Composition and method for treating fibrous material

FIELD: chemistry.

SUBSTANCE: disclosed is a stabilising composition containing (A) a polymer of formula , where R1 is hydrogen or C1-12-alkyl, R2-COOM or -CH2COOM; M is hydrogen, an alkali or alkali-earth metal ion, or an ammonium ion or mixture thereof; n, m and k are molar ratios of monomers, where n ranges from 0 to 0.95, m ranges from 0.05 to 0.9 and k ranges from 0 to 0.8, and (n+m+k)=1, and the weight-average molecular weight ranges from 500 to 20 000 000 g/mol; (B) a chelating agent; (C) poly-alpha-hydroxyacrylic acid or alkaline salt thereof, or corresponding polylactone thereof, and (D) possibly a polycarboxylic acid polymer or alkaline salt thereof. The invention also discloses a method of treating fibrous material with said stabilising composition.

EFFECT: disclosed composition has a synergetic stabilising effect compared to existing stabilisers.

28 cl, 5 tbl, 8 ex

 

The technical FIELD

The present invention relates to compositions comprising at least two polymer chelating agent, and method for processing fibrous material, in particular cellulose fiber material, in the presence of at least two polymers and a chelating agent. The composition can be used as a tool during peroxide bleaching of pulp, mechanical wood pulp, chemical-mechanical pulp and refined wastepaper pulp, and also for processing when the cleansing of the paint recycled fibers and in alkaline peroxide bleaching of wood pulp, cellulose, chemical-mechanical pulp and refined wastepaper pulp. In addition, the composition can be used in the cleansing of the paint fibers from recycled materials. The composition is partially or completely replaces the silicate as a stabilizer, particularly in the processing of wood pulp and refined wastepaper pulp. The present invention also relates to a method of bleaching cellulosic fibrous material peroxide compound in an aqueous-alkaline medium by using the specified composition.

PRIOR art

It is well known that for removal of harmful ions of metals, that is, as a rule, ions such transition metals as iron and manganese, when pre-treatment is before bleaching pulp peroxide compound, such as hydrogen peroxide, peracetic acid or acid Caro, can be used chelating agents. During alkaline peroxide bleaching wood pulp with the bleaching refined deinked pulp (DIP), derived from recycled waste paper, and when ochisheniya from paint recycled waste paper can be added liquid glass (silicate of alkaline metal and chelating agent.

Because conventional chelating agents such as polyaminopolycarboxylate, for example ethylenediaminetetraacetic acid etc (EDTA) and diethylenetriaminepentaacetic acid, DTPA (DTPA), and the corresponding derivatives methylenephosphonic acid and polyamines, are non-biodegradable substances or have low Biodegradability, the aim is to reduce the use of conventional chelating agents in the pre-treatment or as agents for processing.

Solutions of alkali metal silicates, commonly called liquid glass, is used to stabilize solutions of hydrogen peroxide used in alkaline peroxide bleaching wood pulp.

Liquid glass by itself or together with the peroxide used in the cleansing of the paint recycled paper. Sometimes ennobled waste a lot also bleached with alkaline peroxide solution.

Opublikovannye about using liquid glass in alkaline peroxide bleaching of pulp, however, this method cannot be used on an industrial scale, since the silicate can lead to very serious problems caused by sedimentation. Another disadvantage associated with the use of liquid glass, is the fact that when the oxide liquid recyclist and eventually served in the boiler regenerator, where after concentrating burn the so-called black liquor from the pulping process, the silicate will cause severe salt deposition and thereby reduce heat transfer in the boiler-regenerator, which in worst case can lead to an explosion of the boiler of the regenerator. In addition, it is known that silicates break izvesteobzhigatel furnace. The same applies to the case of mechanical or chemical-mechanical installation combined with the pulp mill so that the waste water containing silicates are going to cycle recovery pulp mill. In addition, if the plant for the production of chemi-thermomechanical pulp (STMR) has its own setting for evaporation, deposition of silicates will cause problems, because they are deposited on the site residue, reducing thermal conductivity.

If silicates, for example, is carried out with water, get into the process of getting the paper, they will break the paper manufacturing process, for example, due to osuzhdeni is on a hot surface, leading to the formation of holes in the paper roll and the like.

It is known that hydrogen peroxide will quickly decompose in alkaline medium in the presence of transition metal ions. In the pulp mass of these ions, the most common iron and manganese. Ion copper is also extremely unfavorable for alkaline hydrogen peroxide, however, as a rule, he can get into the process only through the used process water.

In addition, it is known that iron will begin to precipitate at a pH value below 7, first, in the colloidal form. The formed hydroxide, iron hydroxide, etc. are catalytically more active than iron ions. Manganese may also at least partially be present in precipitated form, however, requires that in the presence of hydrogen peroxide manganese was dissolved.

theory of the action of liquid glass is different, but one theory is that liquid glass will deactivate the catalytic surface "precipitation" ions of iron and other heavy metals. In order to avoid the negative effects of manganese ions in the bleaching process are often administered chelating agent or wood pulp previously treated with chelating agent. The most well-known chelating agents are EDTA DTPA, belonging to the group of polyaminopolycarboxylate. Can also be used the corresponding phosphonates, EDTMPA and DTPMPA, however, they are significantly more expensive than polyaminopolycarboxylate. To their nedostatki also true that they contain phosphorus, which is an undesirable component in conditions where environmental standards are becoming more and more hard.

When the cleansing of the paint waste liquid glass performs other functions, such as liquid glass improves the separation of the paint, it will be atomized paint and act as a buffering agent that maintains a constant pH. Thus, it would be useful also partial replacement of liquid glass, which at the same time would lead to the reduction of the problems of precipitation caused by the use of liquid glass.

In accordance with the foregoing, there is a need for partial or complete replacement of liquid glass (silicates) in the processes of alkaline peroxide bleaching and pulping processes that use liquid glass, for example, when alkaline peroxide bleaching wood pulp and refined wastepaper pulp, and also the cleansing from paint recycled paper. There are proposals to use phosphonates, but they should be used in fairly high doses and then in Peenemunde to be the problem of the presence of phosphorus in the wastewater. Since the known phosphonates are non-biodegradable substances, conducted a lot of research regarding their adverse effects on the movement of heavy metals, for example, from the sediment into the watercourse. In the case of phosphonates their dose should be reduced.

In patent document Japan JP 1266295 (published 24 October 1989) described a method of pre-processing when bleaching pulp with hydrogen peroxide in alkaline conditions in the presence of sodium silicate with added during preview processing of 0.05-1 wt.% (based on dry weight) of a copolymer of 3-allyloxy-2-hydroxypropanesulfonic acid (AHPS) and (meth)acrylic acid.

In accordance with the patent application of Japan JP 1148890 (published 12 July 1989) polymer of the same type in the amount of 0.05-1 wt.% (based on dry weight) is used instead, for example, DTPA during alkaline peroxide bleaching. In the patent document JP 1148890 presents bleaching characteristics of the various copolymers of acrylic acid and AHPS in comparison, for example, with the characteristics of DTPA.

In both patent applications JP investigated quantities were large enough, because usually chelating agents are used in quantities of from 0.5 to 2 kg per 1 ton of wood pulp, in terms of 100% sodium salt.

In patent document E is 0814193 not disclosed containing silicate stabilizing agent for peroxide bleaching, includes a) a first component selected from homopolymers of alpha-hydroxyacrylates acid and copolymers of alpha-hydroxyacrylates acid with other comonomers, and water-soluble salts and polylactones the above-mentioned Homo - or copolymers in combination with (b) a second component selected from homopolymers and copolymers of acrylic acid, methacrylic acid and maleic acid, copolymers of at least one of the above acids with other comonomers and salts of the above-mentioned homopolymers and copolymers, and (C) a third component selected from conventional chelating acid DTPA, TNA (Triethylenetetramine acid) and their salts and, optionally, d) a fourth component selected from water-soluble salts of magnesium. Poly-alpha-hydroxyanisole acid (RNA) is used in the form of its sodium salt.

In the patent document WO 2005080673 (hereinafter referred to as WO 1) disclosed a method of bleaching fibrous material with alkaline peroxide solution in the presence of a chelating agent and a copolymer of 3-allyloxy-2-hydroxypropanesulfonic acid (AHPS) with (meth)acrylic acid, maleic acid or takenaway acid. In this patent application also disclosed a composition comprising a specified copolymer and a chelating agent, used as a stabilizer when Melo the but-peroxide bleaching for partial or complete replacement of liquid glass and the bleaching of fibrous material.

In the patent document WO 2005108673 (WO 2) revealed the same composition, optionally comprising salt, alkaline earth metal, and its application.

In the patent document WO 2004063461 (WO 3) disclosed the composition of the alkali metal salts of poly-alpha-hydroxyacrylates acid (RNA) and polycarboxylate polymer, and the use of the composition in alkaline peroxide bleaching wood pulp and the cleansing of the paint, the composition is prepared from alkali metal salts of RNA and the crude acid polycarboxylate polymer.

In the patent document WO 2004063276 (WO 4) disclosed a composition corresponding polylactones RNA and polycarboxylate salt, and the use of the composition in alkaline peroxide bleaching wood pulp and the cleansing of the paint, the composition is prepared by adding the appropriate polylactones RNA in the crude acid polycarboxylate.

