JP2841052B2 - Bleaching aid for cellulose pulp and bleaching method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a bleaching aid for cellulose pulp and a bleaching method.

[0002]

2. Description of the Related Art Cellulose pulp has many uses. However, except for applications in which bleaching degree is not required, such as packaging materials such as corrugated cardboard, chlorine, hypochlorous acid,
It is necessary to bleach using oxygen, hydrogen peroxide or the like. Although chlorine is effective for bleaching colored substances (primarily lignin) in pulp, there is a problem of environmental pollution due to by-products of harmful substances such as dioxin. Under such circumstances, reduction or total elimination of chlorine in the pulp manufacturing industry has become a very important issue for humanity. In order to reduce the amount of chlorine used, a method of performing a part of the bleaching step by oxygen bleaching is becoming widespread worldwide. However, bleaching with oxygen gas
Generally, the bleaching degree of pulp is insufficient, so that the amount of chlorine used has not been sufficiently reduced. When high-pressure oxygen gas is used at a high temperature, the bleaching degree is improved, but there is a problem that the depolymerization of cellulose is accelerated and the strength of pulp is reduced.

The applicant of the present application has previously disclosed a method of improving the bleaching efficiency by adding a bleaching aid during oxygen bleaching (Japanese Patent Laid-Open No. 5-186).
987).

[0004]

However, the effect of improving the bleaching degree of pulp by oxygen bleaching is insufficient, and the effect of reducing the amount of chlorine used is insufficient. Moreover, the foaming of the liquid after bleaching is large, and there is an operational problem in the dehydration step and the like.

[0005]

Means for Solving the Problems The present inventors have increased the bleaching degree of pulp while maintaining the strength of cellulose, and have no troubles in foaming during the process, and are effective for chlorine bleaching agents such as chlorine in the pulp bleaching process. As a result of intensive studies on a method for reducing the load, it has been found that the above-mentioned problems can be solved extremely effectively and economically by using a specific compound as a bleaching aid, and the present invention has been achieved. That is, the present invention provides a method for treating an alkaline water slurry of cellulose pulp with oxygen gas or peroxide, comprising a compound (A) represented by the following general formula (1): Bleaching aid General formula (R ¹ ) _t -X-[(C ₂ H ₄ O) _m / (AO) _n ] -H (1) (wherein R ¹ is a hydrogen atom, a methyl group, an ethyl group or a carbon number. 3 to 12 branched alkyl groups; t is an integer from 1 to 5;
X is a phenol residue; m is an average number of added moles of 4 to 20;
A represents a propylene group, a butylene group or a phenylethylene group; n represents an average number of added moles of 0 to 4; The addition format in [] is a random shape or a block shape. ) And a compound (B) represented by the following general formula (3): A bleaching aid for cellulose pulp, characterized by the general formula (R ⁵ ) _t -X-[(C ₂ H ₄ O) _p / ( AO) _q ]-(AO) _r -H (3) (wherein, R ⁵ is a hydrogen atom, a methyl group, an ethyl group or a linear or branched alkyl group having 3 to 12 carbon atoms; t is an integer of 1 to 5) X is a phenol residue; p is an average addition mole number of 4 to 20; A is a propylene group, butylene group or phenylethylene group; q is an average addition mole number of 0 to 3.9; Average number of moles of addition; [] indicates that the addition form is random or block.) And cellulose treated with an oxygen gas or a peroxide using these bleaching aids. It is a pulp bleaching method.

In the compound (A), examples of the branched alkyl group for R ¹ include those having 3 to 12 carbon atoms, preferably a branched alkyl group represented by the following general formula (2). (Wherein R ² is a methyl group, ethyl group, propyl group or butyl group; R ³ is a linear or branched alkyl group having 1 to 9 carbon atoms; R ⁴ is an alkylene group having 1 or 2 carbon atoms). Specific examples of isopropyl, isobutyl,
Isohexyl, isoheptyl, isooctyl, 2-ethylhexyl; branched alkyl synthesized from isobutylene dimer; isononyl, isodecyl; branched alkyl synthesized from propylene trimer; isodecyl, isoundecyl, isododecyl, branched alkyl synthesized from propylene tetramer; Examples thereof include a branched alkyl group having 6 to 12 carbon atoms synthesized by the oxo method. Particularly preferred are 2-ethylhexyl; branched alkyl synthesized from a dimer of isobutylene; branched alkyl synthesized from a trimer of propylene; and an isodecyl group.

