MXPA00010600A - Liquid de-inking compositions based on polyalkoxylated terpenic compounds and their use for de-inking - Google Patents

Abstract

The invention concerns a liquid de-inking composition comprising at least a surfactant of polyalkoxylated terpenic origin of formula:Z-X-W-[CH(R5)-CH(R6)-O]q-A wherein:Z is a bicycloheptenyl or bicycloheptyl radical, preferably substituted by methyl radicals;X is preferably a -CH2-CH2-O- or -O-CH2-CH2-O- radical;W is a polysequence, preferably polyoxypropylene and polyoxyethylene sequence;[CH(R5)-CH(R6)-O]q is a sequence different from a polyoxyethylene, preferably polyoxypropylene sequence;A is a hydrogen atom, a hydrocarbon or functional group. Said composition can be used for de-inking paper.

Description

LIQUID COMPOSITIONS FOR DISINFORCEMENT BASED ON POLYCOXYCOATED TERPENIC COMPOUNDS AND THEIR USE FOR THE DETONATION OF PAPER Description of the invention The present invention relates to a liquid paper deinking composition, used in the regeneration of pulp from old papers printed from newspapers, magazines, photocopies and computer papers. The present invention also relates to the use of a liquid deinking composition for the de-inking of paper. Mainly, the present invention aims at a liquid deinking composition as well as its use, adapted for the de-inking of paper by flotation and / or washing, which makes it possible to obtain a high-quality regenerated pulp having a high Whiteness Index and a very small residual proportion of ink and that ensures a stable and reliable deinking process. The de-inking operation is very important since it represents one of the stages fundamental for the recycling of old papers. Numerous methods of de-inking old papers are known. The recycling of old papers has become an important industry in which it is desired to develop and to put to the point novel deinking compositions and their procedures that use them, that are little consumers of energy and natural resources that have little impact on the environment, always providing high quality regenerated pulp. The traditional and usual procedures of de-inking old papers to give the raw material for papermaking, are divided into two categories; the first is a flotation deinking process and the second is a washing de-inking process. These deinking processes essentially comprise two phases. The first consists in defibrating the old papers, an operation also called pulping, and the second one in eliminating the ink by flotation or washing. The first phase is carried out by contacting, under agitation, old papers with water and a chemical system comprising in general a silicate, a basic agent, a soap, or a surfactant, for example an ethoxylated fatty alcohol whitening, once the papers have been defibrated, according to a first alternative, the pulp is diluted and transferred to a flotation cell where Air is injected through the bottom of the tank. A foam is then produced which entrains the ink particles, either by overflowing the tub in which the pulp or pulp is located, or by aspiration. According to a second alternative, the pulp or pulp is diluted and washed in water, then separated from the ink particles dispersed in the water by flotation or centrifugation, repeating this step as necessary in order to obtain a pulp whose qualities are suitable for reuse. A third alternative consists of combining the washing and flotation steps to separate the ink from the pulp. The chemical systems used in the de-inking are generally selected according to the mode of separation of the pulp and the ink particles.

