released into the atmosphere. Such installations represent a significant cost in terms of investment and operation (costs of activated charcoal among others).

PTC System, innovating by its simple but particularly effective technology, finds a preponderant place among current purification techniques of biogas.

Purification of biogas with PTC System

It is the only known to completely eliminate in the same operation and on a single unit of treatment CO2, N2, O2, H2O, H2S, NH3, Siloxanes , Organochlorines or Organofluorines.

This technology is the only one that does not require biogas compression throughout the purification cycle and whose methane losses will be less than 0.1%.

For biogas resulting from the metering of the following inputs:

  • Garbage
  • Sludge of Treatment Plant
  • Disclaimer Food

For biogas derived from the mishandling of agricultural waste:
Biogas from agricultural waste inputs producing between 50 and 100 mg / m3 of ammonia will be pretreated with a sulfuric acid solution in the H2SO4 module.

The "AciWash" module is intended for the capture of H2S and other acidic compounds.

The "AmiWash" module produces high purity biomethane (> 98% CH4)
This biogas purification module consists of removing carbon dioxide (CO2) once hydrogen sulphide (H2S) and other undesirable acidic biogas compounds have been captured by the AciWash module.
For this AmiWash proposes to put the biogas in contact with a solution of amines in a physico-chemical absorption column so that the carbon dioxide separates from the methane.
The implementation of a very selective reaction with carbon dioxide makes it possible to obtain both a biomethane and a high purity carbon dioxide after treatment with the AciWash module.

The "GasWash" module completes the chemical modification of the compounds captured by the AciWash module before the final destruction of the capture products in the biological treatment plant.
The organic compounds present and formed during the condensation reaction are digested by the aerobic bio-purification process of the treatment plant.

See an example of treatment
See the biogas treatment model

Biological treatment of liquid effluents in wastewater treatment plants:

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-neutralization pond or a water treatment basin of a treatment plant, moreover, acidification does not regenerate mercaptan, SO2 or hydrogen sulphide.
Biological treatment in wastewater treatment plants does not create any new nuisance either at the station itself or at the level of the sewerage network.
The BOD (Biological Oxygen Demand) and COD (Chemical Oxygen Demand) measurements are consistent with rejection standards and improved compared to conventional oxidative destruction processes.

Currently, what is the CO2 balance of an anaerobic digestion unit ?

Each m3 of biogas from anaerobic digestion helped to avoid the release into the atmosphere of 2.3 kg of carbon dioxide (CO2) responsible for global warming.
An anaerobic digestion unit of 2 MW, by the methanisation principle, thus prevents the emission of about 9000 t of CO2 into the atmosphere.

However, it must be borne in mind that each m3 of biogas produced always contains between 20 and 40% of CO2, ie between 3 kg and 6 kg, which are finally released into the atmosphere, or during biomethane purification by competing techniques, either in the use of biogas without purification.

It should be noted that this same methanisation unit of 2 MW, which consumed about 4 Mm3 of biogas, still emitted between 800 t and 1,600 t of CO2 in the atmosphere depending on the nature of the methanised substances.

The composition of biogas and thus its impurities varies according to the nature

Composants

Ordures ménagères

Boues de station d’épuration

Déchets agricoles

Déchets de l’industrie
 agro-alimentaire

CH4 % vol

50 - 60

60 - 75

60 - 75

68

CO2 % vol

38 - 34

33 - 19

33 - 19

26

N2 % vol

5  -0

1-0

1 - 0

-

O2  % vol

1 - 0

< 0,5

< 0,5

-

H2O % vol

6 (à 40 ° C)

6 (à 40 ° C)

6 (à 40 ° C)

6 (à 40 ° C)

H2S mg/m3

100 - 900

1000 - 4000

3000 – 10 000

400

NH3 mg/m3

-

-

50 - 100

-

Siloxanes mg/m3

20 - 250

Traces

-

-

Organochlorés ou organofluorés mg/m3

100 - 800

-

-

 -

An INERIS report (15/12/2009) mentions carbon oxysulfide (COS) concentrations in the order of 0.047 to 0.29 mg / m3 in biogas from methanisation of sewage sludge.

Biomethane: Towards a cost of production finally competitive ?

The P.T.C. System is the only technology known to date, making it possible to sustainably eliminate and recover CO2 from methanisation in the form of carbonates, which is particularly valuable in industry.
It allows the total capture, sustainable and in a single operation of the CO2 but also of all polluting volatile compounds (N2, O2, H2O, H2S, NH3, Siloxanes, Organochlorines or Organofluorines).

The P.T.C. System allows a cost of production of biomethane 3 times cheaper than the competition and therefore reduces the cost difference between fossil-based methane and biomethane to incorporate it into the network.


 


 

 

 

 

 

 

 

 

 

 

 

 

 

 

The valorization of biogas
Consisting mainly of methane and carbon dioxide, biogas is efficiently recovered in biomethane through purification processes.
This technique, called anaerobic digestion, is caused in digesters, during the treatment of household waste, industrial or agricultural waste and sewage sludge.
Biogas, resulting from the fermentation of this waste, is a source of renewable energy which after purification can replace natural gas of fossil origin.
Farmers, industrialists and local authorities thus treat their waste while enhancing their energy and economic potential. The purification solution P.T.C. allows the valorization of all biogas for the injection to the natural gas network, the production of vehicle fuel (biomethane gas or liquid) or the production of renewable hydrogen after reforming the biomethane.

 

The purification technology by the P.T.C. System
In order to transform biogas into a substitute for natural gas, it must be rid of all pollutants.
The P.T.C. System proposes a technical solution that today allows biogas producers to use it effectively in biomethane through its purification process.
The technology used makes it possible to eliminate carbon dioxide (recyclable CO2) sustainably, and to eliminate in the same operation N2, Siloxanes, Organochlorines or Organofluorines.

The hydrogen sector, based on anaerobic digestion, should logically find its place in the near future.

 


http://www.innovalor.fr/biogaz-biomethane.htm

 

 

 

The cycle of sustainable elimination of pollutants

 

The P.T.C. System is part of this new concept of purification / depollution.

This system is currently the only known to permanently eliminate CO2 and can be recycled in the industrial sector.


In a period that is particularly conducive to the development of alternative energies to fossil fuels, the prospect of integrating biogas into the French energy landscape is of interest from a political, economic and environmental point of view.

In fact, the valorization of domestic, industrial and agricultural organic residues or the treatment of wastewater meet the notions of sustainable development and renewable energy, clearly explained in recent international agreements and commitments.

The environmental impact of the implementation of biogas recovery channels results in a significant reduction in the greenhouse gas emissions.

Recent fluctuations in the costs of importing fossil fuels have also positively influenced the renewed economic interest in energy production from biogas, whether directly in the form of high purity methane gas. or in the form of electricity.

The cost price of biomethane completely purified by P.T.C. System is 0.054 € / kWh. when the cost price in competing systems is
0.15 €/ kWh.

 

 

 

The P.T.C. System allows a cost of production of biomethane 3 times cheaper than the competition and therefore reduces the cost difference between fossil-based methane and biomethane to incorporate it into the network.
On the other hand, the technology of P.T.C. allows extremely simple biogas purification equipment whose investment cost is incommensurate with the currently existing processes.


 
 

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