SE525464C3 - Auxiliary for the boiling of lignocellulosic material and process for mass production - Google Patents

Description

25 30 35 LW i * Q 01 fi; In a conventional method using a quinone-type aid, the problem to be solved has been how to increase the penetration of a quinone into the pulp. For example, even if a penetrant is added as described in Japanese Patent Publication No. Hei 1-20276, it is not sufficient to improve the boiling yield (the yield of pulp after boiling, hereafter), the degree of boiling and the quality of the pulp. Furthermore, the use of a surfactant as described in Japanese Laid-Open Patent Sho 53-28522 in the cooking process is effective for removing resin, but it has not provided sufficient effect to improve the boiling yield, the degree of boiling and the quality of the pulp.

The inventors of the invention have enthusiastically made studies in order to improve the boiling yield, the degree of boiling and the quality of pulp in the cooking process of lignocellulosic material and consequently found that the use of a specified compound as a cooking aid can improve the pulp yield after boiling, lower the Kappa number. for pulp after boiling, improve the degree of boiling, lower the steam energy at the time of boiling, lower the sulfidity of a boiling end, lower the active alkaline of the boiling end, and further improve the tear index, the breaking length and burst index and improve the pulp quality.

SUMMARY OF THE INVENTION The invention relates to an aid for cooking a lignocellulosic material and a method for manufacturing a pulp, and a first aid for boiling a lignocellulosic material according to the invention comprises a non-ionic surfactant (A) comprising one or more compounds represented by the general formula (1): R 1 ~ O - [(C 2 H 4 O) m / (Å10) nl-H (1) in which R * is a branched alkyl group containing 4-24 carbon atoms represented by the general formula (2) R 2 -cH-R * - I R 3 (2) (in which R 2 and R a are independently selected from the group consisting of unbranched or branched alkyl groups containing 1-21 carbon atoms, and R 4 is an alkylene group containing 1 -21 carbon atoms); m is an integer of at least 1, which has an average value of 4-20; A1 is an alkylene group containing 3 or 4 carbon atoms; and n is 0 or an integer of at least 1, which has an average of 0-15; wherein (C2H4O) and (A10), in case the mean value of n is 1-15, are randomly and / or blockwise bound.

A second aid for cooking a lignocellulosic material according to the invention comprises a non-ionic surfactant (B) obtained by adding an alkylene oxide to an aliphatic alcohol, the non-ionic surfactant (B) comprising one or more compounds represented by the general formula (3): R 5 -O - [(C 2 H 4 O) p / (Å 2 O) q 1 -H (3) in which R 5 is an unbranched, branched or cyclic aliphatic hydrocarbyl group containing 4-24 carbon atoms; p is an additive molar number of 4-20; A2 is an alkylene group containing 3 or 4 carbon atoms; and q is an additive molar number of 0 or 1-15; wherein (C 2 H 4 O) and (A 2 O), in the case where the mean value of q is 1-15, are randomly and / or blockwise bound; wherein the non-ionic surfactant (B) has a weight-average molecular weight (Mw) and a number-average molecular weight (Mn) providing a ratio Mw / Mn satisfying the relationship (4): Mw / Mn g -0, 1s3x1 <' ° - ° 3 °> in which LnX is a natural logarithm of X; X is an average addition mol of the alkylene oxide per 1 mole of the aliphatic alcohol; and K is the number of carbon atoms in R5 of the general formula (3). A third aid for cooking a lignocellulosic material according to the invention comprises an anionic surfactant (C) represented by the general formula (5) and / or an anionic surfactant (D) comprising one or more compounds represented by the general formula (6): R 0 -sosml (s) on {R which Re is an unbranched, branched or cyclic aliphatic hydrocarbyl group containing 4-24 carbon atoms; A3 is an alkylene group containing 3 or 4 carbon atoms, r is 0 or an integer of at least 1, having an average value of 15; k is an integer of 1 or 2; and M 'and M2 are monovalent cations.

A fourth auxiliary precooking of a lignocellulosic material according to the invention comprises: (a) a non-ionic surfactant (A) and / or a non-ionic surfactant (B); together with (b) at least one anionic surfactant selected from the group consisting of an anionic surfactant (C), an anionic surfactant (D) and an anionic surfactant (E); in a weight ratio of 100 / 0.1-100 / 30.

Incidentally, the surfactant (A), the surfactant (B), the surfactant (C) and the surfactant (D) are the same as described and the surfactant (E) comprises one or more compounds represented by the general formula (7): R '-o- (Am -6 carbon atoms; A4 is an alkylene group containing 3 or 4 carbon atoms; s is 0 or an integer of at least 1 which has an average of 0-15; M3 is a monovalent cation.

Furthermore, the method for manufacturing a pulp according to the invention comprises boiling a lignocellulosic material with an alkali or sulphite in the presence of a cooking aid, the aid described above being used together with a quinone-type cooking aid and / or a polysulfide as an aid.

In addition, the lignocellulosic material is heated after, during and / or before the addition of the aid described above in some cases.

The cooking aid according to the invention has the following properties when used for alkaline cooking or sulphite cooking of a lignocellulosic material: (1) capable of improving the degree of cooking, the cooking yield and the mass strength; i (2) capable of further enhancing the boiling acceleration effect with a quinone type cooking aid; and (3) capable of suppressing the adhesion of paving stones in a cooking appliance which adversely affects the operating efficiency and maintenance.

Due to the effects described above, the cooking aid according to the invention is extremely practically useful for reducing wood unit consumption and energy unit consumption, which are important in pulp production, and for economically producing a high quality product. Furthermore, the use of the cooking aid according to the invention makes an apparatus for foam suppression and addition of a defoaming agent unnecessary and the cooking aid can very effectively and economically solve the conventional problems described above. o Oludo 10 15 20 25 30 35 C "1 ß.) G1 m; (A -ië- KHIV.. |.

Fig. 1 shows a graph showing the area satisfying the relationship (4) or (a) in the case K is 4.

Fig. 2 shows a graph showing the area satisfying the relationship (4) or (a) in the case where K is 12.

Fig. 3 shows a graph showing the area satisfying the relationship (4) or (a) in the case where K is 24. 5-! .Hm m: I E..

A first example of embodiments of the invention will be described. The cooking aid in this example comprises a non-ionic surfactant (A) comprising one or more compounds represented by formula (1).

R * -o - [(c 2 H -24, preferably 6-20, and especially preferably 8-14. If the number of carbon atoms is less than 4 or higher than 24, the surface activity is reduced and a sufficient penetration effect cannot be provided. Incidentally, a desirable penetration effect can be achieved in case R1 is a branched alkyl group, as described above.

R * -cH-Rt - I R ° (2) In the formula, R 2 and R a are independently selected from the group consisting of unbranched or branched alkyl groups containing 1-21 carbon atoms, and R * is an alkylene group containing 1-21 carbon atoms. Practical examples of R 2 and R a are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, hexyl composed of dimers of propylene, n-heptyl, n-octyl, n-nonyl, nonyl composed of trimers of propylene, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n- 10 15 20 25 30 35 ( F ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene, n-tetradecylene, n-pentadecylene, n-hexadecylene, n-heptadecylene, n-octadecylene, n-nonadecylene, n-eicosylene and the like.

Examples of the alkyl group represented by the formula (2) are isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, 2-ethylhexyl, isononyl, isodekyl, a branched nonyl composed of trimers of propylene, isoundekyl, isododecyl, a branched dodecyl composed of tetramers of propylene, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isoeicosyl, a branched alkyl group containing 4-24 carbon atoms synthesized by an oxo process, and the like. Preferred are 2-ethylhexyl, isononyl, isodecyl, a branched nonyl composed of trimers of propylene, isoundecyl, isododecyl, a branched dodecyl composed of tetramers of propylene and isotridecyl. Particularly preferred are 2-ethylhexyl, isononyl and isodekyl.

The m of formula (1) described above is generally an integer of at least 1, which has an average value of 4-20, preferably an integer of at least 1, which has an average value of 5-18 and particularly preferably an integer of at least 1, which has an average value of 6-16. If the mean value of m is less than 4, the penetration effect is reduced. If, on the other hand, the mean value of m is higher than 20, the penetration effect is reduced and at the same time foaming suppression becomes black.

A1 of formula (1) is an alkylene group containing 3 or 4 carbon atoms. If the number of carbon atoms of the alkylene group is less than 3, the function of suppressing foaming becomes weak, which makes it difficult to improve the drainage capacity of the black liquor in a scrubber. If the number of carbon atoms of the alkylene group is higher than 4, the penetration function is reduced and at the same time, the adsorption amount of the boiling aid in the pulp is increased to change the surface properties of the pulp.

A10 of formula (1) is an oxyalkylene group formed by the addition of alkylene oxide containing three or four carbon atoms. Examples of the alkylene oxide are propylene oxide (hereinafter abbreviated PO), 1,2- or 2,3-butylene oxide (hereinafter abbreviated BO), tetrahydrofuran (hereinafter abbreviated THF) and combinations of two or more alkylene oxides containing 3 or 4 carbon atoms and preferably a PO .

