EP4380725A1

EP4380725A1 - Removal of viruses from water by filtration

Info

Publication number: EP4380725A1
Application number: EP22761979.8A
Authority: EP
Inventors: Martin Welter; Christian Meyer; Kristian LUNGFIEL
Original assignee: Instraction GmbH
Current assignee: Instraction GmbH
Priority date: 2021-08-05
Filing date: 2022-08-04
Publication date: 2024-06-12
Also published as: ZA202401842B; DE102021120424A1; WO2023012251A1; JP2024532725A; AU2022321810A1; CA3226266A1; KR20240034247A; CN117916013A

Abstract

The present invention relates to a method for producing antiviral particles, and to the particles as such that can be produced according to the method of the invention. The particles according to the invention are used to remove viruses from water, but also to remove biological contaminants from water and to bind metal-containing ions from solutions. The present invention further relates to a filter cartridge which contains the particles according to the invention.

Description

Removal of viruses from water by filtration

The present invention relates to a method for producing antiviral particles and the particles themselves, which can be produced using the method according to the invention. The ones according to the invention

Particles are used to remove viruses from water, but also to

Removal of biological contaminants from water and for

Binding of metal-containing ions from solutions is used. The present invention also relates to a filter cartridge containing particles according to the invention.

Biological contamination of drinking water is a well-known problem that is particularly critical in warmer regions of the world. Even after natural disasters are wells with bacteria, germs and also

virus contaminated. Heavy metals in drinking water are still a problem.

Viruses in particular are difficult to physically remove due to their small size. Alternatives are chlorination,

ozonation, UV irradiation, membrane filtration and the like.

Some of these processes are very energy-intensive (high pressure) and expensive, require the use of chemicals or reduce them

Water quality in other respects, for example due to a significant chlorine taste. If necessary, the water must be boiled or filtered through activated carbon to remove the chlorine. Furthermore, some of the techniques e.g. B. the

Membrane filtration only gives low yields, since a large part of the water is lost during the process.

State-of-the-art water purification systems, such as softening systems, water dispensers with and without

Cleaning modules are always under suspicion of

contamination and must be carefully cleaned. Swimming pools that do not use chlorination of the water and biological ones

Using cleaning stages often struggle with virus and bacterial loads in the warmer season. In households with

This hot water tank must always be above a certain level

Temperature must be maintained to counter contamination with listeria. Also systems with closed water circuits also need disinfection procedures to obtain the

water quality, for example in industrial cooling

water cycles.

The removal of unwanted metal ions, in particular

Heavy metal ions from drinking water is also important in this context.

WO 2017/089523 and WO 2016/030021 disclose a sorbent for

Removal of metal ions and heavy metal ions from water and a manufacturing process for such a sorbent. However, the materials disclosed in these publications have only a slight biocidal effect and no antiviral effect whatsoever.

There was therefore a need for an improved sorbent which, in addition to biological contaminants and heavy metals, can also reliably remove viruses from drinking water.

The object was achieved by a method for producing antiviral particles comprising the steps:

(a) providing an aqueous suspension containing a

polyamine, a crosslinker and an inorganic one

Carrier material or an organic carrier material in

particle form at a temperature less than or equal to 10°C in a mixer for coating the inorganic

Carrier material or the organic carrier material with the polyamine;

(b) crosslinking the polyamine of the coated inorganic

Carrier material or the coated organic

carrier material and simultaneous removal of water,

(c) protonating the crosslinked polyamine to obtain antiviral particles.

Steps (a) and (b) can be repeated at least once. This can be important when a high concentration of amino groups is required, for example a concentration of more than 600 μmol/g. Surprisingly, it was found that, on the one hand, this process enables a less complex production method for the

Sorbent can be provided compared to the prior art. In addition, the sorbent thus prepared does not tend to

formation of biofilms and shows a very high biocidal effect against bacteria and germs and, due to the protonation, also a very high effectiveness against viruses. The increased effectiveness against viruses due to the protonation was surprising. The effect against bacteria and germs could also be increased.

According to the invention, the coating and the crosslinking preferably take place in a stirred reactor, for example a Lödige

Mixer. This has the advantage over networking in

Suspension, since crosslinking can be carried out easily in the pores of the already partially crosslinked polymer and in non-critical water. In this case, the temperature in step (b) is increased in contrast to the coating from step (a). A temperature of less than or equal to 10° C. is preferably selected in step (a). It comes in step (b) almost predominantly to a crosslinking in the

Pores of the preferably porous carrier material and at the same time the solvent water is removed during crosslinking, so that step (a) and consequently step (b) can be repeated in the same apparatus. Steps (a) and (b) can be repeated until the desired degree of coating and density of amino groups is achieved. Preference is given to coating only once. However, it is also possible to coat and crosslink at least twice, but it is also possible to coat and crosslink three times, four times or more. Most preferred is once.

Is preferred at the end of the coating and crosslinking, ie before

Step (c) Raise and hold the temperature to about 60°C for about 1 hour.

