EA001855B1 - Liquid composition and its use for de-inking paper - Google Patents

Abstract

1. A de-inking liquid composition, comprising at least one first surfactant (A) and at least one second surfactant selected from (B) and/or (C): - wherein non-ionic surfactant (A) consists of at least one polyoxyethoxylated and polyoxypropoxylated fatty aliphatic alcohol of the following general formula: R1-O-[(CH2CH2O)xò(CH2-CH(CH3)O)y]-H, wherein: - R1 is alkyl comprising 16-22 carbon atoms, - average meaning of x is 5-30, and - average meaning of y is 2-20. - wherein non-ionic surfactant (B) consists of polyoxyethoxylated fatty aliphatic alcohol of the following general formula: R2-O-(CH2CH2O)z-H, wherein: - R2 is a linear alkyl comprising 10-16 carbon atoms, and preferably 12-16 carbon atoms, - average meaning of z is selected in such way, that mass ratio of oxyethylene units was 55-75% with respect to the mass of surfactant (B), preferably z is 6-10, - wherein non-ionic surfactant (C) consists of at least one polyoxyethoxylated fatty aliphatic alcohol of the following general formula: R3-O-(CH2CH2O)w-H, wherein: - R3 is a linear alkyl comprising 10-22 carbon atoms, and preferably 12-14 carbon atoms, - average meaning of w is selected in such way, that mass ratio of oxyethylene units was 35-45% with respect to the mass of surfactant (C), preferably w is 2-4. 3. A liquid composition as claimed in Claim 1, characterised in that the liquid compound comprises at least one surfactant (A), at least one surfactant (B) and at least one surfactant (C). 4. A liquid composition as claimed in Claim 1 or 2, characterised in that mass ratio surfactant (B)/surfactant (A) is 0,02-1. 5. A liquid composition as claimed in any of Claims 1-3, characterised in that mass ratio surfactant (C)/surfactant (A) is 0,02-1. 6. A liquid composition as claimed in any of Claims 1-4, characterised in that non-ionic surfactant (A) is a mixture of fatty alcohol, which radical R1 is a linear alkyl, comprising 16-20 carbon atoms, with 11 oxyethylene units and 4 oxypropylene units. 6. An aqueous solution for refining of liquid composition as claimed in any of Claims 1-5, characterised in that it comprises 0,05-30 wt.% of water with respect to the total mass of aqueous solution. 7. The use of liquid composition as claimed in any of Claims 1-5 for specialty papers manufacture. 8. The use of aqueous solution as claimed in Claim 6 for specialty papers manufacture. 9. The method for printed wastepaper recovery in presence of liquid composition as claimed in any of Claims 1-5, characterised in that it comprises the following stages: - pulping, when printed wastepaper is put into the contact with the above-mentioned composition and water in pulper for conversion the paper into the stock; - flotation, when the stock is diluted with water with invariable pH in the medium or with variable basis pH, which is approximately 8,5-9. 10. The method for printed wastepaper recovery as claimed in Claim 9, characterised in that at least one surfactant (B) or (C) is added after first stage before the second stage.

Description

The present invention relates to a liquid composition for paper refinement used in the regeneration of paper pulp obtained from paper waste from newspapers, magazines, photocopies, computer paper, and a method for its preparation, as well as its use for paper refinement.

The subject of the present invention is mainly a liquid refining composition, as well as its use for refining paper by flotation and / or washing, allowing to obtain regenerated high-quality paper pulp having a high whiteness and very low residual ink content, and providing a stable and reliable method ennoblement. The ennobling operation is very important, because it represents one of the fundamental stages for the recycling of waste paper.

Many methods for refining waste paper are known. Waste paper recycling has become a very important industrial sector, in which they strive to develop and develop new refinement compounds and methods for their use, so that they consume less energy and natural resources and have little impact on the environment, while providing high-quality regenerated paper pulp.

Classical and conventional ways of refining waste paper to obtain raw materials for paper production are divided into two categories: the first is the method of refining by flotation, the second is the method of refining by washing.

These refinement methods comprise mainly two phases. The first is to defibrate the waste paper, this operation is also called pulping, the second is to remove the paint by flotation or washing.