Despite the fact that these songs work well in many areas, apparently, they will cease to act in the case of softwoods (conifers) and/or when the content of manganese and iron in wood weight will be high.

The INVENTION

In accordance with the present invention it was unexpectedly found that when using a copolymer of 3-allyloxy-2-hydroxypropanesulfonic acid (AHPS) and nenasi the military carboxylic acid, such as acrylic acid, methacrylic acid, maleic acid or taconova acid, together with a chelating agent and a polymer composition prepared from alkali metal salts of poly-alpha-hydroxyacrylates acid (RNA) and polycarboxylate polymer, or prepared from the corresponding polylactones RNA and polycarboxylate polymer mixed with each other or added separately, can be achieved with high efficiency bleach, and can be carried out a complete replacement of liquid glass, if necessary from the point of view of the pulping and paper production. Unexpectedly, the combination of these polymers, chelating agent showed the best result compared with the result from the combination of AHPS-containing copolymer and a chelating agent, or from a combination of alkali metal salts of RNA and polycarboxylate polymer or copolymer, or from a combination of the corresponding polylactones RNA with polycarboxylate polymer or copolymer. The test results unexpectedly showed a clear synergistic effect.

The combination of at least two polymers, i.e S-containing copolymer and alkali metal salts of RNA or her respective polylactones, and a chelating agent, and optionally a third polymer, namely polycarboxylate polymer and copolymer, can be effectively used as a stabilizer in bleaching wood pulp or refined wastepaper pulp with peroxide compounds such as hydrogen peroxide, peracetic acid or acid Caro. The present invention by using a combination of at least two polymers and a chelating agent can partially or completely replace the liquid glass in the bleaching and cleansing of the paint.

The present invention provides a method of processing fibrous material, comprising a stage of contacting the fibrous material in the aqueous medium AHPS-containing copolymer, a chelating agent, a poly-alpha-hydroxyacrylates acid or its salt or polylactones and possibly polycarboxylate polymer or copolymer. Components, comprising at least two polymer chelating agent can be added separately or preferably in the form of a ready mix (song).

The present invention also relates to compositions comprising AHPS-containing copolymer, a chelating agent, RNA or its salt or Polyglactin and possibly polycarboxylate polymer or copolymer.

The composition and method according to the invention can be used in the pre-treatment of cellulose, wood pulp, chemical-mechanical pulp and lavorogenova wastepaper pulp, bleach with alkaline peroxide.

The composition and method according to the invention can also be used for bleaching of all types of pulp, wood pulp, chemical-mechanical pulp and refined wastepaper pulp using hydrogen peroxide as a bleaching agent.

In addition, these composition and method are used in the cleansing of the paint waste mass, which typically use liquid glass and hydrogen peroxide.

This composition may also be used for bleaching dithionite sodium wood pulp and refined wastepaper pulp.

Alkaline peroxide bleaching wood pulp, chemical-mechanical pulp and treated paper pulp according to the invention in practice can be done either in the form of a single-stage bleaching, or in the form of a two-stage process, where the pre-bleached the mass is fed to the second stage. Can be used in any concentration, but it is most preferable to use the average concentration in the first stage and a high concentration in the second stage.

If necessary, the bleaching may be preceded by pre-treatment of chelating agent to reduce the amount of transition metals entering the bleaching process.

When the cleansing of the paint composition according to the present from which retenu can be used for secondary grinding or dispersant, or in a kneading machine, after which you may be provided the tower for the locks, which may be hydrogen peroxide. When the cleansing of the paint composition according to the present invention can also be used on single stage bleaching or at any stage of the process where hydrogen peroxide.

The composition, in the form of a ready mix or a combination of at least two polymers and a chelating agent can be used as full or partial replacement of liquid glass in those processes where it is typically used liquid glass.

The composition or components of the composition is preferably not added to the hydrogen peroxide or alkali, or in liquid for alkaline peroxide bleaching, or liquid glass, if liquid glass only partially replace the components or composition according to the invention, as this will reduce effectiveness. The composition or components of the composition should be added to the wood pulp prior to its contacting with the alkali or alkaline oxide liquid. From this time can vary from less than one second to several minutes depending on add whether the composition or components according to the invention separately from the alkaline components in the chemical mixer or composition or components added to the mass, p is improper bleaching, at an earlier stage of the process where it can be guaranteed a good mixing of the compositions or components. The reason for this is unknown, but it is assumed that the alkali will begin to precipitate one or more polymer components, thereby making impossible a good mixing of the composition or polymer components. Thus, the preferred location of the add is the place where can be achieved with good mixing of the composition or components of the pulp mass, subject to bleaching.

It is unknown why it is easier to get good results from bleaching with alkaline peroxide bleaching without the use of silicate pulp from hardwoods (deciduous trees)than in the case of softwoods (coniferous trees). It is known that alkaline peroxide bleaching hardwoods initial pH value, say, 10,5, will quickly be reduced to less than 7, while alkaline peroxide bleaching of softwood final pH will be maintained above 8. It is known that peroxide is less stable at higher pH values. Due to this reason, this particular could be the pH profile during alkaline peroxide bleaching without the use of silicate.

In addition, it is shown that the relative belmost various tree masses derived from the od of sakovych wood, obeys the following laws: GW (groundwood pulp) > PGW (press groundwood pulp) > STMR (chemi-thermomechanical pulp) > TSR (tmp) > RMP (refiner wood pulp) (Presley, J.R, and Hill, R.T., Section V, Section V: The Technology of Mechanical Pulp Bleaching; Chapter 1: Peroxide Bleaching of (Chemi) mechanical Pulps in the Pulp Bleaching - Principle and Practice (Technology of bleaching wood pulp. Chapter 1: Peroxide bleaching chemical-mechanical pulp in the bleaching of pulp - Fundamentals and practice), Dence, W.C. and Reeve, D.W. Tappi Press, Atlanta, Georgia, the USA, p.463). This feature should be taken into account when comparing the results of bleaching for different grades of wood pulp. The processing of wood pulp in the refiner (RMP) is a now obsolete method of processing.

Theoretical basics of how the components will work together, unclear, since the copolymer containing AHPS may not sufficiently stabilize alkaline solutions of hydrogen peroxide and, in addition, gives, as a rule, unsatisfactory efficiency of bleaching. Chelating agents are fairly well stabilized by the above-mentioned alkaline peroxide solution, but can not give good results from bleaching. Common chelating agents mentioned above, will bind soluble manganese ions in alkaline peroxide solutions, but because so is m the case of iron will be in the solid, colloidal or precipitated form, chelating agents will not be able to associate a solid connection. The same is true for solid forms of compounds of manganese. Alkaline salt RNA or appropriate polylactam will give good results from bleaching, particularly at low concentrations of manganese and iron.

Polymer composition with a chelating agent in accordance with the invention can somehow get in contact with a solid surface or inactivate the catalytic activity of solid particles. Thus is obtained the total effect. Common chelating agents can't, when you use them to give a good efficiency of the bleaching of wood mass and refined junk masses, significant strengthening of lightening and a sufficient amount of residual peroxide, indicating that the peroxide is consumed mainly during bleaching, and not as a result of decomposition processes, and unreacted hydrogen peroxide can be recyclebank back in bleaching. Thus, between the components used in accordance with the invention, there must be some synergistic effect.

One of the characteristic features of the invention is that when using the composition or components of the composition according to the invention the characteristics of the dewatering will be significantly improved compared with the options, when using liquid glass. This will mean that you will need significantly less energy for the processes of dehydration, for example, on a paper machine and dewatering presses and augers. Along with this can be increased productivity. The reason for this is unknown, but at least during the bleaching liquid glass should be in colloidal form. Colloids can be the reason that the characteristics of the dewatering of the pulp mass are not the best. Another reason for the negative impact on dehydration can serve the fact that liquid glass breaks the action of microparticles of silicon dioxide in the paper production process.

DETAILED description of the INVENTION

According to the first aspect of the present invention proposed a stabilizing composition comprising the following components:

(A) a polymer having the following formula:

where R1represents a hydrogen atom or an alkyl group containing from 1 to 12 carbon atoms,

R2means-SOOMA or-CH2The SOOMA,

M is a hydrogen atom, an alkali metal ion, alkali earth metal ion, ammonium ion or mixtures thereof,

n, m and k represent molar ratios of the respective monomers, where n comp is made from 0 to 0.95, m is from 0.05 to 0.9, and k is from 0 to 0.8, and the sum (n+m+k) is equal to 1, and

srednevekovaja molecular weight is from 500 to 20000000 g/mol,

(B) a chelating agent,

(C) poly-alpha-hydroxyanisole acid or its alkaline salt or its corresponding polylactam,

(D) optional polymer polycarboxylic acid or its alkali salt. According to the second aspect of the present invention, a method for processing fibrous material, comprising a stage of contacting the fibrous material in the aquatic environment with the following components:

(A) a polymer having the following General formula:

where R1represents a hydrogen atom or an alkyl group containing from 1 to 12 carbon atoms,

R2means-SOOMA or-CH2The SOOMA,

M is a hydrogen atom, an alkali metal ion, alkali earth metal ion, ammonium ion or mixtures thereof,

n, m and k represent molar ratios of the respective monomers, where n is from 0 to 0.95, m is from 0.05 to 0.9, and k is from 0 to 0.8, and the sum (n+m+k) is equal to 1, and

srednevekovaja molecular weight is from 500 to 20000000 g/mol,

(B) a chelating agent,

(C) poly-alpha-hydroxyacrylates acid or its alkaline salt or its corresponding polylactones,

(D) optional what about with polymer polycarboxylic acid or its alkali salt.

