WO2013083771A1 - Method for the pretreatment of process wastewater originating from hydro-thermal carbonization processes - Google Patents

Method for the pretreatment of process wastewater originating from hydro-thermal carbonization processes Download PDF

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Publication number
WO2013083771A1
WO2013083771A1 PCT/EP2012/074774 EP2012074774W WO2013083771A1 WO 2013083771 A1 WO2013083771 A1 WO 2013083771A1 EP 2012074774 W EP2012074774 W EP 2012074774W WO 2013083771 A1 WO2013083771 A1 WO 2013083771A1
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WIPO (PCT)
Prior art keywords
process wastewater
wastewater
pvpp
originating
carbonization processes
Prior art date
Application number
PCT/EP2012/074774
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French (fr)
Inventor
Ingo Bauer
Ute Raab-Brill
Original Assignee
L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude
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Application filed by L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude filed Critical L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude
Publication of WO2013083771A1 publication Critical patent/WO2013083771A1/en

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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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5272—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using specific organic precipitants
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C10L9/086—Hydrothermal carbonization
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • 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
    • Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing

Definitions

  • the invention relates to a method for the pretreatment of process wastewater originating from hydrothermal carbonization processes to prepare it for downstream treatment by means of an adsorption process for the separation of monovalent phenols.
  • HTC processes biomass together with water and a catalyst are exposed to elevated temperatures of, say, between 180 and 350 °C in a pressure-tight reactor, whereby the water in the reactor is held in the liquid phase.
  • the product water obtained as a result of the chemical reactions is taken up by the water fed to the reactor at the beginning of the process.
  • this water phase is described as process water. Part of this water can be used further for the next charge and part has to be discharged from the HTC process for controlling the concentration of byproducts in the process water and must be disposed of as process wastewater.
  • the byproducts contained in the process water include phenolic substances, i.e. both polyphenols and monovalent phenols.
  • the monovalent phenols like phenol and its derivatives such as cresol and guaiacol, call for special atten- tion because many of these compounds are hazardous to health and to the environment.
  • their concentration in the process wastewater can be so high that the process wastewater must not be routed directly into a biological wastewater treatment plant. In this case it is essential to take special measures in order to separate the major part of the monovalent phenols from the process water.
  • HTC process wastewater is treated by dissolving at least one vegetable protein and/or at least one polyvinylpyrrolidone polymer in the process wastewater.
  • the flocculent precipitates composed of polyphenol complexes thus forming in the process wastewater can be removed by applying known mechanical separation processes like filtration, sedimentation, decantation or centrifugation.
  • PVP polymer is also available in a cross-linked form as polyvinylpolypyrrolidone polymer (PVPP). In this form, it is water-insoluble and binds vegetable polyphenols by absorption to form a PVPP polyphenol complex.
  • HTC process wastewater is treated by routing it through a fixed bed composed of PVPP polymer or in which PVPP polymer is added to the process wastewater as a solid such as powder.
  • the vegetable polyphenols are absorbed on the surface of the PVPP polymer.
  • the polyphenol-laden PVPP polymer powder can in turn be removed from the process wastewater by applying known mechanical separation processes like filtration, sedimentation, decantation or centrifugation.
  • the laden PVPP polymer can be regenerated by known methods and reused.
  • HTC process water with a concentration of monovalent phenols of 1000 ppm and unknown content of polyphenols was mixed with 0.1 % of the polyvinylpyrrolidone Povidone ® K90 in the form of a 10% solution and stirred for about 1 minute. Intense flocculation was observed immediately after addi- tion. In order to prompt the sedimentation of the flakes the mixture was allowed to rest overnight. The supernatant was subsequently pumped through an adsorption bed for removing the monovalent phenols. The flow rate was two times the adsorber volume per hour. A styrene divinylbenzene copolymer (Amberlite XAD4 ® ) was used as adsorbent. The adsorption process was op- erated until the capacity of the adsorbent was exhausted.
  • Amberlite XAD4 ® styrene divinylbenzene copolymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Method for the treatment of process wastewater originating from hydrothermal carbonization processes wherein the process wastewater is contacted with at least one substance which is capable of forming water- insoluble complex compounds with polyphenol.