The first phase is carried out by bringing the waste paper into contact with stirring with water and a chemical system that usually contains silicate, a base, soap or a surfactant and a bleaching agent, which are supplied separately. After defibrating the paper, according to the first embodiment, the paper pulp is diluted and transferred to a flotamok, where air is supplied through the bottom of the tank. In this case, a foam is formed, which entrains the particles of paint either by overflow from the tank in which the paper pulp is located, or by suction. In a second embodiment, the pulp is diluted and washed with water, then it is separated from the water particles dispersed in the water by filtration or centrifugation, and this step is repeated as many times as necessary to obtain a pulp of suitable quality for its disposal. The third option is to combine the washing and flotation stages to separate the ink from the paper pulp.

The chemical systems used in the refinement are usually selected depending on how the paper pulp is separated from the ink particles.

For separation methods by washing, the chemical system should be nearly non-foaming under operating conditions in order to limit any mechanical damage to the devices used. In addition, the ink particles to be extracted from the pulp should be thin and well dispersed in the presence of a chemical system to increase the efficiency of separation of these particles and obtain high-quality pulp.

For flotation separation methods, the chemical system should have more significant foaming properties than the chemical system in flushing methods. Indeed, the particles of ink in this case adhere to the foam arising inside the photocamera, which allows them to be separated from the paper pulp. On the other hand, paint particles must be able to accumulate to form large aggregates that facilitate, as well as increase, their separation from the pulp and their removal with air bubbles.

The invention relates to a new liquid paper refining composition that can be used both in flotation and flotation methods and in flotation and washing methods.

The new liquid composition according to the invention allows to obtain high quality regenerated paper pulp with high whiteness and very low residual ink content, while ensuring high performance and reliability of the industrial method of using the specified composition.

Other advantages and characteristics of the invention will appear more clearly upon reading the following description and examples.

A new formulation developed by the applicant includes at least a first nonionic surfactant (A) and at least a second nonionic surfactant selected from (B) and (C).

The nonionic surfactant (A) consists of at least a polyoxyethoxylated and polyoxypropoxylated fatty alcohol of the following general formula:

In ₁ -O - [(CH ₂ CH ₂ O) _x - (CH ₂ -CH <CH ₃ > 0) _y ] -H, in which

In ₁ - alkyl, containing 16-22 carbon atoms, the average value of x is from 5 to 30, the average value of y is from 2 to 20.

The second non-ionic surfactant (B) consists of at least a polyoxyethoxylated aliphatic fatty alcohol of the following general formula:

O-0- (CH _; CHO) ..- 11.

wherein

1 ₂ - linear alkyl containing 10-16 carbon atoms, the average value of ζ is chosen so that the mass ratio of oxyethylene units is 55-75% with respect to the weight of the surfactant (B). For example, when the radical 1 ₂ contains 14 carbon atoms, ζ is 6-13.

The third type of non-ionic surfactant (C) consists of at least polyethoxylated fatty aliphatic alcohol corresponding to the following general formula:

O-0- (C11 _; CH _; ). „- 11.

wherein

1 ₃ - linear alkyl containing 10-22 carbon atoms, the average value of ν is chosen so that the mass ratio of oxyethylene units is 35-45% with respect to the weight of the surfactant (C). In general, the average value of ν is from 1 to 10. For example, when the radical 13 contains 13 carbon atoms, ν is from 1 to 4.

In general, the mass ratio of surfactant (B) / surfactant (A) is from 0.02 to 1, and the mass ratio of surfactant (C) / surfactant (A) is from 0.02 to 1 .

These compositions are either obtained within the working environment itself during the implementation of the industrial paper refinement process, or, preferably, prepared in advance.

If obtained in advance, the compositions are stable in time and do not require the special presence of stabilizers.

Other compounds may be added upon preparation of the compositions or upon their use in the refinement process. In particular, soda, sodium silicate and hydrogen peroxide can be added.

Preferably, the nonionic surfactant (A) is a mixture of fatty alcohols, radical 11 of which is linear alkyl containing 16-20 carbon atoms, with 7-13 hydroxyethylene units and 310 oxypropylene units, and in particular, 11 oxyethylene and 4 oxypropylene units . By way of example, the corresponding fatty alcohols as surfactant (A) are coconut fatty alcohol, fatty fatty alcohol, palmitic, myristic, lauric and oleic fatty alcohols. Type (A) surfactants that can be used in the framework of the present invention are commercially available. In particular, the ΚΗΟΌΙΤΕΚ® 1000 and ΚΗΟΌΙΤΕΚ® 1200 materials sold by Ron-Pulenk give good results with the compositions of the invention.