The composition of the present invention can be used as a stabilizer when the bleaching of fibrous material in the aquatic environment or as a stabilizer when the cleansing of the paint recycled fibrous material.

The above-mentioned alkali metal ion preferably represents a sodium ion or potassium, and ion alkaline earth metal is preferably magnesium ion.

The above-mentioned alkaline salt is preferably a salt of sodium, potassium or magnesium.

With regard to component (A), the preferred co monomer with AHPS are acrylic acid (R1=H), methacrylic acid (R1=CH3), maleic acid (R2=COOM) or taconova acid (R2=CH2COOM). If k is equal to 0 in the formula I, the preferred co monomer is acrylic acid or methacrylic acid, and if n is equal to 0, the preferred co monomer is maleic acid or taconova acid. In cases where neither k nor n is equal to 0, the preferred comonomers with AHPS will be (meth)acrylic acid and maleic acid or taconova acid.

The monomers are randomly distributed along the polymer chain of the formula I, while it is preferable to n ranged from 0.4 to 0.9, m is from 0.1 to 0.5 and k ranged from 0 to 0.5.

If the system is in the pre-treatment or with alkaline peroxide the OTB is ke contains significant amounts of calcium ions, as in the case of the so-called circulating water from paper production, circulating during operations pulping and/or bleaching of pulp, as one of the comonomers, it is desirable to use maleic acid or taconova acid (k>0)to increase binding capacity of the polymer with respect to calcium. In normal cases, it is preferable that the polymer included only AHPS and a monomer containing one carboxylic acid such as acrylic acid as a copolymer containing a variety of monomers, usually more difficult to get.

Srednevekovaja molecular weight of the copolymer of formula I should be in the range from 500 to 20000000 g/mol, preferably from 1000 to 1000000 g/mol and most preferably from 2,000 to 500,000 g/mol.

If srednevekovaja molecular weight less than about 500 g/mol, the effectiveness of the polymer becomes low. If the average molecular weight exceeds 2000000 g/mol, transportation and dispensing of compounded due to the high viscosity of the polymer solution.

To increase the molecular weight of the copolymer and/or improve the efficiency of the copolymer can be used cross-linker (crosslinking agent) in an amount of from 0 to 20 mol.%, preferably from 0 to 10 mol.% of the total monomer content. Suitable cross-linkers include, for example, methylenebisacrylamide, Divin levy ether of ethylene glycol, divinely ether di(ethylene glycol), divinely ether three(ethylene glycol) and polymers with terminal vinyl or allyl groups, but the list is not limited.

To reduce the molecular weight of the copolymer and/or to improve the efficiency of the copolymer can be used, the vector of the kinetic chain in an amount of from 0 to 20 mol.%, preferably from 0 to 10 mol.% of the total monomer content. Suitable vectors kinetic chain are, for example, thiols (e.g., butylmercaptan) and alcohols (e.g. isopropanol), but the list is not limited.

Chelating agent (B)used together with the copolymer (A) of formula I, may be a chelating agent having the formula II, III or IV, below.

The preferred chelating agent is a compound having the following General formula:

where p is 0 or an integer from 1 to 10,

R3, R4, R5, R6and R7independently represent a hydrogen atom or an alkyl chain containing from 1 to 6 carbon atoms and having one or more active chelating ligands such as carboxylic, phosphonic or hydroxyl group (s) or their salts.

The alkyl chain is preferably a methylene-CH2- or ethylene-CH2CH2-.

Fo the mule II R 3, R4, R6and R7preferably represent the same group.

Examples of chelating agents according to the above formula II are polyaminopolycarboxylic acid and polyaminopolycarboxylic acid.

Polyaminopolycarboxylic acid can be obtained in the usual way from polyamine, formaldehyde and sodium cyanide or hydrocyanic acid. A more preferred method for small-scale production is the use of halogenases acid, in particular monochloracetic acid.

Preferred polyaminopolycarboxylic acids are:

DTPA:p=1, R3=R4=R5=R6=R7=-CH2COOH
TNA:p=2, R3=R4=R5=R6=R7=-CH2COOH
EDTA:R=0, R3=R4=R5=R6=-CH2COOH
HEDTA:R=0, R3=R4=R5=-CH2COOH, R5=-CH2CH2OH (N-hydroxyethylenediaminetriacetate)
EDDS:R=0, R3=R5=N, R4=R6=-CH(COOH)CH 2COOH (ethylenediaminetetra acid)

Polyaminopolycarboxylic acid get in the traditional way from the corresponding polyamine, formaldehyde, and phosphonic acid. In the case of higher amines complete substitution of acetyl groups or methylenephosphonate groups will be more and more complex. Such chelating agents will also be effective in the composition, but incomplete substitution will make chelating agents are more prone to decomposition under the action of hydrogen peroxide.

Preferred polyaminopolycarboxylic acids are:

DTPMPA:p=1, R3=R4=R5=R6=R7=-CH2PO2H2
TTMRA:p=2, R3=R4=R5=R6=R7=-CH2PO2H2
EDTMPA:p=0, R3=R4=R5=R6=-CH2PO2H2

Other preferred chelating agent is a compound having the following General formula:

where q is an integer from 3 to 10,

R3, R4, R5and R6independently represent an atom in Dorada or alkyl chain, containing from 1 to 6 carbon atoms and having one or more active chelating ligands such as carboxylic, phosphonic or hydroxyl group (s) or their salts.

The alkyl chain is preferably a methylene-CH2- or ethylene-CH2CH2-

In formula III, R3, R4and R6preferably represent the same group.

Examples of chelating agents in accordance with the above formula III are commercially available hexamethylenediaminetetra acid (q=6) and Tetraethylenepentamine(methylenephosphonate acid) (q=4), having the following formula:

hexamethylenediaminetetra acid,

tetramethylaniline(methylenephosphonate acid).

Another preferred chelating agent is a compound having the following General formula:

where R8represents a hydrogen atom, alkyl group containing from 1 to 6 carbon atoms, or an alkyl chain containing from 1 to 6 carbon atoms and containing carboxylic, phosphonic or hydroxyl group,

R9represents a hydrogen atom, hydroxyl group, phosphonic group, a carboxyl group or an alkyl chain containing from 1 is about 6 carbon atoms and having one or two carboxyl groups, and

R10represents a hydrogen atom, hydroxyl group, carboxyl group, alkyl group containing from 1 to 6 carbon atoms, or an alkyl chain containing from 1 to 6 carbon atoms and having a carboxyl group or its salt.

The alkyl chain is preferably a methylene-CH2or ethylene

-CH2CH2-.

The example does not contain nitrogen chelating agents in accordance with the above formula IV is 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP).

Another preferred chelating agent is a compound having the following General formula:

where R11represents a

a hydrogen atom,

alkyl chain containing 1-30 carbon atoms,

alkyl chain containing 1-30 carbon atoms and 1-10 carboxylic groups attached to the chain, or its salt of the alkali or alkaline earth metal,

alkyl chain containing 1-30 carbon atoms and 1-10 esters of carboxylic acids attached to this circuit,

polyethoxyethanol hydrocarbon chain containing 1-20 ethoxyline groups, or

amide carboxylic acid containing 1-30 carbon atoms, where the N-R11is an amide bond,

R12and R13represent hydrogen, alkali metal ion LiIon alkaline-earth metal or alkyl group, containing 1-30 carbon atoms,

r is 0 or 1, and

s is 0 or 1.

Preferred N-bis - or Tris-[(1,2-dicarboxylate)ethyl]amines of formula V are the following connections:

B1

B2

B3

D

B1 = N-bis-[2-(1,2-dicarboxylate)ethyl]amine,

B2 = N-bis-[2-(1,2-dicarboxylate)ethyl]aspartic acid,

B3 = N-Tris-[2-(1,2-dicarboxylate)ethyl]amine,

D = N-[2-(1,2-dicarboxylate)ethyl]-(N-2-hydroxyethyl)aspartic acid.

Preferred N-bis-(1,2-dicarboxyethyl)with the amine of formula V is iminediately acid (ISA), having the following formula:

Although formula chelating agents shown above as acids, they are usually sold in the form of their alkali salts, mainly in the form of sodium salts, and it should be understood that the formulas presented above, include both the free acids and their salts.

Component (C) is a poly-alpha-hydroxyanisole acid (RNA) or its alkaline salt or Polyglactin PHAA (PLAC). The polymer (C) may have a molecular weight of at least 5000, preferably at least 10000, more preferably at least 15000. Because polylactam is not soluble in water, molecular weight mouthbut measured for the corresponding sodium salt, obtained by alkaline hydrolysis of polylactones.

