FI20176100A1 - Method and apparatus for treating a side water fraction - Google Patents

Method and apparatus for treating a side water fraction Download PDF

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Publication number
FI20176100A1
FI20176100A1 FI20176100A FI20176100A FI20176100A1 FI 20176100 A1 FI20176100 A1 FI 20176100A1 FI 20176100 A FI20176100 A FI 20176100A FI 20176100 A FI20176100 A FI 20176100A FI 20176100 A1 FI20176100 A1 FI 20176100A1
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Finland
Prior art keywords
catalyst
nial
reforming
water fraction
side water
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FI20176100A
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Finnish (fi)
Swedish (sv)
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FI128921B (en
Inventor
Johanna Kihlman
Irene Coronado
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Teknologian Tutkimuskeskus Vtt Oy
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Priority to FI20176100A priority Critical patent/FI128921B/en
Priority to PCT/FI2018/050895 priority patent/WO2019115871A1/en
Priority to EP18830493.5A priority patent/EP3723901A1/en
Publication of FI20176100A1 publication Critical patent/FI20176100A1/en
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Publication of FI128921B publication Critical patent/FI128921B/en

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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • 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
    • C02F1/025—Thermal hydrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
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    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
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    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
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    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
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    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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    • C01B2203/1223—Methanol
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    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
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    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • 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
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    • 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
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
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    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/169—Integration of gasification processes with another plant or parts within the plant with water treatments
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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Abstract

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Description

METHOD AND APPARATUS FOR TREATING A SIDE WATER FRACTION
20176100 prh 11-12-2017
FIELD
The application relates to a method defined in claim 1 and an apparatus defined in claim 14 for treating a side water fraction. Further, the application relates to a use of the method defined in claim 16.
BACKGROUND
Known from the prior art is to convert biomass to biofuels by thermochemical routes such as by a gasification and Fischer-Tropsch (FT) reaction. Also 15 different side fractions form in these processes.
Further, known from the prior art is to treat different feedstocks comprising organic compounds in an aqueous-phase reforming (APR) process. Further, it is known that different catalysts can be used in this 20 process.
The aqueous-phase reforming (APR), such as operating conditions, catalysts and reactor designs, have been studied in the art. For instance, different feedstocks, temperatures, pressures and space veloci25 ties have been tested for APR over numerous catalysts, mainly platinum- and nickel-based in form of particles. These catalysts have been prepared with different supports and metal dopants to enhance the performance of the catalysts. However, product selectivity 30 and durability of the catalysts are questionable. Furthermore, few reactor designs have been tested for APR, with a predominant use of tubular packed-bed reactors. Recently, intensified reactors have been considered to improve mass transport in APR, and conse35 quently, increase the product efficiency. Although platinum-washcoated microchannels and membrane reac tors enhance the performance, catalyst loading and replacement are significant barriers for scale up applications. Further, noble metal-based catalysts are expensive and economically inefficient in large scales.
OBJECTIVE
The objective is to disclose a new type method and apparatus for treating water fractions derived from biorefineries. Further, the objective is to disclose a new type method and apparatus for producing hydrogen from the aqueous solutions derived from biorefineries. Further, the objective is to disclose an improved method and apparatus for treating water fractions in an aqueous-phase reforming. Further, the objective is to produce a new type catalyst to be used in the aqueous-phase reforming. Further, the objective is to prepare a new type catalyst. Further, the objective is to disclose a catalyst composition for coating a substrate.
SUMMARY
The method and apparatus and use are characterized by what are presented in the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are included to provide a further understanding of the invention and constitutes a part of this specification, illustrate some embodiments of the invention and together with the description help to explain the principles of the invention. In the drawings:
Fig. 1 is a flow chart illustration of a method and an apparatus according to one embodiment, and
Fig. 2 shows results from one example carried out according to one method embodiment.
DETAILED DESCRIPTION
In a method for treating a side water fraction (1) which comprises at least one undesired compound and which is formed in a thermochemical treatment of biomass, the side water fraction (1) comprising at least one undesired organic compound is treated by means of a reforming treatment (2) in order to convert the organic compound into at least hydrogen (5) and optionally also other compounds (6) selected from the group comprising organic compounds, such as modified organic compounds, hydrocarbons, carbondioxide, carbonmonoxide and their combinations, and the reforming treatment (2) is catalyzed by Ni/NiAl2O4 catalyst (3), preferably Ni/NiAl2O4 washcoat catalyst.