It is particularly preferred that the sorbent is post-crosslinked before step (c). This is preferably done with epichlorohydrin and

Diaminoethylene at a temperature of 80-90°C, preferably 85°C, by adding the reagents alternately. In step (c) there is a protonation of the amino groups of the

Polyamine at a pH <7, preferably <6, most preferably <

5.5. It is believed that the protonated amino groups with the

Virus envelope and the bacterial envelope come into contact and their

destroy the shell.

According to a further embodiment of the invention, the polyamine is used in the non-desalinated state. During the hydrolysis of the polyvinylformamide, which can be obtained by polymerization, with sodium hydroxide solution and the subsequent blunting with hydrochloric acid, common salt and

sodium formate. The polymer solution is desalinated by

Membrane filtration, where the polymer is retained while the salts permeate through the membrane layer. The membrane filtration is continued until the salinity has been determined according to

incineration residue corresponds to less than 1% of the weight (1% of the polymer content).

Before speaks of non- or partially desalinated polymer, after that of a desalinated polymer.

This saves another cleaning step. Although this may require an additional washing step after step a), the costs for the production of the coating polymer (e.g. PVA) can be drastically reduced by using a polymer that has not been desalinated. This makes the process more economical overall.

By the simultaneous addition of a crosslinking agent to a suspension of an organic polymer, preferably a polyamine, at low temperatures of less than or equal to 10 ° C at the

Coating (step (a)) forms directly in the pores of the

The carrier slowly forms a hydrogel and the polymer is directly immobilized. When using a non-desalinated polymer, the salts formed during hydrolysis can simply be washed out with water. In addition, the subsequent crosslinking in

Consequence of the pre-crosslinking during the coating, for example or preferably with epichlorohydrin and diaminoethylene, in aqueous

Suspension are carried out and must not be carried out in a fluidized bed, as has been the case in the prior art was. This leads to a considerable simplification of the method.

Carrying out the crosslinking in an aqueous suspension has

The use of epichlorohydrin also has the advantage that unreacted epichlorohydrin is simply hydrolyzed with the sodium hydroxide solution and thus rendered harmless or converted into harmless substances (glycerol).

Organic carrier material

The organic carrier material is preferably a polystyrene, a sulfonated polystyrene, a polymethacrylate or a strong or weak ion exchanger.

In another embodiment, the is organic

Carrier polymer a strong or a weak cation exchanger coated with the polymer only on its outer surface. As a strong cation exchanger, such organic

Polymers referred to, which have sulfonic acid groups. Weakness

Cation exchangers are polymers that have carboxylic acid groups.

So far it was only known that the so-called MetCap® particles can successfully remove bacteria from solutions

(DE102017007273.6), which are either based on silica gel or without

porters get by. Production and detection of the activity are in

DE102017007273.6 discloses. There the coating of

Described silica gel particles (as template) with non-desalinated polymer and subsequent dissolution of the inorganic support and its antibacterial activity.

For particles on an organic carrier, for example

Polystyrene based, no corresponding activity was previously known. Surprisingly, this activity could now be determined on the polystyrene-based resin produced by the new process. This observation is surprising because

Polystyrenes usually tend to form a pronounced biofilm and in no way remove viruses or bacteria. Furthermore, unlike the carriers used up to now, polystyrene is markedly lipophilic, and thus has completely different properties than the carriers used up to now.

A simplification of the manufacturing process using

Polystyrene-based resins is achieved by dispensing with the desalination of the polymer hydrolyzate and other process changes, in particular the addition and drying of the

Concern carrier polymers to the polymer solution.

Surprisingly, it is possible to produce MetCap® and BacCap® resins by immobilization on porous polystyrene particles without prior desalination of the polymer solution. This is all the more surprising as earlier studies found that the rate of deposition or immobilization of the polymer on the porous support was clearly dependent on the salt content of the polymer hydrolyzate.

Due to adjustments in the coating process (e.g.

Multiple coating, drying in the Lödige plowshare mixer,

Introduction of new washing strategies) the time-consuming and costly process step of desalination of the polymer hydrolyzate could be dispensed with without restricting the performance of the

having to accept products.

In summary, it can be said that the change in

Manufacturing process, in particular the abandonment of desalination by membrane filtration and the expansion to organic

Carrier materials brings decisive advantages.

The polymer content is now calculated by the approach at the

Polymerization determined. The coating and pre-crosslinking with

To the surprise of the authors, ethylene glycol diglycidyl ether in the Lödige vacuum paddle dryer works in the same way as with the

Polyvinylamine polymer solution that does not contain salts. The salts contained are then partially dissolved out during the preparation of the suspension for post-crosslinking. After the silica gel of

Once the carrier has been dissolved with the help of the sodium hydroxide solution, all salts (silicates, formates, chlorides, etc.) are rinsed out of the cross-linked, purely organic template material. The thus obtained

BacCap® T or MetCap® T material has the same Properties as the absorber resins made by the desalted PVA polymer process. This is the first

Improvement in the process, which comes as a surprise because the previous assumption, also supported by literature data, prevailed that the volume requirement of the highly concentrated salts in the

Polymer solution prevent effective and complete filling of the

Particles with polymer, simply because of its space requirements.