The n of formula (1) described above is generally 0 or an integer of at least 1, which has an average of 0-15, preferably 0 or an integer of at least 1, which has an average of 0-10 and in particular preferably 0 or an integer of at least 1, which has an average of 0-7. If the average value of n is higher than 15, the penetration effect is reduced and at the same time the amount of adsorption of the cooking aid in the pulp is increased to change the surface properties of the pulp.

(C2H4O) m / (AlO), of formula (1) is a polyoxyalkylene group formed by the addition of ethylene oxide (hereinafter abbreviated as EO) in moles or (co) addition of an alkylene oxide containing 3 or 4 carbon atoms in moles together with the EO additive, and (C2H40) and (A10), in case the mean value of n is 1-15, are randomly and / or blockwise bound. Otherwise, the order of additions is not limited.

Practical examples of the nonionic surfactant (A) are those which contain an alcohol represented by R'-OH to which EO, PO and BO are added in the order (a) to (c). Incidentally, in the following, (EO) is EO residue, (PO) is P0 residue and (BO) is BO residue, the number written to the right of each () being the number of moles added, / learn addition in random form, - is an additive in block form and those shown in <> show the relationships between m and ni the respective compounds with a to k.

II Û OI OÛOO OIIO Û OIUI II O 10 15 20 25 30 35 (a) -lE0), - (Bo) ß -u-ïo), - (Po) ¿- (b) 480) .. -l fi øl fl / ( PO) - i 77 (c) - (E0) @ - (Po) ¿-uzmx - (Po) ¿460) '- Among the compounds represented by the formula (1), the preferred ones are those which are composed of an alcohol represented by a formula R1-OH and either E0 added to the alcohol or EO and PO added together to the alcohol.

Next, a second example of an embodiment of the invention will be described. The cooking aid according to this example comprises a non-ionic surfactant (B) obtained by adding an alkylene oxide to an aliphatic alcohol. The nonionic surfactant (B) comprises one or more compounds represented by the formula (3) and the nonionic surfactant (B) has a weight-average molecular weight (Mw) and a number-average molecular weight (Mn). providing a ratio Mw / Mn satisfying the relationship (4): Rs -o - [(c2H., o) ,, / (A2o) q1-H (s) is represented as Mw =) 3 (NixM; 2) -: - Z (NixM;) in polydisperse systems comprising molecules with molecular weight of Mi in N; to the number (i = 1, 2, ...). The equation is in summary (hereafter the same). The number-average molecular weight (Mn) can be defined as Mn = (NixMi) -z- ZNi, in polydisperse systems comprising molecules with molecular weight of Mi in Ni to the number (i = 1, 2, ...).

Furthermore, R 5 is an unbranched, branched or cyclic aliphatic monovalent hydrocarbyl group, and the number of carbon atoms is generally 4-24, preferably 6-20 and especially preferably 8-14. If the number of carbon atoms is less than 4 and higher than 24, a sufficient penetration effect can not be obtained and it is not preferred for a cooking aid. Practical examples of R 5 are an unbranched alkyl group such as n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-nonadecyl and the like; a branched alkyl group practically exemplified as the alkyl group of formula (2); a cycloalkyl group such as cyclohexyl, ethylcyclohexyl, propylcyclohexyl, octylcyclohexyl, nonylcyclohexyl, adamantyl and the like; an unbranched alkenyl or alkadienyl such as allyl, butenyl, hexenyl, octenyl, dodecenyl, tridekenyl, pentadekenyl, oleyl, gadoleyl, linoleyl and the like; a branched alkenyl or alkadienyl group such as 2-methyl-2-propenyl, 2,3-dimethyl-1,3-butadienyl, 2-ethyl-1-hexenyl, 2-ethyl-3-hexenyl, 2,6-dimethyl -7-octenyl, 2,5,8-trimethyl-3,7-nonadienyl, 2,15-dimethyl-9,10-hexadecadienyl and the like; and a cyclic alkenyl group such as 4-methyl-1-cyclopentenyl, 6-ethyl-1,3-cyclohexadienyl, 3,5-diethyl-1-cyclopentenyl, 3- (1-methylbutyl) -1-cyclohexenyl (2-propenyl) -cyclohexenyl and the like. Among them, the preferred are unbranched or branched alkyl or alkenyl groups containing 6-20 carbon atoms and especially preferred are n-octyl, n-nonyl, n-decyl, isooctyl, 2-ethylhexyl, isononyl, and isodekyl.

The p of formula (3) described above is generally an integer of 4-20, preferably 5-18 and particularly preferably 6-16. If p is less than 4, the penetration effect is reduced. On the other hand, if p is higher than 20, the penetration effect is reduced at the same time as foaming increases.

A2 of formula (3) is an alkylene group containing 3 or 4 carbon atoms. If the number of carbon atoms in the alkylene group is less than 3, the foaming suppression function becomes weak, which makes it difficult to improve the drainage capacity of the black liquor in a scrubber. On the other hand, if the number of carbon atoms of the alkylene group is higher than 4, the penetration effect is reduced at the same time as the amount of adsorption of the cooking aid in the pulp is increased to change the surface properties of the pulp. Practical examples of A20 are the same as those exemplified as the practical examples A10 of formula (1) and are preferably PO-residue.

The q of formula (3) described above is generally an integer of 0 or 1-15, preferably 0 or 1-10 and particularly preferably 0 or 1-7. Those with q higher than 15 are not preferred as a cooking aid because the penetration effect is reduced.

(C 2 H 4 O) 2 / (A 2 O) q of formula (3) is a polyoxyalkylene group formed by the addition of EO in p moles or (co) addition of an alkylene oxide having 3 or 4 carbon atoms in q moles together with the EO additive.

Practical examples of the type of additive of (C2H4O) ,, / (A2O) q are the same as described in the description for formula (1). Otherwise, m is replaced by p 'and n is replaced by q in the relationship between m and n described above with a to k.

Furthermore, according to the invention, the non-ionic surfactant (B) fulfills the connection (4).

Mw / Mn is ~ x, 1s3x1 <'° -93 °> The ratio Mw / Mn between the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) shows the degree of molecular weight distribution. Mw / Mn is 1 or higher and that Mw / Mn = 1 means in particular a monodispersion (composed of compounds with only a single molecular weight).

Measurement of Mw and Mn is performed by gel chromatography (GPC) using tetrahydrofuran as a developing agent.

LnX is a natural logarithm of X; X is an average addition mol of the alkylene oxide (including EO) per 1 mole of the aliphatic alcohol; K is the number of carbon atoms in R5 of formula (3).

If the Mw / Mn of the non-ionic surfactant (B) satisfies the relationship (4), an excellent penetration effect can be obtained and at the same time foaming control is made simple. Particularly preferred are those which satisfy that the value calculated by subtracting the value of Mw / Mn to the left from the value calculated to the right in the relation (4) is 0.02 or higher. Incidentally, the value of Mw / Mn is small, the molecular weight distribution range is narrow and the ratio of a major component which has a penetration effect is increased. Furthermore, it is preferred that Mw / Mn satisfies the relationship - (a). - Mw / Mn is -o, 1s3x1 <'° - ° ~' * ° xl_nx + 1, a1> <1 <'° - °° 5 (a) In the relation LnX, X and K respectively are the same as those in the relation ( 4).

Examples of a preparation process for the nonionic surfactant (B) having Mw / Mn satisfying the above-described compound (4) are as follows: [1] a process for adding an alkylene oxide to an aliphatic alkali W cohol using a catalyst which is capable of making the molecular weight distribution narrower compared to a well-known general catalyst (a base catalyst such as hydroxides, carbonates or amine compounds of alkali metals such as lithium, sodium, potassium, cesium and the like); [2] a process comprising the steps of adding 1 to 3 moles of an alkylene oxide to an aliphatic alcohol using a well-known general catalyst, removing the unreacted alcohol, and then adding an alkylene oxide using a well-known general catalyst. ; and in [3] a process comprising a step of further adding an alkylene oxide using a well known general catalyst after an alkylene oxide is added by the process described above [1]. Preferred is the manufacturing method [1] or [3].

As a catalyst which is capable of making the molecular weight ratio narrower in the country, exemplary catalysts are selected from a compound comprising fired magnesium oxide (Laid-Open Japanese Patent Application No. Hei 1-164437), fired hydrotalk (Laid-Open Japanese Patent Application No. Hei 2-71841), perchloric acid salt (U.S. Patent No. 4,112,231), perhalic acid (salt), sulfuric acid (salt), nitric acid (salt) and alcoholates of di- or tri-valent metals. Among them, the preferred perchloric acid salt and perhalic acid (salt) and more preferred are magnesium salt, zinc salt, and / or aluminum salt of perchloric acid.

Fig. 1 to Fig. 3 show the areas which meet the relationship (4) or (a), and in the figures the regions shown in oblique lines show the areas which meet the relationship (4) and the areas shown in cross-section show the areas which meet the relationship - bandet (a). In addition, the abscissa axis of each figure shows X in the relation (4) or (a); the ordinate axis shows Mw / Mn. Further, Fig. 1 shows a graph showing the case K is 4 in the relation (4) or (a): Fig. 2 shows a graph showing the case K is 12 in the relation (4) or (a): and Fig. 3 shows a graph showing the case K is 24 in relation (4) or (a).

