CZ2008545A3 - Process to carry out nano-processes on material based on polysaccharides - Google Patents

Abstract

A method for performing active nanoprocessing on a polysaccharide-based material to adjust the ability of a polysaccharide-based material to induce agglomeration of particles in a nanoparticle around a microstructure or pore of a polysaccharide-based material. In particular, the material is a cellulose-based material, and the active nanoprocesses include separation nanoprocesses and an increase in the release of materials during washing of the material. The invention further relates to the use of a modified polysaccharide-based material for performing active nanoprocessing and sorption filter plates utilizing the material treatment of the present invention.

Description

Process for carrying out active nanoprocesses on polysaccharide-based material

Technical field

The invention relates to a process for carrying out active nanoprocesses, such as separation processes and washing, on polysaccharide-based material, in particular cellulose-based material.

^{state of the} art

We are already living at the time of managing the microworld of matter at the nanometer level - actually the nano-world.

Thanks to the external action of concentrated energy, particles, oriented fields, etc., we are able to intervene from the outside into the microworld of matter and make appropriate changes in its structure and organization, or to produce sub-microscopic formations. The current conception in influencing and interfering with the interior and organization of the nano-space of matter is based on its passive behavior - inanimate matter. There are two basic concepts for the preparation of nanomaterials (P. Vasar et al: Opportunities for Pulp and Pipe Industry Carbon Management through Nanotechnology, Proceedings of PULPAPER 2004 Conferences, Energy and Carbon Management, Helsinki, Finland, 1-3 June 2004).

In the first conception, the nanopspace of matter is intervened from the outside by so-called top-down nanoprocesses. Macroscopic material is treated mechanically, electrically or electromagnetically in an effort to change its size (nanoparticles), shape (nanofibers), nanostructure (arrangement of molecules, supramolecular structures, etc.). The most widespread are spinning methods enabling to obtain nanometer thickness fibers from macromolecular substances or to obtain colloidal particles from particles by means of high-energy milling processes.

In the second, the so-called bottom-up concept of nanomaterials arise from the basic building units represented by molecules or atoms by their suitable coupling. This is typical of colloidal processes. Nano-building units, due to their properties in the nano-space, combine to form nanoparticles and various nano-shapes. The direction and orientation of this connection is already anchored in the basic nano-building units. Inert gas condensation was one of the first such methods used to elaborate nanostructured materials such as nanostructured metals, alloys, ceramic oxides and composites. However, these are always stochastic processes, the course of which is random, depending on the energy, orientation and concentration of interacting nanoobjects. The environment, whether gaseous or liquid, in which these processes take place is usually passive to these ongoing processes, for example only plays a transport role. However, activation of these processes plays a key role. So far, it is carried out by targeted intervention from the outside, ie the entire system behaves passively until it receives a thermal, mechanical, chemical, etc. stimulus from the outside. It is therefore dependent on a targeted external stimulus.

In this sense, the most spatially organized living matter behaves actively because of its inner intelligence. We are only at the beginning of the preparation of an actively behaving mass, which is able to respond to the relevant changes in the micro-world environment formed by various spatial meshes. In this case, the respective nanoprocesses are started independently of the outside world only on the basis of internal stimuli discernible by this micro-world. Targeted and random external stimuli will produce an appropriate response in this micro-world (induce appropriate nanoprocesses) only on the basis of the decision of this micro-world equipped with the appropriate nano-tools with different selectivity. The influence of the outside world is thus reflected in these nanoprocesses through the environment in which these processes take place and the nano-tools (usually chemical) available to the micro-world. It is therefore no coincidence that such a suitable environment is water having the ability to form a hydration bonding system between hydrophilic micro-interfaces of spatial meshes at the nano level. The great advantage of such processes is that there is no unnecessary dissipation of the spent energy and therefore these processes are unlike passive nanoprocesses as effective as possible.

In living organisms, such nanoprocesses do not occur in isolation independently of each other, but are part of a higher organized biostructure with the ability to control, use, and possibly adapt to their higher goals with respect to the behavior of the environment in which they occur and move. Individual bio-units then form closed units with all the functions enabling them to exist and move in the given environment relatively independently of each other. They are able to reconstruct or reproduce. This is the highest level of organized matter behavior.

Recently, a phenomenon known as surface flocculation has been described (M. Milichovsky, M. Vodenicarova, Cellulose Chem. And Technol., 33, 503-511 (1999), M. Milichovsky, Br. Cesek, Adsorption Science & Technology 20, 9, 883 -895 (2002)) consisting of agglomerating molecules of ionic or non-ionic nature, colloidal particles and the like in the nanospace around suitable groups on a solid support (see Figure 1). The phenomenon has been demonstrated on a cellulosic fibrous substrate - pulp into which cationic oligomeric groups have been incorporated, which have the ability to attract a particular group of substances in an aqueous environment and then react, agglomerate (see Fig. 2), eg flocculate. It is no coincidence that these processes are typical of the aqueous environment, since only the aqueous environment allows the formation and application of electrostatic (electrokinetic behavior of colloidal particles) and hydration forces.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention provides a process for carrying out active nanoprocesses on a polysaccharide-based material, comprising adjusting the ability of the polysaccharide-based material to induce agglomeration of particles in the nanospace around the micro-surfaces of the fibers or pores of the polysaccharide-based material. Depending on the treatment, this nanoparticle either accumulates or releases particles, for example colloidal particles of anionic nature and cations, especially heavy metals.