The second method involves coating commercial strong or weak ion exchangers with an antiviral as well as antibacterial PVA polymer shell.

Commercial ion exchangers, specifically those used here

Cation exchangers usually have acid groups that are covalently bonded to the polymer carrier (e.g. polystyrene, acrylates, etc.). The acid groups are carboxylic acids or carboxylates in the case of weak ion exchangers or sulfonic acids or sulfonates in the case of strong ion exchangers. In the softening of

Both types are used for drinking water.

To these ion exchangers with antiviral and antibacterial

Equip properties and at the same time their

not significantly reduce the softening capacity, only an outer coating of the particles is aimed at, without the acid

Groups in the pores of the particles, where the majority of the

Capacity-bearing acid groups is to modify.

This goal is achieved by using a corresponding

Polymer, due to its size and hydrodynamic

Radius cannot penetrate into the pores of the ion exchange particles. The pore sizes in commercial ion exchangers are in

Range from 20 nm to 100 nm. These pores are inaccessible to polymers with a size of 10,000 - 20,000 g/mol.

In this procedure, in a preferred embodiment, only the outer 2-25% of the particle, measured at the radius of the

particles, coated. Only the outer 2 are more preferred

10% of the particle measured by the radius of the particles coated. At the most preferably only the outer 2-5% of the particle measured by radius is coated.

In this way, the vast majority of the groups capable of ion exchange remain available for softening the water.

The non-desalinated polymer of the appropriate size can also be used for this, but this is not a mandatory requirement.

Coating with desalted polymer is also possible, as is the use of non-desalted polymer.

After hydrolysis of the amide groups, the polymer contains

Polyvinylformamide with caustic soda and subsequent blunting with hydrochloric acid approx. 15-25% by weight of salt in the form of sodium formate and

table salt. In the case of the non-desalinated polymer, the polymer content of the aqueous solution corresponds to 9-13% by weight.

In previous processes, the salts were removed by reverse osmosis, which was a laborious process, and the polymer used had a salt content of less than 2.5% by weight. The new process allows this time-consuming and expensive desalination step to be dispensed with. It is therefore preferred with the new method, the polymer partially desalinated with a

Salt content of 2.5-15 wt .-% use. More preferred is a partially desalted polymer having a salt fraction of 10-15

% by weight. It is most preferred to use a non-desalinated polymer with a salt content of 15-25% by weight.

Inorganic carrier material

The inorganic support material in particulate form is a macroporous, meso-porous or non-porous support material, preferably a mesoporous or macroporous support material. The mean pore size of the porous support material is preferably in the range of 6 nm to 400 nm, more preferably in the range of 8 to 300 nm and most preferably in the range of 10 to 150 nm. For industrial applications there is also a

Particle size range from 100 to 3000 nm preferred. Furthermore, it is preferred that the porous support material has a pore volume in Range from 30% to 90% by volume, more preferably from 40 to 80%

% by volume and most preferably from 60 to 70% by volume, based on the total volume of the porous support material.

The mean pore size and pore volume of the porous

Carrier material can be determined using the pore-filling method with mercury in accordance with DIN 66133.

In another embodiment, the is inorganic

Carrier material is not porous, which means its pore size is in the

Range below 4nm.

The porous inorganic material is preferably one that is soluble in aqueous alkaline conditions at pH greater than 10, more preferably pH greater than 11, and most preferably pH greater than 12.

According to a further embodiment, the preferably porous inorganic carrier material is dissolved out at a pH>10. This enables the creation of a porous hydrogel, which

Accessibility and capacity for metal ions and biological

impurities increased. The extraction of the inorganic

Carrier material preferably takes place before step (c), the protonation.

In other words, the step of dissolving out the inorganic support material takes place in the aqueous-alkaline ones mentioned, with the porous particles being obtained from a crosslinked polymer

conditions. The porous inorganic material is preferably one based on or consists of silicon dioxide or silica gel.

With the dissolving out of the inorganic carrier material after step

(b) and before step (c), it is understood that from the after step (b) obtained composite particles of porous inorganic

Carrier material and the applied polyamine, the inorganic

carrier material is removed. The step of dissolving the inorganic carrier material to obtain the porous particles from a crosslinked polymer is preferably carried out in an aqueous alkaline solution with a pH greater than 10, more preferably pH greater than 11, even more preferably pH greater than 12 Base preferably an alkali hydroxide, more preferred

Potassium hydroxide or sodium hydroxide, even more preferred

Sodium hydroxide used. It is preferred that the

Concentration of the alkali hydroxide in the aqueous solution at least

10% by weight, even more preferably 25% by weight, based on that

total weight of the solution. In step (c) of the process according to the invention, the particles obtained from step (b) are treated with the corresponding aqueous alkaline solution for several

hours contacted. The dissolved inorganic carrier material is then rinsed out with water from the porous

Washed particles of the crosslinked polymer that the inorganic carrier material is no longer contained in the product substantially. This has the advantage that when using the porous particles produced according to the invention from a crosslinked

Polymer, for example, as a binding material for metals, which consists only of organic material and is therefore subject to whereabouts or

Recovery of the metals can be burned completely or residue-free.