An apparatus for treating a side water fraction (1) which comprises at least one undesired compound and which is formed in a thermochemical treatment of biomass can comprise at least one reforming treatment device (12) in which the side water fraction (1) comprising at least one undesired organic compound is treated in order to convert the organic compound into at least hydrogen (5) and optionally also other compounds (6) selected from the group comprising organic compounds, such as modified organic compounds, hydrocarbons, carbondioxide, carbonmonoxide and their combinations, and Ni/NiAl2O4 catalyst (3), preferably Ni/NiAl2O4 washcoat catalyst, which is arranged inside the reforming treatment device (12) for catalyzing the reforming treatment (2).
One embodiment of the method and the apparatus is shown in Fig 1.
In this context, the biomass means any biomass. In one embodiment, the biomass is a lignocellu losic based biomass. Preferably, the biomass has been treated by converting into biofuels. The biomass may be converted into the biofuels by thermochemical routes such as by a gasification and Fischer-Tropsch (FT) reaction of syngas or other feedstock, or by a pyrolysis and bio-oil reforming. In one embodiment, the biomass has been treated by means of at least one process step which is selected from the group comprising the gasification, Fischer-Tropsch (FT) reaction of syngas, pyrolysis, bio-oil refining and their combinations. In one embodiment, the biomass has been treated by means of the gasification and/or the FischerTropsch (FT) reaction of syngas. In one embodiment, the biomass has been treated by means of the pyrolysis and/or the bio-oil refining. In one embodiment, the side water fraction (1) is formed in the FischerTropsch reaction or in the bio-oil refining.
In this context, the side water fraction (1) means any water fraction, biorefinery water fraction, water based side fraction or water based residue fraction, in which fraction may be any fraction, separated fraction, flow, stream, outflow or their combination. The side water fraction may comprise at least one harmful organic compound, such as hydrocarbon, oxygenated hydrocarbon or other organic compound or the like, for example alcohols, aldehydes, ketones, acids, aliphatic, aromatic and cyclic hydrocarbons. In one embodiment, the side water fraction comprises at least one organic compound, e.g. MeOH, organic compound with longer carbon chain or other compound. In one embodiment, the side water fraction comprises at least MeOH. In one embodiment, the side water fraction comprises organic compound with longer carbon chain, such as alcohol, ketone, aldehyde and/or organic acid. In one embodiment, the side water fraction comprises 1 - 40 % by volume organic compounds, e.g. organic hydrocarbons or other organic compounds. In one embodiment, the side water fraction comprises over 5 % by volume, preferably 5 - 40 % by volume, more preferably 5-20 % by volume, organic compounds. In one embodiment, the side water fraction comprises 1 - 10 % by volume organic compounds .
In one embodiment, the Ni/NiAl2O4 catalyst (3) is arranged in the form of a film, preferably a thin film, onto a substrate. The substrate can be formed from a metal material or a ceramic material or other suitable material. In one embodiment, the substrate can be a wall, reactor wall, static mixer, mesh, fibres, fillers or other suitable substrate which are formed from the metal or ceramic material, or for example, open cell foams which are formed from the ceramic material.
In one embodiment, the Ni/NiAl2O4 catalyst is Ni/NiAl2O4 washcoat catalyst, more preferably Ni/NiAl2O4 spinel washcoat catalyst, wherein the Ni/NiAl2O4 is as a thin washcoat layer on the substrate, such as on the metal or ceramic surface of the substrate.
In one embodiment, the washcoat catalyst can be formed by preparing a catalytically active washcoat composition from a carrier material, preferably with a high surface area, e.g. aluminium oxide based carrier material, and one or more catalyst agents, e.g. metals, and by arranging the formed catalytically active washcoat composition onto the substrate, such as the metal or ceramic structure.