Furthermore, the results are shown in the case of the addition of EO using a well-known general catalyst (potassium hydroxide) with thin curved lines in the respective figures.

The HLB of the nonionic surfactant (A) or the nonionic surfactant (B) of the invention is preferably 6-18, particularly preferably 10-16.5. If the HLB is 6-18, a higher penetration effect can be obtained. In this case, HLB (Hydrophilic-Lipophilic Balance) can be calculated by adding the numerical values showing the organic and inorganic properties (Oda, Teramura, Synthesis and Application of Surfactant, page 501, Maki Publisher).

A third example of an embodiment of the invention will be described. The cooking aid according to this example comprises an anionic surfactant (C) represented by formula (5) and / or an anionic surfactant (D) comprising one or more compounds represented by formula (6).

IIIOO I 10 15 20 25 30 35 CT1 PD 01 Ja.

The C hydrocarbyl group and the number of carbon atoms is generally 4-24, preferably 6-20 and particularly preferably 8-14. If the number of carbon atoms is lower than 4 or higher than 24, a sufficient penetration effect cannot be obtained and a cooking aid is not preferred. Practical examples of Re are the same as those exemplified as the practical examples of R 5 in formula (3) and a preferred one is an unbranched or branched alkyl group or alkenyl group containing 6-20 carbon atoms. An especially preferred is an unbranched or branched alkyl group containing 8-14 carbon atoms.

A3 of formula (6) is an alkylene group containing 2-4 carbon atoms. If the number of carbon atoms is less than 2, it is difficult to improve the penetration effect function. If, on the other hand, the number of carbon atoms is higher than 4, the amount of adsorption of the cooking aid in the pulp is increased to change the surface properties of the pulp.

Practical examples of A3 are ethylene, propylene, 1,2- or 2,3-butylene, tetramethylene and combinations of these groups. Among them, a preferred one is ethylene or propylene.

The r of formula (6) described above is generally 0 or an integer of at least 1, which has an average value of 0-15, preferably 0 or an integer of at least 1, which has an average value of 1-10 and in particular preferably 0 or an integer of at least 1, which has an average of 0-7. If the mean value of r is higher than 15, the penetration effect is reduced and it is not preferred for the cooking aid.

Useful as the anionic surfactant (D) is a monophosphate in which k is 1 in the formula (6), a diphosphate in which k is 2 and a mixture thereof. Preferred is a monophosphate or a mixture (which comprises essentially a monophosphate (55% by weight or higher). In addition to mono- and / or di phosphate, a triphosphate in which k is 3 can be prepared in a small ratio (5% by weight or less) as a by-product. or triphosphate is prepared as a by-product.

M 'of formula (5) and M2 of formula (6) are monovalent cations. If M1 and M2 are cations with di- or higher valence, these surfactants become easily insoluble and the penetration function is reduced, which makes it difficult to increase the pulp yield. Furthermore, adsorption of the cooking aid to the pulp takes place easily to change the surface properties of the pulp. Like the cation described above, examples are hydrogen ions; an alkali metal ion such as sodium, potassium, lithium and the like; and ammonium ion, an organic ammonium ion.

Among them are examples of the organic ammonium ion quaternary ammonium ions containing 4-26 carbon atoms, for example tetramethylammonium ion, hexyltrimethylammonium ion, octyltrimethylammonium ion, 2-ethylhexyltrimethylammonium ion, didecyldimethylammonium ion, trioctylmethyluronium ammonium ion, trioctylmethylammonium ion; cations obtained by binding hydrogen ions to primary, secondary or tertiary alkylamines containing 1-25 carbon atoms, for example cations obtained by binding hydrogen ions to methylamine (mono-, di- or triamine, hereinafter the same) ethylamine, propylamine, laurylamine , stearylamine, lauryldimethylamine and cyclohexylamine, trioctylamine, dílaurylmonomethylamine, and the like; cations obtained by bonding hydrogen ion to alkanolamine containing 2-24 carbon atoms, for example cations obtained by bonding hydrogen ion to ethanolamine (mono-,) di- or tri-amine, hereinafter the same), propanolamine, butanolamine, octanolamine, and the like. Among them, particularly preferred are sodium ion as an alkali metal, 2-ethylhexyltrimethylammonium ion and octyltrimethylammonium ion as an organic ammonium ion and triethanolamine cation.

In the case of k = 1 in the formula (6), M2 is similar or different ka fi on. l 10 15 20 25 30 35 C "1 i J (_71 JE.

A fourth example of an embodiment of the invention will be described. The cooking aid according to this example comprises: (a) a non-ionic surfactant (A) and / or a non-ionic surfactant (B and (b) at least one anionic surfactant selected from the group consisting of an anionic surfactant (C), an anionic surfactant (D) and an anionic surfactant (E), in combination with each other.

Incidentally, the surfactants (A) to (D) are the same as those described above, and the anionic surfactant (E) is one or more compounds represented by the formula (7).

R '-o- (Atms-Rkzoomz (v) in the formula R 7 is an unbranched or branched alkyl group, alkenyl group or mono- or dihydroxyalkyl group and the number of carbon atoms is generally 4-24, preferably 6-20 and especially preferably 8-14.

If the number of carbon atoms is less than 4 or higher than 24, a sufficient penetration effect cannot be obtained and it is not preferred for a cooking aid. Practical examples of R? are unbranched, or branched mono- or di-hydroxyalkyl groups, which can be prepared by bonding hydroxyl to the final carbon chain or middle carbon chain, such as monohydroxyhexyl, monohydroxyoctyl, monohydroxydecyl, monohydroxydodecyl, dihydroxydodecyl and demyla or the branched alkyl group and the alkenyl group which are exemplified as the practical examples of R 5 in formula (3). A preferred one is an unbranched or branched alkyl group, or hydroxyalkyl group containing 6-20 carbon atoms, and especially preferred is an unbranched or branched alkyl group, or monohydroxyl group containing 8-14 carbon atoms. 10 15 20 25 30 35 (“l |» J (fl Jx.

Ch -lë- 1.7 A4 of formula (7) is an alkylene group containing 2-4 carbon atoms. If the number of carbon atoms is less than 2, it is difficult to improve the penetration function. On the other hand, if the number of carbon atoms is higher than 4, the amount of adsorption of the cooking aid in the pulp is increased to change the surface properties of the pulp. Practical examples of A4 are ethylene, propylene, 1,2- or 2,3-butylene, tetramethylene and combinations of these groups. Among them, a preferred one is ethylene or propylene.

The s of the formula (7) described above is generally 0 or an integer of at least 1, which has an average of 0-15, preferably 0 or an integer of at least 1, which has an average of 0-10, and particularly preferably 0 or an integer of at least 1, which has an average value of 0-7. If the average value of s is higher than 15, the penetration effect is reduced and it is not preferred for the cooking aid.

The RB of formula (7) is an unbranched or branched alkylene group, and the number of carbon atoms is generally 1-6, preferably 1-4 and particularly preferably 1 or 2. If the number of carbon atoms is less than 1, it is chemically unstable. If, on the other hand, the number of carbon atoms is higher than 6, the preparation is not simple. Incidentally, the anionic surfactant (E) is unstable without R? Practical examples of Ra are methylene, ethylene, 1,3-propylene, methylethylene, ethylmethylene, 1,4-butylene, 1-methyl-1,3-propylene, 1,2-dimethylethylene, 1,1-dimethylethylene , 1-ethylethylene, n-propylmethylene, isopropylmethylene, 1,5-pentylene, 2-methyl-1,4-butylene, 1,3-dimethyl-1,3-propylene, 1,1,2-trimethyl ethylene, 1,1-methyl-2-ethylethylene, 1,6-hexylene, 4-methyl-1,5-pentylene, 2,4-dimethyl-1,4-butylene and the like.

M3 of formula (7) is a monovalent cation. Practical examples of M3 are the same as those exemplified as the practical examples of M 'in formula (5), and among them, particularly preferred are sodium ion as an alkali metal ion, 2-ethylhexyl trimethylammonium ion and n-octyltrimethylammonium ion as an organic ammonium ion. monium ion, and triethanolamine cation. The weight ratio of the nonionic surfactant (A) and / or the nonionic surfactant (B) to at least one anionic surfactant selected from the anionic surfactants (C) to (E) is 100 / 0.1-100 / 30, preferably (100 / 0.3) - (100/20) and more preferably 100 / 0.5-100 / 10. In the case where the weight ratio is in a range of 100 / 0.1-100 / 30, the penetration effect is especially increased.

Incidentally, although each of the surfactants (A) to (E) can be used alone to obtain a good effect, combination (mixed) use of them in the manner described above can provide a sufficiently high penetration effect. even at a high temperature accompanied by almost no increase in foaming compared to the case of using the surfactants alone.

For the individual use or combination use described above, it is preferred: (a) a single use of the nonionic surfactant (B1: (b) a combination use of the nonionic surfactant (A) with the anionic surfactant (C) and (c) a combination use of the nonionic surfactant (B) with the nonionic * surfactant (C) or the anionic surfactant (E). - the combination use gene c.