The porous inorganic carrier material is preferably a particulate material with an average particle size in

range from 5 μm to 2000 μm, more preferably in the range from 10 μm to 1000 μm. The shape of the particles can be spherical

(spherical), rod-shaped, lenticular, donut-shaped, elliptical or irregular, with spherical particles being preferred.

Coating and Crosslinking

The proportion of polyamine used in step (a) is one

Range of 5% to 50% by weight, more preferably 10 to 45%

% by weight and even more preferably 20 to 40% by weight, each based on the weight of the porous inorganic or organic

Carrier material without polyamine.

The polyamine can be applied to the support material in particle form in step (a) of the process according to the invention by various processes, such as impregnation processes or by the pore-filling method, with the pore-filling method being preferred. The pore filling method brings compared to conventional Impregnation process has the advantage that a larger total

Amount of dissolved polymer can be applied to the porous inorganic support material in one step, whereby the

Binding capacity increased and the conventional method is simplified.

In all conceivable methods in step (a), the polymer must be dissolved in a solvent. The solvent used for the polymer applied in step (a) is preferably one in which the polymer is soluble. The concentration of the polymer for application to the porous inorganic support material is preferably in the range from 5 g/L to 200 g/L, more preferably in the range from 10 g/L to 180 g/L, most preferably in the range from 30 to 160g/L.

Under the pore filling method, general becomes a special one

Understood coating process in which a solution containing the polymer to be applied is applied to the porous inorganic support material in an amount which corresponds to the total volume of the pores of the porous support material. The total volume of the pores [V] of the porous inorganic carrier material can be determined by the solvent absorption capacity (CTE) of the porous inorganic

Carrier material are determined. Likewise, the relative

pore volume [% by volume] can be determined. This is the volume of the freely accessible pores of the

Carrier material, since only this through the

Solvent absorption capacity can be determined. The

Solvent absorption capacity indicates the volume of a

Solvent is required to completely fill the pore space of one gram of dry sorbent (preferably stationary phase). Both pure water or aqueous media and organic solvents with a high

polarity such as dimethylformamide. If the sorbent at

If its volume increases when moistened (swelling), the amount of solvent used for this is automatically recorded. To measure the

CTE is an accurately weighed quantity of the porous inorganic

Carrier material moistened with an excess of well-wetting solvent and excess solvent from the Interstitial volume removed in a centrifuge by rotation. The

Solvent remains within the pores of the sorbent due to the

capillary forces in the pores. The mass of the restrained

Solvent is determined by weighing and the density of the

Solvent converted to volume. The CTE of a sorbent is reported as volume per gram of dry sorbent (mL/g).

During crosslinking in step (b) the solvent is removed by drying the material at temperatures in the range 40°C to 100°C, more preferably in the range 50°C to 90°C and most preferably in the range 50°C removed up to 75°C. In this case, drying is carried out in particular at a pressure in the range from 0.01 to 1 bar, more preferably at a pressure in the range from 0.01 to 0.5 bar.

The crosslinking of the polyamine in the pores or the accessible

Surface of the inorganic or organic carrier material in

Step (b) of the process according to the invention is preferably carried out in such a way that the degree of crosslinking of the polyamine is at least 10%, based on the total number of crosslinkable groups of the polyamine.

The degree of crosslinking can be adjusted according to the desired amount

Crosslinking agents are set. It is thereby assumed that

100 mole percent of the crosslinking agent reacts and forms crosslinks.

This can be done by analytical methods such as MAS NMR

Spectroscopy and quantitative determination of the amount of

Crosslinking agent are verified in relation to the amount of polymer used. This method is preferable in the present invention. However, the degree of cross-linking can also be

Spectroscopy related to e.g. C-O-C or OH vibrations can be determined using a calibration curve. Both

Methods are standard analytical methods for one skilled in the art. The maximum degree of crosslinking is preferably at

60%, more preferably 50% and most preferably 40

%. If the degree of crosslinking is above the specified upper limit, the polyamine coating is not sufficiently flexible. If the degree of crosslinking is below the specified lower limit, the resulting porous particles of the crosslinked polyamine are not rigid enough, for example as particles of a to be used in the chromatographic phase or in a water purification cartridge, in which sometimes higher pressures are applied. If the resulting porous particles of the crosslinked polyamine are used directly as a material for an antibacterial or antiviral absorbent resin, the

Degree of crosslinking of the polyamine preferably at least 20%.