In one embodiment, Ni content of the Ni/NiAl2O4 catalyst (3) is 8 - 20 wt%. In one embodiment, Ni content of the Ni/NiAl2O4 catalyst is 8 - 15 wt%, in one embodiment 10 - 14 wt%, and in one embodiment about 11 - 13 wt%.
In one embodiment, the Ni/NiAl2O4 catalyst (3) is prepared such that a catalyst agent, e.g. Ni, is impregnated, e.g. by an incipient wetness impregnation method, to a carrier material, e.g. boehmite, to form a catalytic material. Ni catalyst agent can be a Niprecursor such as nickel nitrate or other precursor. The resulting catalytic material, e.g. in form of powder, is dried and calcined, for example to transform nickel nitrate/boehmite into nickel oxide/boehmite. A slurry is prepared. In one embodiment, the slurry is prepared by mixing the resulting catalytic material with a binder, an acid and water. The slurry is arranged by washcoating onto a substrate, such as a metal or ceramic substrate, and the washcoated substrate is thermally treated, e.g. by means of a high temperature calcination. Then a thin layer of Ni/NiAl2O4 can be formed onto the substrate.
In one embodiment, the Ni/NiAl2O4 catalyst (3) is prepared such that Ni-precursors are impregnated into a boehmite carrier material to form a catalytic material, and the catalytic material, preferably in a powder form, is dried and calcinated, and a slurry comprising at least the catalytic material, and preferably at least suitable liquid, is prepared and stirred, and the substrate is washcoated with the slurry, and the washcoated substrate is thermally treated, such as dried, calcinated and treated by reduction. In one embodiment, the catalytic material is dried by means of under pressure or vacuum drying or their combination. In one embodiment, the catalytic material is dried under vacuum. In one embodiment, the catalytic material is calcinated at a temperature of 450 - 550 °C, preferably at 490 - 510 °C. In the calcination, Ni-precursor can be converted, e.g. from nickel nitrate to nickel oxide. In one embodiment, the slurry comprises at least the catalytic material and water, preferably ion-exchanged water. Further, the slurry may comprise a suitable solution and acid, such as HNO3, and a binder. In one embodiment, the substrate is pre-treated and calcinated before the washcoating. In one embodiment, the formed washcoated substrate is dried at a temperature of 400 - 600 °C, preferably 450 - 550 °C, for a sufficient time, e.g. about 3-7 min, such as about 5 min. In one embodiment, the washcoated substrate is slowly dried by air flow at ambient temperature and pressure before the above flash-drying. In one embodiment, the washcoated substrate is calcinated at a temperature of 700 - 900 °C, preferably 750 - 850 °C, for a sufficient time, e.g. about 1.5 - 2.5 hours, such as about 2 hours, to fix the catalytic material on the substrate. In one embodiment, the formed washcoat catalyst is treated by reduction at a temperature of 350 - 450 °C, preferably 370 - 430 °C, with a sufficient H2:N2 ratio. In one embodiment, H2:N2 ratio can be about 1.
In one embodiment, the reforming treatment (2) is a 3-phase reforming treatment. In one embodiment, the reforming treatment (2) is an aqueous-phase reforming (APR). In one embodiment, the aqueous-phase reforming (APR) is carried out at temperature which is 200 - 250 °C, preferably about 230 °C, and under pressure which is 30 - 34 bar, preferably 32 bar. In one embodiment, an aqueous solution which comprises 0.1 10 wt%, preferably 3-7 wt%, organic compounds and which is formed from the side water fraction (1) is fed to the aqueous-phase reforming (APR) . In one embodiment, the side water fraction (1) is diluted with water before the feeding to the aqueous-phase reforming (APR) . In this context, the aqueous-phase reforming means any aqueous-phase reforming, catalytic aqueous-phase reforming or the like.