The compound (A) is obtained by adding one or more kinds of phenol or phenol substituted with an alkyl group to an average of 4 to 20 mol of ethylene oxide, an average of 0 to 4 mol of propylene oxide, butylene oxide or styrene oxide. The addition form may be a block form or a random form. However,
Excluding those in which propylene oxide, butylene oxide or styrene oxide is added in a block shape at the terminal. The number of alkyl groups substituted with phenol may be any of 1 to 5, but is more preferably 1 or 2, and particularly preferably 1. Alkylene oxide added to phenol substituted with an alkyl group having more than 12 carbon atoms, alkylene oxide having an average addition mole number of less than 4 or more than 20, and propylene oxide, butylene oxide or styrene oxide having an average addition mole number If the total is more than 4, a sufficient bleaching improvement effect cannot be obtained. The cloud point of a 2% aqueous solution of the compound (A) is preferably from 40 to 110 ° C, more preferably from 60 to 100 ° C. Specific examples of the compound (A) of the present invention include the following. (A1) Tripropylene-X- (EO) _10- H (A2) 2-Ethylhexyl-X- (EO) _12- H (A3) 2,4-dimethylheptyl-X-[(EO) ₉
// (PO) ₂ ] -H (A4) di (isobutyl) -X-[(EO) ₁₀ /// (P
_{O) 1 // (BO) 0.5} ] -H (A5) isodecyl _{-X- (EO) 4 - (BO} ) 1 - (S
_{O) 1 - (EO) 5} -H (A6) diisobutylene _{-X- (PO) 1 - (EO} ) 8 -
H In the above formula, X represents a phenol residue, EO represents ethylene oxide, PO represents propylene oxide, BO represents butylene oxide, and SO represents styrene oxide.
The suffix on the right side indicates the average number of moles added, // indicates that they are added randomly, and-indicates that they are added in blocks.

In the compound (B), the alkyl group R ⁵ may be linear or branched. Examples of the straight chain having 3 to 12 carbon atoms include n-propyl, n-butyl, n-pentyl,
Examples include n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl groups and the like, and the branched ones are exemplified by the branched alkyl group R ¹ in the compound (A). It is similar.

The compound (B) is obtained by adding one or two types of phenol or phenol substituted with an alkyl group to an average of 4 to 20 mol of ethylene oxide and an average of 0 to 3.9 mol of propylene oxide, butylene oxide or styrene oxide. On the other hand, an average of 0.1 or more is added to the ends of those added in the form of more than one kind (block or random).
It is obtained by adding 1 to 4 mol of propylene oxide, butylene oxide or styrene oxide. The number of alkyl groups substituted with phenol may be any of 1 to 5, preferably 1 or 2, and more preferably 1. Those obtained by adding an alkylene oxide to a phenol substituted by an alkyl group having more than 12 carbon atoms, having an average addition mole number of ethylene oxide of less than 4 or more than 20, and propylene oxide;
If the total number of moles of butylene oxide or styrene oxide added is more than 4, a sufficient bleaching improvement effect cannot be obtained. In addition, propylene oxide, butylene oxide or styrene oxide having a total of less than 0.1 of the average addition mole number of the terminal portion,
The foam suppressing effect is inferior to those having a total of the average addition mole number of the terminal portion of 0.1 to 4. The cloud point of a 2% aqueous solution of the compound (B) is preferably from 40 to 110 ° C, more preferably from 60 to 100 ° C. The following are specific examples of the compound (B) of the present invention. (B1) isooctyl _{-X- (EO) 8 - (PO} ) 0.5 -
H (B2) tripropylene _{-X- (EO) 11 - (SO} )
_1.5- H (B3) n-octyl-X- (EO) _10- (PO) _1-
H (B4) diisobutylene _{-X- (EO) 12 - (PO} )
_0.5- (BO) _1.5- H (B5) isononyl-X-[(EO) ₅ // (PO) _0.3
// (SO) ₁ ]-(PO) _0.2- (BO) _0.2 -H (B6) 2,4-dimethylheptyl-X-[(EO) _{6
// (BO) 0.5] - (} PO) 1 -H (B7) 2- ethylhexyl _{-X- (EO) 4 - (PO} )
_1.5- (EO) _5.5- (BO) _0.5- H (B8) di (isobutyl) -X- (BO) _1- (E
_{O) 12 - (BO) 1} -H (B9) n- decyl _{-X- (PO) 0.5 - (EO} ) 10 -
(PO) _0.5- (SO) _0.5 --H In the above formula, X is an alkyl-substituted phenol residue, EO is ethylene oxide, P
O indicates propylene oxide, BO indicates butylene oxide, SO indicates styrene oxide, () the subscript on the right side indicates the average number of moles added, // indicates that they are added in a random manner, and-indicates block-like. Indicates that it has been added.

The compounds (A) and (B) both have the effect of improving the bleaching degree. Furthermore, (B) has an effect of suppressing foaming under conditions such as bleaching-washing-dehydration, and has the advantage of reducing the amount of commonly used antifoaming agents. Compounds (A) and (B) may be used alone or in combination.

The amount of (A) and / or (B) added at the time of bleaching is not limited because it cannot be determined uniformly depending on the demand for whiteness after bleaching, but is not limited. It is 0.1 to 2% by weight based on the absolutely dry pulp weight.
If the amount is less than 0.1% by weight, a sufficient effect cannot be obtained, and if it exceeds 2% by weight, the bleaching effect reaches equilibrium. In the general bleaching process, since (A) or (B) is recycled together with the washing solution, the replenishment amount for maintaining the above addition amount may be extremely small, and is economical.