Preferably, the nonionic surfactant (B) is a mixture of fatty alcohols, radical 12 of which is a linear alkyl containing 12-16 carbon atoms, with a weight ratio of oxyethylene units of 55-65% with respect to the weight of surfactant (B). In particular, the surfactant (B) contains 6-10 oxyethylene units. Type (B) surfactants that can be used in the framework of the present invention are commercially available. In particular, material 8 shrink A7 sold by 1C1 gives good results with the compositions of the invention.

Preferably, the nonionic surfactant (C) is a mixture of fatty alcohols, the K ₃ radical _of which is a linear alkyl containing 12-14 carbon atoms with a weight ratio of oxyethylene units of 38-42% with respect to the weight of the surfactant (C). In particular, the surfactant (C) contains 2-4 oxyethylene units. Type (C) surfactants that can be used in the framework of the present invention are commercially available. In particular, material 8 shrink A3 sold by 1C1 and the material YubazigGA 30 sold by RonPulenk give good results with the compositions of the invention.

The liquid composition according to the invention can be prepared in various forms and ensures its use in all types of industrial plants for the refinement of printed waste paper. So, the liquid composition is prepared in the form of a solution, emulsion or dispersion, while no significant changes in its performance are noted. However, in one embodiment of the invention, the liquid composition is in the form of an aqueous solution. In this case, the amount of water is 0.05-30 wt.%.

The mass percentage of surfactants in the liquid composition varies depending on the types of surfactants and is usually 70-100 relative to the total weight of the liquid composition.

Surfactants used in the framework of the invention are obtained by methods known to those skilled in the art. By way of example, surfactants are prepared by spraying ethylene oxide or spraying ethylene oxide and propylene oxide in turn onto a fatty alcohol base;

the reaction is carried out at a temperature of about 160 ° C in the presence of a basic catalyst.

The liquid compositions of the invention can be used according to methods known in the art. However, the applicant has developed a more advanced refinement method comprising at least one flotation step.

The refinement method using the liquid composition of the invention does not consume much energy and natural resources; in addition, it has little effect on the environment, while providing high-quality regenerated paper pulp. This original method, which uses a liquid composition, includes two phases.

The first phase is a pulping stage, in which the waste paper is brought into contact with the specified composition and water in the pulper to convert the waste paper into paper pulp. The second phase includes at least one flotation step in which the pulp is diluted with water. At this stage, the pH either does not change or is mainly regulated to the basic pH. The basic pH is preferably 8.5-9.

During the first phase, if necessary, add conventional additives not contained in the liquid composition. In general, the composition of the invention is preferably used with a surfactant concentration of about 0.01 wt.% In the first phase medium, although higher or lower concentrations are not excluded. The content of the recycled paper waste paper is 5-20 wt.%, And in particular 10-15 wt.% In the medium.

This contacting operation can be carried out at ambient temperature, in particular, it is carried out at a temperature of 30-70 ° C. It occurs in any known type of pulping apparatus equipped with means of mixing and freeing from fibers.

After the impregnation of the waste paper with a liquid mixture and possible additives, the paper pulp can be left alone for 0.5-4 hours. In general, before the second phase, which includes at least one flotation stage, the pulp is diluted so that get the concentration of paper pulp in water 1-3 wt.%.

Then proceed to the second phase, called flotation. It is carried out by forcing air through the bottom of the tank. The resulting foam captures the particles of paint and separates it from the paper pulp. Foam is removed from the tank by overflow or by suction.

The paper pulp freed from the ink particles can then be used in paper production.

As an embodiment of the invention, at least one surfactant (B) or (C) can be added after pulping and before the flotation phase.

The following non-limiting examples and tests illustrate the preparation and use of the compositions of the invention.

Examples

Example 1 illustrates the use of a refinement composition known in the art.

Other examples illustrate methods for preparing the enrichment compositions of the invention. These formulations are prepared inside the medium in which the paper to be refined is located, with the exception of Example 5, in which the substance KobakitGL 30 is supplied after the pulping step.

The effectiveness of the refinement treatment is determined by measuring the brightness of the ISO of a sheet of paper obtained from pulp subjected to pulp and flotation. This effectiveness is expressed for the examples of our invention through an increase in whiteness compared to that obtained with compositions of the prior art.

The compositions of examples 1 and 2 have the same number of components, except for the composition of the example, containing, in addition, the substance 8 is shorter than A7. The mixture 50/50 old newspapers and old magazines in examples 1 and 2 are the same.