In the reforming treatment (2) at least hydrogen (5) and optionally some other compounds (6), such as organic compounds, hydrocarbons, carbondioxide
20176100 prh 11-12-2017 and/or carbonmonoxide are formed. Preferably, at least hydrogen (5) is formed. In one embodiment, also carbondioxide and carbonmonoxide can be formed during the reforming treatment (2) . In one embodiment, hydrogen and carbondioxide are formed. In one embodiment, also some hydrocarbons, e.g. methane, ethane or other hydrocarbon, can be formed during the reforming treatment (2). In one embodiment, methane is formed. In one embodiment, also some organic compounds, e.g. alcohol, ketones, aldehydes and organic acids or other organic compounds, can be formed during the reforming treatment (2) . In one embodiment, at least a part of the reforming treatment products are gaseous products. In one embodiment, at least a part of the reforming treatment products are liquid products. In one embodiment, the reforming treatment products are mainly gaseous products. In one embodiment, the reforming treatment products are mainly liquid products. In one embodiment, the gaseous reforming treatment products can comprise at least CO, CO2, CH4, C2H6, C2H4 and/or C3H6. In one embodiment, the liquid reforming treatment products can comprise alcohol, ketones, aldehydes and/or organic acids.
In one embodiment, the method comprises more than one reforming treatment step or device (12), such as aqueous-phase reforming (APR) step or reactor. In one embodiment, the apparatus comprises more than one reforming treatment device (12), such as aqueous-phase reforming reactor.
In one embodiment, the hydrogen (5) is fed back to the thermochemical treatment, e.g. to the Fischer-Tropsch (FT) unit, to adjust H2/CO ratio. In one embodiment, the hydrogen (5) is fed back to the bio-oil refining unit for hydrotreatment, e.g. to improve hydrotreatment of pyrolysis oils, e.g. hydrogenation, hydrodeoxygenation or the like.
In one embodiment, the apparatus comprises at least one feed inlet for supplying the side water fraction (1) to the reforming treatment device (12) . The feed inlet of the side water fraction may be any suitable inlet known per se, e.g. pipe, port or the like. In one embodiment, the apparatus comprises at least one feeding device. In this context, the feeding device can be any feeding device, equipment or other suitable device for feeding the side water fraction (1) to the reforming treatment device (12). In one embodiment, the feeding device is selected from the group comprising pump, compressor, tube, pipe, other suitable feeding device and their combinations. In one embodiment, the apparatus comprises at least one addition device for adding the catalyst (3) to the reforming treatment device (12). The addition device may be any suitable addition device. In one embodiment, the apparatus comprises at least one product outlet for supplying hydrogen (5) or other compound stream (6), such as organic compound, hydrocarbons, carbondioxide and/or carbonmonoxide stream or product out from the reforming treatment device (12) . The product outlet may be any suitable outlet known per se, e.g. pipe, outlet port or the like. Any suitable reforming treatment device (12), e.g. aqueous-phase reforming reactor, known per se can be used as the reforming device in the apparatus .
In one embodiment, the reforming treatment device (12) is an aqueous-phase reforming reactor.
In one embodiment, the apparatus comprises more than one reforming treatment devices (12). In one embodiment, at least two reforming treatment devices are arranged in parallel. In one embodiment, at least two reforming treatment devices are arranged sequentially .
In one embodiment, the method is based on a continuous process. In one embodiment, the apparatus is a continuous apparatus. In one embodiment, the method is based on a batch process. In one embodiment, the apparatus is a batch apparatus.
In one embodiment, the apparatus and the method is used and utilized in the aqueous-phase reforming, in the production of biofuels, in the treatment of the side water fraction after a FischerTropsch (FT) reaction, in the treatment of the side water fraction after bio-oil refining, in the treatment of the side water fraction after pyrolysis and/or
its post-process, in the treatment of the water f rac-
tion comprising at least organic compound, or their
combinations . Thanks to the invention the different water
based streams with harmful organic compounds can be treated effectively. High conversion rates and hydrogen selectivity can be obtained when the reforming treatment, such as the aqueous-phase reforming, is catalyzed with Ni/NiAl2O4 catalyst. The performance of this catalyst is remarkably superior compared to nickel-based catalysts in a packed-bed tubular reactor. The improvement derives from the high activity of the catalyst and the reduction of the internal mass transfer limitations. Further, this catalyst represents a much less expensive alternative to the traditionally used platinum-based catalysts.