Description

Method for the Pretreatment of Process Wastewater Originating from Hydro- thermal Carbonization Processes
Field of Invention
The invention relates to a method for the pretreatment of process wastewater originating from hydrothermal carbonization processes to prepare it for downstream treatment by means of an adsorption process for the separation of monovalent phenols. State of the Art
In connection with hydrothermal carbonization processes, also referred to as HTC processes, biomass together with water and a catalyst are exposed to elevated temperatures of, say, between 180 and 350 °C in a pressure-tight reactor, whereby the water in the reactor is held in the liquid phase. The product water obtained as a result of the chemical reactions is taken up by the water fed to the reactor at the beginning of the process. Hereinafter, this water phase is described as process water. Part of this water can be used further for the next charge and part has to be discharged from the HTC process for controlling the concentration of byproducts in the process water and must be disposed of as process wastewater.
The byproducts contained in the process water include phenolic substances, i.e. both polyphenols and monovalent phenols. The monovalent phenols like phenol and its derivatives such as cresol and guaiacol, call for special atten- tion because many of these compounds are hazardous to health and to the environment. Depending on the nature of the biomass used in the HTC pro- cess and on the process technology applied, their concentration in the process wastewater can be so high that the process wastewater must not be routed directly into a biological wastewater treatment plant. In this case it is essential to take special measures in order to separate the major part of the monovalent phenols from the process water.
Known methods for separating phenols from water are extraction processes such as the Lurgi Phenolsolvan Process, and adsorption processes such as the activated carbon method of BERGBAUFORSCHUNG, cf. Lurgi Manual, issue 1970, Lurgi Gesellschaften, Frankfurt am Main and Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 14, chapter 6.1 .2.
If an adsorption process is to be employed to remove the phenols, this in- volves the problem that the polyphenolic substances which are rated less critical for the downstream biological wastewater treatment are also retained by the adsorber which implies an unnecessary constraint of the adsorber capacity- The problem to be solved was therefore to provide a pretreatment technology capable of removing by an economically efficient method polyphenolic substances from the process water of hydrothermal carbonization processes upstream of an adsorption process for the separation of monovalent phenols. Description of the Invention
The problem is solved by a technology which comprises the features of Claim 1 wherein the process wastewater is contacted with at least one substance which is able to form water-insoluble complex compounds with the polyphenol. In the process, stable and water-insoluble complex compounds are formed specifically with polyphenols of a tannic character. Preferred embodiments of the process according to the invention are specified in the sub-claims.
It is known that a large group of vegetable polyphenols feature a pronounced tannic character and they are used for this purpose in tanneries. The basis for this tannic character is the ability of polyphenols to react with proteins to form protein-polyphenol complexes. Such complexes are typically insoluble in water so that they will form flocculent precipitates. Just like vegetable proteins, synthetically produced polyvinylpyrrolidone polymer (PVP) reacts with poly- phenols. PVP is dissolved in the aqueous phase and will likewise form polyphenol complexes which in turn produce flocculation.
In a specific embodiment of the invention, HTC process wastewater is treated by dissolving at least one vegetable protein and/or at least one polyvinylpyrrolidone polymer in the process wastewater. The flocculent precipitates composed of polyphenol complexes thus forming in the process wastewater can be removed by applying known mechanical separation processes like filtration, sedimentation, decantation or centrifugation. PVP polymer is also available in a cross-linked form as polyvinylpolypyrrolidone polymer (PVPP). In this form, it is water-insoluble and binds vegetable polyphenols by absorption to form a PVPP polyphenol complex. In a specific embodiment of the invention, HTC process wastewater is treated by routing it through a fixed bed composed of PVPP polymer or in which PVPP polymer is added to the process wastewater as a solid such as powder. In the process, the vegetable polyphenols are absorbed on the surface of the PVPP polymer. The polyphenol-laden PVPP polymer powder can in turn be removed from the process wastewater by applying known mechanical separation processes like filtration, sedimentation, decantation or centrifugation. The laden PVPP polymer can be regenerated by known methods and reused.
Advanced modifications, advantages and potential applications of the invention also result from the description of examples of embodiment and quantities as well as the drawings provided below. All features described and/or illustrated per se or in any discretionary combination constitute the invention, irrespective of their summary in the Claims or their back-reference.
Based on the example below, the process according to the invention is explained in detail.
HTC process water with a concentration of monovalent phenols of 1000 ppm and unknown content of polyphenols was mixed with 0.1 % of the polyvinylpyrrolidone Povidone® K90 in the form of a 10% solution and stirred for about 1 minute. Intense flocculation was observed immediately after addi- tion. In order to prompt the sedimentation of the flakes the mixture was allowed to rest overnight. The supernatant was subsequently pumped through an adsorption bed for removing the monovalent phenols. The flow rate was two times the adsorber volume per hour. A styrene divinylbenzene copolymer (Amberlite XAD4®) was used as adsorbent. The adsorption process was op- erated until the capacity of the adsorbent was exhausted.
For determining the monovalent phenols, method DIN 38409-H16-3 was applied. The table below shows in column 2 the phenol concentration trend in the HTC process water pretreated according to the invention, at the outlet of the ad- sorption bed. The values demonstrate that the adsorbent is exhausted after a test period of 13 hours.
For comparison, untreated HTC process wastewater was passed through the Amberlite XAD4® adsorber. The values of the total phenol concentration at the outlet of the adsorption bed are shown in column 3 of the table. It can be seen that the adsorbent is already exhausted after 7 hours.
Table: Phenol concentration trend in HTC process water at the outlet of the adsorption bed
Figure imgf000006_0001