For washing separation procedures, the chemical system must be almost non-foaming in operating conditions, in order to limit any mechanical problems at the level of the devices used. In addition, the ink particles to be extracted from the pulp must be fine and well dispersed in the presence of the chemical system to increase the efficiency of separation of said particles and obtain a high quality pulp. For flotation separation processes, the chemical system must have more important foaming properties than those of the washing processes. Indeed, the ink particles in this case adhere to the foam generated within the flotation cell, thus allowing their separation from the pulp. On the other hand, the ink particles must be of a measure to agglomerate in order to form aggregates of important size, facilitating and also increasing their separation from the pulp and its elimination by air bubbles. The applicant has put to the spot a new liquid paper deinking composition that it can be used both in flotation deinking procedures and in flotation and washing deinking procedures. The novel liquid composition according to the invention procures a high quality regenerated pulp with a high whiteness index and a small residual proportion of ink, always ensuring a great performance and reliability to the industrial process using said composition. Furthermore, the liquid composition according to the invention has the advantage of being totally non-ecotoxic, and therefore its use for de-inking the paper has almost no impact on the environment. Other advantages and features of the invention will appear more clearly upon reading the description of the following examples. The novel liquid deinking composition put into place by the Applicant comprises at least one surfactant of polyalkoxylated terpene origin of the formula: Z-X-W- [CH (R5) -CH (R6) -0] q-A wherein: the symbol Z represents a radical bicyclo [a, b, cjheptenilo or bicyclo [a, b, c] heptyl, optionally substituted with at least one alkyl radical of 1 to 6 carbon atoms, methyl preferably, * a , b, and c are such that: * a + b + c = 5, * a = 2, 3 or 4, * b = 1 or 2, * c = 0 or 1, the symbol X represents a group: * -CH ? -CFR1) (R2) -0- in which the symbols R1 and R2, identical or different, represent a linear or branched (cyclo) alkyl or (cyclo) alkenyl group of 1 to 6 carbon atoms, mainly methyl, or preferably a hydrogen atom, * or -O-CH (R '1) -CH (R' 2) -O- in which the symbols R'1 and R'2, identical or different, represent a group (cycle ) straight or branched alkyl or (cyclo) alkenyl having from 1 to 22 carbon atoms, mainly methyl, or preferably a hydrogen atom; the symbols R ™% R6, different, represent? one a hydrogen atom and the other a group (cyclo) alkyl or linear or branched (cyclo) alkenyl of 1 to 22 carbon atoms, preferably methyl; q is a mean value between 1 and 30, preferably between 5 and 20, represents a polysequenced group consisting of different sequences -B] n- and - [c] p-, * B represents a group -CH (R3) - CH (R4) -O-, in which R3 and R4, identical or different, represent a hydrogen atom or a linear or branched (cyclo) alkyl or (cyclo) alkenyl group of 1 to 22 carbon atoms, preferably methyl , R3 and R4 are different when one of them represents hydrogen, * C represents an oxyethylenated group -CH2-CH2-0- (EO) where n is an average value between 1 and 10, preferably between 2 and 4, * p it is a mean value between 1 and 100, preferably between 3 and 20, * said poly-sequenced group W is linked to the portion X by one of its sequences - [B] n-, - A represents a hydrogen atom, an alkyl radical of 1 to 6 carbon atoms, an aryl or alkylaryl radical, a halogen atom, a group -CH2-CH (OH) R7, where the symbol R7 represents a linear alkyl radical or branched or cyclic of 1 to 22 carbon atoms or aryl, or a group selected from -S03M, -OP03 (M) 2, - (CH2) a-COOM, - (CH2) b-S0M, with a and b ranging from 1 to 6, M representing hydrogen, sodium, potassium, lithium, N (RR'R "R" ') + where the symbols R, R', R "and R" 'are identical or different and represent a hydrogen atom or a linear or branched or cyclic alkyl radical of 1 to 22 carbon atoms optionally hydroxylated. Preferably, the symbol Z represents a radical Z1 or Z2, * Z1 is a radical: - bicyclo [3.1. l-heptenyl, preferably substituted on its carbon atom in position 6 by at least one alkyl radical of 1 to 6 carbon atoms, more particularly by two methyl radicals, said bicyclo radical [3.1. Ljheptenyl is linked to the X portion of the formula -CH2-C (R1) (R2) -O-, by means of its carbon atom in position 2; - or bicycle [2.2. l-heptenyl, preferably substituted on its carbon atom in position 7 by at least one alkyl radical of 1 to 6 carbon atoms, more particularly by two methyl radicals, said bicyclo radical [2.2. L-heptenyl is linked to the X portion of the formula -CH2-C (R1) (R2) -O-, via its carbon atom in position 2 or position 3; * Z2 is a radical bicyclo [2.2. l-heptyl, preferably substituted on its carbon atom in position 7 by at least one alkyl radical of 1 to 6 carbon atoms, more particularly by two methyl radicals, the bicyclo radical [2.2. Ljheptyl is linked to the X portion of the formula -O-CH (R '1) -CH (R' 2) -O-, via its carbon atom in position 2 or position 3. Preferably, the sequences [ B] "and [CH (R5) -CH (R6) -0] q are the polyoxypropylenated sequences [PO] n and [P0] q.