The method and apparatus offers a possibility to treat different water based side and residue streams easily, and energy- and cost-effectively. The present invention provides an industrially applicable, simple and affordable way to treat the water based streams. The water based streams can be treated under mild conditions, such as at low temperature and under medium pressure. Further, no evaporation stages are needed. The method and apparatus are easy and simple to realize in connection with production processes of biofuels, also in a small scale process. Then more environmentally friendly biofuel production process can be provided. Further, the biofuel production process can be optimized by utilizing the hydrogen produced in the reforming treatment device. Further, an amount of waste water for disposal can be decreased.
EXAMPLES
Example 1
Figure 1 presents the method and also the apparatus for treating a side water fraction (1) derived from a biorefinery.
The side water fraction (1) has been formed in a thermochemical treatment of lignocellulosic based biomass. The lignocellulosic based biomass can be treated by converting into the biofuels by means of the thermochemical routes such as by a gasification and Fischer-Tropsch (FT) reaction of syngas or other feedstock, or by a pyrolysis and bio-oil reforming. The side water fraction (1) has been formed in the Fischer-Tropsch reaction or in the bio-oil refining.
The side water fraction (1) comprises at least one undesired organic compound. The side water fraction (1) may comprise 1 - 40 % by volume organic compounds. The apparatus comprises at least one reforming treatment device (12), in this embodiment an aqueous-phase reforming (APR) reactor, in which the side water fraction (1) is treated by a reforming treatment (2) in order to convert the organic compound into at least hydrogen (5) and optionally also other compounds (6), such as organic compounds, hydrocarbons, carbondioxide and/or carbonmonoxide. Further, the method and apparatus comprise Ni/NiAl2O4 catalyst (3), preferably Ni/NiAl2O4 spinel washcoat catalyst, which is arranged inside the reforming treatment device (12) for catalyzing the reforming treatment (2) . Preferably, the aqueous-phase reforming can be carried 5 out at temperature of 200 - 250 °C and under pressure of 30 - 34 bar.
The Ni/NiAl2O4 spinel washcoat catalyst (3) is arranged in the form of a film, preferably a thin layer, onto a substrate, such as a metal substrate or a 10 ceramic substrate. Preferably the Ni/NiAl2O4 spinel washcoat catalyst (3) is prepared in a catalyst preparing stage (4). The Ni/NiAl2O4 spinel washcoat catalyst can be formed such that a Ni-precursor, e.g. nickel nitrate, is impregnated by an incipient wetness 15 impregnation method to a boehmite carrier material to form a catalytic material. The resulting catalytic ma20 terial example nickel in form of powder is dried and calcined, for nickel nitrate/boehmite into to transform oxide/boehmite.
the catalytic material
A slurry comprising at least is prepared by mixing the re20176100 prh 11-12-2017 suiting catalytic material, for example with a binder, an acid and water. The slurry is arranged by washcoating onto a metal or ceramic substrate, and the washcoated substrate is thermally treated, e.g. by means 25 of drying, calcination and treatment by reduction.
Then a thin layer of Ni/NiAl2O4 can be formed onto the substrate. Preferably, Ni content of the Ni/NiAl2O4 spinel washcoat catalyst is 10 - 16 wt%.
The hydrogen (5) may be recirculated and fed 30 back to the thermochemical treatment, e.g. to the Fischer-Tropsch (FT) unit or to the bio-oil refining unit, to adjust H2/CO ratio or to improve hydrotreatment of pyrolysis oils.
20176100 prh 11-12-2017
Example 2
The aqueous-phase reforming (APR) was studied with different catalysts in a laboratory scale process. The main problems of the APR were mass transfer 5 limitations, and the low activity and stability of the catalysts. Both external and internal mass transfers were limited in a 3-phase system of the APR, with solid catalyst, liquid feedstock and gaseous products. This limitation negatively affected the conversion of 10 reactants and the selectivity towards desired products. Further, catalysts with low activity, such as typical, previous known Ni-based and Ce-promoted catalysts, decreased the conversion and selectivity. Platinum-based catalysts commonly exhibit good performance 15 in terms of activity. However, the noble metal-based catalysts are expensive and economically inefficient in large scales. Furthermore, low stability results in catalyst deactivation by sintering or leaching of the active metal due to, for example, the nature of the 20 feedstock or the hydrothermal, high pressure operating conditions. APR feedstocks are frequently a highly diluted mixture of organic compounds, which exact composition is frequently unknown. Therefore, to design an active, selective and stable catalyst to convert such 25 mixture constitutes a challenging task.