The crosslinking agent used for the crosslinking preferably has two, three or more functional groups, the crosslinking being effected by their binding to the polyamine. The

Crosslinking agent used to crosslink the polyamine applied in step (b) is preferably selected from

Group selected consisting of dicarboxylic acids, tricarboxylic acids,

Urea, bis-epoxides or tris-epoxides, diisocyanates or

triisocyanates, dihaloalkylene or trihaloalkylene and

Halogen epoxides, with dicarboxylic acids, bis-epoxides and

Halogen epoxides are preferred, such as terephthalic acid,

Biphenyldicarboxylic acid, ethylene glycol diglycidyl ether (EGDGE), 1,12-bis(5-norbornene-2,3-dicarboximido)decanedioic acid and

Epichlorohydrin, where ethylene glycol diglycidyl ether, l,12-bis-(5-

norbornene-2,3-dicarboximido)-decanedioic acid and epichlorohydrin are more preferred. The crosslinking agent is in a

Embodiment of the present invention preferably a linear, molecule with a length between 3 and 20 atoms.

The polyamine used in step (a) preferably has a

Amino group per repeat unit. under one

Repeat unit means the smallest unit of a

Polymers, extending at periodic intervals along the

Polymer chain repeated. Polyamines are preferably polymers that have primary and/or secondary amino groups. It can a

Be polymer from the same repeating units, but it can also be a co-polymer, which is preferably simple as comonomers

Has alkene monomers or polar, inert monomers such as vinylpyrrolidone.

Examples of polyamines are the following: Polyamines, such as any

Polyalkylamines, eg polyvinylamine, polyalkylamine, polyethyleneimine and polylysine, etc. Among these, preferred are polyalkylamines, more preferably polyvinylamine and polyallylamine, wherein

Polyvinylamine is particularly preferred.

The preferred molecular weight of the polyamine used in step (a) of the process according to the invention is preferably in the range from 5,000 to 50,000 g/mol, which applies in particular to the polyvinylamine specified.

Furthermore, the crosslinked polyamine after step (b) in its

Side groups are derivatized. In this case, an organic radical is preferably bound to the polymer. This radical can be any conceivable radical, such as an aliphatic and aromatic group, which can also have heteroatoms. These groups can also be substituted with anionic or cationic radicals or radicals that can be protonated or deprotonated. If the crosslinked porous polyamine obtained by the process of the invention

When attaching metals from solution is used, the group with which the side groups of the polymer are derivatized is one

Group that exhibits the property of a Lewis base. An organic radical which has the property of a Lewis base is understood to mean, in particular, radicals which enter into a complex bond with the metal to be bonded. Organic radicals which have a Lewis base are, for example, those which have free heteroatoms

Electron pairs such as N, O, P, As or S have.

Preferred organic residues for the derivatization of the polymer are the ligands shown below:



Particularly preferred are the ligands PVA, i.e. the amino group of the PVA, EtSr, NTA, EtSH, MeSH, EDTA and iNic or combinations of the above. For example, a combination of PVA with EtSr, NTA or EtSH is particularly preferred.

Particularly preferred as the polymer in the present invention

Process polyvinylamine used because the amino groups of the

Polyvinylamine itself represent Lewis bases and also by their

Property as nucleophilic groups are easily coupled to a molecule with an electrophilic center. In doing so, preference is given to

Coupling reactions that produce a secondary amine rather than an amide are used because Lewis basicity is not lost through formation of a secondary amine. The present invention also relates to crosslinked polymer antiviral particles obtainable or produced by the above process of the invention. It is preferred that the particles produced by the process according to the invention have a maximum swelling factor in water of 300

% if it is assumed that a value of 100% applies to the dry particles. In other words, the particles according to the invention can increase by a maximum of three times in water

increase in volume.

A further subject of the present application are also antiviral particles made from a crosslinked polyamine, these

Particles have a maximum swelling factor of 300%, assuming that the percentage of dry particles is 100%. In other words, these inventive porous

Particles that swell in water have a maximum increase in volume by

have triples.

However, it is even more preferred that according to the invention

Process produced antiviral particles or the antiviral particles according to the invention have a maximum swelling factor in water of 250%, even more preferably 200% and most preferably less than 150%, since otherwise the

Rigidity of the particles obtained, at least for chromatographic

Applications and in drinking water cartridges under pressure is not sufficiently high.

The biocides produced by the process according to the invention

(antiviral and antibacterial) particles are preferably made of a crosslinked polyamine. The polyamine or the porous particles consisting of it preferably have a concentration of the amino groups, determined by titration, of at least 300 μmol/mL, more preferably at least 600 μmol/mL, and even more preferably of at least 1000 μmol/mL. under the through

Titration determines the concentration of amino groups

Concentration understood according to the example part of this

Application specified analytical methods is obtained by breakthrough measurement with 4-toluenesulfonic acid. The particles produced according to the invention preferably have a dry bulk density in the range from 0.25 g/mL to 0.8 g/mL, even more preferably from 0.3 g/mL to 0.7 g/mL. In other words, the porous particles are extremely light particles overall, which is ensured by the high porosity obtained. Despite the high

Due to the porosity and the low weight of the particles, they have a relatively high mechanical strength or rigidity and can also be used in applications as resins under pressure.