Preferably more particularly, the symbol W represents a bisected group - [B] "- [Cjp-, sequence [B] n is a polyoxypropylenated sequence [P0]" and sequence [C] p is a polyoxyethylenated sequence [EO] p. The present invention is more particularly aimed at the novel polyalkoxylated terpene compounds of formula Z1-CH2-CH2-0- [PO] n- [EOJp- [PO] q-A Z2-0-CH2-CH_-0- [P0] "- [E0jp- [P0] q-A Having Z1 and Z2 definitions identical to those given above. As examples of these novel compounds, those of the formula can be mentioned in particular; CH_-CH_-0- [PO] n- [EO] p- [PO] q-A ? - \ - 0-CH2-CH2-0- [P0] n- [E0] p- [P0] q-A These compounds are either prepared in the very medium of operation after the operation of the industrial process of de-inking of papers or, preferably, already prepared in advance. In the case of preparation in advance, the compositions are stable over time and do not particularly need the presence of stability additives. Other compounds may be added in the preparation of the compositions or at the time of their use in the deinking process. You can add mainly soda, sodium silicate or hydrogen peroxide. The liquid composition according to the invention can be conditioned in different forms and allows its use in all types of industrial devices used to de-indent the old inked papers. In this way, the liquid composition is used as it is or in the form of a diluted solution, without noticeable sensible modifications of its operations.

The surfactants used in the context of the invention are prepared according to different procedures.

By way of example, the surfactants forming the object of the invention can be prepared by successive polyalcoxylation reactions of reagent of the formula Z-XH, by at least two types of different alkoxylation agents, where one is ethylene oxide and the one or the other is a higher alkylene oxide, with the final alkoxylation with the aid of a higher alkylene oxide, then the eventual functionalization of the terminal hydrogen atom. More precisely, said reagent Z-XH is subjected to successive polyalcoxylation reactions with: - the alkylene oxide (OAl) of the formula: \ / O the alkylene oxide (EO) of the formula: CH2-CH2 / O and the alkylene oxide (0A2) of the formula: \ / O R3, R4, R5, and R6 have the identical definitions as those given above. Said alkylene oxides (OAl) and (OE) are introduced successively and the alkylene oxide (0A2) is introduced at the end, to obtain a product of the formula: Z-X- - [CH (R5) -CH (R6) -0] qH in which W and q have the identical definitions to those given above, then eventually the functionalization to transform the terminal hydrogen atom into one of the substituents A other than hydrogen as defined above. In this way, the novel polyalkoxylated terpene compounds of the formula (I) form the object of the invention, wherein X represents -CHz-CIR1) (R2) -0-, which can be obtained by polyalkoxylation reaction of a Reagent of the formula (I '): in which the symbols Z, R1 and Rz have definitions identical to those given above, with the alkylene oxide (OAl), the alkylene oxide (OE) and the alkylene oxide (0A2). Said oxides of alkylanes (OAl) and (OE) are introduced successively and the alkylene oxide (0A2) is introduced at the end, to obtain a product of the formula: Z-CH2-C (R1) (R2) -0-W- [CH (R5) -CH (R6) -0] qH wherein W and q have the definition given above, then eventually functionalization to transform the terminal hydrogen atom into one of the substituents A other than hydrogen, as defined above. The novel polyalkoxylated terpene compounds of the formula (I) form the object of the invention, a formula in which X represents -O-CH (Rr 1) -CH (R '2) -O-, which can be obtained by polyalkoxylation reaction of a reagent of the formula (I "): Z-O-CHIR'1) -CH (R'2) -OH (I ") in which the symbols Z, R 'and R'2 have the identical definitions to those given above, with the alkylene oxide (OAl), the alkylene oxide (OE), and the alkylene oxide (OA2), by introduction successive of the alkylene oxides (OAl) and (OE) and final introduction of alkylene oxide (OA2), to obtain a product of the formula: Z-O-CHfR'1) -CH (R'2) -0-W- [CH (R5) -CH (R6) -0] qH in which y have the definition given above, then eventually the functionalization to transform the terminal hydrogen atom into one of the substituents A other than the hydrogen atom, as defined above.

The preparation methods of the reagents of formula (I ') and (I ") are described in the international application WO 96/01245. Preferably, the oxides of alkylene (OAl) and (OA2) are propylene oxide. .