The polysaccharide-based material may advantageously be a material derived from phytomass, e.g. wood or annual plants, in particular a cellulose-based material. Any cellulose-based fiber may be used as the cellulosic starting material, including cotton, silk and pulps such as unbleached and bleached broadleaf, coniferous kraft pulp and unbleached and bleached pulp of annual plants, unbleached and bleached coniferous kraft pulp, as well as high alpha pulp - celluloses (more than 95% alpha-cellulose) or mixtures thereof on the one hand or vice versa high-lignin-containing pulp such as wood pulp, thermomechanical pulp (TMP) or chemothermomechanical pulp (CTMP) on the other, or mixtures of all these pulps one of the fibrous, microfibrous, granular or powder forms is ground to 15 to 70 degrees according to Schopper-Riegler, optionally mixed with up to 60% by weight of other fibrous materials and fillers, such as inorganic and mineral fibers, polyolefin and other synthetic organic fibers on and fillers with filtering and sorption effects such as diatomaceous earth, perlite, alumina, silica, talc, kaolin, potassium or sodium alumosilicate, zeolite, apatite, hydroxyapatite, activated carbon or activated charcoal and the like.

The ability of the polysaccharide-based material to induce agglomeration of particles around the material can be influenced both towards increasing particle agglomeration and decreasing particle agglomeration.

Increasing the ability of a polysaccharide-based material to induce particle agglomeration in its nano-environment can be achieved by activating the polysaccharide-based material

By means of an activator, wherein the activation consists in reacting 1 part by weight of the polysaccharide-based material in the form of a pulp of paper pulp at room temperature, i.e. at a temperature in the range of 15 to 30 ° C, and a pH of 7 to 10, with 0.001 to 0.1 parts by weight of activator during at least 10 minutes of reaction. This activation induces surface agglomeration, e.g., flocculation of anionic colloidal particles in the nanospace around the active cationic center of the cellulosic substrate, or allows the mixture of this activated pulp and modified anionic polysaccharide in fibrous or hydrocolloid form to cause enormous sorption of cations, especially heavy metals. Any oxycellulose or oxidized starch containing 1.0 to 25% by weight of carboxyl groups, usually 5 to 18% by weight of COOH groups, and carboxymethylcellulose having a degree of substitution of 0.1 to 1.0 in the fibrous, particulate, particulate, hydrocolloid or completely soluble form.

The activator is a water-soluble epoxy-based oligomeric substance containing quaternary amino groups derived from aliphatic amines. Preferred are water-soluble activators containing quaternary 2-hydroxy-propyl-dimethylammonium chlorides of formula I:

CH ₃

R-CH ₂ -CH-CH ₂ -N ⁺ -CH ₂ -E X '

OH CH ₃ CH ₃ wherein R is N ⁺ -CH ₂ -EX 'or Cl; E is CH-CH ₂ or CH-CH ₂ Cl a

CH ₃

OH

X 1 is a chloride anion prepared by the reaction between epichlorohydrin and dimethylamine in a molar ratio of 1.2 to 2.0: 1 and containing at least 0.1% by weight of epoxy groups in the raw state. A commercially available activator of this type is prepared by reacting epichlorohydrin with dimethylamine in a molar ratio of 1.2-2.0: 1. Many polyamide-polyamino epichlorohydrin resins and charge modifiers, such as 2,3-epoxypropyltrimethylammonium chloride, require treatment prior to the reaction because, in order to maintain sufficient stability during storage, their epoxy groups are reduced to prevent crosslinking. Therefore, prior to using the activator, it is advisable to treat the activator by regenerating its epoxy groups by adding the necessary amount of sodium hydroxide and thereby converting its inactive chlorohydrin to the active epoxy form. The amount of aqueous alkaline solution needed varies from case to case and is specified by the supplier. The activation of the activator is completed within about 30 minutes, after which the activator solution is ready for use.