A lignocellulosic material to which the cooking aid according to the invention is applied is wood (trees with pointed leaves, trees with broad leaves), non-wood (plants and the like) and pulp obtained from them. Practical examples of non-wood are kenaf, bagass, bamboo and the like.

As the cooking process according to the invention, applicable cooking processes are power process, soda process, carbonate process, polysulfide process and the like. The cooking device may be either of the continuous type or batch type. Furthermore, the method is applicable to a conventional system of the continuous cooking type and in addition to the system, the method is also applicable to a system of the modified power cooking (MCC) type, an isothermal cooking system (ITC) type or a low-solid (LO-solid) cooking system. An example of boiling conditions in a power process, which is the most frequently used, will be described below.

That is: the amount of addition of the active alkaline (the active alkaline refers to the sum of NaOH and NagS) is 12-23% by weight (relatively absolute dry chips, conversion to Na 2 O); the total cooking time is 90-500 minutes; the boiling temperature is 120-175 ° C; the ratio between the chips and the cooking end is 1/2 - 1/6; the concentration of the white liquor (the alkaline solution to be used for boiling) to be used for boiling is 80-150 g / l; and sulfidity is 20-35% by weight.

As the sulfite boiling process of the invention, useful are an alkali sulfite process, a neutral sulfite process, and bisulfite process and the like.

The amount of additive of the surfactants (A) to (E) is generally 0.001-2% by weight, preferably 0.0015-1.0% by weight and particularly preferably 0.002-0.5% by weight relative to the absolute dry weight of a lignocellulosic material. If the amount of additive is 0.001-2% by weight, it is economical and the boiling yield and the degree of boiling can also be improved. In a process for producing a mass with alkali cooking or sulphite cooking of a lignocellulosic material in the presence of a cooking aid, the cooking aid according to the invention can be used alone as a cooking aid or the cooking aid according to the invention can be used in combination with a quinone type cooking aid and / or a polysulfide. More excellent effects in the Kappa number for pulp after cooking, the boiling yield and the pulp strength can be provided in the case of using the cooking aid according to the invention in combination with a quinone type cooking aid and / or a poly - sulfide.

In the case of using the cooking aid according to the invention in combination with a quinone type cooking aid and / or a polysulfide, a quinone type cooking aid, a polysulfide, an alkaline cooking liquor (white liquor) and a sulfuric acid salt may be added singly or a combination of two or several of them can be added simultaneously.

Compounds included in cyclic keto compounds are generally used as the quinone-type cooking aid, and in practice are examples of these benzoquinone, naphthoquinone, anthraquinone, anthron, phenanthrenequinone and nucleus-substituted compounds of these quinone-type compounds, for example their alkyl, alkoxy, amino, nitro, hydroxy, halogen or carboxy derivatives, sulfonic acid salts or carboxylic acid salts.

As the quinone-type cooking aid, hydroxyquinone-type compounds are used, which are reduced-type compounds of the quinone-type compounds described above, and in practice examples are choosing anthrahydroquinone, alkylanthrahydroquinone, alkoxyanthrahydroquinone, aminoanthrahydroquinone, haloanthrahydroquinone, hydroxyanthraquinone, hydroxyanthraquinone carboxyantrahydroquinone, tautomer of the above-described anthrahydroquinone compounds and mixtures of a plurality of any of the above compounds.

As the tautomer described above, examples are 10-hydroxy-anthron, 1- and 2-alkyl-10-hydroxy-anthron, 1- and 2-amino-10-hydroxy-anthron, 1- and 2-hydroxy -10-hydroxy-anthron, 1- and 2-halo-10-hydroxy-anthron, and mixtures of any of any of the above-mentioned anthron compounds.

Also useful as the cyclic keto compound for use as the quinone type cooking aid are one or more compounds selected from 9,10-diketohydroanthracent type compounds (TT 21 and 9,10-dioxihydroanthracent type compounds which are obtained as intermediates). of the anthraquinone synthesis process according to the Diels-Alder reaction method and are stable compounds.

Useful as the above-mentioned compounds of the 9,10-diketo-hydroanthracene type are mixtures of 1,4-dihydro-9,10-diketoanthracene, 1,2,3,4-tetrahydro-9,10-diketoanthracene, 1,4 , 4a, 9a-tetrahydro-9,10-diketoantracene, 2-ethyl-1,4,4a, 9a-tetrahydro-9,10-diketoanthracene, 2,3-dimethyl-1,4,4a, 9a -tetrahydro-9,10-diketoantracene, 1,3-dimethyl-1,4,4a, 9a-tetrahydro-9,10-diketoantracene, 1-methyl-1,2,3,4-tetrahydro-9,10-diketoantracene , 2,3,4,5,8-hexahydro-9,10-diketoantracene, 1,4,4a, 5,8,8a, 9a, 10a-octahydro-9,10-diketoantracene, 2,3 , 6,7-tetramethyl-1,4,4a, 5,8,8a, 9a, 10a-octahydro-QAO-diketoanthracen, 1,2,3,4,5,6,7,8-octahydro-9 , 10-diketoantracene and 2,6- and 2,7-diethyl | -1,4,4a, 5,8,8a, 9a, 10a-octahydro-9,10-diketoanthracene. Among them, preferred compounds are selected from unsubstituted naphthoquinone and benzoquinone and lower alkyl-substituted Diels-Alder addition product, and in terms of efficacy and economic property, 1,4-dihydro-9,10-diketoantracene, 1, 4,4a, 9a-tray-hydrohydro-9,10-diketoantracene and 1,4,4a, 5,8,8a, 9a, 10a-octahydro-9,10-diketoantracene are suitable.

Also useful as the above-mentioned 9,10-oxihydroanthracentane type compounds are 1,4-dihydro-9,10-dioxiantracene, 1,4,5,8-tetrahydro-9,10-dioxiantracene and 1,4 5,8,8a, 10a-hexahydro-QAO-dioxiantracene and sodium and potassium salts of 1,4-dihydro-9,10-dioxianthracene are also useful.

The amount of quinone type additive is generally 0.005-3% by weight and preferably 0.01-1% by weight relative to the absolute dry weight of a lignocellulosic material. If the additive amount is 0.005-3% by weight, it is economical and the boiling yield and pulp strength can be improved and the Kappa number of pulp can be reduced.

Examples of the polysulfides are those obtained by oxidizing the boiling point of the lignocellulosic material, or mixtures of simple sulfur with caustic soda and the like. The amount of addition of the polysulfides is generally 0.1-2% by weight and preferably 0.5-1.5% by weight. terms of simple sulfur in relation to the absolute dry weight of a lignocellulosic material.If the amount of additive is 0.1-2% by weight, it is economical and the boiling yield and pulp pour strength can be improved and the Kappa number of pulp can be reduced. use of the quinone-type cooking aid and / or the polysulfides in combination with the surfactants (A) to (E), is the weight (mixing ratio of the quinone-type cooking aid and / or the polysulfides and the surfactants (A) to (E) in generally 1 / 400-5 000/1, preferably 1 / 100-1 667/1 and especially preferably 1 / 50-1 250/1 If the weight (mixture) ratio is 1 / 400-5 000/1 The boiling yield and pulp strength can be improved and the Kappa number of pulp can be lowered. In a pulping process using adding them in advance to the lignocellulosic material before boiling, in case the cooking aid according to the invention is added, a method by adding the cooking aid itself to the lignocellulosic material or a method by adding an aqueous solution of the cooking aid to the lignocellulosic material is useful. Of the methods, the method of adding the cooking aid according to the invention in the form of an aqueous solution of 1-50% by weight concentration is particularly preferred since the water in the lignocellulosic material is barely increased and the cooking aid can be added evenly to each corner of the lignocellulosic material.

Applicable as the method of adding the cooking aid according to the invention to the lignocellulosic material is further a method by spraying the cooking aid on the lignocellulosic material, a method by applying the cooking aid to the lignocellulosic material and a method of immersing the lignocellulum in cooking material. simplicity of equipment, the method of spraying on the lignocellulosic material is preferred.

The time of addition of the cooking aid according to the invention to the lignocellulosic material may be any time (for example immediately before) if it is before cooking. Because the boiling end can penetrate the lignocellulosic material by doing so when the cooking starts. Incidentally, if it is possible for the added cooking aid to be washed away at the time of starting the cooking process, it is preferable to carry out counteracting treatment to avoid this. Applicable as an example of counteracting treatment is a process for storing the lignocellulosic material to which the cooking aid is added indoors or in a storage tank.

At the time (after addition, during addition, and / or before addition (by the way, these mean any time after addition, during addition, before addition or any two or more times of the above-mentioned times), hereinafter the same) for addition of the surfactant (A) to (E) to the lignocellulosic material, it is preferred that the lignocellulosic material is heated.

When heating an alkali boiling liquor (white liquor), a sulfuric acid salt, a quinone type cooking aid and a polysulfide penetrate deep inside the lignocellulosic material.

Although the time for heating the lignocellulosic material may be any time before addition, during addition and / or after addition of the surfactants (A) to (E), it is preferred to maintain a 0.5 minute or longer duration of contact. heating the lignocellulosic material with the added surfactants (A) to (E).