The polyalkoxylation reactions are carried out according to well-known methods at a temperature above 100 ° C, preferably between 120 and 250 ° C, more particularly between 150 and 200 ° C, in the presence of a catalyst (strong bases, amines aliphatic, Lewis acids). Advantageously, the operation is carried out in the presence of an inert gas such as nitrogen or a rare gas such as argon or carbon monoxide, preferably at a pressure of 1 to 4 bar. More extensive details concerning this type of reaction are given in the international application WO 96/01245. The alkylene oxide (OAl) and the ethylene oxide (OE) are introduced in succession, before the final introduction of the alkylene oxide (OA2). The amounts of alkylene oxide or ethylene put into operation correspond to the numbers of molar equivalents n, p and q sought. The conditions of realization in a mode of operation of this type are well known to the person skilled in the art. The eventual functionalization operation for transforming the terminal hydrogen atom into one of substituents A, can be, for example, an etherification or esterification operation of the terminal hydrogen atom; this stage is well known by itself; it is preferably carried out after neutralization. In this way, the preparation: of ether sulfates (A = -S03M), according to the operation mode described in the British patent GB 1 111 208 or the US patent US-A-3, 392, can be carried out. 185; - of ether phosphates (A = OP03 (M) 2), according to the mode of operation described in United States Patent US-A-3,331,896; - of ether carboxylates (A = - (CH2) a-COOM), according to the mode of operation described in US Pat. No. US-A-2, 623, 900 or in the United States patent US-A -2, 983, 738 - of ether sulfonates (A = (CH2) b-S03M), according to the mode of operation described in United States patents US-A-2, 115, 192, US-A-4, 978, 780 or K SUGA, Austr. J. Chem. 21, 2333 (1968) - of alkyl ethers (A = alkyl), according to the mode of operation described in US Pat. No. 2,913,416. Further details regarding functionalization modalities are described in WO 96/01245 . The deinking process using the liquid composition according to the invention consumes little energy and natural resources; In addition, it has little impact on the environment, always providing the pulp of high quality regenerated paper. This original procedure in which the liquid composition according to the invention is put into operation includes two phases. The first phase is the step of pulping or pulping where the inked papers are put in contact with said composition and water, in a shredder to transform the papers into pulp or pulp. The second phase includes at least a flotation stage where the pulp or pulp is diluted in water. In this step the pH is either unmodified or advantageously adjusted to alkaline pH. The alkaline pH is preferably between 8.5 and 9. In the course of the first phase, the usual additives not contained in the liquid composition are added as the case may be. In general, the composition according to the invention is advantageously employed with a surfactant concentration of the order of 0.01 to 0.02% by weight in the medium of the first phase, although higher or lower concentrations are not excluded. The proportion of inked old papers to be treated represents 5 to 20% by weight, and more particularly between 10 and 15% by weight of the medium. This contacting operation can be carried out at room temperature, but more particularly this is carried out at a temperature comprised between 30 and 70 ° C. This takes place in any type of known pulping apparatus, provided with agitation and defibration means. Once the operation of impregnation of the old papers with the mixture of the liquid composition and the optional additives has been done, the Pulp can be left at rest for 0.5 to 4 hours. In general, before the second phase which includes at least one flotation step, the pulp is diluted in a manner to obtain a concentration of the pulp in water of 1 to 3% by weight. We proceed immediately to the second phase, called flotation. This is done by injecting air through the bottom of the tank. The foam that is formed entrains the ink particles and separates them from the pulp. The foam is dragged out of the tank by overflow or by aspiration. The waste pulp discharged from the ink particles can then be used in the preparation of papers. As a variant according to the invention, one or more surfactants can be added after pulping and before the flotation phase. The following examples and tests, of a non-limiting nature, illustrate the preparation and putting into operation of the compositions according to the invention.

EXAMPLES Examples 1 and 3 illustrate the use of deinking preparations according to the invention, examples 2 and 4 illustrate the use of a deinking composition according to the prior art. The effectiveness of the de-inking treatment is carried out by measuring the ISO whiteness of a sheet of paper formed from the pulp coming from the pulp and flotation treatments.