Optional component (D) is a polymer polycarboxylic acid or its alkali salt. Preferably, the polymer polycarboxylic acid was homopolymer acrylic acid or methacrylic acid or a copolymer of (meth)acrylic acid and other unsaturated carboxylic or dicarboxylic acid. The polymer polycarboxylic acid can be obtained by homopolymerization acrylic or methacrylic acid or by copolymerization of acrylic acid and/or methacrylic acid with an unsaturated carboxylic or dicarboxylic acid, such as maleic or taconova acid. The polymer (D) may have a molecular weight of at least 4000, preferably at least 10000, and more preferably at least 30,000. Molecular weight may be greater, although in the case of very large molecular masses at high concentrations the viscosity of the product will significantly increase.

It is preferable that the polymer (D) was comprised of a copolymer of acrylic and/or methacrylic acid with maleic acid, where the molar ratio of acrylic acid and/or methacrylic acid and maleic acid is from 80:20 to 20:80, preferably from 70:30 to 50:50. Maleic acid in the polymerization processes typically uses the I in the form of maleic anhydride.

The components of the invention can be in the form of alkaline salts, especially if the components are added separately or in the composition without alkaline salt RNA.

The composition in accordance with the invention can be prepared by mixing the alkaline salts. In order to avoid phase separation or sediment preferably, the pH value was less than 9, more preferably lower than 8 and most preferably below 7.

The composition may be prepared in any order of mixing. It can be prepared using the method presented in the patent applications WO3 and WO4. This means that the alkaline salt RNA or her polylactam add in raw polycarboxylate polymer (C). While the pH is maintained below 7. Then, in the above-mentioned polymer composition can be added alkali salt polymer (a) and the alkaline salt of the chelating agent (B), and thereby be able to avoid a very high pH.

If the composition comprises component (D), preferably to first admix the components (a) and (b) to component (D) and then to the resulting mixture add salt RNA or her Polyglactin (C). In order to obtain good stability of the composition during storage it is preferable that the polymer (D) was in the form of crude acid. Acidic pH values also provide good stability of the magnesium salt, is if one is to be used in the mixtures. Components (A), (b) and (D) as commercial products are usually available in the form of alkaline salts. Component (C), that is, RNA, also available in the form of alkaline salts. Of course, these alkaline salts can be mixed and react with the alkaline salt of RNA or her polylactones. This can cause phase separation and/or precipitate formation. Such mixtures can be used if storage tanks equipped with a stirrer. It is not typical for pulp and paper mills. Consequently, it is advisable that the composition had a pH value below 9, preferably lower than 8 and most preferably below 7, that is, had an acidic pH.

Polymers and chelating agent can be added separately or as a mixed composition.

The mass ratio of the compounds (A):(B):(C) may be from 0.1 to 1: 0.1 to 1:1, preferably from 0.25 to 1: 0.25 to 1:1, more preferably from 0.5 to 1: 0.5 to 1:1, in terms of the active substance.

The mass ratio of the compounds (A):(B):(C):(D) may be from 0.1 to 1: 0.1 to 1:1: 0.1 to 1, preferably from 0.25 to 1: 0.25 to 1:1: 0.25 to 1, more preferably from 0.5 to 1: 0.5 to 1:1: 0.5 to 1, 1, in terms of the active substance.

It is extremely important to have a sufficient amount of the polymer (A) or/and (D)not to deactivate the polymer (C). This will also facilitate and gelatin is the tender agent (component b).

The total amount of components (A), (b) and (C) and a possible component (D) (in the form of an aqueous product containing the component (C) in the form PLAC maximum 10%), added separately or in a mixture, is preferably 2 to 10 kg per ton of dry fiber material, more preferably 2-6 kg per tonne of dry fibrous material, and most preferably from 2 to 5 kg per ton of dry fibrous material.

The fibrous material preferably is a cellulose fiber material, in particular wood pulp, chemical-mechanical pulp or treated waste mass. Cellulosic fibrous material may be cellulose or any regenerated cellulose material, such as rayon, or linen, or cotton.

For composite mixture, prepared in accordance with the invention, the normal concentration of active substances in a mixture can be at least 10%, preferably at least 15% and more preferably at least 20 wt.%, but in the claimed process can also be used and more diluted solutions by increasing dosage.

According to one of embodiments of the method of the present invention, the processing includes bleaching fibrous material, alkaline peroxide solution in the presence of polymers is a chelating agent.

When the pulp bleaching stage can also be enriched with oxygen, the abbreviated name of the stages identified in the professional literature as EOR, EOR, RO or EOS.

Peroxide bleaching of wood pulp using a method in accordance with the invention may include all types of wood mass, such as groundwood mechanical pulp (SGW), refiner mechanical pulp (RMP), press groundwood mechanical pulp (PGW), thermomechanical pulp (TSR), as well as chemically treated high-yield pulp such as chemical-thermomechanical pulp (STMR). The invention may also be used for bleaching refined wastepaper pulp. Treated waste mass can be prepared using as the raw material mixed office waste (MOW), newsprint (ONP), magazines (OMG), and so forth, and the composition of the present invention can be used at any stage of the process, which uses peroxide. The invention can also be implemented in the refiner in bleaching wood pulp and alkaline peroxide mechanical pulp (the APMP or P-RC the APMP), in which wood chips impregnorium alkaline peroxide solution before or during refining. In these applications the invention is very effective, as the first is th complexity, associated with the use of hydrogen peroxide in these applications is the inability to use liquid glass, since sodium silicate is deposited on the refiners, dewatering presses or in auxiliary chemical systems, thereby making the method impractical.

Length of stay on the bleaching may vary in a wide interval from 30 to 240 minutes, preferably from 45 to 180 minutes, and most preferably from 60 to 120 minutes. Length of stay will also depend on the temperature used in the bleaching.

The composition in accordance with the invention can be used in the form of a mixture, or ingredients can be added separately.

Bleaching wood pulp can be carried out at a temperature of from 30 to 95°C., preferably at a temperature of from 50 to 90°C. In the case of the APMP process temperature may be increased up to 150°C in the refiner and up to 100°C in the bleaching tower. Bleaching may be conducted at the chosen concentration, but it is most preferable to carry out the bleaching at high concentration, i.e. about 30% or higher. In addition, the bleaching may be carried out in two stages with the implementation stage of dehydration between stages. The stage can be conducted at the chosen concentration, but it is most preferable to use a medium to the concentrations in the first stage and high - in the second stage. This allows you to effectively remove harmful substances.

Stage bleaching may be preceded by the stage of processing of chelating agent and dehydration, and thus will improve the efficiency of bleaching. At the processing stage of the chelating agent may be used any of the above chelating agents.

The ratio between the alkali and hydrogen peroxide can vary in a wide range depending on the raw materials and the degree of bleaching. In addition, can be used alternative sources of alkali, such as sodium carbonate. Sodium carbonate is particularly preferable to use at least as a partial replacement of sodium hydroxide, to clean from paint waste paper with complete replacement of liquid glass composition in accordance with the invention. Therefore, it may be provided with the necessary buffer capacity.

In addition, as full or partial replacement of the common alkali, sodium hydroxide, it is possible to use magnesium hydroxide and magnesium carbonate and/or sodium carbonate.

According to another variant of the method of the invention, the processing includes processing of chemical fiber material in an aqueous medium containing polymers, and chelating agent.

Processing may include Atsa a peroxide bleaching compound optionally in the presence of a chelating agent and a polymer. The peroxide compound may be hydrogen peroxide, peracetic acid or acid Caro.

The concentration of such treatment is preferably about 10%to ensure efficient extraction of metals. The pH is preferably from 3 to 7, more preferably from 4 to 6.5 and most preferably from 4.5 to 6. Processing can be performed at any temperature, but preferably it is conducted at the same temperature as that at the stage of bleaching, but still lower than 100°C.

According to another variant of the method of the present invention, the processing includes cleaning of paint recycled fibrous material in an aqueous medium containing a chelating agent and polymers.

When the cleansing of the paint polymer composition in accordance with the invention can be used for secondary refining of waste paper or in the dispersing device or Bracamonte, after which you can placed the tower for the locks, which may be hydrogen peroxide. When the purification of the polymer paint composition of the present invention can also be used on single stage bleaching or at any stage of the process where hydrogen peroxide.

The pH value in the alkaline bleaching, including the cleansing of the paint in the presence of peroxide of odor is Yes, ranges from 7 to 13, preferably from 7 to 12 and Eolie preferably from 7 to 11.

The present invention is illustrated in the following examples, not intended to limit the scope of the invention.

In this specification, percentages are wt.%, unless otherwise agreed. In the following tables the number of chemicals are given as kg/TC, which means kg per ton of dry pulp.

DESCRIPTION of embodiments of the INVENTION

EXPERIMENTAL PART

Bleaching

1. STMR (chemi-thermomechanical pulp).

Technical STMR (from softwood, spruce) was bleached in the laboratory, using different stabilizing mixture. The pulp contained Fe<10 mg/kg, Mn 24 mg/kg, Sa 824 mg/kg and Cu<1 mg/kg Initial whiteness of pulp ISO was 60,9%. The reaction temperature was 78°C, a reaction time of 72 minutes, the concentration of 12%.

