WO2020012371A1 - Procédé de récupération d'eau contaminée par des composés fluorés et élimination de polluants - Google Patents

Procédé de récupération d'eau contaminée par des composés fluorés et élimination de polluants Download PDF

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Publication number
WO2020012371A1
WO2020012371A1 PCT/IB2019/055867 IB2019055867W WO2020012371A1 WO 2020012371 A1 WO2020012371 A1 WO 2020012371A1 IB 2019055867 W IB2019055867 W IB 2019055867W WO 2020012371 A1 WO2020012371 A1 WO 2020012371A1
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WO
WIPO (PCT)
Prior art keywords
water
pollutants
treatment
concentration
concentrated
Prior art date
Application number
PCT/IB2019/055867
Other languages
English (en)
Inventor
Massimo Neresini
Manuel ASNICAR
Marco Piva
Mauro BALDRANI
Michele CRISTOFANI
Alessandro Zaggia
Original Assignee
Sicit Chemitech S.P.A.
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 Sicit Chemitech S.P.A. filed Critical Sicit Chemitech S.P.A.
Publication of WO2020012371A1 publication Critical patent/WO2020012371A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/26—Multiple-effect evaporating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/28—Evaporating with vapour compression
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/06—Flash distillation
    • B01D3/065—Multiple-effect flash distillation (more than two traps)
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/061—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating
    • F23G7/063—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating electric heating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/06—Flash evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen

