Classifications

• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
  • B01D15/08—Selective adsorption, e.g. chromatography
  • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
  • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction, e.g. ion-exchange, ion-pair, ion-suppression or ion-exclusion
  • B01D15/361—Ion-exchange
• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/26—Synthetic macromolecular compounds
  • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/26—Synthetic macromolecular compounds
  • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
  • B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
  • B01J20/28042—Shaped bodies; Monolithic structures
  • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
  • B01J20/28052—Several layers of identical or different sorbents stacked in a housing, e.g. in a column
• • 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
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/34—Regenerating or reactivating
  • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
  • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
• • 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
  • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
  • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
  • B01J39/16—Organic material
  • B01J39/18—Macromolecular compounds
• • 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
  • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
  • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
  • B01J41/12—Macromolecular compounds
• • 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
  • B01J47/00—Ion-exchange processes in general; Apparatus therefor
  • B01J47/02—Column or bed processes
  • B01J47/026—Column or bed processes using columns or beds of different ion exchange materials in series
• • 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
  • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
• • 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
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
  • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
• • 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
  • C02F2101/10—Inorganic compounds
  • C02F2101/101—Sulfur compounds
• • 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
  • C02F2101/10—Inorganic compounds
  • C02F2101/105—Phosphorus compounds
• • 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
  • C02F2101/10—Inorganic compounds
  • C02F2101/16—Nitrogen compounds, e.g. ammonia
  • C02F2101/163—Nitrates
• • 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
  • C02F2101/10—Inorganic compounds
  • C02F2101/16—Nitrogen compounds, e.g. ammonia
  • C02F2101/166—Nitrites
• • 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
  • C02F2101/10—Inorganic compounds
  • C02F2101/20—Heavy metals or heavy metal compounds
  • C02F2101/206—Manganese or manganese compounds
• • 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
  • C02F2101/10—Inorganic compounds
  • C02F2101/20—Heavy metals or heavy metal compounds
  • C02F2101/22—Chromium or chromium compounds, e.g. chromates
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2303/00—Specific treatment goals
  • C02F2303/16—Regeneration of sorbents, filters
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2303/00—Specific treatment goals
  • C02F2303/20—Prevention of biofouling

Definitions

• the present invention relates to collection of ions and molecules from fluid using a hybrid scavenger system containing at least one laser sintered porous body with a chemical functionality and granular active material, typically granular ion exchange material.
• Said system has selective properties for collecting chosen ions or molecules from a fluid flow and releasing the collected ions or molecules upon specific elution treatment.
• Ion exchange resins and their macroporous, granular form have been industry standard for decades and are described for example in documents US2366007 and US4246386A.
• the equipment for traditional operation and use of granular ion exchange material is described for example in US2810692.
• US 2016310871 Al relates to a scavenging unit having two porous partitions and between them a scavenging chamber filled with a scavenging medium for removing metal ions from a liquid.
• the porous partitions are not laser sintered or tailored for scavenging metal ions and have smaller particle sizes than a particle size of the scavenging medium.
• the present invention is based on the concept of using a novel equipment, a hybrid scavenger system, for selective recovery or removal of dissolved ions and molecules from fluid.
• the system combines the most advantageous features of laser sintered scavengers or porous bodies and granular ion exchange and/or adsorbent materials and optionally powdered ion exchange material into an equipment that is performing better compared to the sum of its components.
• a hybrid scavenger system for scavenging of ions and molecules, in particular metal ions and complexes and non-metal anions and cations, from fluid, the hybrid scavenger system comprising a section of granular active material with adsorbent properties, with functional groups providing ion exchange properties or both, and at least one laser sintered porous body comprising functional groups, wherein said laser sintered body is arranged upstream or downstream or in both positions in relation to the section of granular active material and flow of the fluid.
• a method for scavenging of ions and molecules from fluid using the hybrid scavenger system of the invention comprises the steps of: feeding the fluid through the system until the designed scavenging capacity is reached, and eluting scavenged ions or molecules using a separate elution solution, which simultaneously regenerates the system enabling immediate reuse of the system.
• Embodiments of the invention comprise hybrid scavenger systems, which comprise or consist essentially of: (i) a section of granular active material and a laser sintered porous body arranged upstream of the section of granular active material; or (ii) a section of granular active material and a laser sintered porous body arranged downstream of the section of granular active material; or (iii) a section of granular active material and laser sintered porous bodies arranged both upstream and downstream in relation to the granular active material and flow of the fluid.