The different catalysts were studied in the APR process in which the feedstock comprised methanol. Surprisingly, Ni/NiAl2O4 spinel washcoat catalyst was found to overcome these problems. The mass transfer 30 limitations can be decreased by means of the inexpensive and durable Ni/NiAl2O4 spinel washcoat catalyst which actively and selectively converts the feedstock into targeted products in the operating conditions of the APR process.
Example 3
In this example, a side water fraction formed from lignocellulosic biomass in a Fischer-Tropsch reactor was treated with the catalyst in the aqueousphase reforming (APR) reactor according to the process of Fig. 1. The results are presented in Fig. 2.
The aqueous-phase reforming (APR) was carried out at about 230 °C under pressure of about 32 bar. The feedstock of the APR was an aqueous solution, formed from the side water fraction, with 5 wt% organic compounds, especially MeOH. The treatment was carried out with the Ni/NiAl2O4 spinel washcoat catalyst in the aqueous-phase reforming (APR) reactor. Further, the treatment was carried out with two comparative catalysts, NiAl-catalyst and NiCeAl-catalyst, in the aqueous-phase reforming (APR) reactor. The Ni/NiAl2O4 spinel washcoat catalyst comprised about 10 - 13 wt% Ni. NiAl-catalyst and NiCeAl-catalyst comprised about 10 - 13 wt% Ni on /-A12O3 support. Further, NiCeAlcatalyst was Ce-promoted.
The results are presented in Fig. 2. Y (%) means yield. CtG is calculated as total mol of carboncontaining gaseous products divided by the mol of carbon-containing compounds in the feeding solution.
It was observed surprisingly that the Ni/NiAl2O4 spinel washcoat catalyst was more highly active in the aqueous phase reforming (APR) when compared to the comparative catalysts. The performance of the Ni/NiAl2O4 spinel washcoat catalyst was remarkably superior compared to nickel-based catalysts. High conversion rates and hydrogen selectivity could be obtained when the aqueous-phase reforming was catalyzed with the Ni/NiAl2O4 spinel washcoat catalyst. The improvement derives from the high activity of the cata lyst and the reduction of the internal mass transfer limitations in the thin layer of the washcoat.
Example 4
In this example, the Ni/NiAl2O4 spinel washcoat catalyst with 13 wt% Ni content was prepared. This catalyst was used in the tests of Example 3.
Ni-metal precursor such as nickel nitrate was impregnated by means of an incipient wetness impregnation into a boehmite carrier material in a powder form in order to form a catalytic material. The catalytic material in a powder form was dried by means of a vacuum drying and calcinated at 500 °C to convert nickel nitrate/boehmite into nickel oxide/boehmite. After that a slurry composition comprising 44.4 wt% catalytic material, 2.01 wt% Disperal 10 solution, 1.05 wt% HNO3 and 52.54 wt% ion-exchanged water was prepared and stirred by means of a magnetic stirring at 700 rpm for 24 hours. A metal substrate was washcoated with the slurry. The substrate was pre-treated by an acetone/isopropanol wash and water rinsing, and the substrate was calcinated at 900 °C for 6 hours before the washcoating. The washcoated substrate was dried by a slow drying with hot air flow and by a fast drying at 500 °C for 5 min. Further, calcination at 800 °C for 2 hours was made. After that, catalyst reduction was made at 400 °C in which H2:N2 is about 1. Then the thin layer of Ni/NiAl2O4 spinel washcoat catalyst had been prepared on the substrate. It was observed that the strong washcoat can be provided on the metal surface of the substrate.
The devices and equipments of the aqueousphase reforming process used in these examples are known per se in the art, and therefore they are not described in any more detail in this context.
The method, apparatus and catalysts are suitable in different embodiments for treating different kinds of water fractions and streams.
The invention is not limited merely to the examples referred to above; instead many variations are possible within the scope of the inventive idea defined by the claims.