Increasing the ability of the polysaccharide-based material to enhance agglomeration of particles in its vicinity can be used to perform active separation nanoprocesses. Active separation nanoprocesses with this material can be carried out either by its application in fibrous, particulate or hydrocolloid form or by a mixture of its various forms of cationic or anionic character directly in water suspension, which is then separated from it by sedimentation, resp. so-called rheosedimentation, flotation or filtration through a conventional or sorption filter, or in the form of a porous fibrous wall through which a contaminated water mixture permeates, which porous wall acts as a so-called sorption filter, i.e. the filtered suspension is separated enormous sorption induced by surface flocculation. This means that they can be done as:

- colloid-sorption sedimentation consisting of three steps of first reacting a hydrocolloid of an anionic nature, eg oxycellulose, with heavy metal ions to form a supersolecular hydrocolloid adduct with a heavy metal, followed by the addition of activated fibrous cellulosic material, eg pulp, to induce surface flocculation of hydrocolloids and rheosedimentation of complex fibrous web with all components and finally separation of sediment in the form of fibrous sludge by a conventional method;

colloid-sorption filtration, proceeding in the same way as the previous process, with the last separation step being performed by filtration through any filter;

• · · · v ·· · · · · · · · ·

4 «··

- colloid-sorption activated filtration consisting of two steps, in which, in the first step, a hydrocolloid of an anionic nature, eg oxycellulose, first reacts with heavy metal ions to form a supermolecular heavy metal hydrocolloid adduct followed by filtration through the activated fiber filter plate with respect to oxycellulose, whereby these substances, including heavy metals, are trapped in this sorption filter plate and separated from the originally contaminated water (of course, any conventional fiber filter plate or other filtration may be used, but with lower efficiency);

- sorption filtration in one step, wherein the contaminated water with cationic substances, eg heavy metals, is directly filtered through a sorption filter plate containing 1 to 20% by weight of carboxyl groups.

For example, it is possible to carry out, for example, separation of hardly isolable colloidal and low molecular weight substances of primarily ionic nature from water, such as colloidal, hydrocolloid particles of anionic nature or hydrated cations or their complexes such as heavy metals and alkaline earths, by conventional separation methods such as sedimentation, flotation or filtration.

In this way, it is possible to conduct a targeted accumulation of dilute molecules and colloidal particles in water into the micro-space of the fiber cavities of polysaccharide-based material, such as pulp lumen, thereby causing a change in the behavior of both fibrous suspensions and especially paper systems made therefrom. E.g. by transferring hydrocolloid particles from water to the surface of the fibers and pores of filter plates, papers and the like, but especially to the interior of the fibers thus activated, the dewatering ability of these fibrous suspensions during their dewatering during paper sheet preparation is increased. By concentrating the molecules and colloidal particles in the microfaces of the fibrous cavities, further interactions and reactions can occur to form various compounds and supermolecular adducts located in these microfaces, thereby altering the properties of the fibers. Thus, it is possible, for example, to place fillers in these cavities, the so-called lumen filling.

By reducing the ability of the polysaccharide-based material to induce agglomeration of particles in its vicinity, a targeted inverse process can be performed by releasing randomly dispersed particles, e.g., molecules of a specific substance, etc., deliberately releasing spatially oriented polysaccharide-based material (e.g., pulp). An example is a process in which the release of unwanted, predominantly lignin components, from the cell matrix of the lignin-cellulosic material wall is facilitated. This reduction can be accomplished by washing the base material

polysaccharides by a substance affecting the behavior of immobilized water in hydrating shells of polysaccharides selected from the group consisting of urea, acetamide, formamide and N, N-dimethylformamide. One possible application is to increase the residual washable pulp content by using substances affecting the behavior of immobilized water in hydration coatings of polysaccharides such as urea, acetamide, formamide or N, N-dimethylformamide. In this way, it is possible to intensify some washing processes of fibrous structures of complex cellulose-based wall morphology, such as selective cleaning of cell walls of complex cellulose structures, e.g., pulp washing.

It is a further object of the present invention to use polysaccharide-based material to perform active separation nanoprocesses, particularly nanoprocesses allowing to capture and separate from water and aqueous systems colloids of anionic nature and heavy metal cations by conventional separation processes such as filtration, sedimentation or flotation, and to increase permeability of filter beds with active hydrocolloids. It has been found that in this way it is possible to solve, for example, the dilemma between the low separation efficiency and the high flow of filter materials and to separate with high efficiency also soluble and colloidal substances such as toxic heavy metals, undesirable colored or non-colored substances etc. from water by conventional methods such as is filtration or sedimentation. This behavior is caused by so-called surface flocculation, i.e. flocculation of molecules, colloidal particles and the like in the vicinity of the active center located on the cellulosic surface both directly in the fibrous suspension and inside the porous filter medium, attracted and concentrated by the center. active center.

Preferably, the polysaccharide-based material for use in the present invention is a sorption filter plate which is prepared from an aqueous suspension containing cellulosic material with an increased ability to induce agglomeration of particles in its vicinity, i.e. with a significantly increased sorption activity and optimized amount of fine fillers such as diatomaceous earth. and / or perlite. It is also desirable to add a strength agent such as polyamide-polyamine epichlorohydrin resin in an amount of 1-5% by weight based on the weight of the filter medium. The filter plates may then be prepared in a conventional papermaking process, for example, on a papermaking machine with a longitudinal screen or the like, or by some papermaking process making it possible to produce various shaped forms of paper pulp, such as suction technology, and ending drying. A further advantage of the present invention is the increased retention of fines, including fillers, in the dewatered filter cake compared to plates prepared in a conventional manner.