Definitions

  • the present invention relates to a process for the recovery of water contaminated by organofluorine compounds, comprising steps involving filtration, concentration, reverse osmosis and heat treatment of the concentrated fraction of organofluorine compounds.
  • WO2017131972 discloses a process of decontamination of water or soil contaminated by perfluoroalkyls and polyfluoroalkyls involving treatment with reagents such as persulphates, oxygen, ozone and phosphates.
  • step c Treatment of the concentrated water from step b) in a reverse osmosis plant to give a concentrated fraction of organo fluorine compounds and a fraction of recovered water;
  • the process of the invention is unexpensive and sustainable and produces very small amounts of wastewater, with a consequent environmental improvement.
  • the process is applicable to water originating from facilities or consortiums operating in various industries that use PFAs, such as the textile industry, the tanning industry, the metallurgical/galvanising industry, the pharmaceutical industry and the chemical industry, and from civil and industrial water purification plants.
  • PFAs such as the textile industry, the tanning industry, the metallurgical/galvanising industry, the pharmaceutical industry and the chemical industry, and from civil and industrial water purification plants.
  • Said water can be treated by the process according to the invention either in situ with small-capacity units tailormade to their requirements, or on a centralised site able to treat water originating from various manufacturers.
  • Water polluted by PFAS, PFOS, PFOA or other compounds, selected at the starting plants on the basis of the concentration and origin of the pollutants, is sent to a suitable storage plant, for example by road transport (tanker) or through a sewer that collects the water and conveys it to the treatment plant.
  • PFAS PFAS
  • PFOS PFOS
  • PFOA PFOA
  • suitable storage plant for example by road transport (tanker) or through a sewer that collects the water and conveys it to the treatment plant.
  • Water is then suitably pretreated (step a) to remove foreign bodies, for example by screening or initial filtration.
  • Solids are then removed from solution by centrifugation in a vertical centrifuge, by passing through a two- or three-phase decanter (if an organic substance lighter than water is present), or alternatively by cloth filtration.
  • a chemical treatment can also be performed by adding acidifying and basifying agents to precipitate some organic substances or inorganic salts which can optionally be separated and conveyed directly to the combustion stage (step d) before or after the separation stage.
  • reagents examples include slaked lime, caustic soda, ammonia, sulphuric acid, hydrochloric acid, nitric acid, ammonium sulphate, acetic acid and phosphoric acid.
  • step b The wastewater, clarified in step a, is then reduced in volume (step b) to concentrate the solid or dry part, which thus acquires value in terms of heat value.
  • a multiple-effect (or step) concentration system is used at this stage.
  • Multi-effect evaporation is a low-pressure steam process wherein each effect allows steam already used in the previous step to be reused. Such reuse is possible if the uncondensed steam is used at a lower pressure in the next step.
  • the thermal concentration system uses energy to evaporate the water, and then condenses it again.
  • Multiple-effect concentration is one of the most reliable, soundest and cheapest solutions in the industry, with capacities ranging from 600 to 25,000 rnVday per unit.
  • the modular design allows the number of effects in the process to be optimised to suit the specific plant environment and site conditions;
  • step b The condensate obtained in step b is then treated in a reverse osmosis plant (step c) to recover the incoming per-/polyfluorinated substances and obtain water with qualities such as to be recoverable in industrial cycles.
  • the water can then be reused as industrial water in manufacturing cycles in the same industry or the same facility.
  • the residual fluorinated substances in the concentrated water are conveyed to a final thermal destruction or post-combustion plant (step d).
  • Said final treatment can be performed in an“in-flight gasification” plant or another type of thermal destruction unit that generates very little slag, fluorinated substances being absent or at any event trapped in“glassy” matrices with practically zero release.
  • the concentrated suspension of organofluorine compounds is pumped by a volumetric pump to the subsequent thermal destruction unit.
  • This step can be performed in a reducing environment (pyrolysis/gasification) or an oxidising environment (incineration), the former being preferred due to its greater simplicity in the purification of effluent gases.
  • the crucial parameter of the fluorinated organic compound destruction process is the temperature which, to guarantee their total breakdown, must exceed l,l00°C for a sufficient time, and in any event longer than 2 seconds (as specified in European Directive 2010/75/EU, art. 50, regarding incineration and co-incineration).
  • the destruction system in a reducing environment involves the use of plasma torches as a powerful energy source.
  • the plasma-producing gas can be air, oxygen-enriched air, an inert gas such as nitrogen or argon, etc.
  • the gas is cooled by heat recovery and then purified in a wet scrubber (a Venturi scrubber or the like) operating with an alkaline solution, so that acid gases, primarily hydrofluoric acid, are removed in the form of saline solution.
  • a wet scrubber a Venturi scrubber or the like
  • the saline water after filtration, is disposed of as wastewater.
  • a final dedusting system for example with a wet electrostatic filter, enables a combustible gas usabld for energy recovery to be obtained.
  • the water vapour necessary for the operation of the other sections of the integrated process schematically illustrated in Figure 1, can be produced.
  • the destruction system in an oxidising environment uses combustion of an external fuel (usually natural gas) to maintain the desired temperature conditions in the combustion chamber (T>l l00°C).
  • Fuel combustion takes place in an industrial burner; the aqueous suspension is nebulised in the combustion chamber.
  • the effluent gases are then dedusted with a suitable system (such as ceramic filters) and undergo heat recovery in a suitable regenerator.
  • a suitable system such as ceramic filters
  • the water vapour necessary for the operation of the other sections of the integrated process can be produced.
  • the effluent gases are purified in a wet scrubber (a Venturi scrubber or the like) operating with an alkaline solution to remove acid gases.
  • a wet scrubber a Venturi scrubber or the like
  • the saline water after filtration, is disposed of as wastewater, as schematically illustrated in Figure 2.
  • Solid waste containing heavy metals such as chromium is preferably added at the reducing stage, producing a gaseous waste that can be conveyed to the subsequent oxidative stage, whereas liquid waste can be suitably dispersed at the oxidative stage to produce energy, which is suitably recovered in a “cogeneration” system that produces electricity and steam, as schematically illustrated in Figure 3.
  • the plants used in these stages can be small, and therefore suitable for small local facilities wishing to solve their own wastewater problem, or large, possibly also using internal heat recovery systems, electricity and steam cogeneration systems, and integrated water treatment and recirculation systems.
  • Figure 1 illustrates the balance of a process according to the invention with a destruction system in a reducing environment.
  • Figure 2 shows the balance of a process according to the invention with a destruction system in an oxidising environment.
  • Figure 3 shows the balance of a process according to the invention with a destruction system in a reducing environment followed by a destruction system in an oxidising environment.
  • Figure 4 shows the balance of a process according to the invention applied to the tanning industry.
  • the solid-free water is concentrated in a pilot concentration unit such as a rising- film plate evaporator at the flow rate of 300 litres/hour of evaporated water.
  • the condensate is concentrated in a reverse osmosis plant at about 6 litres/minute until a further 310 litres of concentrate have been obtained. On exit from the osmosis plant the water has total PFAS concentrations below 1 ng/litre.
  • the outgoing gas is analysed and treated with an absorber supplied with a dilute solution of sodium hydroxide before emission into the atmosphere.
  • the result is about 400 kg of sludge, with dry matter of about 30% w/w.
  • Said sludge is mixed with other solid waste:
  • the resulting paste is further dried in an airstream at 60°C for 24 hours to obtain a product with about 90% dry matter. 900 kg of dry sludge is obtained.
  • the solid-free water is concentrated in a pilot concentration unit such as a rising- film plate evaporator at the flow rate of 300 litres/hour of evaporated water. 440 kg of concentrate and about 19,100 kg of condensate are obtained.
  • the condensate is concentrated in a reverse osmosis plant at about 6 litres/minute until a further 480 litres of concentrate have been obtained. On exit from the osmosis plant the water has total PFAS concentrations below 1 ng/litre.
  • 900 kg of dry sludge is fed into a pilot gasification plant based on the shaft furnace, using air as gasification gas.
  • 920 kg of concentrate containing fluorinated compounds is injected into the crude syngas.
  • the crude syngas is mixed with a stream of air plasma to adjust the temperature of the gaseous mass to a value ranging between 1250 and l300°C, to completely break down the perfluorinated substances and any organic substance that may be present.
  • the outgoing gas is analysed and treated with an absorber supplied with a dilute solution of sodium hydroxide, and then burned in a torch before emission into the atmosphere.
  • the result is about 2 tons/hour of sludge, with dry matter of about 30% w/w.
  • Said sludge is mixed with other solid waste:
  • the resulting mixture is further dried in an industrial flash dryer, obtaining about 3 tons/hour of powdery material with about 90% dry matter.
  • the solid-free water is concentrated in a multiple-effect concentration unit such as a rising- film plate evaporator at the flow rate of 100 tons/hour of evaporated water. 2.5 tons/hour of concentrate and about 95 tons/hour of condensate are obtained.
  • the condensate is concentrated in a reverse osmosis plant at about 2,000 litres/minute until a further 3 tons/hour of concentrate have been obtained. On exit from the osmosis plant the water has total PFAS concentrations below 1 ng/litre.
  • the 2.5 tons/hour of first concentrate and 3 tons/hour of reverse osmosis concentrate are combined to give a final concentrate rich in fluorinated polymers.
  • the 3 tons/hour of dry sludge, after suitable compacting treatment to increase the mechanical properties of the material, are fed into an industrial gasification unit based on the shaft furnace, using air as gasification gas.
  • the contaminated process gases originating from the drying and evaporation stages are also mixed into the gasification air.
  • the molten inorganic mass (about 1 ton/hour) is extracted from the bottom of the shaft furnace at a temperature of about l500°C, and rapidly cooled in a stream of water.
  • the inert glassy matrix can be sent for recovery as inert filler material, while the metal alloy is recoverable in the metallurgical industry.
  • 5.5 tons/hour of concentrates containing the fluorinated compounds are injected into the crude syngas exiting from the top of the shaft furnace.
  • the crude syngas is mixed with a stream of air plasma to adjust the temperature of the gaseous mass to a value ranging between 1250 and l300°C, to completely break down the perfluorinated substances and any organic substance that may be present.
  • the crude syngas after energy recovery of sensible heat, undergoes a process of dedusting and purification to remove gaseous components hazardous to the environment (such as acid gases and heavy metals).
  • the syngas is used as combustible gas (about 10,000 Nm 3 /h is produced with a net heat value of about 1.4 kWh/Nm 3 ) for energy recovery in endothermic engines or steam generators, for the production of electricity, steam and hot water.
  • Electricity and steam can be used in the operation of the industrial waste treatment plant, while any hot water can be used in district heating/air-conditioning plants.
  • combustion gases analysed with a continuous system after the optional step of reduction of nitrogen oxides, are expelled into the atmosphere.