Example 1 The first stage corresponding to the pulping is carried out in a pulp or pulp crusher of 2 liters equipped with a KENWOOD type robot. The surfactant of terpene origin used, NOPOL 30E / 3 OP, is of the formula: CH_-CH_-0 [PO] 3- [EOJ3-_PO] 3-A The following mixture is introduced into the pulp crusher: Old newspapers of approximately 6 200 g months Sosa (25%) 5.6 g Hydrogen peroxide (30% 5.3 g Terpene surfactant 0.44 g Sodium silicate 7N34 2.94 g Water of controlled hardness (3xl0 ~ 3 mol / 1 of Ca2 +) at 50 ° C 1330 g The old papers are introduced in the pulper or pulper former with the reagents, except for the oxygenated water that is introduced after 2 minutes of pulping. Pulping is carried out for approximately 20 minutes. The pulp is immediately left at rest at 45 ° C for 30 minutes. The second stage, corresponding to the flotation is put into operation in a flotation cell of 15 liters of type LAMORT. The pulp obtained above is diluted with water of controlled hardness, such as that defined above, so as to obtain a solid suspension at 1% solids. The flotation stage is carried out at natural pH for 5 minutes by air injection. The floating suspension is then filtered on a shape copier. The shape is then dried and its whiteness ISO (diffuse reflectance factor in blue), measured according to the standard NF Q 03-039, is 46.

Example 2 - Previous technique Under the same conditions as Example 1, the propoxylated ethoxylated fatty alcohol marketed under the name Rhoditek 1000 by the company Rhodia Chimie is used instead of the composition according to the invention. The suspension is then filtered on a shape copier. The shape is then dried and its whiteness ISO (diffuse reflectance factor in blue), measured according to the norm NF Q 03-039, is 46.6.

Example 3 The first stage corresponding to the pulp or pulp formation is carried out in a 2 liter shredder equipped with the KENWOOD type robot. The surfactant of terpene origin used is of the formula: The following mixture is introduced into the crusher: Mix of old newspapers (40%) and old magazines (60%) 200 g Sosa (25%) 5.6 g Hydrogen peroxide (30%) 5.3 g Terpene tenside 0.44 g Sodium silicate 7N34 2.94 g Water of controlled hardness (3xl0 ~ 3 mol / 1 of Ca2 +) at 50 ° C 1330 g The old papers are introduced in the crusher with the reagents, except for the hydrogen peroxide that is introduced after 2 minutes of the crushing. The grinding is carried out for approximately 20 minutes. The pulp is then left to stand at 45 ° C for 30 minutes. The second stage, corresponding to the flotation, is put into operation in a LAMORT 15-liter flotation cell. The preceding pulp obtained is diluted with water of controlled hardness such as that defined above, so as to obtain a solid suspension of 1% solids. The flotation stage is carried out at natural pH for 5 minutes by injection of air. The floating suspension is then filtered on a format copier. The shape is then dried and its ISO whiteness (diffuse reflectance factor in blue) measured according to standard NF Q 03-039, is 57.2.

Example 4 - Previous technique Under the same conditions as Example 3, instead of the composition according to the invention, the propoxylated ethoxylated fatty alcohol marketed under the name Rhoditek 1000 by the company Rhodia Chimie is used instead. The suspension is then filtered on a shape copier. The shape is then dried and its whiteness ISO (diffuse reflectance factor in blue) measured according to the NF Q standard 03-039, is 56.7.

Claims (9)