»Φ and ΦΦΦ

The filler with filtering effects of the present invention preferred diatomaceous earth, perlite and the like. Or mixtures of these fillers and cationically or anionically activated cellulosic material, wherein the activated material comprises all or a portion of the cellulosic material contained in the filter and having a freeness in the range 15-70 ^Ù SR. The first step in the preparation of the filters is the grinding of the pulped cellulosic materials to achieve the desired degree of grinding, mixing of the selected types of fibers and their activation. Fillers and other components such as a wet strength agent are then added. However, the composition may be added continuously before or into the headbox. The thus prepared filter plates with increased sorption activity are then characterized by a significant improvement of their separation ability against microorganisms and are particularly suitable for trapping soluble and insoluble colloidal substances of anionic or cationic nature. However, the excellent sorption activity of these filters depends on the amount of activator used. The filters also have good pyrogenic effects and dye retention.

A further advantage of the filters made according to the invention is that the improved cleaning effect is achieved with acceptable filter flow characteristics. A significantly improved regenerative capacity of these filters is also due to the fact that the activating agents are bound to the cellulosic material by chemical bonding.

A practically suitable composition of the papermaking suspension for preparing the filters of the present invention comprises up to 60% by weight of a filler, such as diatomaceous earth and perlite, of modified polysaccharide materials selected from oxycellulose or oxidized starch containing 1.0 to 25% by weight of carboxyl groups, preferably 5 up to 18% by weight of COOH groups, and carboxymethylcellulose having a degree of substitution of 0.1 to 1.0 in fibrous, particulate, hydrocolloid or completely soluble form, and / or mixtures thereof and 100 to 40% by weight of pulps optionally activated by the process of the present invention as the main filter plate forming the component, added to the total balance of the furnish.

The preparation of materials and the performance of active nanoprocesses with these materials and the properties of the filter plates corresponding to the present invention are documented in the following examples.

Overview of pictures

Giant. 1 is a schematic representation of the surface flocculation of colloidal particles A in the vicinity of a cellulose micro-interface provided with an active nanocentre C.

· · · · · · · · · · · ·

Fig. 2 shows the surface flocculation within the pores of the filter medium. A pore detail with flocculated particles of colloidal or dissolved substances around the active center is shown. In this case, the entrapped particles are small compared to the pore sizes, which prevents it from clogging.

Fig. 3 shows the principle of the use of surface flocculation for controlled super-molecular-chemical reactions and processes. Due to the very low concentrations of the components A in the medium, supermolecules and molecular reactions leading to product P (reaction 1) cannot occur. However, due to the action of the active component C firmly associated with the micro-interface of the substrate, the molecules, nanoparticles or the like of component A in the nanopspace around C accumulate and eventually induce appropriate reactions or supramolecular interactions to form P. products.

Giant. 4 shows a graph of the separation efficiency versus a specific amount of filtrate. These dependencies are compared here for the filter plates made according to the present invention and the prior art filter plates.

Figure 5 shows the dependence of separation efficiency on activated and non-activated pulp content and the effect of fibrous and hydrocooidal forms of oxidized cellulose on the colloidal sedimentation separation of iron from water.

Giant. 6 shows the effect of various substances in an aqueous environment on the removal of residual washable fractions in the pulp.

Examples

Example 1

A series of filter plates were prepared from bleached coniferous sulphite pulp pulped and ground with a 3% consistency of the pulp at 18 ° SR. The following paper was then added:

- 2.5% by weight of untreated activator, calculated on the weight of a.s. pulp,

1.5% by weight of treated activator, calculated on a.s. pulp,

- no activator, but also to all fouling of 1,5% by weight of wet strength agent, calculated on the weight of a.s, filter plate.

φ 9 · »· 99 9 9 9 9 9 • 9 9 · 99

All ingredients were added with vigorous stirring to each pulp of the pulp at pH = 8. After 40 minutes of gentle agitation, each pulp was successively diluted to a 0.5% consistency and filter plates were prepared in a conventional papermaking process. The commercial cationic composition based on polyamine-polyamide epichlorohydrin resin XP 4025 by AKZO NOBEL, Activator containing 2-hydroxypropyl-dimethylammonium chloride oligomer, Refaktan K, by CHEMOTEX, was used as a wet curing agent in both modified and untreated form. It contained 3.0% epoxy groups in untreated form and 4.6% epoxy groups in modified form. The treatment was carried out by carefully mixing 2 parts by weight of a commercial activator with 1 part by weight of a 10% sodium hydroxide solution. The activation of the activator was completed after 30 minutes of gentle stirring of the reaction mixture so that its temperature did not exceed 40 ° C.