Download reagents were as follows: N2About222 kg/TC, NaOH 13 kg/SC, dosage stabilizing mixture was 3 kg/TC in the form of the product. The bleaching was carried out in plastic containers. The pulp weight was pre-heated in a microwave oven to the reaction temperature. A certain amount of deionized water at the reaction temperature was added to the pulp mass after the addition of reagents. Reagents to allali in the following order: 1) the stabilizer, 2) NaOH and 3) H2About2when this was thoroughly mixed after each addition. The stabilizer was diluted 1:10, NaOH and H2About2before adding also diluted in warm deionized water. Using deionized water having a temperature of reaction, the concentration was brought to 12%. Measured initial pH, after which plastic containers tightly corked and placed in a water bath. After the desired exposure time separated filtrate for analysis of residual peroxide, NaOH and the final pH of the pulp mass was washed with warm deionized water, was obezvozhivani, homogenized and acidified SO2-containing water (pH 4.5, the concentration of 2%, 15 minutes). After acidification of the pulp mass was obezvozhivani and homogenized. Test sheets for optical measurements were made in accordance with ISO 3688 and the sheets were evaluated in accordance with ISO 2470.

2. TMP (thermo mechanical pulp).

Technical TMP (from softwood, spruce) was bleached in the laboratory, using different stabilizing mixture and roll products. The pulp contained Fe<10 mg/kg, Mn 18 mg/kg, Sa 787 mg/kg and Cu<1 mg/kg Initial whiteness of pulp ISO accounted for 61.1 per cent. The reaction temperature was 73S, the reaction time of 80 minutes, the concentration of 12%.

C is the load of the reagents were as follows: N 2O245 kg/TC, NaOH to 37.9 kg/TC (total alkali), dosage of stabilizer or mixture changed 3 times. The bleaching was carried out in plastic containers similar bleaching STMR.

The preparation of compositions

Example 1

Preparation of copolymer And

The copolymer was prepared in accordance with example 1 of patent document WO1.

Example 2

Preparation of polymer D

Polymer D was prepared in accordance with example 2 of patent document WO4.

Example 3

Preparation of compositions in accordance with the invention

The beaker was placed a certain amount of deionized water. Copolymer of MA-AA (D), DTPA (IN) and the copolymer AHPS-AA (A) was added to water at room temperature and under moderate stirring (magnetic stirrer). In the Cup they dosaged PLAC (polymer C). The mixture was heated to a temperature of 50-60°C, was stirred on a magnetic stirrer for at least 30 minutes or until until the mixture will look transparent. For regulating the mass loading was added deionized water. The mixture was cooled to room temperature and filtered through a filter with a porosity of 300 microns.

Starting materials and their amounts are shown in table 1.

Table 1
Source Dose
materialsConcentrationDose, gproduct
as
PHAS100%8,38,30%PHAS13,0%
MA-AA44%12,50912,50%
DTPA50%11,00411,00%
AHPS50%10,843or 10.60%
Water100%57,60%

PHAS was in the form of polylactones PLAC molecular weight of about 20,000.

MA-AA was neitralizovannykh copolymer raw acrylic acid and maleic acid in a ratio of 40:60 with a molecular weight of 44,000 g/mol.

DTPA was an industrial solution containing 50% pentanitrate salt diethylenetriaminepentaacetic acid.

AHPS was a sodium salt of a copolymer AHPS-AA with a molecular mass of 5000 g/mol.

Example 4

Experiments on bleaching was performed as described above. When bleaching used TSR from coniferous wood.

The composition of the mixture S06035 was as follows:

The mixture SO6035As suchSolidThe ratio to the invention
PLAC (connection)8,3%1,0
the copolymer MA:AA (D)12,5%5,5%1,0

The mixture S0015 was the same as the mixture And patent document WO1, and the stabilizer in the form of a mixture speakers met the invention in table 3 (described below in table 3).

The results are shown in table 2.

Table 2
TSR from coniferous woodPPPPPPPP
Standard23456789
T, °C7373737373737373
t min8080 808080808080
Concentration %1212121212121212
The original pH10,811,010,810,710,510,510,710,6
The final pH9,69,89,89,69,59,69,49,5
H2O2kg/TC4545454545 454545
NaOH, kg/TC35of 37.9of 37.9of 37.9of 37.9of 37.9of 37.9of 37.9
Silicate, kg/TC (cont.)25
The mixture S06035, kg/TC (cont.)4
The mixture S06015, kg/TC (cont.)4
Stabilizer C, kg/TC (cont.)246810
Residual N2About2kg/TC18,74,27,314,914,220,42,7the 5.7
Residual NaOH, kg/TCof 5.42,62,32,62,13,11,91,8
Whiteness, % ISO61,177,075,476,477,377,277,373,975,4
Yellow7,8 of 17.519,018,2of 17.517,817,419,819,3
The CIE whiteness D65/10+UV8,439,836,638,0of 40.339,640,732,034,7
L*to 89.995,8095,4795,7295,996,095,995,1095,59
a*1,29-1,90-1,73-1,80-1,88-1,91-1,8-1,85-1,80
b*14,2710,9711,7211,3 10,911,110,812,2411,98
Fe, mg/kg<10
Mn, mg/kg18
CA, mg/kg787
Cu, mg/kg<1
Acidification pH 4.5********

The results show that by using a composition with a concentration of less than 10 kg/TC in accordance with the invention can be obtained equally good results bleaching, as when using silicate. In addition, you can see that even with a low dosage of various stabilizers composition works better than compositions in accordance with the invention WO 1 WO 4. This is despite the fact that extra PLAC added to the mixture according to the patent document WO 4 (mixture S06035). Adding PLAC should lead to improved performance.

Example 5

Comparison of bleaching commercial sample STMR of coniferous wood, with and without the use of silicate, bleaching was performed in accordance with the patent is diversified documents WO 1, WO 2 WO 4, and the present invention. Conditions of the experiments and the results are presented in table 3.

Table 3
Conditions/properties/room experienceControl the pulp#2#4#3#5And
WO 1
In
WO 2
With
WO 4
AC inventions
T, °C7878787878787878
t min7272727272727272
Concentration %1212 121212121212
H2O2(100%), kg/TC2222222222222222
The silicate product, kg/TC18,418,4
Supplement as a product, kg/TC3333
NaOH (100%), kg/TC1513151313/td> 131313
The original pH10, 710, 610,710,710,810,710,710,7
The final pH9,29,09,59,48,89,19,19,0
Residual N2About2kg/TC4,35,59,59,86,37,96,711,1
Residual NaOH, kg/TC0,60,42,41,80,40,4 0,50,5
Whiteness, % ISO60,967, 267, 269,970,168,568,668,269,8
Fe, mg/kg<10
Mn, mg/kg24
CA, mg/kg824
Mg, mg/kg40
Cu, mg/kg<1

AC = the inventionAs suchSolidThe base ratio
the polymer (A)50%or 10.60%5,30%1,00
DTPA-5Na 50% (Conn. In)11,00%of 5.50%1,00
PLAC (connection)8,30%1,00
the copolymer MA:AA (D)12,50%5,5%1,00
44%

A = the ratio of the compounds as 100% (A):(B)=1:1,67, the total content as 100%=13,4%

A=WO 1As suchSolidRatio
invention
the polymer (A) 50%10,0%to 5.00%0,94
DTPA-5Na 50% (Conn. In)16,7%8,35%1,52

The ratio of compounds (A):():(E*)=1:1,67:3,34, the total content of (A)+(B) as 100%=8%

B=WO 2AsInRatio
suchsolidinvention
the polymer (A) 50%12,0%6,0%1,13
DTPA-5Na 50% (Conn. In)20,0%100%1,82
MgSO4*7H2About41,0%20,0%as
MgSO4
Water27,0%64,0%
Only100%10,0%
* (E) means MgSO4·7H2O
C=WO 4As suchSolidRatio
invention
PLAC (connection)3,245%0,39
the copolymer MA:AA (D)22,40%to 3.58

You can see that when the silicate is not used, the degree of whiteness will increase, however, the residual peroxide will stay relatively low. Since the residual peroxide is usually fully or partially recyclized as possible are desired high content of residual peroxide and a high degree of whiteness.

If silicate is used, the degree of whiteness will exceed the whiteness, which can be obtained by using one of caustic soda. Residual peroxide also increases.

While conducting experiments in accordance with the invention WO 1 WO 2 WO 4 whiteness increased, however, the residual peroxide remained lower than those obtained when using as the stabilizer silicate.

The composition in accordance with the invention gave good whiteness and even higher residual switch is camping, than was obtained when bleaching with the use of silicate. Since the silicate contains about at least 10% of free sodium hydroxide and acts as a buffer, the residual hydroxide will be higher than when using the composition in accordance with the invention.

At higher content of residual peroxide can be added a greater amount of caustic soda to increase the content of hydroxide and thereby spend more amount of peroxide and increase the degree of whiteness.

Example 6

The effect of dosages

The same composition as (in accordance with the invention, as in example 5, in these experiments were used at different dosages. Experience number 5 was the same as in table 3. Conditions of the experiments and the results are presented in table 4.

Table 4
Conditions/properties/room experienceIn accordance with the invention
#19#20#6#21#22#23#5
T, °C78 787878
t min72727272
Concentration %12121212
H2O2(100%), kg/TC22222222
The silicate product, kg/TC18,4
Supplement as a product1234 56
kg/TC
NaOH (100%), kg/TC13131313131313
The original pH10,810,810,710,910,810,810,7
The final pH8,88,89,08,98,78,99,4
Residual N2About2kg/TC6,59,511,112,412,9 13,59,8
Residual NaOH, kg/TC0,30,30,50,40,40,41,8
Whiteness, % ISO68,369,369,870,1to 70.270,470,1

You can see that the concentration of 2 kg/TC composition gives very good results from bleaching, measured as the degree of brightness and residual peroxide.