As a means of heating, a method is available by contacting steam directly with the lignocellulosic material, a method of heating the lignocellulosic material by means of an infrared heater and a method of heating a container containing lignocellulosic material from a heating medium. In the former process, the lignocellulosic material is generally heated by contacting steam directly with the material after filling the lignocellulosic material into a steam vessel. The heating temperature is preferably 50-180 ° C and particularly preferably 80-160 ° C. Maintaining the temperature below 180 ° C is preferred because the reduction in the strength of the lignocellulosic material after boiling is made more difficult. The heating duration is generally 0.5-30 minutes and preferably 1-10 minutes.

At the time of addition of the cooking aid according to the invention to the lignocellulosic material, it is more preferable to add a quinone-type cooking aid and / or a polysulfide after the lignocellulosic material has been heated. It is particularly preferred to add a quinone-type cooking aid and / or a polysulfide after the cooking aid according to the invention has been added and then heating is carried out at 50-180 ° C.

The surfactants (A) to (E) can be prepared by a known method as follows. For example, in the case of the non-ionic surfactant (A), the surfactant can be prepared by causing addition reaction of an alkylene oxide to an aliphatic alcohol at 80-200 ° C in the presence of a well-known catalyst.

Furthermore, in the case of the nonionic surfactant (B), the surfactant can be prepared by [1] a process comprising a step of adding an alkylene oxide to an aliphatic alcohol using a catalyst capable of making the molecular weight distribution narrower; [2] a process comprising the steps of adding 1 to 3 moles of an alkylene oxide to an aliphatic alcohol using a well-known general catalyst adding an alkylene oxide using a well-known general catalyst after removing the unreacted alcohol.

Furthermore, in the case of the anionic surfactant (C), the surfactant can be prepared by a process comprising the steps of preparing a sulfonic acid compound by reacting SO 2 with paraffin (in practice by an oxysulfonation process or by an oxychlorination process). and then neutralizing the sulfonic acid compound with a prescribed amount of at least one compound selected from an alkali metal hydroxide (e.g., sodium hydroxide, potassium hydroxide and the like), an ammonia, and an organic amine. In the case of the anionic surfactant (C) in which M 'is a quaternary ammonium ion, the preparation process further comprises a step of exchanging salt with a methanol solution of a quaternary ammonium carbonate such as a methanol solution of triethylmethylammonium methyl carbonate after the above-described the tralization and then removal of methanol to obtain the surfactant.

Furthermore, in the case of the anionic surfactant (D), the surfactant can be prepared by a process comprising the steps of preparing a phosphoric acid ester compound by reacting a phosphoric acid compound (eg, phosphoric anhydride, polyphosphoric acid, phosphorus oxychloride, and the like) with an aliphatic alcohol. and then neutralizing (salt exchange) the compound in the same manner as for the anionic surfactant (C).

Furthermore, in the case of the anionic surfactant (E), the surfactant can be prepared by a process comprising the step of preparing a carboxylic acid compound by reacting a monochloroalkylcarboxylic acid (e.g., monochloroacetic acid, and the like) with the nonionic surfactant ( A), the nonionic surfactant (B), or their precursor (eg aliphatic alcohol or its alkylene oxide adduct in a low molecular weight ratio), and then neutralization (salt exchange) of the compound in the same way as for the anionic surfactant (C) ). In the case of the anionic surfactant (E) in which R 7 is mono- or di-hydroxyalkyl, the preparation process comprises the steps of preparing a carboxylic acid compound by reacting a monochloroalkylcarboxylic acid (e.g., monochloroacetic acid, and the like) with an alkenyl monoalkylene oxide performing the reaction product with diborane for boron hydroxylation and then performing the reaction product with hydrogen peroxide in the alkaline state (e.g. with NaOH, and the like). 15 20 25 30 35 c ~ 1 ra ut VX (_; \ -få Practical examples of the surfactants (A) to (E) individually or mixtures thereof are described as follows. EO residue, (PO) is PO residue, (BO) is 1,2-BO residue, (THF) is THF residue, the number written on the right side of () is the number of average moles added (the numeric value is calculated - taken from the molar average for mixtures of a few individual molecules), // is added in random form and - is added in block form (hereinafter the same) (Mw / Mn) in {} the value is calculated from the actual measured value, ( Mw / Mn) ca | _ i {} is the value on the right side of the relation (4), and HLB is a value calculated from the numerical values showing the organic and inorganic properties.

[Practical examples of surfactant (A)] A1: isodekyl-O- (PO), - (EO) 10-H {(MwlMn) = 1.213, (Mw / Mnkai. = 1.091, HLB; 14.5} unreacted alcohol : 3.1 wt% A22 A3: isooctadecyl-O- (EO) 4- (BO) 1- (EO) 5-H A4: Z-ethylhexyl-O- (PO), - (EO) 8- (P0 ) 1-H A5: isobutyl-O- (PO) 1 - [(EO) 12 // (PO) 1] -H A6: isodekyl-O - [(E0) 1a // (P0) 3] - (PO ) 7-H A7: isobuty | -O- (EO) 7- (PO) 1-H A8: isotetraeicosyl-O- (EO) 16 // (PO) 5-H A9: isoeicosyl-O- (EO) 16 // (BO) O_1-H A10: 2-ethylhexyl-O - [(EO) 10l / (PO) 1] -H {(MwlMn) = 1.201, (Mw / Mn) ca | _ = 1.096, HLB; 14 Unreacted alcohol: 3.7% by weight of isodecyl-O- (EO) 10-H 2-ethylhexyl-O- (EO) 12-H '2,4-dimethylheptyl | -O - [(EO) 9 // (PO) 2] ~ H isooctadecyl- (EO) 20- (THF) 1-H isOtetfadecyl-OÅEÛUhQ- (Po fl5 'H isohexyl-O - [(EO) 4 // (PO) 0,1] - H isoeicosyl-O- (EO) 20- (PO) 10-H A12: A13: A14: A15: A16: A17: A18: 10 15 20 25 30 35 (Fl i Q UT 'X (] \ JÅ 27 [Practical examples of surfactant (B)] B1: n-octyl-O - [(EO) 10 // (PO) 1] -H {(Mw / Mn) = 1.056, (Mw / Mn) ca | _ = 1.096, HLB; 14.3} unreacted alcohol: 0.5% by weight B2: 2-ethylhexyl-O - [(EO) 10 // (PO),] - H {(M w / Mn) = 1.053, (Mw / Mnkar. = 1.096, HLB; 14.5} unreacted alcohol: 0.4% by weight of B3: n-octyl-O - [(EO) 1 ° // (PO) 2] -H {(Mw / Mn) = 1.043, (Mw / Mn) ca._ = 1.093} B4: n-trideca-2-enyl-O- (EO) 15- (PO) 7-H {(Mw / Mn) = 1.037, (Mw / Mn)., a | _ = 1.071 } B5: isodecyl-O- (PO fi- (EO), 8- (PO) 4-H {(Mw / Mn) = 1.039, (Mw / Mnkal. = 1.073} B6: n-octadeca-2-enyl-O - (EO) 1s-H {(Mw / Mn) = 1.041, (Mw / Mnkar. = 1.066, HLB; 14.8) unreacted alcohol: 0.7% by weight in B7: 4-ethylcyclohexyl-O- (EO 1z-H {(Mw / Mn) = 1.039, (Mw / Mn) ca. H {(Mw / Mn) = 1.041, (MwlMn) cal. = 1.109} B9: 4-ethylcyclohexyl-O- (EO) 1s-H {(Mw / Mn) = 1.036, (Mw / Mn) ca, _ = 1.086} B10: 2-ethylhexyl-O- (EO) 10-H {(Mw / Mn) = 1.038, (MW / Mmm = 1.098} <9 Preparation procedure for B1 to B10 An intermediate was obtained by adding 0.0003 mol of aluminum perchlorate hydrated with 9 H 2 O to 1 mole of an aliphatic alcohol, and carrying out addition reaction with 2.5 moles of E the ol 'ratio shown in the respective chemical formula in the case of a random adduct at 100 ° C. Furthermore, the intermediate was mixed with sodium hydroxide in an appropriate amount equivalent to 0.7% by weight of the final product, and EO or PO 10 was added at 110 ° C alone or in a block form. or random form.