The average pore size of the particles produced according to the invention or according to the invention, determined by inverse size exclusion chromatography, is preferably in the range from 1 nm to 100 nm, more preferably 2 nm to 80 nm.

According to one embodiment, the antiviral particles produced according to the invention are preferably particles which have a shape similar to that of the dissolved porous inorganic

Carrier material had, but with the proviso that the particles according to the invention essentially with their material

reflect the pore system of the dissolved porous inorganic carrier material, i.e. they are in the case of the ideal pore filling in

Step (b) of the method according to the invention, the inverse pore image of the porous inorganic support material used. The porous particles according to the invention are preferably in an im

Substantially spherical shape. Their mean particle size is preferably in the range from 5 μm to 1000 μm, more preferably in the range from 100 to 500 μm.

Furthermore, the particles according to the invention are made of the crosslinked

Polymer according to one embodiment characterized in that they consist essentially of the crosslinked polymer. "In the

Essential" in this case means that only unavoidable

Residues of, for example, inorganic carrier material, which may still contain porous particles, but the proportion of which is preferably below 2000 ppm, even more preferably 1000 ppm and most preferably 500 ppm. In other words, it is preferred that the porous particles of the crosslinked polymer of the present invention are substantially free of an inorganic Material, such as the material of the inorganic

Carrier material are. This is also meant above in connection with step (c) of the method according to the invention, when it is said that the inorganic carrier material in

Essentially no longer contained in the product.

Another embodiment of the present invention relates to

Use of the particles according to the invention or the particles produced according to the invention for removing viruses and biological ones

Impurities and for the separation of metal ions from solutions, especially water. Here, the particles according to the invention or the particles produced according to the invention are preferably

filtration process or solid phase extraction used to remove viruses and biological contaminants

allow water or the separation of metal-containing ions from solutions. The material according to the invention can, for example, be used in a simple manner in a stirred tank or in a "fluidized bed" application, in which the material is simply added to a biologically contaminated and metal-containing solution and stirred for a certain time.

The present invention also relates to a filter cartridge, for example for the treatment of drinking water, which contains particles according to the invention. The filter cartridge is preferably shaped in such a way that the drinking water to be treated can pass through the cartridge and comes into contact with the particles according to the invention in its interior, with biological

Removes impurities and viruses and metal-containing ions from the

water are removed.

The filter cartridge can have an additional material for removing

contain micropollutants. Activated carbon is preferably used for this. The different materials in separate

Zones can be arranged within the filter cartridge, or in one

Mixture of the two materials. The filter cartridge can also contain several different materials (with and without derivatization) which have been produced using the method according to the invention. The filter cartridge can be designed in all conceivable sizes. For example, the filter cartridge can be designed in a size that is suitable for daily drinking water needs in one

budget is sufficient. However, the filter cartridge can also be of a size that allows the drinking water requirement for several people

to cover households, i.e., for example, a need of more than 5

liters daily.

The filter cartridge can, for example, have the shape of a cylinder with linear flow or the shape of a radial flow

have hollow cylinders.

The present invention will now be explained using the following examples, which, however, are only to be regarded as exemplary:

example 1

1712 g moist carrier material Lewatit S1567 ion exchanger

(monodisperse strong cation exchanger based on a crosslinked polystyrene with sulfonic acid groups, Lanxess) are conveyed directly in a Lödige VT5 plowshare mixer.

The ion exchanger is then dried at 80° C. for 60 minutes. Through

The dried ion exchanger is weighed

determined moisture loss. 380g of water was removed. The

Product temperature in the dryer is set to 10°C. The

Mixer is operated at 180 revolutions per minute. After the

When the product temperature in the mixing drum has reached 10 °C, add 350 mL of a coating solution that has been cooled to 10 °C. For the

Solution 225 g non-desalinated polyvinylamine solution Lot.: PC

18007 (polymer content 10%) and 1 g ethylene glycol diglycidyl ether

(EGDGE) [2224-15-9] was weighed into a vessel and deionized water was added until a total volume of 350 ml was reached. The

Mixture is added to the mixer within 10 minutes and mixed for 1 hour at 10°C. Subsequently, the polymer adsorbate at 80

° C and reduced pressure of 50 mbar crosslinked for 2 h. The polymer coated ion exchanger was then cooled down to room temperature. The particles are then transferred to a suitable suction filter and washed with the following solvents (BV=bed volume): 3 BV 0.1

M NaOH, 3 BV deionized water, 6 BV 0.1 M NaOH, 3 BV water, 3 BV 0.2 M

HCl, 6 BV deionized water. The product is obtained as water-moist particles.