All filter plates were then subjected to the same tests with clean water and contaminated water. Water containing 10 mg / l water of black pigmented anionic dye was used as contaminated water. Test filtration was carried out in a laboratory apparatus of Minicol from Hobra Janitor consisting of 6 filtration units under the same conditions, ie a filtration area of 30 cm ² and a filtration pressure of 20 kPa. Prior to each measurement, each filter cake was washed for 5 minutes at 50 kPa pressure with drinking water, measuring the specific flow rate through the pure water filter. The amount of filtrate passed through the filter, expressed as specific flow rate, V _s (lm ') and dye concentration in the filtrate were then determined under the same conditions for all measurements. From the results found, the filtration efficiency of the filtration was expressed as a percentage of the separation efficiency of the filter relative to the input concentration of the dyed water according to the relation:

Input concentration - output concentration

Filtration efficiency, Y (%) = x100

Input concentration

At the same time, the water flow at the beginning and at the end of the experiments remained approximately the same, namely 150 + 10 n.m · ² ]! ¹ at a pressure of 150 kPa. The results are shown in Figure 4.

As can be seen from FIG. 4, samples containing only the wet strength agent practically show no separation capability at all. However, this ability is dramatically improved when activated pulps are used, although the permeability of the filter plate is high. As the activation of the cellulosic material increases, the filtration efficiency increases, but this is greatly supported by the use of a modified activator.

Example 2

A series of experiments were performed, similar to Example 1, but using conifer bleached sulphite pulp and deciduous bleached sulphate pulp, both separately pulped and ground at 3% consistency to 22 ^° SR. 20% by weight of perlite were used as fillers.

A commercial cationic composition based on polyamine-polyamide epichlorohydrin resin XP 4025 by AKZO NOBEL in an amount of 1.5% by weight based on the total a.s. filter plate weight.

Quaternary oligomeric 2-hydroxy-propyl-dimethylammonium chloride containing the activator in a modified form similar to that described in Example 1 was used, namely in an amount of 5% by weight calculated on a.s. cellulosic material. The composition of furnishings in individual experiments is summarized in Tab. 1.

The additives were metered into a pulp of 3.0% consistency at pH = 7.5 during vigorous stirring prior to the addition of perlite. After 60 minutes of gentle agitation, the stock was diluted to a 0.5% consistency and was prepared in a conventional paper mill using the appropriate filter plates.

The obtained filter plates were subjected to similar tests as in Example 1, i.e. with water and water contaminated with pigment black pigment at a concentration of 10 mg / l. Flow rate for

The water of all the filters tested was approximately the same, namely 70 + 5 m / m at 150 kPa. The contaminated water experiments were carried out with a 30 cm filter baffle at a filtration pressure of 50 kPa. Prior to each measurement, the filter bed was purged for 5 minutes at 50 kPa pressure with potable water, after which the water filter flow rate was determined. Again, as in Example 1, the filtration efficiency, Y (%), and the specific filtrate flow rate, q ₅₀ (lm 2 min ^-1 ), were monitored at a filtration pressure of 50 kPa depending on the specific amount of filtrate,

AND

Vs (lf). The results of these measurements are shown in Tab. 2.

The dramatic improvement in activated cellulose filtration efficiency has a decreasing tendency as the sorption capacity of the activated cellulose material is exhausted during filtration.

· · Φ «φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ

Table 1.

Plate C. Listnáč, bun. Weight % Needle. pulp Weight % Perlíte Hm. % Prostř. for wet strength Weight % Activator modified Weight % 1 30 50 20 May - - 2 30 50 20 May 1.5 - 3 30 50 20 May - 5 4 30 50 20 May 1.5 5

Table 2.

Board no. 1 Board No. 2 Board No. 3 Board No. 4 In _p Y qso Y qso Y qso Y qso (Μ (%) (l.mÁmm ¹ ) (%) (l.mAMmin ¹ ) (%) (LmAM ¹ ) (1). m ' ² .min') 177 48.4 346 - - 96.3 364 94.8 358 350 2.6 345 13.8 449 95.8 301 95.0 301 704 - - 10.4 - 92.3 215 92.4 220 760 - - 8.8 - 89.0 203 91.3 198 1592 - - 5.0 - 75.6 154 - - 1769 - - 4.0 429 73.1 152 - -

Marks used: V _s - specific amount of filtrate; Y - filtration efficiency; qso specific filtrate flow at 50 kPa.

Example 3

The filter plates prepared according to Example 1 were subjected to filtration tests with 10 mg / l contaminated alkilignin water and pH = 7.6. The tests were carried out by filtering the contaminated liquid through 100 cm ² filters at 50 kPa for 30 minutes. Prior to each measurement, the filter bed was purged for 5 minutes at 50 kPa pressure with potable water and the water filter flow rate was determined. The cleaning effect of the filters was

Assessed by measuring the whiteness of air-dry filter plates before and after filtration. Indeed, by increasing the amount of captured alkilignins, the whiteness of the filter plates decreases.