By increasing the concentration of the bleaching results will continue to improve, although not type the extension of caustic soda, which could improve the results of the whiteness.

Example 7

The influence of composition

In these experiments studied the effect of composition stabilizers. In experiments were used STMR from coniferous wood. Conditions of the experiments and the results are presented in table 5.

Table 5
Conditions/properties/the ratio(A=AHPS):(B=DTPA):(C=PHAS):(D=MA-AA)
1:1:1:11/2:1:1:11/2:1:1:1/21/2:1/2:1:11:1/2:1:1/21/2:1/2:1:1/21/2:1:1:0
The number of mixture#6006#6010#6021#6012#6019#6017#6013
T, °C78787878787878
t min72727272727272
Concentration %12121212121212
H2About2(100%), kg/TC 22222222222222
Supplement as a product, kg/TC3333333
NaOH (100%), kg/TC13131313131313
The original pH10.610.710.510.610.410.510.8
The final pH8.98.88.88.78.88.78.9
Residual N2About2,
kg/TC11.311.210.110.410.79.011.2
Residual
NaOH, kg/TC0.40.40.40.40.40.50.4
Whiteness,
% ISO69.669.869.669.368.769.7 69.9

It should be noted that all experiments were performed under laboratory conditions. For example, a series of tests with sample 1 (STMR) on an industrial scale have shown that only works well composition in accordance with the invention. Received the same levels of brightness and residual peroxide, as with the use of silicate, and significantly better removal of water. Products in accordance with the patent documents WO 2 WO 4 did not pass the tests that can be seen to reduce the degree of brightness and residual peroxide, when the content of silicate in the circulating water began to fall.

Example 8

Water retention capacity (wrv ranges)

In the experiments on determination of wrv ranges used technical STMR (from softwood, spruce), taken from an existing process after the tower for peroxide bleaching at high concentration (HC) (before proryvnym press). The method of stabilization of peroxide in the peroxide NS-bleaching in the pulp samples was different: sodium silicate or stabilizer C. Method of determining wrv ranges based on the standard SCAN-C 62:00. Prior to testing in accordance with standard weighed 6 g of dry pulp, diluted with 2 liters of deionized water and getintegervalue for 60 minutes at a speed of 500 Rev/min

The mixture speakers releases water better than liquid the glass. Liquid glass holds water in the amount of 1.52 g/g, and the mixture speaker holds water in the amount of 1.47 g/year

1. A stabilizing composition comprising the following components:
(A) a polymer having the formula

where R1represents a hydrogen atom or an alkyl group containing from 1 to 12 carbon atoms,
R2means-SOOMA or-CH2COOM,
M is a hydrogen atom, an alkali metal ion, alkali earth metal ion, ammonium ion or mixtures thereof,
n, m and k represent molar ratios of the respective monomers, where n is from 0 to 0.95, m is from 0.05 to 0.9, and k is from 0 to 0.8, and the sum (n+m+k) is equal to 1, and
srednevekovaja molecular weight is from 500 to 20000000 g/mol,
(B) a chelating agent,
(C) poly-alpha-hydroxyanisole acid, or its alkali salt, or its corresponding polylactam and
(D) polymer polycarboxylic acid or its alkali salt.

2. The composition according to claim 1, wherein in formula I n is from 0.4 to 0.9, m is from 0.1 to 0.5 and k is from 0 to 0.5.

3. The composition according to claim 1, characterized in that srednevekovaja molecular weight of the copolymer (a) is from 1,000 to 100,000 g/mol, preferably from 2000 to 500000 g/mol.

4. The composition according to claim 1, characterized in that components (A), (b) and (C) are present in the following mass with the relationship: 0.1 to 1: 0.1 to 1:1, preferably from 0.25 to 1: 0.25 to 1:1, more preferably from 0.5 to 1: 0.5 to 1:1, in terms of the active substance.

5. The composition according to claim 1, characterized in that the polymer (A) is a copolymer of 3-allyloxy-2-hydroxypropanesulfonic acid and at least one of the monomers acrylic acid, methacrylic acid, maleic acid and basis of itaconic acid or its salt.

6. The composition according to claim 1, characterized in that the chelating agent is a compound having the following formula:

where p is 0 or an integer from 1 to 10,
R3, R4, R5, R6and R7independently represent a hydrogen atom or an alkyl chain containing from 1 to 6 carbon atoms and having one or more active chelating ligands such as carboxylic, phosphonic or hydroxyl group (s) or their salts.

7. The composition according to claim 1, characterized in that the chelating agent is a compound having the following General formula:

where q is an integer from 3 to 10,
R3, R4, R5and R6independently represent a hydrogen atom or an alkyl chain containing from 1 to 6 carbon atoms and having one or more active chelating ligands such as carboxylic, phosphonic or hydroxyine the group (groups) or their salts.

8. The composition according to claim 1, characterized in that the chelating agent is a compound having the following General formula:

where R8represents a hydrogen atom, alkyl group containing from 1 to 6 carbon atoms, or an alkyl chain containing from 1 to 6 carbon atoms and containing carboxylic, phosphonic or hydroxyl group,
R9represents a hydrogen atom, hydroxyl group, phosphonic group, a carboxyl group or an alkyl chain containing from 1 to 6 carbon atoms and having one or two carboxyl groups, and
R10represents a hydrogen atom, hydroxyl group, carboxyl group, alkyl group containing from 1 to 6 carbon atoms, or an alkyl chain containing from 1 to 6 carbon atoms and having a carboxyl group or its salt.

9. The composition according to claim 1, characterized in that the chelating agent is a compound having the following General formula:

where R11represents a hydrogen atom, an alkyl chain containing 1-30 carbon atoms, alkyl chain containing 1-30 carbon atoms and 1-10 carboxylic groups attached to the chain, or salt of alkali or alkaline earth metal, alkyl chain containing 1-30 carbon atoms and 1-10 esters carbó the OIC acid, attached to this circuit, polyethoxyethanol hydrocarbon chain containing 1-20 ethoxyline groups, or carboxylic acid amide containing 1-30 carbon atoms, where N-R11is an amide bond,
R12and R13represent hydrogen, alkali metal ion or alkali earth metal ion or an alkyl group containing 1-30 carbon atoms,
r is 0 or 1 and
s is 0 or 1.

10. The composition according to claim 1, characterized in that the composition comprises component (D)containing a homopolymer of acrylic acid or methacrylic acid or a copolymer of methacrylic acid and other unsaturated carboxylic or dicarboxylic acid.

11. Composition according to any one of claims 1 to 10, characterized in that components (A), (B), (C) and (D) are presented in the following mass ratios: 0.1 to 1: 0.1 to 1:1: 0.1 to 1, preferably from 0.25 to 1: 0.25 to 1:1: 0.25 to 1, more preferably from 0.5 to 1: 0.5 to 1:1: 0.5 to 1, in terms of the active substance.

12. The use of a composition according to any one of claims 1 to 11 as a stabilizer when the bleaching of fibrous material in the aquatic environment.

13. The use of a composition according to any one of claims 1 to 11 as a stabilizer when cleaning from paint fibrous material from recycled materials.

14. Method for processing fibrous material, comprising a stage of contact in the fibrous material in the aquatic environment with the following components:
(A) a polymer having the General formula

where R1represents a hydrogen atom or an alkyl group containing from 1 to 12 carbon atoms,
R2means-SOOMA or-CH2COOM,
M is a hydrogen atom, an alkali metal ion, alkali earth metal ion, ammonium ion or mixtures thereof,
n, m and k denote the molar ratio of the respective monomers, where n is from 0 to 0.95, m is from 0.05 to 0.9, and k is from 0 to 0.8, and the sum (n+m+k) is equal to 1, and
srednevekovaja molecular weight is from 500 to 20000000 g/mol,
(B) a chelating agent,
(C) poly-alpha-hydroxyacrylates acid, or its alkali salt, or its corresponding polylactones,
(D) possible with polymer polycarboxylic acid or its alkali salt.

15. The method according to 14, where the components (A), (B) and (C) and optionally component (D) is injected in the form of a mixture or components (A), (B) and (C) and optionally component (D) is injected separately.

16. The method according to 14 or 15, where the fibrous material is a cellulosic fibrous material, including wood pulp, or chemical-mechanical mass, or fibrous material made from recycled materials.

17. The method according to 14, where the processing involves the bleaching of fibrous material, alkaline peroxide solution in the presence of components (A), (b) and (C) and possibly the comp is the component (D).

18. The method according to 17, where the pH is alkaline peroxide solution is from 7 to 13, preferably from 7 to 12 and more preferably from 7 to 11.

19. The method according to 17 or 18, where the bleaching is preceded by processing chelating agent.

20. The method according to 14 or 15, where the fibrous material includes a fibrous material made from recycled materials and processing includes cleaning of the paint fibrous material from secondary raw materials in the aqueous medium containing the components (A), (B) and (C) and optionally component (D).

21. The method according to 14 or 15, where in formula I n is from 0.4 to 0.9, m is from 0.1 to 0.5 and k is from 0 to 0.5.