• the hybrid scavenger system has the ability to induce higher selectivity towards desired ions or molecules while maintaining high capacity and required physical properties.
• the scavenger system of the invention provides faster kinetics for recovery and scavenging of ions and molecules from feed fluid, including unparalleled ion exchange rate and thus utilization of capacity, optionally with further improvement compared to the use of powdered ion exchange material (lower pressure drop, higher capacity).
• high scavenging capacity induced by the hybrid arrangement (defined as comprising a section of granular active material with adsorbent properties, with functional groups providing ion exchange properties, or both, and at least one laser sintered porous body comprising functional groups, arranged upstream or downstream or in both positions in relation to the section of granular active material and flow of the fluid) enables longer elution intervals compared to scavenger systems consisting of a single laser sintered porous body.
• high capacity will enable smaller equipment size and longer operation cycles, which will reduce the cost and improve the lifetime of the system.
• the hybrid scavenger system efficiently traps solid particles into the structure, allowing good scavenging performance to continue without notable increase in backpressure.
• the hybrid scavenger system comprises a scavenging enhancing internal structure that allows increasing the metal scavenging performance of the laser sintered scavenger while allowing solid particles to efficiently pass through the scavenger.
• FIGURES 1A and IB illustrate an example of the overall structure of a hybrid 4D scavenger with upstream laser sintered porous body, designed for flow and suspended solids control, middle section with granular ion exchange material, designed for additional scavenging capacity, and downstream laser sintered porous body, designed for flow and residence/hydraulic retention time control in accordance with at least some embodiments of the present invention;
• FIGURE 2 presents an example of the internal structure of the suspended solids controlling upstream laser sintered porous body with alternately plugged channels. Dark grey bars represent the upstream flow channels, light grey bars represent the downstream flow channels while semi-transparent area between and around the channels represents the sintered porous material enabling horizontal fluid flow through channel walls (horizontal wall flow).
• FIGURE 3A illustrates the top view of a porous body with laser sintering controlled flow channels and FIGURE 3B shows the split view of a CAD designed zig-zag flow channels of the porous body.
• the terms “selective laser sintering” and “laser sintering” define manufacturing technique that uses a laser as the power and heat source to sinter powdered material, aiming the laser automatically at points in space defined by a 3D model, binding the material together to create a solid structure.
• the above-disclosed manufacturing technique i.e. selective laser sintering or laser sintering, is used to create porous solid structures comprising functional groups.
• hybrid scavenger As used herein, the terms such as “hybrid scavenger”, “hybrid 4D scavenger” and “hybrid scavenger system” refer to the scavenging system according to the present invention, which comprises at least two different scavenging materials.
• upstream and downstream define the position of a component in relation to each other and to the flow of the fluid stream.
• the component that is first interacting with the fluid is considered to be located upstream, compared to any following component in the system.
• any component after the said first component is considered to be located downstream in relation to the first component.
• the hybrid scavenger system efficiently removes metal ions and metal complexes as well as non-metal anions and cations from various fluids.
• the hybrid scavenger system may also remove any suspended material from said fluids.
• the “active material” or “granular active material” is selected from ion exchange materials and adsorbents.
• the active material may thus comprise functional groups with ion exchange properties, adsorber properties or both.
• the granular active material comprises adsorbent properties, functional groups providing ion exchange properties or both.
• Ion exchange materials typically belong to group of strong cation exchange resins (SAC), weak cation exchange resins (WAC), strong base anion exchange (SBA), weak base anion exchange (WBA) or chelating exchange resins. More specifically, the functional groups in the active materials may belong to group of carboxylates, primary amine or ammonium, secondary amine or ammonium, tertiary amine or ammonium, sulphates, sulfonic acids, phosphonic acids, diethanolamines, thioureas, thiols, thiouronium, ethylenediaminetetraacetic acid or any combination of these.
• SAC strong cation exchange resins
• WAC weak cation exchange resins
• SBA strong base anion exchange
• WBA weak base anion exchange
• chelating exchange resins More specifically, the functional groups in the active materials may belong to group of carboxylates, primary amine or ammonium, secondary amine or ammonium, tertiary amine
• Adsorbents include but are not limited to activated carbon, graphene, inorganic metal oxides, inorganic metal hydroxides, zeolites, aluminas, chitosan, lignin and other mostly carbon containing biobased materials or any combinations of these.
• Metal ions typically include but are not limited to cations and anions containing transition metals (groups 3-12 in periodic table), lanthanides and actinides.