The results obtained again confirm the enormous sorption capacities of filter plates made of activated cellulose material, especially when a modified activator is used.

ISO whiteness of all filter plate samples before filtration - 85%

ISO whiteness of filter plate samples after filtration, the plates containing:

- no activator, only 1,5% by weight of wet strength agent (based on a.s. pulp) - 83%

- 2.5% by weight of untreated activator and 1.5% by weight of wet strength agent (a.s. pulp) - 64%

1.5% by weight of the treated activator and 1.5% by weight of the wet strength agent (a.s. pulp) of - 56%.

Example 4

This example demonstrates the preparation and properties of so-called sterile filter plates as compared to filter plates of this type but containing activated cellulosic material as in accordance with the present invention.

Two types of filter plates were prepared containing 5% by weight of coniferous bleached sulphite pulp, 50% by weight of diatomaceous earth and 1.0% by weight (based on pulp) of a wet strength agent (commercial cationic polyamine-polyamide epichlorohydrin resin XP 4025 by AKZO NOBEL) . However, the pulp in the No. 5 filter plate was pulped and milled to a milling degree of 65 ^° SR while the pulp in the No. 6 filter plate sample was milled under the same conditions but to a milling degree of only 47 ° SR. 5% by weight of the treated activator (see Example 1) based on pulp time (see Table 3) was then added to both samples. The two filter plate samples were then prepared under the same conditions as described in the example

1.

The filter plates were then subjected to the same tests as in Example 1, i.e. tests with water and contaminated water with a black pigment dye at a concentration of 10 mg / l. The filtration area was again 30 cm ² , but the filtration pressure was 150 kPa.

Prior to each measurement, the filter bed was purged for 5 minutes at 150 kPa pressure with potable water and the water filter flow rate was determined. Filtration was detected

• « • · • • · * 9 • • * * • · • * • · • «I • • ··· · • • ··· • 9 • • * • * ♦ • t • • • • * · * *  · ♦ • «

the characteristics described in Examples 1 and 2, i.e. filtration efficiency, Y (%) (see Example 1), and specific filtrate flow rate, qiso (lmAMmin ¹ ), at a filtration pressure of 150 kPa depending on the specific amount of filtrate, Vs ( lm ' ² ). The results of these measurements are shown in Table 4.

Table 3.

Plate C. Coniferous pulp Weight % Grinding degree ° SR Kieselguhr Weight % Wet strength agent Weight % Activator modified Weight % 5 50 65 50 1 - 6 50 47 50 1 5

Table IV.

Board No. 5 Board No. 6 in ₅ Y Q150 Y qi5o (%) (l.mAMmin ¹ ) (%) (lm ' ² , min'') 150 85.3 76.8 96.7 68.7 300 83.0 76.8 96.7 71.1 450 80.2 75.7 96.9 61.9 600 78.4 63.1 97.2 52.8 775 77.7 50.5 97.5 64.3 1050 80.2 40.0 98.2 32.6 1325 83.4 29.6 96.8 23.1 1600 85.2 21.5 95.6 22.1 1875 85.7 16.4 94.1 18.0 2150 90.4 12.4 91.6 13.8 2425 92.0 10.0 97.7 10.2 2700 94.0 8.1 98.5 9.8

, "* · · · · ·» · «(* · ·· ·· · * * * * * · ·· · ** ·» · t _"(t *» * · ·· · ** ♦

Marks used: V _s - specific amount of filtrate; Y - filtration efficiency; qi50 - specific filtrate flow rate at 150 kPa

Example 5% conifer bleached kraft pulp and 60% deciduous bleached kraft pulp were mixed in a pulper and then milled at 3% consistency to 37 ^° SR. 20% by weight of perlite and diatomaceous earth mixed 1: 1 based on the total weight of the pulp were used as fillers. This pulp was further blended with fibrous oxycellulose containing 15 wt% COOH groups of 0, 20 and 40% oxycellulose va.s. pulp - designation FD 0, FD 20, FD 40. In addition, pulp of the same composition was prepared by adding 2.5% of the untreated activator, calculated on weight and pulp, after milling the fibrous raw materials, as described in Example 1 of the designation FD R0 , FD R20 and FD R40.

As a wet strength paper, commercially available polyamine-polyamide epichlorohydrin resin XP 4025 by AKZO NOBEL was used in an amount of 1.5% by weight based on the total a.s. filter plate weight.

After mixing all of the above components, the individual stock was diluted to 0.5% consistency and made into a 3 mm sheet of filter plate on a dewatering apparatus and dried.

Already in the dewatering of individual pulp there were noticeable differences in their dewatering. The order of their drainage capabilities follows:

FD R40 FD R20 FD R0 FD 0 FD 20 FD 40

Pulp containing cationic activator was the fastest to dewater, and pulp containing oxycellulose was the worst.