22. The method according to 14 or 15, where srednevekovaja molecular weight of the copolymer (a) is from 1000 to 1000000 g/mol and preferably from 2,000 to 500,000 g/mol.

23. The method according to 14 or 15, where the polymer (A) is a copolymer of 3-allyloxy-2-hydroxypropanesulfonic acid and at least one of the monomers acrylic acid, methacrylic acid, maleic acid and basis of itaconic acid or its salt.

24. The method according to 14 or 15, where the chelating agent (B) is as defined in any of PP-9.

25. The method according to 14 or 15, where the components (A), (b) and (C) are present in the following proportions: 0.1 to 1: 0.1 to 1:1, preferably from 0.25 to 1: 0.25 to 1:1, more preferably from 0.5 to 1: 0.5 to 1:1, in terms of active substances is O.

26. The method according to 14 or 15, where component (D) is present and comprises a homopolymer of acrylic acid or methacrylic acid or a copolymer of methacrylic and other unsaturated carboxylic or dicarboxylic acid.

27. The method according to 14 or 15, where the components (A), (B), (C) and (D) are present in the following mass ratios: 0.1 to 1: 0.1 to 1:1: 0.1 to 1, preferably from 0.25 to 1: 0.25 to 1:1: 0.25 to 1, more preferably from 0.5 to 1: 0.5 to 1:1: 0.5 to 1, in terms of the active substance.

28. The method according to 14 or 15, where the total of components (A), (B) and (C) and optionally component (D) when processing ranges from 2 to 10 kg per ton of dry fibrous material, preferably from 2 to 6 kg per tonne of dry fibrous material, and more preferably from 2 to 5 kg per ton of dry fibrous material.



 

Same patents:

FIELD: textile, paper.

SUBSTANCE: method is carried out by means of subsequent soaking of cellulose-containing herbal raw materials in alkaline solution, thermomechanical treatment, squeezing, washing, bleaching, squeezing, washing, squeezing and drying, besides, squeezing and washing are done in pulsating centrifuge.

EFFECT: higher yield of cellulose, reduced norms of consumption of initial reagents and water and reduced power inputs.

1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: method involves treating cellulose with sulphuric acid at the first step after oxygen-alkaline treatment. At the second step, peroxide bleaching is carried out in an alkaline medium in the presence of a stabiliser - magnesium sulphate. The third step involves treating cellulose with chlorine dioxide with its consumption not more than 0.5% for hardwood pulp and with chlorine dioxide consumption of 0.5-0.7% of the weight of absolutely dry cellulose for soft wood pulp. At the fourth step, cellulose is treated with hydrogen peroxide in an alkaline medium.

EFFECT: reduced consumption of chlorine dioxide, reduced corrosion of equipment and high environmental safety of the process.

1 tbl, 7 ex

FIELD: textile, paper.

SUBSTANCE: method relates to production of mechanical or chemical-mechanical wood pulp applied as raw material for manufacturing of paper or cardboard, and may be used and pulp and paper industry. According to this method wood pulp is exposed to fibrillation. Produced wood pulp is screened to separate wastes from acceptable materials. At the same time wastes are removed in amount of maximum 60% of overall amount of wood pulp. Wastes and acceptable material are bleached separately. Wastes are bleached with the help of peroxide or peroxy acid. After that bleached wastes are mixed with bleached acceptable material. After combination they are exposed to finishing grinding, at the same time amount of consumed energy makes approximately 10-1000 kW-hr/ton. Finishing grinding is carried out at low concentration. Then wood pulp is batched into paper- or cardboard-making machine. Wastes are bleached in alkaline medium.

EFFECT: improved strength of wood pulp and reduction of energy consumed for grinding.

12 cl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: absorbent material is made by treating lignin-cellulose material in the presence of a catalyst from a transition metal with oxidation. The oxidising agent is selected from a group consisting of hydrogen peroxide, hypochlorite, hypochloric acid or any combination thereof. The lignin-cellulose material is treated at pH from approximately 2 to approximately 6. The treated lignin-cellulose material has viscosity equal to or less than approximately 17 cP. The treated lignin-cellulose material is subjected to dry grinding. The dry ground lignin-cellulose treated material is used as an absorbent intermediate layer for making absorbents.

EFFECT: improved bacteria inhibition properties.

2 cl, 17 ex, 16 tbl

FIELD: paper industry.

SUBSTANCE: cellulose containing material from herbaceous plants is soaked in alkaline solution, washed, bleached, again washed, squeezed and dried. After soaking thermal-mechanical-chemical treatment is carried out in double-auger device, which consists of heated working chamber with impermeable wall and two parallel joined shafts arranged in it. Alternating injection auger and grinding cam tips are installed on shafts. At the same time prior to washing they additionally execute thermal-mechanical-chemical treatment in double-auger device, on shafts of which there are alternating injection and braking auger tips.

EFFECT: invention provides for cost-efficient method of cellulose making.

2 cl, 1 tbl

FIELD: textile, paper.

SUBSTANCE: method is referred to bleached wood pulp production from hardwood chips for their further use in different compositions for paper and cardboard production. Chipped wood is impregnated with alkali solution of sodium sulfite. Spent impregnating solution is then removed. Chipped wood is milled in two stages. In between components are treated by alkali solution of hydrogen peroxide at weight concentration 14-18% and final pH=9.5-10.0. Following the second stage of milling, pulp is dissolved to concentration 3.0-5.0% and cured during 30-60 minutes to pH=7.5-8.0. Pulp is chemically treated by alkali solution of hydrogen peroxide between milling stages at 75-85°C during 15-20 minutes.

EFFECT: decrease of chemicals consumption for impregnation and improvement of mechanical and optical properties of target product.

2 cl, 1 tbl, 4 ex

FIELD: paper-and-pulp industry.

SUBSTANCE: cellulose delignification process comprises alkali treatment, delignification with hydrogen peroxide with sodium hydroxide and sodium silicate additive, and acid treatment. Alkali treatment consumes 0.5% hydrogen peroxide and 2.0% sodium hydroxide based on the weight of absolutely dry cellulose and is conducted for 2.0-2.5 h at 60-90°C. Acid treatment of delignified product is accomplished with aqueous hydrochloric acid, which is consumed in amount 1.0% based on the weight of absolutely dry fibers, while treatment is conducted for 30-60 min at ambient temperature.

EFFECT: enhanced economical efficiency without loss cellulose characteristics.

2 tbl, 11 ex

FIELD: pulp-and-paper industry.

SUBSTANCE: unbleached sulfate cellulose obtained from hardwood is subjected oxygen-alkali delignification, after which treated with chlorine dioxide in presence of oxyethylidenediphosphonic acid and then consecutively hydrogen peroxide and chlorine dioxide solutions. Process may be used in production of bleached fibrous intermediates.

EFFECT: increased whiteness and strength characteristics of cellulose and improved environmental safety of bleaching process.

2 cl, 1 tbl

FIELD: pulp-and-paper industry, in particular method for pulp whitening.

SUBSTANCE: pulp mass with concentration of 5-10 % after oxygen-alkaline treatment in step I is treated with sulfuric acid in consumption of 5 % based on dry cellulose mass and pH 2.6-3.0. In step II peroxide treatment is carried out in alkali consumption of 1.0-1.3 % based on dry cellulose mass, and in step III pulp is treated with chlorine dioxide in consumption of 1.0-1.6 % based on dry cellulose mass at 70°C.

EFFECT: pulp with increased whiteness.

1 tbl, 17 ex

FIELD: pulp-and-paper industry, in particular method for PULP whitening.

SUBSTANCE: craft pulp mass with concentration of 2.5-5.0 % after oxygen-alkaline treatment is treated with potassium permanganate in consumption of 0.01-0.1 % based on dry cellulose at 40-80°C and pH 1.6-3.0 or with sulfuric acid solution in consumption of 1.0-1.5 % at 90°C for 30 min. In steps II and IV cellulose with concentration of 10 % is treated with hydrogen peroxide in consumption of 2 % based on mass of dry cellulose for 120 min at 80-90°C and pH 9.5-10.5 wherein consumption of sodium alkali and sodium silicate is 1.3 % and 2.5 %, respectively. In step III cellulose is treated with potassium permanganate in consumption of 0.01-0.4 % under step I conditions.

EFFECT: reduced consumption of whitening agents.

1 tbl, 9 ex

FIELD: textile, paper.

SUBSTANCE: cellulose-containing textile material is processed in a bleaching solution, which contains hydrogen peroxide, diarin, which is a mixture of aqueous solutions of sodium salts of phosphorus-containing complexons, carbamide, a penetrating agent EM. Diarin is mixture of aqueous solutions of sodium salts of phosphorus-containing complexons. The penetrating agent EM is a composition based on anion-active and non-ionogenic surfactants. Besides, treatment in the bleaching solution is carried out simultaneously with ultrasonic exposure at the frequency of 25-35 kHz, capacity of 1.5-2.5 kW for 20-30 minutes.

EFFECT: invention makes it possible to considerably reduce power inputs, to increase material quality, to improve process ecological compatibility and to reduce its labour intensiveness.

1 tbl

FIELD: textile, cotton.