• alkaline and alkaline earth metal cations from groups 1 and 2 may be targeted.
• other metal and metalloid ions from groups 13-16 may be targeted.
• halogen ions from group 17 may be targeted.
• cations or anions of toxic or environmentally harmful metals or metalloids vanadium, chromium, nickel, copper, zinc, cadmium, arsenic, antimony, mercury and/or lead may be targeted.
• cations or anions of typical battery metals such lithium, cobalt, nickel, zinc, copper or manganese may be targeted.
• cations or anions of precious metals ruthenium, rhodium, palladium, silver, osmium, iridium, platinum or gold may be targeted.
• cations or anions of rare earth elements may be targeted.
• metal complexes of the above-mentioned metals may also be scavenged by the hybrid scavenger system of the invention.
• Target non-metal anions include but are not limited- to nitrate, nitrite, sulfate, hydrogen sulfate, sulfite, hydrogen sulfite, carbonate, hydrogen carbonate, hypochlorite, cyanide, perchlorate, phosphate, phosphite, hydroxide, thiosulfate, acetate, formate and oxalate.
• targeted non-metal anions are nitrate, nitrite, sulfate, sulfite, phosphate and/or phosphite.
• a hybrid scavenger system provides a high selectivity towards desired ions and molecules while maintaining high capacity and required physical properties for scavenging of metal ions and complexes and non-metal anions and cations from fluid.
• the hybrid scavenger system of the invention comprises a section of granular active material with adsorbent properties, with functional groups providing ion exchange properties, or both, and at least one laser sintered porous body comprising functional groups, arranged upstream or downstream or in both positions in relation to the section of granular active material and flow of the fluid.
• the structure of the hybrid scavenger system comprises or consists of three different components or sections (Fig. 1):
• An upstream laser sintered scavenger or porous body comprising polymer powder and active material or consisting solely of the active material
• a middle section comprising granular active material, located between the laser sintered scavengers
• a downstream laser sintered scavenger or porous body comprising polymer powder and active material or consisting solely of the active material
• the upstream or downstream or both of the laser sintered scavengers or porous bodies comprise of at least 30 % of active material, preferably of at least 50 % of active material, more preferably of at least 70 % of active material, defined as the weight percentage of the active material compared to total weight of the material.
• powdered material in particular sinterable polymer powder, typically nylon or polyamide, is sintered to create the structure of the porous body.
• polymer powder may be mixed with the active material, typically an ion exchange resin, for example in a 50:50 ratio, before laser sintering.
• the proportion of the active material in the laser sintered scavenger may be adjusted to at least 30 % of active material, preferably at least 50 % of active material, more preferably at least 70 % of active material, by weight of the mixture of the polymer powder and the active material.
• the structure of the hybrid scavenger system thus comprises or consists of three different components or sections:
• An upstream laser sintered scavenger or porous body comprising polymer powder and at least 30 % of active material, preferably at least 50 % of active material, more preferably at least 70 % of active material, by weight of the laser sintered scavenger
• a middle section comprising granular active material, located between the laser sintered scavengers
• a downstream laser sintered scavenger or porous body comprising polymer powder and at least 30 % of active material, preferably at least 50 % of active material, more preferably at least 70 % of active material, by weight of the laser sintered scavenger
• the hybrid scavenger system consists of an upstream laser sintered porous body or scavenger and a section of granular active material.
• the hybrid scavenger system consists of a section of granular active material and a downstream laser sintered porous body or scavenger.
• the structure of the hybrid scavenger system consists of upstream and downstream laser sintered scavengers or porous bodies, optionally separated by an empty space, wherein said upstream and downstream laser sintered scavengers are different from each other.
• the volumetric ratio between the laser sintered scavenger(s) and the granular active material is between 1 :500 and 1 :0.1, preferably between 1 :50 and 1 :0.5 or most preferably between 1 :20 and 1 :1, depending on the application.
• the hybrid scavenger system comprises an empty space between the upstream laser sintered scavenger and the section of granular active material.
• said empty space is typically 0-200 % of the height of the granular active material section, preferably 20-150 % and most preferably 50-100 %, depending on the application.
• the granular scavenger may be separated from the laser sintered scavenger(s) by a semi-permeable membrane, fabric, foam, or corresponding porous material to prevent granular material intrusion to the flow channels of the up- or downstream laser sintered scavenger.
• the hybrid scavenger system is arranged in a column or columnshaped reactor.