The filter plates obtained were subjected to similar tests as in Example 1, i.e. with water and water contaminated with Fe ions of 3 mg / l and pH = 5.7. Determination of ferrous ions was performed spectrophotometrically. The water flow rate of all filters tested was measured at 100 kPa. The contaminated water experiments were carried out with a 30 cm filter baffle at a filtration pressure of 100 kPa. Prior to each measurement, the filter bed was purged for 5 minutes at 50 kPa pressure with potable water, after which the water filter flow rate was determined. Again, as in Example 1, the filtration efficiency, Y (%), and the specific flow rate of the filtrate, q max (lmAMmin ¹ ), were monitored at a filtration pressure of 100 kPa depending on the specific amount of filtrate, V s (lm '). The results of these measurements are shown in Tab. 5 and compared at constant Vs = 300 (l.m ^-2 ). The results show a positive effect of oxycellulose on the separation of dissolved iron by a filter plate from water. The presence of oxycellulose in non-activated filter plates results in a decrease in their permeability. The transfer of hydrocolloid forms of oxycellulose from the pore surface to the interior of the activated pulp fibers then removes this deficiency while maintaining the original separating properties of the filter plate.

Table 5.

Marking of filter plates Qioo (lm ^ .mm ¹ ) Y (%) FD0 61 5.80 FD 20 26.5 17.8 FD 40 25.5 30.5 FDR0 65.3 5.6 FDR20 65.5 20.0 FDR40 64.8 35.6

Marks used: V _s - specific amount of filtrate, (l.m ' ² ) = 300; Y - filtration efficiency, qioo - specific filtrate flow at 100 kPa

Example 6

The separation of heavy metals in this case again represented by iron Fe in the form of ferroin by means of colloidal sorption sedimentation is demonstrated in this example.

Oxycellulose from cotton liners, its H-form, was used as the main separation component of anionic nature. The oxycellulose used in the fibrous form contained 18% of COOH groups and a polymerization degree of DP = 36. For the experiments it was used in the fibrous form - OC VI and the hydrocolloid form - OC H1, obtained by suitable grinding of the fibrous form of oxycellulose into hydrogel form %. For use, both forms of oxycellulose OC VI and OC H1 were further diluted with distilled water to a concentration of 4 g / L to form a suspension of OC VI and an OC H1 hydrocolloid system.

Pulped bleached MgBi-sulphite spruce pulp pulled at 3% consistency in a laboratory pulper at 15 ° SR - unactivated pulp was also used. This pulp was also activated by the procedure of Example 1 by adding 2.5% treated activator by adding 10% sodium hydroxide solution. , calculated on the weight as pulp - activated pulp.

The model water system consisted of 40 parts by volume of variously concentrated Fe solutions in the form of ferroin (complex with 1,10-phenanthroline, then acetate buffer and hydroxylamine hydrochloride) and 50 parts by volume of diluted oxycelluloses OC VI and OC H1. After 30 minutes of reaction of oxycellulose and Fe solution (sorption), the pulp was added to the suspension at 0%, 57.5%, 72.1%, 82.6% and 100% pulp of the total polysaccharide content. After the pulp was added, the contents of the container were mixed well and allowed to stand for some time. After rheosedimentation, 10 ml of the filtrate was pipetted from the top of the contents of the roller so as not to contain suspension fibers. Absorbance was measured for the filtrate and the remaining ferroin content was determined. Similar to Example 1, the separation efficiency was calculated. If c _{0 is the} initial feroin concentration in the mixture without the polysaccharide components (g / l) and c the feroin concentration in the mixture with the polysaccharide components in g Fe / 1, then the amount of Fe ²⁺ (Fe ² 'dose) captured in g Fe ²⁺ / g oxycellulose is given by the formula na naad, where ^{X is} oxy

wherein the resulting oxycellulose concentration in the fiber suspension in g OC / l and the separation efficiency is a relationship

Co C _o

Activated and non-activated pulp samples were tested side by side.

The results are presented in Fig. 5. The results show the enormous effect of the hydrocolloid form of oxycellulose on the separation efficiency compared to its fibrous form. There is also a significant positive effect on this separation efficiency of the activated pulp as a carrier that induces flocculation of the fibrous form of oxycellulose and surface flocculation of their hydrocolloid forms with entrapped iron.

Example 7

An active inverse nanoprocess with biomaterials from phytomass is demonstrated by this example in the washing of pulp obtained by chemical treatment of coniferous wood by the sulfate process.

The unbleached kraft softwood pulp in the form of a fibrous wet cake of 25% consistency was thoroughly washed under equilibrium with clean water after a batch, and finally washed with distilled water. Then the content of its contamination by lignin and other accompanying substances was determined using the Kappa number, which increases in proportion to the increasing content of these substances in the cellulose. For the original pulp, the Kappa Number was 31.5, after washing with distilled water, it fell to 24.2 for the pulp bed. After washing with test substances, the Kappa numbers of the pulp bed were reduced by up to 4 units relative to distilled water. The pretreated pulp was then washed under the same conditions with variously concentrated KCl solutions (0.8 and 1% by weight) as inert, followed by 1 and 3% by weight solutions of urea, formamide, N, N dimethylformamide and acetamide.