Claims

Claims:
Method for the pretreatment of process wastewater originating from hydrothermal carbonization processes containing monovalent phenolic compounds and polyphenols to prepare it for downstream treatment by applying a technology for removing monovalent phenolic compounds, comprising the following process steps:
(a) Making available process wastewater originating from hydrothermal carbonization processes,
(b) Contacting it with at least one complexation agent which is capable of forming water-insoluble complex compounds with the polyphenol,
(c) Removal of the polyphenol complex precipitate by applying a mechanical separation process, (c) Submission of the pretreated process wastewater from step (c) to a downstream treatment process for separating monovalent phenolic compounds.
The method of Claim 1 wherein as substance polyvinylpyrrolidone (PVP) or a protein is dissolved in the process wastewater.
The method of Claim 2 wherein the flocculent precipitates formed are separated from the process wastewater.
The method of Claim 1 wherein as a substance polyvinylpolypyrrolidone (PVPP) is employed in the form of a fixed bed or as a solid added to the process wastewater. The method of Claim 4 wherein when added as a powder the PVPP laden with turbid particulate matter is separated from the process wastewater.
A method according to one of the preceding claims wherein filtration, sedimentation, decantation or centrifugation are applied as mechanical separation processes.
A method according to one of the preceding claims wherein the downstream treatment process comprises adsorption.
Use of proteins, polyvinylpyrrolidone (PVP) or polyvinylpolypyrrolidone (PVPP) as complexation agents to remove polyphenols from process wastewater originating from hydrothermal carbonization processes.
PCT/EP2012/074774 2011-12-09 2012-12-07 Method for the pretreatment of process wastewater originating from hydro-thermal carbonization processes WO2013083771A1 (en)

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DE102011120629.2 2011-12-09
DE201110120629 DE102011120629A1 (en) 2011-12-09 2011-12-09 Process for the pretreatment of process waste water originating from hydrothermal carbonization processes

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435115A (en) * 2013-08-26 2013-12-11 苏州富奇诺水治理设备有限公司 Phenol-containing wastewater treatment agent

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4910182A (en) * 1985-03-19 1990-03-20 Westfalia Separator Ag Process for the secondary purification and stabilization of liquids containing polyphenols and/or proteins, particularly beverages and more especially beer
US5484620A (en) * 1990-12-22 1996-01-16 Schenk-Filterbau Gesellschaft Mit Beschrankter Haftung Method of manufacturing stabilizing and/or filtering aids for use in the processing of liquids, especially beverages
EP2206688A1 (en) * 2008-12-16 2010-07-14 Suncoal Industries Gmbh Thermo-chemical preparation of the process water of a hydrothermal carbonisation
US20100237010A1 (en) * 2006-02-24 2010-09-23 Robert Gibbison Use of pvpp to remove contaminants from produced water of an oil or gas well

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4910182A (en) * 1985-03-19 1990-03-20 Westfalia Separator Ag Process for the secondary purification and stabilization of liquids containing polyphenols and/or proteins, particularly beverages and more especially beer
US5484620A (en) * 1990-12-22 1996-01-16 Schenk-Filterbau Gesellschaft Mit Beschrankter Haftung Method of manufacturing stabilizing and/or filtering aids for use in the processing of liquids, especially beverages
US20100237010A1 (en) * 2006-02-24 2010-09-23 Robert Gibbison Use of pvpp to remove contaminants from produced water of an oil or gas well
EP2206688A1 (en) * 2008-12-16 2010-07-14 Suncoal Industries Gmbh Thermo-chemical preparation of the process water of a hydrothermal carbonisation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Ullmann's Encyclopedia of Industrial Chemistry", vol. 14
BERGBAUFORSCHUNG: "Lurgi Manual", 1970, article "Lurgi Gesellschaften"
GUPTA V K ET AL: "UTILIZATION OF BAGASSE FLY ASH GENERATED IN THE SUGAR INDUSTRY FOR THE REMOVAL AND RECOVERY OF PHENOL AND P-NITROPHENOL FROM WASTEWATER", JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY, JOHN WILEY & SONS LTD, UNITED KINGDOM, vol. 71, no. 2, 1 February 1998 (1998-02-01), pages 180 - 186, XP000766448, ISSN: 0268-2575 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435115A (en) * 2013-08-26 2013-12-11 苏州富奇诺水治理设备有限公司 Phenol-containing wastewater treatment agent

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