Abstract

L'invention concerne un procédé de décontamination d'eau contaminée par des composés organofluorés, en particulier des composés perfluoroalkyle (PFAS), au moyen d'étapes de filtration, de concentration et d'osmose inverse. Le résidu d'eau concentrée riche en polluants est ensuite soumis à un traitement de pyrolyse. Selon l'invention, le procédé est avantageux, car il peut être appliqué à différents types de déchets, même en présence de corps solides, de corps étrangers et d'autres polluants, et produit une eau si pure qu'elle peut être réintroduite dans le cycle de fabrication ou rejetée sans aucun problème dans les usines de traitement des eaux industrielles.
PCT/IB2019/055867 2018-07-11 2019-07-10 Procédé de récupération d'eau contaminée par des composés fluorés et élimination de polluants WO2020012371A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102018000007111 2018-07-11
IT102018000007111A IT201800007111A1 (it) 2018-07-11 2018-07-11 Processo per il recupero di acque contaminate da composti florurati e eliminazione degli inquinanti

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WO2020012371A1 true WO2020012371A1 (fr) 2020-01-16

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IT (1) IT201800007111A1 (fr)
WO (1) WO2020012371A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11407666B2 (en) 2020-08-06 2022-08-09 Battelle Memorial Institute Salt separation and destruction of PFAS utilizing reverse osmosis and salt separation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1314700A1 (fr) * 2001-11-22 2003-05-28 Asahi Glass Company Ltd. Procédé d'absorption et récupération d'émulsifiants contenant du flour
EP1323460A1 (fr) * 2000-08-11 2003-07-02 Daikin Industries, Ltd. Procede de recuperation d'un tensioactif fluorochimique
WO2008109219A1 (fr) * 2007-03-06 2008-09-12 3M Innovative Properties Company Système et procédé permettant une cavitation induite de manière ultrasonore de produits chimiques fluorés
EP2102113A1 (fr) * 2006-11-22 2009-09-23 Siemens Water Technologies Corp. Système et procédé pour le traitement des nappes phréatiques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1323460A1 (fr) * 2000-08-11 2003-07-02 Daikin Industries, Ltd. Procede de recuperation d'un tensioactif fluorochimique
EP1314700A1 (fr) * 2001-11-22 2003-05-28 Asahi Glass Company Ltd. Procédé d'absorption et récupération d'émulsifiants contenant du flour
EP2102113A1 (fr) * 2006-11-22 2009-09-23 Siemens Water Technologies Corp. Système et procédé pour le traitement des nappes phréatiques
WO2008109219A1 (fr) * 2007-03-06 2008-09-12 3M Innovative Properties Company Système et procédé permettant une cavitation induite de manière ultrasonore de produits chimiques fluorés

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11407666B2 (en) 2020-08-06 2022-08-09 Battelle Memorial Institute Salt separation and destruction of PFAS utilizing reverse osmosis and salt separation

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Publication number Publication date
IT201800007111A1 (it) 2020-01-11

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