example 2

3 L Lewatit S 8227 (macroporous, weakly acidic

Cation exchange resin with carboxylate groups based on a crosslinked acrylate) from Lanxess on a frit with the

Porosity 3 washed with 15 L deionized water. It will then

2270 g moist ion exchanger in a vacuum paddle dryer VT

5 from the Lödige company. The ion exchanger is at a

Jacket temperature of 80° C and a pressure of 30 mbar and a

Dried at a speed of 57 rpm for 2 hours. After drying will be

915 g of dried ion exchanger back into the

Vacuum Paddle Dryer VT 5 filled. The jacket temperature is set to 4

° C set and if the product temperature is below 20 ° C, within 15 minutes 600 ml of deionized water in the

Mixer, which is operated at a speed of 180 rpm, promoted by means of a peristaltic pump. For the coating, 227 g

Polyvinylamine solution (polymer content 10%) Solder: PC 18007 and 227 g of deionized water are weighed out in a vessel. 9.20 g of ethylene glycol diglycidyl ether (EGDGE) [2224-15-9] as crosslinking agent are weighed out in another vessel. The crosslinker becomes the

Given polymer solution and mixed intensively. Then the mixture is pumped into the Lödige mixer within 5 minutes using a peristaltic pump. The speed of the mixer is set to 240 rpm and the jacket temperature is left at 4°C. After

Addition was mixed for 15 min at 240 rpm. Then the

Jacket temperature on the dryer set to 80° C and the speed reduced to 120 rpm. The particles are then cooled down again to room temperature and are then transferred to a suitable suction filter and washed with the following solvents: 3 BV 0.1 M NaOH, 3 BV deionized water, 6 BV 0.1 M NaOH, 3 BV

Water, 3 BV 0.2M HCl, 6 BV DI water. The product is obtained as water-moist particles. Example 3

500 g carrier material sulfonated polystyrene PRC 15035 (middle

pore size 450 Å, mean particle size 500 μm) with a

Water absorption capacity of 1.35 ml/g are directly in one

Ploughshare mixer VT5 from Lödige sucked. The

Product temperature in the dryer is set to 10 °C. The

Mixer is operated at 180 revolutions per minute. after the

When the product temperature in the mixing drum has reached 10° C., 225 g of non-desalinated polyvinylamine solution Lot.: PC

16012 (polymer content 12%), 20 g ethylene glycol diglycidyl ether

(EGDGE) CAS no. [2224-15-9] and 430 g deionized water are weighed into a vessel. The mixture is added to the mixer within 10 minutes and mixed at 10° C. for 1 hour. Then it will

Polymer adsorbate at 65°C and crosslinked. The product is then on

cooled down to room temperature. The particles are then transferred to a suitable suction filter and washed with the following solvents: 3 BV 0.1 M NaOH, 3 BV deionized water, 6 BV 0.1 M NaOH, 3 BV

Water, 3 BV 0.2M HCl, 6 BV DI water. 1297 g of product are obtained as water-moist particles. Anion Capacity (AIK):

471 µmol/g.

example 4

Specification for the production of a porous particle of a crosslinked

Polymers with a particle size of 100 μm (Batch: BV 18007): 1. Production

Polymer adsorbate: 750 g carrier material silica gel (AGC Si-Tech Co. M.S

Gel D-200-100 Lot.: 164M00711) are directly in a

Ploughshare mixer VT5 from the Lödige company. The

Product temperature is set to 10°C. The mixer comes with

operated at 180 revolutions per minute. After the

When the product temperature in the mixing drum has reached 10°C, 1125 g of non-desalinated polyvinylamine solution Lot.: PC

18007 (polymer content 10%) was weighed into a jar and 23.2 g

Ethylene glycol diglycidyl ether (EGDGE) CAS no. [2224-15-9] offset. The mixture is added to the mixer within 10 minutes and mixed for 1 hour at 10°C. Then it will

Polymer adsorbate dried at 80°C and 50 mbar (approx. 2 h). The coated silica gel was then cooled down to 10°C. For the 2nd coating was 750 g of polymer solution PC cooled to 10°C

18007 (polymer content 10%) is weighed into a jar and 15 g

Ethylene glycol diglycidyl ether (EGDGE) CAS no. [2224-15-9] offset. The polymer solution was within 5 min in the

mixing drum filled. The polymer adsorbate was mixed for 30 min at 10°C. The temperature in the Lödige mixer was then increased again to 65° C. for 1 hour. The polymer adsorbate was mixed with 3 L VE

water added. This suspension is used for crosslinking.