The results of these experiments are shown in Figure 6. These show the positive effect of substances known to significantly affect the hydration forces - usually increasing the repulsive hydration forces, i.e., loosening the binding system of the hydration bonds - on the intensity of the washing process.

Industrial applicability

BACKGROUND OF THE INVENTION The present invention relates to materials enabling active nanoprocesses to capture and separate from water and aqueous systems colloids of anionic nature and heavy metal cations by conventional separation processes such as filtration, sedimentation or flotation, to increase the permeability of filter beds with active hydrocolloids and to increase the release of accompanying substances. in the washing of cellulose-based pulp in both fibrous and leaf form, so that the treated water is more applicable in all areas of human activity, particularly in the treatment of wastewater and various water-containing systems.

Claims (9)

PATENT CLAIMS What is claimed is: 1. A method for carrying out active nanoprocesses on a polysaccharide-based material, characterized in that the ability of the polysaccharide-based material to induce agglomeration of particles in the nanospace around the micro-surfaces of the fibers or pores of the polysaccharide-based material is modified. Method according to claim 1, characterized in that the polysaccharide-based material is a phytomass-derived material, in particular a cellulose-based material, preferably any cellulose-based fiber selected from the group comprising cotton, silk and pulp such as unbleached and bleached broadleaved, coniferous sulphate pulp and unbleached and bleached pulps of annual plants, unbleached and bleached coniferous sulphite pulp, pulp containing more than 95% alpha-cellulose or mixtures thereof and high lignin-containing pulp, such as wood pulp, thermomechanical pulp (TMP) or chemothermomechanical pulp (CTMP) or mixtures of all of these fibers, at least one of the fibrous, microfibrous, granular or powder forms being milled to 15 to 70 degrees according to Schopper-Riegler, optionally mixed with up to 60% by weight of other fibrous materials and fillers. The method of claim 1, wherein the active nanoprocess is an active separation nanoprocess, and wherein the ability of the polysaccharide-based material to induce agglomeration of particles around the material is increased by activating the polysaccharide-based material with an activator which is a cationic oligomeric substance. an epoxy base comprising quaternary amino groups derived from aliphatic amines, wherein the activation is carried out by reacting 1 part by weight of a polysaccharide-based material in the form of a pulp slurry at a temperature in the range of 15-30 ° C at pH 7-10, with 0.001 to 0.1 parts by weight of activator for at least 10 minutes. 4. A process according to claim 3, wherein the activator is an activator comprising quaternary 2-hydroxypropyl dimethylammonium chlorides of the formula I: ch ₃ AND R-CH ₂ -CH-CH ₂ -N ⁺ -CH ₂ -E X '(I), II OHCH ch ₃ wherein R is N ⁺ -CH ₂ -EX 'or Cl; Eje ch-ch ₂ or CH-CH ₂ Cl a 1 (l) 1 ch ₃ 0 OH X 'is a chloride anion prepared by the reaction between epichlorohydrin and dimethylamine in a molar ratio of 1.2 to 2.0: 1 and containing, in the untreated state, at least 0.1% by weight of epoxy groups, optionally with the addition of sodium hydroxide. The method of claim 1, wherein the active nanoprocess is targeted particle release, and wherein the ability of the polysaccharide-based material to induce agglomeration of particles in its vicinity is reduced by washing the polysaccharide-based material with a substance selected from the group consisting of urea, acetamide, formamide and N, N-dimethylformamide. Use of the activated polysaccharide-based material according to claim 3 for carrying out active separation nanoprocesses, in particular nanoprocesses making it possible to capture and separate from water and aqueous systems colloids of anionic nature and cations of particularly heavy metals by conventional separation processes such as filtration, sedimentation or flotation and permeability of filter beds with active hydrocolloids. Use according to claim 6, wherein the polysaccharide-based material is in admixture with a modified anionic polysaccharide selected from the group consisting of oxycellulose or oxidized starch containing 1.0 to 25% by weight of carboxyl groups, preferably 5 to 18% by weight of COOH and carboxymethylcellulose having a degree of substitution of 0.1 to 1.0 in fibrous, particulate, hydrocolloid or completely soluble form. Use according to claim 6, wherein the activated polysaccharide-based material is a sorption filter plate obtainable from an aqueous suspension comprising cellulosic material with increased ability to induce agglomeration of particles in its vicinity and fine fillers, optionally the addition of a wet strength agent, by conventional paper method or by a papermaking process making it possible to produce shaped molds from paper pulp. Sorption filter plates, characterized in that the papermaking suspension for their preparation comprises up to 60% by weight of the filler, modified polysaccharide materials according to claim 7 and / or a mixture thereof and 100 to 40% by weight pulps according to claim 2, preferably activated by the process according to claim 3 and 4 as the main filter plate forming the component, added to the overall balance of the furnish.