[Practical examples of surfactant (C)] C1: C2: C3: C4: C5: n-tetradecyl-SOaNa fl-dekenyl-so3H a isotetradecyl-SOaNa isohexyl-SO3H. N: O-POaH. N (CH 2+) 3C 8 H 1 -, {monoalkyl phosphate content: 85.3%} isododecyl-O-PO 3 (Na) 2 {monoalkyl phosphate content: 84.2%} [Practical examples of surfactant (E)] E1: E2: E3 E4: E5: isododecyl-O- (EO fi-CH2COONa 2-ethylhexyl-O-C3H6COOK 2-hydroxidodecyl-O-CH2COONa 2-ethylhexyl-O-CH2CO0. N (CH) 3C8H11 n-dodecyl-O- (EO) 3- CH2COONa [Practical examples of combinations (mixtures) of surfactant (A) to (E)] AC1: BE2: AE3: AD4: AC5: BC6: use of A1 and C1 in 100/1 weight ratio in combination use of B1 and E3 in 100/20 weight ratio in combination use of A1 and E3 in 100/10 weight ratio in combination use of A1 and D1 in 100 / 0.1 weight ratio in combination use of A10 and C1 in 100 / 0.3 weight ratio in combination use of B2 and C1 »i 100 / 0.5 weight ratio in combination [Example] 10 15 20 25 30 35 G1 i« J (I1 Cí \ ~ ï> 29 In the following, the invention will be described in more detail with reference to the examples and the comparative examples , but the invention is by no means limited to these examples. In addition, the above-described A1, B2, Bö, B7, C1, C2, D1, AC1 (combination (mixture) of A1 and C1), BE2 (combination (mixture) of B1 and E3), and AE3 (combination (mixture) of A1 and E3) for the examples and the following X1 to X6 were used for comparative examples.

X1: n-octyl-O-KEO), O // (PO) 1] -H {(Mw / Mn) = 1.204, (Mw / Mnkai. = 1.096, HLB; 14.3} unreacted alcohol: 0.9 weight% X2. 2,4,6-triethyl-eicosyl-O- (EOho-H {(Mw / Mn) = 1.024, (Mw / Mn) ca. 0.3 wt% X3: isopropyl-O- (PO) 1- (EO) 6- (PO) 1-H {(Mw / Mn) = 1.047, (Mw / Mn) ca | _ = 1.099, HLB; 15.1} unreacted alcohol: 0.6 wt% X4: isooctadecyl-O - [(EO) 22 // (PO) 1ej-H {(Mw / Mn) = 1.022, (Mw / Mn) ,, a | _ = 1,054, HLB; 10.2} unreacted alcohol: 0.3% by weight X5: n-propyl-SOaNa X6: X1 and X5 in the ratio 100/10 l combination X7 n-octylphenyl-O- (E Preparation procedure for X1 Sodium hydroxide in an appropriate amount equivalent to being 0.07% by weight of the final product was added to an n-octyl alcohol and a mixture of EO and PO in 10/1 molar ratio was added at 110 ° C for addition reaction. for X2 to X4 An intermediate was obtained by adding 0.0003 mol of aluminum perchlorate hydrated with 9 H2 O to 1 mol of an aliphatic alcohol, and those of addition reaction with 2.5 mol of EO in the case of X2, 1 mol of PO and 1.5 mol of EO added in this order in the case of X3, and 2.5 mol in total of a mixture of EO And PO in a molar ratio of 22/16 in the case of X4 at 100 ° C. Furthermore, the intermediate was mixed with sodium hydroxide in an appropriate amount equivalent to being 0.07% by weight in the final product, and EO or PO was added at 110 ° C alone or in a block form or a random form.

The following is a description of a post-boiling pulp production process (for testing) performed in Examples 1 to 71 and Comparative Examples 1 to 62, Measurement procedures for the Kappa number for post-boiling pulp, Boiling yield, tear index, refractive index, burst index and foaming (foaming height), and the measurement procedures for boiling steam quantity and the amount of paving stones deposited.

After boiling, pulp was introduced into a cloth bag and washed sufficiently with tap water, and knots were removed from a flat sieve (manufactured by Kumagai Riki Kogyo Co.), and then the resulting pulp was sucked and filtered by Nutsche and formed into a sheet-like form. This mass is defined as mass after cooking. Further, the obtained pulp was processed to produce a handmade sheet (which was used as a pulp for paper quality testing) according to the procedure described in .JlS P 8209 after preparing the pulp at 450 ml according to Canada standard freeness described in JlS P 8121 with PF1 -mill described in JlS 8210.

The kappa number of pulp after cooking was measured according to a method described in JIS P 8211.

The boiling yield was calculated by measuring the absolutely dry weight of pulp before cooking and the absolutely dry weight of pulp after cooking and dividing the latter with the former to obtain the yield in% by weight. 10 15 20 25 30 35 40 52- * 5 4.64 ff? The tear index was measured according to the procedure described in JlS P 8116 using the pulp for paper quality testing.

The amount of bromine was measured according to the procedure described in Jls P 8113 using the pulp for the paper quality test.

The burst index was measured according to the procedure described in JlS P 8112 using the pulp for the paper quality test.

The foaming (foaming height) was measured by filling 10 ml of black liquor prepared by removing mass from the boiling black liquor to a measuring cylinder with 100 ml capacity and with closing means, closing the measuring cylinder, holding at 80 ° C, and then shaking the measuring cylinder 20 times by 30 cm amplitude in perpendicular direction at a rate of two reciprocating movements per second and measuring the height from the upper surface of the black liquor before shaking to the upper surface of the foam after shaking as the foaming (foaming height).

The boiling steam quantity was measured by measuring the quantity of steam which is used as a heating medium for heating the autoclave for boiling with a flow meter of the collective type. the inside of the autoclave in which boiling was completed was washed 5 times with water and dried at 105 ° C for 2 hours with a circulating dryer. Then, 195 ml of 5% hydrochloric acid was filled into the autoclave and kept for 24 hours, and then the hydrochloric acid was transferred to a 300 ml capacity eggplant bottle and concentrated to 10 ml with a rotary evaporator at 700 mmHg and 95 ml. ° C, and after that the resulting solution was transferred to a ceramic crucible whose weight was known and heated with a gas burner to evaporate and dry. The weight after evaporation and drying was measured and the weight was subtracted with the weight of the empty crucible to obtain the value which is defined as the amount of scale deposited. 30 g of hardwood chips were charged to an autoclave with 200 ml capacity, and a Kraft boiling end with 15% active alkali and 30% sulfidity, prepared from NaOH and NasS reagents, was added in a leach ratio of 4, and then each was added. one of the cooking aids (A1, B2, B6, B7, C1, C2, D1, AC1, BE2 and AE3) according to the invention or the cooking aids (X1 to X6) according to the comparative examples and / or 1,4-dihydro-9, The 10-dihydroxyanthrace in the amount of additive shown in the following Table 1, and boiling was carried out at 160 ° C for 2 hours. The evaluation results are shown in Table 1. 25 oooo 10 0 OOOO On 0 1 0 oooo IQ a 0 o uuooo 00:00 525 '464 33 TabeH1 - Q - RU \ lI mmwßmw mnanmnnnmnnmmmmnu ænæamæ flfi mæææ m ...% W_.mm/ \ ÛÛÛÛOÛÛÛÛÛÛÛ12 121211111113 nm \ | I 85 7 mwm% ä %%%%%% U %% 22 %%%%% ä %%% ö %% 2% üü Sm / \ .nuX 42263443443468387 725377877752 fi ß 44545444433334534 3444 nmluh 55556555555555555 565555555556 yl .e 9:08 a.m. 0 .I 97 4 5 5 2 m, etc. mmnmnmmummmmmmnmm mnmnmwmmmmmn W .al flfl fl t .em wWW) 33ßAß53JJß33JSJßJ ßáJJAß3ÅßÅ FL5 m MMMM Mßß al ß flflflflflflflflfl ß flfl ß al ß al ßßßßßßß al www I. NNW 00d Wræ 92240785989927023 724187878833 KU Ga al nH AHL Q o U cnonua: c ~ ø annoon - O u I onn I 0 0: ll || II wwamm INBBBBHEBEHBBEBHE üæüü fl üüüüüüm ww9 Kwmek bbw aad. rrV. . .d 5 5 ÖÖh nßQ * Ü Û æ ü ß Û ffi Oan .x. ÛÛ .Û .ÛOÛÛÛÛÛÛÛ .ÛÛ Û .Û .ÛÛÛÛÛÛÛ. Mmd _ 0 Û Û 0 0 0 .w..v | 4.

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| G98 e .md lamdl 111 1111 111 m .. 11 111111 ddd. .m æm. * 0. .QNMOßONÛOÛONOOO n. OÛWWÛOOOOO mwm .m ÛÛ011Û.ÛÛ.LÛ.0 “nwÛ.LÛ.Û.Û. w nu.nu..LLÛ.Û.nu.Û.Û. fi. ÛÛ M fl m SD. f. i hhn gin I a ffä hmm. 99 ÖÖV .ih | .m 11123 8 WHWHH M mw fl ßw 111112671121CCCEE .M 1111234556__ %% .. lm K Hmm W AAAAABBBCCCDAAABA M XXXXXXXXEX mmm I f ww (ä. R fi 01234567111111111121121. I * = ** aina 0 UIN 0 Oho fi 0000 0%! Minä n.§I. "". "J" “: ..