Compositions 3, 4 and 5 have the same number of components, with the exception of the compositions of examples 4 and 5, containing, in addition, the substance KobakitG LA30. The mixture 50/50 old newspapers and old magazines in examples 2, 3 and 5 are the same.

Example 1

The first stage, corresponding to pulping, is carried out in a pulper with a capacity of 25 l, equipped with a screw turbine and a flotation chamber with a capacity of 15 l (LAMOKT equipment).

The following mixture is fed to pulper:

A mixture of 50/50 old newspapers and old magazines 1500 g

Soda (25%) 60 g

Hydrogen Peroxide (30%) 50 g

Kyobeyek 1000 3.37g

Sodium silicate (33.8%, Kt ^ O / YeO = 3.3) 111 g

Water at 45 ° С10 l

Water has an adjustable hardness, i.e. [Ca ²⁺ ] = 3 · 10 ^-3 mol / l and [Md ²⁺ ] = 1-10 ^-3 mol / l. Pulping is carried out for 12 minutes with a screw rotation speed of about 1500 rpm. Then the paper pulp is left for 30 minutes.

The second stage, corresponding to flotation, is carried out in a flotation chamber with a capacity of 15 liters.

The previously obtained pulp is diluted with water with adjustable stiffness, as defined above, so as to obtain a solid suspension with

1.2% solid, which is heated to a temperature of 45 ° C. The flotation stage is carried out for 6 minutes with a natural pH by air injection.

The flotated suspension is then filtered on a mold casting machine. After that, the mold is dried, and its white ISO (reflectance in blue), measured according to the standard FS O 03-039, is 59.7.

Example 2

The first stage, corresponding to pulping, is carried out in a pulper with a capacity of 25 l, equipped with a screw turbine and a flotation chamber with a capacity of 15 l (LAMOKT equipment).

The following mixture is fed to pulper:

A mixture of 50/50 old newspapers and old magazines 1500 g

Soda (25%) 60 g

Hydrogen Peroxide (30%) 50 g

K / o / Iek 1000 3.37g

Zutregoshs A7 0.27g

Sodium silicate (33.8%, CT 81O ₂ / IA ₂ O = 3.3) 111 g

Water at 45 ° С10 l

Water has an adjustable hardness, that is, [Ca ²⁺ ] = 3 · 10 ^-3 mol / L and [Md ²⁺ ] = 1 · 10 ^-3 mol / L.

Pulping and flotation are carried out under the same conditions as before.

The flotated suspension is then filtered on a mold casting machine. The mold is then dried, and its ISO whiteness (reflectivity in blue), measured according to the standard FS O 03-039, is 60.4.

Example 3

The first stage, corresponding to pulping, is carried out in a pulper with a capacity of 25 l, equipped with a screw turbine and a flotation chamber with a capacity of 15 l (LAMOKT equipment).

The following mixture is fed to pulper:

A mixture of 50/50 old newspapers and old magazines 1500 g Soda (25%) 60 g

Hydrogen Peroxide (30%) 50 g

Koyoyek 1000 3.37g

Zushregosh A7 0.18g

Sodium silicate (33.8%, Kt 81O ₂ / Ia ₂ O = 3.3) 44.40 g

Water at 45 ° С10 l

Water has an adjustable hardness, that is, | Ca ² '| = 3 · 10 ^-3 mol / L and [Md ²⁺ ] = 1 · 10 ^-3 mol / L.

Pulping and flotation are carried out under the same conditions as before.

The flotated suspension is then filtered on a mold casting machine. After that, the mold is dried, and its ISO whiteness (reflectance in blue), measured according to the standard FS O 03-039, is 51.7.

Example 4

The first stage, corresponding to pulping, is carried out in a pulper with a capacity of l, equipped with a screw turbine and a chamber

15 L flotation (equipment HAMOCT). The following mixture is fed to pulper: 50/50 mix of old newspapers and old magazines 1500 g Soda (25%) 60 g Hydrogen peroxide (30%) 50 g Koyek 1000 3.37 g Zutregoshs A7 0.18 g [KkLashgG ba 30 0.75 g Sodium silicate (33.8%, Cr 81O ₂ / Na ₂ O = 3.3) 44.40 g Water at 45 ° C 10 l

Water has an adjustable hardness, i.e. [Ca ²⁺ ] = 3 · 10 ^-3 mol / L and [Md ²⁺ ] = 1 · 10 ^-3 mol / L.