The coated silica gel suspended in water is placed in a 101

Glass reactor transferred with automatic temperature control. The suspension is stirred and heated to 80°C. Then 317 g

Epichlorohydrin CAS no. [106-89-8] was added within 20 min so that the temperature in the reactor did not exceed 85°C. Then 211 g of 1,2-diaminoethane [107-15-3] are added dropwise within 20 minutes. Then the second addition of 317 g of epichlorohydrin takes place

CAS no. [106-89-8] followed within 20 minutes by another 211 g of 1,2-diaminoethane CAS no. [107-15-3]. Finally, 317 g of epichlorohydrin CAS no. [106-89-8] was added and the reaction stirred at 85°C for 1 h. The reaction mixture is then cooled to 25°C and 1500 mL of 50% NaOH is added and the reaction mixture is stirred for 12 hours. The

Template particles are then transferred to a suitable suction filter and washed with the following solvents: 3 BV 0.1 M NaOH, 3 BV

DI water, 6 BV 0.1 M NaOH, 3 BV water, 3 BV 0.2 M HCl, 6 BV DI

Water.

The product is obtained as a wet filter cake.

Example 5

In each case, an aqueous suspension of the crosslinked resins

Polyvinylamine (BV 16037, BV 16084, BV 18002 and outside coated BV 18009 only).

A suspension of adenoviruses (added and

Room temperature shaken over a period of time.

The result of the investigations is shown in FIG. 1: There are no viruses in the effluent over the entire investigation area verifiable. That means that the viruses in drinking water are relevant

concentration are completely removed.

As can be seen in Figure 1, the virus load of the used decreases

Resins to zero or near zero within 3 hours.

This proves the antiviral effect of the resins claimed in the present application, i.e. the crosslinked polyamines and the coated polystyrenes.

Example 6

A suspension of adenoviruses over a column, which with the

Resins from Example 6 is filled, passed and filtered. After

Viruses are no longer detectable after passing through the resin bed.

The use of the antiviral particles according to the invention thus allows the removal of viruses from drinking water by a simple

filtration step.

This results in the following advantages over the previously known methods:

Complete removal of viruses (and also bacteria) by binding/killing

No addition of chemical additives

Gravity operation possible

Little to no energy expenditure

No pump or UV radiation necessary

100% yield based on the water used

Chemical regeneration of the resin by rinsing with

Hydrochloric acid/caustic soda possible

Simultaneous removal of bacteria, viruses and heavy metals by appropriate addition of other resins of the

applicant

Use of inexpensive single-use materials is possible

Claims

patent claims

1. A method for producing antiviral particles comprising the steps:

(a) providing an aqueous suspension containing a

polyamine, a crosslinker and an inorganic one

Carrier material or an organic carrier material in

particle form at a temperature less than or equal to 10 °C in a mixer for coating the inorganic

Carrier material or the organic carrier material with the polyamine;

(b) crosslinking the polyamine of the coated inorganic

Carrier material or the coated organic

carrier material and simultaneous removal of water,

(c) protonating the crosslinked polyamine to obtain antiviral particles.

2. The method according to claim 1, wherein steps a) and b) are repeated at least once.

3. The method according to any one of claims 1 or 2, wherein the

Crosslinking takes place in a stirred reactor.

4. The method according to any one of claims 1 to 3, wherein the polyamine is used in the desalted or non-desalted state.

5. The method according to any one of claims 1 to 4, wherein the inorganic support material is porous.

6. The method according to any one of claims 1 to 5, wherein the inorganic carrier material is a material which can be dissolved in aqueous-alkaline conditions at pH>10.

7. The method according to any one of claims 5 or 6 further comprising the step of dissolving the inorganic carrier material after step (b) and before step (c) at a pH> 10 below

Obtaining particles from a crosslinked polyamine with an inverse pore structure of the inorganic carrier material.

8. The method according to any one of claims 1-4, wherein the organic

Support material a polystyrene, a sulfonated polystyrene, a polymethacrylate or a strong or weak

ion exchanger is.

9. The method according to any one of claims 1 to 8, wherein the polyamine is a polyvinylamine.

10. The method according to any one of claims 1 to 9, wherein the crosslinked polyamine is derivatized in its side groups after step (c).

11. Antiviral particles by a method according to any one of

Claims 1 to 10 are obtainable or manufactured.

12. Antiviral particles according to claim 11, wherein the polyamine is at least partially protonated.

13. Antiviral particles according to any one of claims 10 to 12, wherein the particles have a maximum swelling factor in water of 300%, based on 100% dry particles.

14. Antiviral particles according to any one of claims 11 to 13, wherein the dry bulk density is in the range from 0.25 g/mL to 0.8 g/mL.

15. Use of antiviral particles according to any one of claims 11 to 14 or produced by a method according to any one of

Claims 1 to 10 for removing viruses from water by contacting the contaminated water with the antiviral particles.

16. Use according to claim 15, further comprising bacteria, germs,

Yeasts or fungi are removed.

17. Use according to any one of claims 15 or 16, wherein the contacting of the contaminated water takes place in a pH range of 6-9.

18. Filter cartridge containing antiviral particles according to any one of

Claims 11 to 14 or produced or obtainable by a process according to any one of claims 1 to 10.