OO I 'O. O O Û. 10 g of soft wood chips were filled into an autoclave with a capacity of 200 ml, and a soda boiling end equivalent to 19% of NaOH to absolutely dry chips was added in a ratio of 5, and then each of the cooking aids was added ( A1, B2, B6, B7, C1, C2, D1, AC1, BE2 and AE3) according to the invention or the cooking aids (X1 to X6) according to the comparative examples and / or the 9,10-dihydroxyanthrace in the following Table 2 showed the amount of additive and boiling was carried out at 165 ° C for 2 hours The evaluation results are shown in Table 2. * 25 4-'114 = == -.- '= .. = -' cccc lb 0 nooølu c 0 nnnn 00 no coon: ooiuo o oooo om 35 TabeH2 4344 ß fl äæülßlælßl fl æ fl ßm nwnwnwnwnwßnwünwnwnmnwnwünußml 7 74 3442 ßw fl9 H77ß7759 uoou Q un | oooo d1212mm11 Pg \ mm. .s kgw) n% mmm (wræ M Pwæwm mmmmm .a fi vm * mm »* Knmm _ I. ßd e M .vb Tm Nä .Q mm .mm k Wen m på Hmf a MM Example .äüä fl ïääuäüääüïïäää _äM¶¶MMää% ä & æ 005 15223132222632 I I I I I I I I I I I I O O I I I I I O O 77777777777777777 QZQÅQÉÉÛSSÃÅ 57577657G667 762638897777713187 - | . . «. . . . . . . -. «. . 77979777777778977 546456656544 I I I I I I I Û I I I I Q C 787877777778 434 numn lß MEEMMMMEBEKR 1111111111 .. ll HEHERHHBHHHE llllllllllll 21161425622173657. . . . -. -. -. -. -. . . . ßßwßæßßßßßßßßßßæßß 354633434414 Mß fl ß flflflflflflfl ß 46701§Åm44044407l10 ææævæææææææææææææææææææææææææææææææ. s 5 5 5 5 al. mmmmmmmmmmmmmmmmm ÛOÛIIOÛÜIOÛUOIÛQQ mmmmmmmmmmo 0 0011000000 11123 llllln / fl nO-.fllzalcccEE AAAAABBBCCCDAAABA 1111234556__ XXXXXXXXEX 89012345670090223412 11242212121212121212 1112 1 | ¿al; QIL 1l¿ 1lL 1I¿ fl l fl ñ / HO / u fi lu O / U * In% by weight relative to weight for absolutely dry fl ice _ _> | = * z weight% relative to weight for absolutely dry fl ice (using QAO 20 g of flax was filled into an autoclave with a capacity of 200 ml, and a boiling point containing 17% of Na 2 SO 3 and 3.5% of NaOH was added, and then each of the cooking aids (A1 , B2, B6, B7, C1, C2, D1, AC1, BE2 and AE3) according to the invention or the cooking aids (X1 to X6) according to the comparative examples and / or 9,10-anthraquinone in the additive shown in Table 3 below, and boiling was performed at 170 ° C for 4.5 hours. The evaluation results are shown in Table 3.

I oooo o: nu o: co non: nnnn nu oooo Du N TabeH3 ._ d).

S .Q 24178112 3222 23 175 75 75 3 fi wæßumnma JÅJOIJIIWIIIIWWII 4fi l fi34 M44ßæl Päwmml 00000000000000000 121211111113 _. m) 992 mwm NIIZÜNBNüBWWHüÉEE Bßüüßßæß fl æßß Sm / mx WW) 56908381198882899 251521121184. . . . . . . . . . . . . . . . . . . . . . . . . . . . . % .mlw \ 7788877887- / 778877 787877777768 X 10.13 215 7.116 765 4 .b .l .I 553 .e 7787æ77 m7 man æ7 ”w” w lllllll fl ll flfl IIUU ll fifl lvm fi ßlßrb fl WWW) 6473322424778. . . . . . . . . . . . . . . . . . . . . . . . . . . . b 77989 8 7 8. / 7 Mmmm 55555Ü fl m5ævcw¶¶æææææ .bæw fi sï flfiflflfl wæ 9 Wüæ .m ÅÅÅÅÅJÃnNÅÄBÅQKNInNÉ 270511 / “222158 Pfswunn 00898000900099809 181811111118 k. * 00ß0 .000000000ü00 0fi0 0000000æ * 0 0 0 0 0 0 .AU - .m ßW .. l fl læwlllællllælll I. llæollllll .m än * 0. .0. . .0.Û ... O .. 0.000 00.0 N. 00 .000000000 .m 00011000100001000 m 0011000000 SD. e ga g X .Jßm 11.123 E .W manw. “Om IIIIIZAOnIIIr / .ICCCEE .fi 1 K www .... .W AAAAABBBCCCDAAABA m XXXXXXXXEX fl Ö .ošlv .I m 5678901234-3678901 W 567890123456 .w N Ü 33333444444444455 h .. 22 vikt- for% i :) absolute dry fl ice _ _> | <* z weight-Wo in relation to weight for absolutely dry chips (using 9,10-anthrac | non) 10 525 '4-64 38 30 g of soft wood chips were filled in an autoclave with 200 ml capacity and a power boiling end with 15% of active alkali and 30% sulfidity, prepared from NaOH and Na 2 S reagents, were added in a ratio of 5, and then each of the boiling aids (A1, AC1) the invention or the cooking aid (X1) according to the comparative examples together with 1,4-dihydro-9,10-dihydroxyanthracene and / or polysulfide prepared by dissolving sulfur powder in a caustic soda solution in the additive amount shown in Table 4 below and boiling was performed at 160 ° C for 2 hours. The evaluation results are shown in Table 4. <"1 l -J G1 -ß- (ß ~ $> - 39 Table 4 Test Koknings- hl fi pmwf 'lfinon- pay. Kappa. Knk. Riv. Brott- Skum- Pann- Wsats' sul fi d- number for nings- index length ning stone- Nr _ _. quantity imsaas- mass yield (km) (mm) derived Hfâm 'Tmsats' quantity after (96) 0095 'quantity n * * * *' KOKHÜÜQ * Example 5 2 A 1 0.01 0 0 33.3 49.1 176 7.9 35 0.16 5 3 A 1 0.01 0.05 0 31.4 51.0 180 9.3 36 0.27 5 4 A 1 0.01 0.05 0.5 31.1 52.1 183 9.5 35 0.27 5 5 A 1 0.01 0 0.5 32.8 50.8 179 9.2 35 0.15 5 6 AC 1 0.01 '0 0 32.8 49.6 178 8.1 35 0.14 5 7 AC 1 0.01 0.05 0 30.7 51.5 183 9.5 35 0.26 5 8 AC 1 0.01 0.05 0.5 30.5 52.8 185 9.8 34 0.27 5 9 AC 1 0.01 0 0.5 32.2 51.3 182 9.4 35 0.14 Comparative Example 3 7 X1 0 1 0 0 34.4 48.1 174 7.6 35 1.72 3 8 X1 0 01 0.05 0 32.7 49.4 177 8.6 35 3.13 3 9 X1 0 01 0.05 0.5 32.3 50.2 179 8.8 36 3.15 4 0 X1 0 01 0 0.5 33.9 49.2 178 8.6 35 1.71 4 1 - 0 0 0 34.5 48.1 174 7.6 34 2.56 4 2 0 0.05 0 32.8 49.3 177 8.6 35 3.82 4 3 - 0 0.05 0.5 32.4 50.1 17 9 8.7 35 3.91 4 4 0 0 i 0.5 34.0 49.0 177 8.6 35 2.61 * '-_% by weight in relation to weight for absolutely dry chips> l <= l = -% by weight in relation to weight for absolutely dry chips ( using 1A-dihydro-Q, 10-dihydroxyanthracene) * * *; % by weight relative to the weight of absolutely dry ice (as single sulfur) in the ratio of 4, and then the cooking aid (A1) according to the invention or the cooking aid (X1) according to the comparative examples were added together with 1,4-dihydro-9,10-dihydroxyanthracene and / or polysulfide prepared by dissolving sulfur powder in a caustic soda solution in the amount of additive shown in the following Table 5, and boiling was carried out at 160 ° C for 2 hours. The evaluation results are shown in Table 5.

Incidentally, in the examples and the comparative examples (except Comparative Example 52), the boiling conditions of the test (active alkali, the sulfidity, the boiling temperature, the boiling time) were set to keep the Kappa number for them to be the same as the Kappa number 22.3 of the Comparative Example 52 (boiling conditions: no »cooking aid additive, active alkali: 15%, sulphidity: 30%, boiling temperature: 160 ° C, cooking time: 2 hours). These boiling conditions are shown in Table 5. 0 000090 0 00 Q 0 0 9 I 00 0 0 0 IIIQ ß I OO 0 0 0 aulan! 0 I 0 OIIIOO 0 n: hat u 0 00000 nu 0 c I 0 0 0 unønil 0 000000 .fO å] fo 2 41 .So EE .ä ___. .wo æqewoæøo = fi oosmoo ïoøEozoïwocošoox oooE> o ocëoooåm ooE: Emo _ oøozo>> m ococëoomuo Bg: xooë. Eow omwï u * * * * su> m> ø: oxcø Eowo mo: .zoo ošomom .oo oš> __: øoc fl zwfoo o $ .o. => N * * * ocoomoocmoxoooooooo-o _ .. oo._o> c_o-v ._. > m mcococmšom v25 mo: too: this .oo oš> __: oocøšzooo o .. \ ... oš> n * * _ mo: too ošoøan .Bo oš> __: oocmâzooo _ ... o-oš> o * .oo __: oo. .ooëoxo ooEEooEoo zoo oo¿o: wäêøxo m = ~ .oo ooocxov. .Boo nmwmë .oo m.ww ä> omomoàoowz So wo.w ow om wo moo ooo w ooo om méo oo oo .I oo S mo.w ow om wo ooo ooo w ßoo om oo oo oo I. o. O 8 om.m ow om mo ooo wdo w ooo oo oo od ood o I oo om mm.m ow om mo ooo woo oo ooo. om o.wo o.o ood o ..... o o o.m wmd ow o.m w.o ooo odo o.o ooo om o.o o oo.o o i. o. o So. om.m ow om wo So odo w ooo oo oo o oo.oo | .. oo So omno ow om wo moo ooo w ooo om oo ooo .I wo So ow.o ow om wo ooo oow w ooo om odo oo o Sd oN oo om owo. ow o.m m.o ooo o.o .. w ooo om oo od o Sd o N o o om S.w ow omm m.o ooo moo w moo. oo oo o.o oo.o Sd oN o oo S oo.w ow omm m.o ooo wdo o.o ooo om o.wo o.o ood Sd o N o o. om oouw ow o.m w.o ooo o.o .. o.o ooo. om o.o o ood Sd o N o. o So mod ow o.m m.o ooo odo w ooo oo. oo o ood Sd o N o v So mmá S o.m w.o ooo odo w ooo odw oo o o Sd o N oo.