Pulping and flotation are carried out under the same conditions as before.

The flotated suspension is then filtered on a mold casting machine. After that, the mold is dried, and its ISO whiteness (reflectivity in blue), measured according to the standard FS O 03-039, is 53.5.

Example 5

The first stage, corresponding to pulping, is carried out in a pulper with a capacity of 25 l, equipped with a screw turbine and a flotation chamber with a capacity of 15 l (LAMOKT equipment).

The following mixture is fed to pulper:

A mixture of 50/50 old newspapers and old magazines 1500 g

Soda (25%) 60 g

Hydrogen Peroxide (30%) 50 g

Koyek 1000 3.37g

Zutregoshs A7 0.18g [KyuSashgG LA 30 0.75g

Sodium silicate (33.8%, Kt 81O ₂ / Ia ₂ O = 3.3) 44.40 g

Water at 45 ° С10 l

Water has an adjustable hardness, i.e. [Ca ²⁺ ] = 3 · 10 ^-3 mol / L and [Md ²⁺ ] = 1 · 10 ^-3 mol / L.

Pulping and flotation are carried out under the same conditions as before, with the exception of the substance Kyobaigia 30, which is fed after the pulp stage.

The flotated suspension is then filtered on a mold casting machine. After that, the mold is dried, and its ISO whiteness (reflectance in blue), measured according to the standard FS O 03-039, is 53.6.

Claims (10)

CLAIM 1. A liquid composition for improving paper containing at least one first surfactant (A) and at least one second surfactant selected from (B) and / or (C), with non-ionic surfactant the active substance (A) consists of at least one polyoxyethoxylated and polyoxypropoxylated fatty aliphatic alcohol of the following general formula B1-O - [(CH2CH2O) _x - (CH2-CH (CH3) O) _y ] -H, in which K is alkyl containing 16-22 carbon atoms, the average value of x is from 5 to 30, and the average value of y ranges from 2 to 20; moreover, the non-ionic surfactant (B) consists of a polyoxyethoxylated fatty aliphatic alcohol of the following general formula 1C-O- (C11 ₃ CH ₃ O) ..- H. in which K ₂ is a linear alkyl containing 1016 carbon atoms and preferably 12-16 carbon atoms, the average value of ζ is chosen so that the mass ratio of oxyethylene units is 55-75% relative to the weight of surfactant (B), preferably ζ is 610; moreover, non-ionic surfactant (C) consists of at least polyoxyethoxylated aliphatic fatty alcohol of a number corresponding to the following general formula H _; -O- (C11; C11; O) ...- 11, in which K ₃ is a linear alkyl containing 1022 carbon atoms and preferably 12-14 carbon atoms, the average value of ν is chosen such that the mass ratio of oxyethylene units is 35- 45% by weight of the surfactant (C), preferably ν is 2-4. 2. A liquid composition according to claim 1, characterized in that the liquid composition contains at least one surfactant (A), at least one surfactant (B) and at least one surfactant substance (C). 3. A liquid composition according to claim 1 or 2, characterized in that the weight ratio of surfactant (B) / surfactant (A) is 0.02-1. 4. The liquid composition according to any one of claims 1 to 3, characterized in that the mass ratio of surfactant (C) surfactant (A) is 0.02-1. 5. A liquid composition according to any one of claims ₁ to ₄ , characterized in that the non-ionic surfactant (A) is a mixture of a fatty alcohol, the K ₁ radical _of which is a linear alkyl containing 16-20 carbon atoms, with 11 oxyethylene units and 4 oxypropylene units. 6. Aqueous solution for upgrading the liquid composition according to any one of claims 1 to 5, characterized in that it contains from 0.05 to 30 wt.% Water relative to the total mass of the aqueous solution. 7. The use of a liquid composition according to any one of paragraphs. 1-5 for paper refining. 8. The use of an aqueous solution according to claim 6 for refining the paper. 9. The method of refining printed waste paper in the presence of a liquid composition according to any one of claims 1 to 5, comprising the step of pulping, in which the printed waste paper is brought into contact with said composition and water in a pulper to convert paper into pulp; flotation, in which the paper pulp is diluted with water with a constant pH in the medium or a variable basic pH of approximately 8.5-9. 10. The method of refining printed waste paper according to claim 9, characterized in that at least one surfactant (B) or (C) is added after the first stage before the second stage.