1. Liquid deinking composition comprising at least one polyalkoxylated terpene surfactant of the formula: Z-X-W- [CH (R5) -CH (R6) -0] q-A (I) in which: - the symbol Z represents a radical bicyclo [a, b, cjheptenilo or bicyclo [a, b, cjheptyl, optionally substituted with at least one alkyl radical of 1 to 6 carbon atoms, methyl preferably, * a, b, and e are such that: * a + b + c = 5, * a = 2, 3 or 4, * b = 1 or 2, * c = 0 or 1, - the symbol X represents a group: * -CH .-CfR1) (R2) -0- in which the symbols R1 and R2, identical or different, represent a linear or branched (cyclo) alkyl or (cyclo) alkenyl group of 1 to 6 carbon atoms, primarily methyl, or preferably a hydrogen atom, * or -O-CHIR'1) -CH (R'2) -0- in which the symbols R'1 and R'2, identical or different, represent a group (cyclo) alkyl or linear or branched (cyclo) alkenyl of 1 to 22 carbon atoms, mainly methyl, or preferably a hydrogen atom; the symbols R5 and R6, different, represent one a hydrogen atom and the other a group (cyclo) alkyl or linear or branched (cyclo) alkenyl of 1 to 22 carbon atoms, preferably methyl; q is a mean value between 1 and 30, preferably between 5 and 20, W represents a polysequenced group consisting of different sequences - [B] "- and * B represents a group -CH (R3) -CH (R4) -O-, in which R3 and R4, identical or different, represent a hydrogen atom or a linear or branched (cyclo) alkyl or (cyclo) alkenyl group from 1 to 22 carbon atoms, preferably methyl, R3 and R4 are different when one of them represents hydrogen, * C represents an oxyethylenated group -CH2-CH2-0- (EO), where n is an average value comprised between 1 and 10, preferably between 2 and 4, * p is a mean value comprised between 1 and 100, preferably between 3 and 20, * said poly-sequenced group W is linked to the portion X by one of its sequences - [B] n-, - A represents a hydrogen atom, an alkyl radical of 1 to 6 carbon atoms, an aryl or alkylaryl radical, a halogen atom, a group -CH2-CH (OH) R7, where the symbol R7 represents a linear or branched or cyclic alkyl radical of 1 to 22 carbon atoms or aryl, or a group selected from -SO3M, -OP03 (M) 2, - (CH2) to-C00M, - (CH2) b-S03M, with a and b ranging from 1 to 6, M representing hydrogen, sodium, potassium, lithium, N (RR'R "R" ') + where the symbols R, R', R "and R" 'are identical or different and represent a hydrogen atom or a linear or branched alkyl radical or cyclic of 1 to 22 carbon atoms optionally hydroxylated.

2. Liquid deinking composition according to claim 1, characterized in that the symbol Z represents a radical Z1 or Z2: * Z1 is a radical: - bicycles [3.1. l-heptenyl, preferably substituted on its carbon atom in position 6 by at least one alkyl radical of 1 to 6 carbon atoms, more particularly by two methyl radicals, said bicyclo radical [3.1. L-heptenyl is linked to the X portion of the formula -CHi-CfR1) (R2) -0-, by means of its carbon atom in position 2; - or bicycle [2.2. l-heptenyl, preferably substituted on its carbon atom in position 7 by at least one alkyl radical of 1 to 6 carbon atoms, more particularly by two methyl radicals, said bicyclo radical [2.2. L-heptenyl is linked to the X portion of the formula -CH2-C (R1) (R2) -O-, via its carbon atom in position 2 or position 3; * Z2 is a radical bicyclo [2.2. L-Heptyl, preferably substituted on its carbon atom in position 7 by at least one alkyl radical of 1 to 6 carbon atoms carbon, more particularly by two methyl radicals, the radical b? c? clo [2.2. Ikhheptyl is bonded to the X portion of the formula -O-CH (R'1) -CH (R'2) -0-, through its carbon atom in position 2 or position 3.

3. Composition according to any of claims 1 and 2, characterized in that the sequences [Bj "and [CH (R5) -CH (R6) -0] q are polyoxypropylenated sequences [P0]" and [P0] q.

4. Composition according to any of claims 1 and 3, characterized in that the symbol W represents a bisected group - [B] n- [C] P-, the sequence [B] being "a polyoxypropylenated sequence [P0]" and the sequence [C] p is a polyoxyethylenated sequence [E0] p.

5. Composition according to claim 2, characterized in that the novel polyalkoxylated terpene compounds are of the formula: Z1-CH2-CH2-0- [P0] n- [E0] p- [P0] q-A or Z2-0-CH2-CH2-0- [P0] n- [E0] p- [P0jq-A

6. Composition according to claim 5, characterized in that they have by formulas:

A 7. The use of a liquid composition according to any of claims 1 to 6, for the de-inking of paper.

8. DETERING PROCEDURE OF INKED old papers, in the presence of a liquid composition according to any of claims 1 to 6, comprising two phases: The first phase consists of a step of pulping or grinding where the inked old papers are put in contact with the composition and the water in a shredder to transform the papers into pulp or pulp, the second phase comprises at least one step of flotation where the pulp is diluted in water at unmodified pH in the medium or alkaline modified pH, between 8.5 and 9.