. Boâoxm oocEooEno.

So wod ow fi m m.o ooo moo w ooo S oAo od o Sd o <o. O oo ood ow o.m mo ooo mdo w omo om oo od o Sd o <o o oo owd ow o.m o.o So ooo w omo WS. oo od ood Sd o <. o o oß wwd ow o.m o.o ooo odo o.o ooo om oáo od ood Sd o. <o. o oß ow.o ow o.m o.o ooo ozoo o.o ooo om oo o ood Sd o <o o So owd ow omm m.o ooo m.oo. w ooo ßéo oo o oo.o Sd o <w o So oozo ow o.m o.o ooo wdo. w ooo om odo oo Sd o <oo So ood ow om mo ooo wdo w ooo ow oo oo Sd o <oo .øoâmxm * ucoc ooufi: AOL * * * * * oocmë -Soo * æ u .. * o. ä 2 E .man .åoøe .âë ss os; äs _. w - _ a o .z .sšæi .šoæ oss os; 2.35 u .. .mass se se -ansa ... äns .E ä: -då - .. ëoom V os: xooc. some. xooš .wosc -mococ -mosa .Boo: man .ooäm -mommš ïooëozoo; -øococgox -ccmm -Ešow .ocwšw oooom im - .. ox -xox àov. -oäw> o .. <-zon -cocox -øocëxox owuo. o: amok 000 o o o 0 nya 10 15 20 (“1 i O Uï JE.

GN -ß 42 l case of heating (steaming) after addition of the cooking aid (A1) according to the invention or the cooking aid (X1) according to the comparative example: 30 g of soft wood chips were filled into an autoclave with a capacity of 200 ml and a power boiling end of 15% of active alkali and 30% sulfidity, which is prepared from NaOH and Na 2 S reagents, was added in a ratio of 5, and then the cooking aid (A1) according to the invention or the cooking aid (X1) according to the comparative examples and steam were added. was performed at 100 ° C for 5 minutes. After that, 1,4-dihydro-9,10-dihydroxyanthracene and / or polysulfide prepared by dissolving sulfur powder in a caustic soda solution in the addition amount shown in the following Table 6 were added, and boiling was carried out at 160 ° C for 2 hours. The evaluation results are shown in Table 6.

Compared with the results of Table 4, the cooking aids of the invention were found to be more effective by being added after heating. l IOIC OJQQ g. . 43 Table 6 TeSt Kgknings- Ång_ Kino ”p ° | y_ Kappa- Kgk-« Riv- BfO fi- Skum- Partn- hlälvmed fl l nings- tinsats- sul fi u- tal for ninss- index leng ning Sle fl s- tid amount of additive mass Ulbyl fl (km ) (mm) Évlag Nr Hjäb .mh (min) amount after (%) _ nnQs-d medew saw cooking föfe- mg d ning ng * * * Example 6 8 A1 0.01 5 0 0 32.6 49.9 179 8.1 35 0.09 6 9 A 1 0.01 5 0.05 0 30.7 51.9 183 9.6 36 0.19 7 0 A1 0.01 5 0.05 0.5 30.3 53.2 185 9.7 35 0.19 7 l A l 0.01 5 0 0 5 32 J. 51.8 182 9 4 35 0.09 Comparative Example 5 9 X1 0.01 5 0 O 34.3 48.2 174 7.7 35 1.72 6 0 X1 0.01 5 0.05 0 32.5 49.5 177 8.6 35 3.12 6 1 X1 0.01 5 0.05 0.5 32.4 50.3 179 8.9 36 3.14 6 2 X1 0.01 5 0 0.5 33.9 49.3 179 8.6 35 1.70 * in weight- % by weight for absolute dry ice * * 1% by weight by weight for absolutely dry ice (using t, 4-dihydro-9,10-dihydroxyanthraoert) a: = | = = | <: % in relation to weight for absolutely dry chips (as single sulfur) "f Industrial applicability _ * 30 As described o For example, the aid for cooking a lignocellulosic material according to the invention is useful as a cooking aid for alkali cooking and a sulphite cooking of a lignocellulosic material. Furthermore, the process for producing a pulp according to the invention is useful for a process for producing pulp by alkali boiling or sulphite boiling of a lignocellulosic material in the presence of the cooking aid.

Claims (1)

10 15 20 25 30 35 40 1. F 'r * lf' lf 'rf __r' 1 0 O l I OI \ _, ___ \ _ 1 '_' _ _ 'a u. O: na co nu Patent claim Aids for cooking of a lignocellulosic material comprising a non-ionic surfactant (A) comprising one or more compounds represented by the general formula (1): R '-O - [(C 2 H 4 O) m / (Å 10) nl-H (1 ) in which R 'is a branched alkyl group containing 4-24 carbon atoms represented by the general formula (2): R 2 -cH-R t - I R 5 (2) (in which R 2 and R 3 are independently selected from the group consisting of of unbranched or branched alkyl groups containing 1-21 carbon atoms, and R * is an alkylene group containing 1-21 carbon atoms); m is an integer of at least 1, which has an average value of 4-20; A1 is an alkylene group containing 3 or 4 carbon atoms; and n is an integer of at least 1, having an average of 1-15; wherein (C2H4O) and (A10) are randomly and / or blockwise bound. Excipient according to claim 1 in which the nonionic surfactant (A) has an HLB of 6-18. Aids for cooking a lignocellulosic material, comprising: (a) a non-ionic surfactant (A); together with (b) at least one anionic surfactant selected from the group consisting of an anionic surfactant (C) and an anionic surfactant (E); in a weight ratio of 100 / 0.1-100 / 30; wherein the nonionic surfactant (A) comprises one or more compounds represented by the general formula (1); wherein the anionic surfactant (C) comprises one or more compounds represented by the general formula (5); and the anionic surfactant (E) comprises one or more compounds represented by the general formula (7): R '-O-1 (C 2 H 4 O) m / (A'O) nl-H (1) R ) and R? -o- (A 2+), - R 0 cooM 3 (7) in which R 'is a branched alkyl group containing 4-24 carbon atoms represented by the general formula (2): R 2 -cH-R R 5 (2) (in which R 2 and R a are independently selected from the group consisting of unbranched or branched alkyl groups containing 1. -21 carbon atoms, and R 'is an alkylene group containing 1-21 carbon atoms); R 5 is unbranched, branched or a cyclic aliphatic hydrocarbyl group containing 4-24 carbon atoms; R? is an unbranched or branched alkyl group, alkenyl group, or mono- or dihydroxyalkyl group containing 4-24 carbon atoms; Ra is an alkylene group containing 1-6 carbon atoms; m is an integer of at least 1, which has an average value of 4-20; A 'and A4 are alkylene groups containing 3 or 4 carbon atoms; n, and s is an integer of at least 1, which has an average of 1-15; M 'and M3 are monovalent cations; wherein (C 2 H 4 O) and (A'O), are randomly and / or blockwise bound. . Auxiliary according to any one of claims 1, 3 or 5, which is used in combination with a quinone-type cooking aid and / or a polysulfide. . A process for producing a pulp, which comprises boiling a lignocellulosic material with an alkali or a sulphite in the presence of a cooking aid; wherein an aid (a) 10 15 co u o n ç Q p ø o o o n n u. too 46 according to any one of claims 1, 3, 5 or 6 is used as an aid. A process for the manufacture of a pulp, which comprises boiling a lignocellulosic material with an alkali or sulphite in the presence of a cooking aid; wherein an adjuvant (a) according to any one of claims 1, 3 or 5 is used together with a quinone type cooking aid and / or a polysulfide as an aid. . A method according to claim 6, in which the aid (a) is added in advance before the addition of the quinone-type cooking aid and / or the polysulfide, and after the addition thereof, boiling is carried out. . A method according to claim 7, in which the lignocellulosic material is heated after, during and / or before addition of the excipient (a).