• other reactor forms in addition to column-shaped reactors may be applicable, such as containers, barrels, square-shaped reactors, cylinders, tube reactors with horizontal flow, scrubber type reactors or turbine type reactors, reactors with horizontal flow, scrubber type reactors or turbine type reactors.
• the laser sintered porous body of the hybrid scavenger system are manufactured so that the width and height ratio, defined by dividing the width of the sintered porous body with the height of the sintered porous body, of the system is typically between 0.01 to 1 , preferably between 0.05 to 1 and most preferably between 0.1 to 1.
• the laser sintered porous body of the hybrid scavenger system are manufactured so that the width and height ratio, defined by dividing the width of the sintered porous body with the height of the sintered porous body, of the system is typically between 100 to 1, preferably between 25 to 1 and most preferably between 10 to 1.
• Preferred porosity and bulk density of the laser sintered scavengers are used to control the chemical performance and flow performance of the laser sintered scavenger, with these parameters not connected to the particle size of granular material in preferred embodiments.
• the sinterable polymers typically comprise any one or several of polyamide, polypropylene, polyurethane, polystyrene, polylactic acid, polyetheretherketone, polyethylene terephthalate, polycarbonate, polyaryletherketone, polyetherimide and other thermoplastic polymers.
• the sinterable polymer itself can be the active component providing scavenging functionality similar to that provided by separate active materials such as adsorbent or ion exchange resin.
• Manufacturing method of the laser sintered scavenger enables manufacturing different internal structures, which can either allow solid particles to efficiently be trapped into the structure, allowing good scavenging performance to continue without notable increase in backpressure, or scavenging enhancing internal structure that allows increasing the metal scavenging performance of the laser sintered scavenger while allowing solid particles to efficiently pass through the scavenger.
• the laser sintered scavenger section(s) have parallel, alternately plugged channels, manufactured by first designing the alternately plugged channels into a CAD model used for controlling the laser sintering during manufacturing, enabling horizontal fluid flow through channel walls (wall flow), allowing greater surface area for fluid to pass through the scavenger while providing space for solid particles to be trapped without notable increase in the pressure drop (Fig. 2). It should be noted that the alternatively plugged channels differ from CAD designed flow channels that go through the entire body of laser sintered scavenger.
• the suspended solid particles that are efficiently passed through the scavenger system with CAD designed alternatively plugged channels typically possess particle size of less than 30 pm.
• the laser sintered porous body has scavenging enhancing internal structure, manufactured by controlling the laser sintering process by changing the hatching distance parameter, defined as the distance between adjacent laser passes during sintering process, from typical 0.25-0.35 mm to 0.5-1.5 mm, preferably between 0.6-1.4 mm and most preferably between 0.7-1 mm, allowing greater surface area for fluid and solid particles to pass through the scavenger and thus leading to lower pressure drop and better scavenging performance (Fig 3A, Example 2).
• the hatching distance parameter defined as the distance between adjacent laser passes during sintering process
• the suspended solid particles that are efficiently passed through the scavenger system with hatching controlled structure typically possess particle size of less than 100 pm.
• the at least one laser sintered porous body may have scavenging enhancing internal structure, CAD designed flow channels, allowing greater surface area for fluid and solid particles to pass through the scavenger and thus leading to lower pressure drop for the whole assembly (Fig. 3B).
• the scavenging enhancing internal structure comprising flow channels is manufactured by designing the flow channels into the CAD model used for controlling the laser sintering during manufacture.
• the upstream or downstream scavenger or both are composed of material having a particle size ranging from 10 to 400 pm, defined by laser diffraction methods using for example Malvern Mastersizer 3000 particle size analyzer according to ISO 13320:2020.
• both the polymer powder material and the optional active material included in the upstream and/or downstream scavenger have a particle size within the above mentioned range.
• the granular active material section of the scavenger systems contains material having a particle size ranging from 0.1 to 3 mm, defined by laser diffraction methods using for example Malvern Mastersizer 3000 particle size analyzer according to ISO 13320:2020.
• the upstream laser sintered porous body may have flow controlling design and/or parallel, alternately plugged channels enabling horizontal fluid flow through channel walls (horizontal wall flow), for suspended solids resistance and faster scavenging kinetics.
• the upstream laser sintered scavenger section has a honeycomb structure, i.e. parallel, alternately plugged channels with porous walls enabling horizontal wall flow and capacity for trapping undissolved particulate matter, thus lowering the pressured drop induced by accumulating solids (Fig. 2).