Claims (16)

1. A method for treating a side water fraction (1) which comprises at least one undesired compound and which is formed in a thermochemical treatment of biomass, characterized in that
- the side water fraction (1) comprising at least one undesired organic compound is treated by means of a reforming treatment (2) in order to convert the organic compound into at least hydrogen (5) and optionally also other compounds (6) selected from the group comprising organic compounds, hydrocarbons, carbondioxide, carbonmonoxide and their combinations, and
- the reforming treatment (2) is catalyzed by Ni/NiAl2O4 catalyst (3) .
2. The method according to claim 1, characterized in that the Ni/NiAl2O4 catalyst (3) is Ni/NiAl2O4 washcoat catalyst.
3. The method according to claim 1 or 2, characterized in that the Ni/NiAl2O4 catalyst (3) is Ni/NiAl2O4 spinel washcoat catalyst.
4. The method according to any one of claims 1 to 3, characterized in that the Ni/NiAl2O4 catalyst (3) is formed by arranging Ni/NiAl2O4 as a thin washcoat layer onto a substrate.
5. The method according to any one of claims 1 to 4, characterized in that Ni content of the Ni/NiAl2O4 catalyst is 8 - 15 wt%.
6. The method according to any one of claims 1 to 4, characterized in that the Ni/NiAl2O4 catalyst (3) is prepared such that Ni-precursors are impregnated into a boehmite carrier material to form a catalytic material, the catalytic material is dried and calcinated, and a slurry comprising at least the catalytic material is prepared and stirred, and the substrate is washcoated with the slurry, and the washcoated substrate is thermally treated.
7. The method according to any one of claims 1 to 5, characterized in that the Ni/NiAl2O4 catalyst (3) is prepared such that Ni-precursors are impregnated by means of an incipient wetness impregnation into a boehmite carrier material to form a catalytic material, the catalytic material is dried and calcinated, and a slurry comprising at least the catalytic material is prepared and stirred, and the substrate is washcoated with the slurry, and the washcoated substrate is dried, calcinated and treated by reduction.
8. The method according to any one of claims 1 to 7, characterized in that the reforming treatment (2) is an aqueous-phase reforming (APR).
9. The method according to any one of claims 1 to 8, characterized in that the aqueousphase reforming (APR) is carried out at temperature of 200 - 250 °C and under pressure of 30 - 34 bar.
10. The method according to any one of claims 1 to 9, characterized in that the biomass is a lignocellulosic based biomass.
11. The method according to any one of claims 1 to 10, characterized in that the biomass has been treated by means of at least one process step which is selected from the group comprising a gasification, Fischer-Tropsch (FT) reaction of syngas, pyrolysis, bio-oil refining and their combinations.
12. The method according to any one of claims 1 to 11, characterized in that the side water fraction (1) comprises 1 - 40 % by volume organic compounds .
13. The method according to any one of claims 1 to 12, characterized in that the hydrogen (5) may be recirculated to the thermochemical treat
20176100 prh 11-12-2017 ment to adjust H2/CO ratio or to improve hydrotreatment .
14. An apparatus for treating a side water fraction (1) which comprises at least one undesired compound and which is formed in a thermochemical treatment of biomass, characterized in that the apparatus comprises
- at least one reforming treatment device (12) in which the side water fraction (1) comprising at least one undesired organic compound is treated in order to convert the organic compound into at least hydrogen (5) and optionally also other compounds (6) selected from the group comprising organic compounds, hydrocarbons, carbondioxide, carbonmonoxide and their combinations, and
- Ni/NiAl2O4 catalyst (3) which is arranged inside the reforming treatment device (12) for catalyzing the reforming treatment (2).
15. The apparatus according to claim 14, characterized in that the reforming treatment device (12) is an aqueous-phase reforming (APR) reactor .
16. A use of the method according to any one of claims 1 to 13, characterized in that the method is used in the aqueous-phase reforming, in the production of biofuels, in the treatment of the side water fraction after Fischer-Tropsch (FT) reaction, in the treatment of the side water fraction after bio-oil refining, in the treatment of the side water fraction after pyrolysis and/or its post-process, in the treatment of the water fraction comprising at least organic compound, or their combinations.
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