SUBSTANCE: invention refers to the textile industry in particular, to the technology of the bleaching of flax-containing fabrics and can be used for the production of the bleached woven linens or for the preparation of the fabrics for colouring and stamping. It describes the method of the fermentation and peroxide bleaching of the flax-containing fabrics including enzymatic procession by the soaking into the 40-45°C solution of the multienzyme preparation with the indicator the enzyme activity, in un/ml: endopolygalacturonase - 7-10; α-amylase - 8.8-9.2; β- amylase - 0.5-0.6; γ- amylase - 0.2-0.5; pectinesterase - 1.0-1.5; exopolygalacturonase - 0.5-0.7; exogalactosidase - 0.3-0.4; exoxylosidase - 0.2-0.3; exoglucanase - 0.3-0.5, with the addition of the sodium bicarbonate 20-25 g/l and penetrating agent, maturing the wet squeezed fabric and its steaming in 85-95°C temperature during 20-30 min.; intermediate washing with the acidification in oxalic acid solution 2.5-5 g/l, high-temperature peroxide bleaching by the stabilised alkaline-peroxide solution with the peroxide concentration 2.2-2.9 g/l with active oxygen for one stage, washing and drying.

EFFECT: invention helps to increase the level of the removal of starch size before peroxide bleaching up to 80-85%; it increases the speed of the capillary soaking of water solution and improves uniformity of the capillary characteristics of the fabric; it increases the strength properties of the fabric, decreases its rigidity to 96-125 mN·cm2 because of larger removal of the lignin; it decreases the attenuationof the dyeing of colour warpings of the tapestry linens; it simplifies the process and reduce its duration.

2 cl, 1 tbl, 3 ex

FIELD: textile, paper.

SUBSTANCE: invention concerns method of flaxen roving preparation for spinning and can be applied in textile industry. Method of enzyme and peroxide preparation of highly lignified flaxen roving for spinning involves deacidification, enzyme processing at 40-50°C for 90-95 minutes by polyenzyme preparation solution with enzyme activity indicators, units per ml: endopolygalacturonase - 20-25; pectinesterase - 2.5-4.7; protease - 0.2-0.3; exopolygalacturonase - 0.6-0.1; exogalactosidase - 0.2-0.4; exoxylosidase - 0.3-0.5; and exoglucanase - 0.6-0.8. Further the roving is heated to the boiling point and matured for 20-25 minutes, flushed by water and processed for 90-95 minutes in alkaline peroxide solution at hydro peroxide concentration of 0.6-0.8 g/l of active oxygen and total alkalinity of 6.5-7.0 g/l rated per caustic soda. Then the roving is flushed with detergent and water and undergoes counter-microbe processing.

EFFECT: fiber whitening degree enhanced up to 54-56%; obtainment of thin yarn meeting the requirements for both "1 high-flaxen" and "1 high tow" grades by GOST 10078-85 in line density and line density and tear load variation rates; reduced yarn tear rate in weaving process to 40-50 tears for 100 spindles per hour; enhanced yarn strength in 1,2-1,4 times; improved esthetics of woven canvas exterior.

1 tbl, 3 ex

FIELD: textile, paper.

SUBSTANCE: invention concerns method of flaxen roving preparation for spinning and can be applied in textile industry. Method of enzyme and peroxide preparation of flaxen roving for spinning involves deacidification performed before enzyme processing for 90-95 minutes by polyenzyme preparation solution with enzyme activity indicators, units per ml: endopolygalacturonase - 20-25; pectinesterase - 0.8-4.7; protease - 0.2-0.3; and exopolygalacturonase - 0.2-0.4. Further the roving is flushed by water and processed for 90-95 minutes in alkaline peroxide solution at hydro peroxide concentration of 0.4-0.5 g/l of active oxygen and total alkalinity of 6.5-7.0 g/l rated per caustic soda, then flushed with detergent and water and undergoes counter-microbe processing.

EFFECT: reduced tear load in moist unprocessed roving up to 50-61%; obtainment of thin yarn meeting the requirements for 1 grade in thickness and stability of physical and chemical yarn properties; enhanced yarn strength in 1,2-1,4 times; improved esthetics of woven canvas exterior.

1 tbl, 3 ex

FIELD: textile, paper.

SUBSTANCE: invention concerns methods of flax fiber dyeing and preparation for spinning and can be applied in textile industry. Combined method of dyeing and preparation for spinning involves deacidification, processing by digester dye solution for 90-95 minutes at 40-50°C, the solution including vat colour, sodium bicarbonate, sulfonol NP-3 and anhydrous synthanol, polyenzyme preparation with enzyme activity indicators, units per ml of solution: endopolygalacturonase - 20-40; pectinesterase - 2.5 - 8.0; protease - 0.2-0.4; exopolygalacturonase - 0.6-1.5; exogalactosidase - 0.3-0.5; exoxylosidase - 0.3-0.8; exoglucanase - 0.4-1.0. Further the mass is heated to the boiling point, matured for 30-60 minutes, flushed by cold water. Oxidising processing is performed for 15-25 minutes at 20-25°C in stabilised peroxide solution including 0.3-0.4 g/l of hydro peroxide (100%), 1-2 g/l of laundry soap, and alkaline agents to comprise total alkalinity of 5.5-6.0 g/l rated per caustic soda, with further heating for 20-50 minutes to 95-100°C and maturing for 20-30 minutes, followed by double flush with detergent first and with water next, and further deacidification at 45-50°C for 15-20 minutes and flushing.

EFFECT: reduced irregularity of geometrical parametres and durability of flax semiproducts; improved colorability and colour evenness of textile semiproducts; more environment-friendly process and improved labour health.

1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to bleaching compositions, which in fact do not contain peroxide bleaches, for bleaching of fabrics. Described is liquid bleaching composition with pH 10 or lower, which contains: (a) complex compound of transitional metal as catalyst of bleaching in air, (b) from 0.001 for 3 wt/wt % of odorant.

EFFECT: obtaining composition, whose bleaching activity is more, than 10 times higher as compared with bleaching activity of composition, containing as odorant molar equivalent of citronellal.

5 cl, 3 tbl, 62 ex

FIELD: chemistry.

SUBSTANCE: particles contain inner coating layer that consist of at least one hydrate-forming mineral salt, and outer coating layer, including 0.2-3 wt % alkali metal silicate with module more than 2.5, particularly 3 to 5. Outer layer is obtained using alkali metal silicate solution with alkali metal silicate concentration 2 to 20 wt %. Dissolution time can be extended by alkali metal silicate concentration lowering in solution used, coating material amount being the same. Dissolution time can be extended significantly according to coating layers sequence and solution concentration with low quantity of alkali metal silicate.

EFFECT: extension of dissolution time.

18 cl, 7 tbl, 18 ex

FIELD: process for treatment of textile materials, in particular, whitening of flax fiber for producing of hygroscopic wool used for medicine purposes.

SUBSTANCE: method involves subjecting flax fiber to oxidizing cooking followed by whitening with the use of hydrogen peroxide in the presence of stabilizing preparation based on oxyethylidene diphosphonic acid; after final rinsing, providing brightening processing, preferably with the use of solution containing higher fatty acid based softener used in an amount of 0.5-1.0 g/l. Method is realized in industrial plants with the use of proper equipment and chemical substances available and produced on industrial scale by home enterprises. Said method does not require substantial alterations in chemical processes.

EFFECT: increased whitening extent, capillarity and moisture absorbing capacity of wool produced.

2 tbl, 5 ex

FIELD: light industry, in particular, raw material dyeing processes used, for example, in whitening of mink skin fur hair.

SUBSTANCE: method involves providing additional tinning of skin with aqueous composition containing sodium chloride, composition based on low-molecular alcohol polyacetals, mixture of non-ionogen surfactants and cyclic terpenes; whitening for 2.0-4.5 hours with the use of aqueous composition containing sodium chloride, potassium persulfate, composition based on mineral and organic acids as pH stabilizers, mixture of primary fatty alcohols as protective admixture and 30%-hydrogen peroxide; providing reduction with the use of aqueous composition comprising sodium chloride, oxalic acid and mixture of non-ionogen surfactants with cyclic terpenes.

EFFECT: improved consumer properties of fur skins.

2 tbl

FIELD: light and fur industry.

SUBSTANCE: invention relates to a composition used for whitening hair cover of fur hides. The composition comprises sodium chloride, hydrogen peroxide, potassium persulfate, the composition based on mineral and organic acid salts - "Antikolor 1" or "Antikolor-2" as an agent for stabilizing pH value, and a mixture of primary saturated alcohols - "Antikolor-3" as a protective additive. The composition provides reducing the negative effect of leather and hair cover of hide. The composition can be used in raw-dye manufacture in treatment of hides with pigmented hair cover, for example, hides of karakul group.

EFFECT: valuable properties of composition.

2 tbl

FIELD: textile, paper.

SUBSTANCE: method of paper preparation includes application of aqueous dispersion onto paper. Aqueous dispersion comprises one or more copolymers of ethylene with acrylic acid and one or more N,N-dialkylalkanolamines in amount suitable for efficient dispersion of water dispersion including dispersed solid substances with average particle size of less than approximately 100 nm. Specified aqueous dispersion does not contain hydroxides of alkaline metals. Paper is also described for use in electrophotographic or digital offset printing technologies.

EFFECT: paper has improved adhesion of toner.

22 cl, 2 tbl, 6 ex

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