• the structure resembles diesel particulate filters structure with alternately plugged channels.
• the upstream laser sintered porous body with a honeycomb structure with horizontal wall flow channels effectively decreases accumulations of solid particles and thus reduces the pressure drop of the hybrid scavenger system. Accumulation of solid particles is a known problem also in ion exchange, where solid impurities may have detrimental effects for the ion exchange performance but also for the durability of the active material.
• Inorganic, organic or oil fouling may also reduce the lifetime and scavenging performance of the active material by attaching to the surfaces of the material and therefore blocking the chemically active sites of the material.
• the upstream laser sintered scavenger operates as protection against organic or inorganic fouling, thus improving the lifetime and scavenging performance of all downstream scavenging components.
• the upstream laser sintered scavenger is prepared from hydrophilic material and operates as protection against fouling by polar or moderately polar inorganic or organic impurities, thus improving the lifetime and scavenging performance of all downstream scavenging components.
• the upstream laser sintered scavenger is prepared from hydrophobic material and operates as protection against fouling by oil or other non-polar impurities, thus improving the lifetime and scavenging performance of all downstream scavenging components.
• the hydrophobicity/hydrophilicity of the material of the laser sintered scavenger may thus be adjusted according to the fluid to be treated, by selecting suitable polymer powder and active material for laser sintering.
• the downstream laser sintered porous body enables the flow and pressure control which allows the optimization of feed residence/hydraulic retention time inside the hybrid scavenger system.
• the downstream laser sintered scavenger also provides accurate control over the reaction kinetics and allows for smaller size of the whole unit due to the faster reaction kinetics.
• the upstream (top) laser sintered porous body will act as pressure/flow control system to ensure optimal residence/hydraulic retention time for the regenerant. This allows more efficient scavenging or regeneration, which in turn realizes in notably lower chemical consumption.
• the structure of the above described hybrid scavenger system allows unique flow properties within the system.
• Material density inside the hybrid 4D scavenger will induce highly efficient mixing and fluid movement at the microscopic level, which will improve the film diffusion and thus the kinetics of scavenging reaction.
• Local pressure differences between the fixed particles inside the laser sintered porous body will increase the film diffusion increasing the rate of scavenging reaction.
• the present invention also relates to a method for scavenging of ions and molecules from fluid using the hybrid scavenger system according to the invention.
• the fluid is fed through the hybrid scavenger system until the designed scavenging capacity is reached, scavenged ions and molecules are eluted using a separate elution solution, which preferably simultaneously regenerates the system enabling immediate reuse of the system.
• the hybrid scavenger system is conditioned by pumping conditioning solution through the system prior to a next scavenging cycle.
• the hybrid scavenger system is regenerated by pumping regeneration solution through the system after the elution cycle.
• the space velocity defined as the quotient of the entering volumetric flow rate of the fluid divided by the volume of the hybrid scavenger system which indicates how many scavenger volumes of feed fluid can be treated in a unit time, is between 10 and 10 000 1/h, preferably between 30 and 5000 1/h and most preferably between 50 and 2000 1/h.
• the elution, conditioning and regeneration solution are independently selected from sulphuric acid, nitric acid, hydrochloric acid, formic acid, ascorbic acid, acetic acid, sodium hydroxide, potassium hydroxide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, urea and its derivatives, thiourea and its derivatives, ammonia, ammonium chloride and ammonium hydroxide.
• the elution cycle is performed by feeding the elution solution in opposite direction to the scavenging flow direction, i.e. in opposite direction to the flow of the fluid.
• the regeneration cycle is performed by feeding the regeneration solution in opposite direction to the scavenging flow direction.
• the elution and regeneration cycles are performed by feeding the corresponding solutions in the same direction as the scavenging flow direction.
• the temperature of the feeding fluid is typically between 20 and 90 °C.
• the regeneration cycle is performed after 5 - 50 operation cycles, preferably after 5 - 30 operation cycles and most preferably after 5 - 10 operation cycles.
• hybrid structure of the above-described hybrid scavenger system provides several process design benefits, including but not limited to low chemical consumption due to fast reaction kinetics and compact scavenger size, which allows even smaller fluid volumes to be treated effectively.
• modular structure allows easy maintenance of the system as well as combining different material easily in the same system, which is an advantage compared to using the different scavenging materials separately.
• the hybrid scavenger system of the present invention provides in particular the following advantages:
• the hybrid scavenger system may be operated even without external power supply.
• the fluid can be passed through the hybrid scavenger system by gravitational force or if needed or desired, by pumping.
• Example 1 Comparative metal scavenging from water using different scavenger types (granular ion exchange material, laser sintered scavenger and hybrid 4D Scavenger).
• the exceptional scavenging performance of the hybrid 4D scavenger of the invention is obvious.
• the granular active material displays lowest selectivity towards heavy metals whereas the laser sintered scavenger displays the most selective recovery (i.e. low Ca recovery with high Cd, Zn and Cu recovery).
• the hybrid 4D Scavenger demonstrates notably increased heavy metal recovery when compared to granular ion exchange material.
• Example 2 The effect of the internal structure to the flow properties
• the porous body with flow channels prepared using control of the sintering process showed lowest pressure increase after the treatment.
• the body with CAD designed structure for increased solids resistance displayed 4-5 times higher pressure drop by the solid material accumulation to collection channels as designed.
• the body without any designed flow channels displayed over 10-fold increase in the pressure drop compared to body with laser sintering controlled internal structure.
• the different scavengers for nutrient recovery were tested by pumping liquid containing 63 mg L 1 nitrate (NCh ), 53 mg L 1 phosphate (PO4 2 ) and 64 mg L 1 sulfate (SO4 2 ) at 0.25 dm 3 min 1 through the scavenger units (volume of 1.0 dm 3 ) and by measuring the recovery efficiency of nutrients, defined as percentage of reduction in effluent concentration after passing through the scavenger compared to the feed solution. The results are shown in Table 3.
• Hybrid arrangement improved the nutrient scavenging properties notable compared to both granular resin and scavenger comprising of only laser sintered material. [0099] Example 4.
• the different scavengers were compared by pumping liquid containing 15 mg L 1 of Ca as well as 5 mg L 1 of Cd, Cu, Ni, Pb and Zn at 0.3 dm 3 min 1 through the scavenger units (volume of 0.03 dm 3 ) and by measuring the recovery efficiency of said metals defined as percentage of reduction in metal concentration in the feed solution after passing through the scavenger. Missing upstream sintered porous body induced poor flow distribution and hence lower scavenging performance but also worse suspended solids resistance. Missing granular material caused notable increase in the backpressure and lower overall capacity while missing downstream sintered porous body induced too high flowrate and thus lower scavenging performance.
• At least some embodiments of the present invention find industrial application in various water intensive industries, such as municipal water treatment, process, mining and recycling industries. Quick adaptation of the technology can be expected because of the improved performance and lower operating and capital costs compared to currently available metal scavenging solutions. [00107] The invention can be further understood with reference to the following embodiments:
• a hybrid scavenger system for scavenging of ions and molecules from fluid comprising:
• the laser sintered porous body/bodies is/are arranged upstream or downstream or in both positions in relation to the section of granular active material and flow of the fluid.
• the functional groups in the laser sintered porous body and in the section of granular active material are selected from the group consisting of carboxylates, primary amine or ammonium, secondary amine or ammonium, tertiary amine or ammonium, sulphates, sulfonic acids, phosphonic acids, diethanolamines, thioureas, thiols, thiouronium, ethylenediaminetetraacetic acid and any combinations of these.
• hybrid scavenger system according to any one of the preceding embodiments, wherein the system comprises an upstream arranged laser sintered porous body, which has parallel, alternately plugged channels enabling horizontal fluid flow through channel walls (wall flow) and trapping undissolved particulate matter.
• the at least one laser sintered porous body has scavenging enhancing internal structure, wherein the scavenging enhancing internal structure is manufactured by using hatch distance parameters between 0.5- 1.5 mm or comprises CAD designed flow channels.
• the granular active material has a particle size ranging from 0.01 to 3 mm, defined by laser diffraction methods according to ISO 13320:2020X.
• hybrid scavenger system which comprises a laser sintered porous body arranged upstream in relation to the granular active material, a section of granular active material, and a laser sintered porous body arranged downstream in relation to the granular active material.
• elution, regeneration or conditioning solutions are selected independently from sulphuric acid, nitric acid, hydrochloric acid, formic acid, ascorbic acid, acetic acid, sodium hydroxide, potassium hydroxide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, urea and its derivatives, thiourea and its derivatives, ammonia, ammonium chloride and ammonium hydroxide and any combination of these.

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• 2022
  • 2022-12-29 EP EP22835861.0A patent/EP4457019A1/de active Pending
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