The cellulose-containing materials to be subjected to the bleaching method of the present invention include chemical pulp [CGP (chemical ground pulp), SCP (semi-chemical pulp), SP (sulfite pulp), kraft pulp), AP (alkali pulp) ) Etc .; mechanical pulp [GP (ground wood pulp),
RMP (refiner mechanical pulp), TMP (thermomechanical pulp), etc.];
It can be applied to both wood (conifer, hardwood) and non-wood (herbaceous) pulp. The addition is carried out in the bleaching step, but can be applied at any stage during or after the digestion. Further, the slurry concentration of the cellulose-containing material can be applied to any of a low concentration (less than 10% by weight), a medium concentration (10 to 20% by weight), and a high concentration (20% by weight or more).

The oxygen gas used in the bleaching method of the present invention is oxygen or oxygen-enriched air, and the peroxide used in the bleaching method of the present invention includes hydrogen peroxide, peracid [peracetic acid]. , Percarbonate, perboric acid (salt), etc.], chlorine dioxide,
Ozone and the like. Among these, the general bleaching conditions of (1) oxygen gas bleaching, (2) ozone bleaching, and (3) hydrogen peroxide bleaching at medium concentrations are shown below. (1) Oxygen bleaching Pulp concentration: 10 to 14% by weight, oxygen concentration: 10 to 30
kg / pulp t, alkaline medium: 20-30 kg / pulp t, magnesium sulfate: 0-2 kg / pulp t, treatment temperature: 90-120 ° C., treatment time: 50-60 minutes, top internal pressure: 3.5-5 kg / cm ² G. (2) Ozone bleaching Pulp concentration: 10 to 15% by weight, ozone added amount: 0.4 to
2.0% by weight, processing temperature: 20 to 70 ° C, processing time: 5
~ 30 minutes. (3) Hydrogen peroxide bleaching Pulp concentration: 10 to 20% by weight, hydrogen peroxide concentration: 0.1% by weight.
2-2% by weight / based on pulp, treatment temperature: 60-80 ° C, treatment time: 120-240 minutes. Before or after the bleaching step using oxygen gas or peroxide, a bleaching step using a normal chlorine-based bleach (chlorine, hypochlorous acid, etc.) is usually used in combination. Further, an enzyme may be used in combination.

As the oxygen gas used in the oxygen bleaching method of the present invention, either oxygen or oxygen-enriched air can be used, but oxygen gas is used in consideration of the volume of the reaction vessel and the reaction efficiency. Is preferred. The pressure of oxygen ranges from high pressure (10 kg / cm ² G or more) to low pressure (10 Kg / cm ² G or more).
g / cm ² G), but to exert the effects of the present invention to the maximum, a relatively low pressure (1 to 10 kg / cm ² G).
).

The alkaline medium used in the bleaching method of the present invention includes sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonia, Kraft white liquor, oxidized white liquor,
Green liquor, oxidized green liquor, sodium tetraborate, sodium metaborate and the like can be used, but usually sodium hydroxide is used. An amount of an alkali to be added per bone dry pulp weight is preferably 0.5 to 3% by weight ₍₂ O Na) in terms of sodium oxide.

In the present invention, an agent for preventing a decrease in the degree of polymerization of cellulose, such as an alkaline earth metal salt such as a magnesium compound and a chelating agent, together with (A) or (B);
Alternatively, it can be used in combination with a stabilizer in peroxide bleaching such as condensed phosphate and silicate.

As the bleaching apparatus used in the bleaching method of the present invention, any of vertical and horizontal reactors can be used. In the present invention, the method of adding (A) and / or (B) may be carried out from the bottom of an upflow type bleaching tower or before, simultaneously with, or after the cellulose-containing material is mixed with oxygen gas or peroxide. May be added at the same time, but from the viewpoint of stirring efficiency, it is preferable that they are added at the same time as mixing or before mixing. Usually, the temperature is from room temperature to 200
C., the reaction time is 30 seconds to 20 hours.

[0018]

The present invention will be further described with reference to the following examples.
The present invention is not limited to this. The pulp used in the examples is hardwood kraft pulp, but the same effect can be obtained with softwood pulp and other pulp.
% In the table indicates% by weight. Various test methods are shown below. Kappa number measurement method: Pulp kappa number measurement method (JI
S-P8211). The smaller the value, the higher the bleaching degree. Pulp viscosity measurement method: Pulp viscosity measurement method using copper ethylenediamine as a solvent (TAPPI T230-S
U-66). The higher the viscosity, the higher the cellulose strength. Foaming test method: Pulp slurry after oxygen bleaching (9
(0 ° C.) into a glass cylinder having an inner diameter of 11 cm, and air was introduced at a liquid temperature of 90 ° C. using an air stone (flow rate: 1 L / min × 10 minutes).
m) was measured. Chlorine reduction rate 1.3% by weight (absolute dry weight of pulp) of sodium hydroxide and water are blended with pulp after oxygen bleaching to prepare a 3% by weight (pulp absolute dry weight) test pulp slurry did. This was charged into an autoclave, the air was replaced with chlorine gas, and the amount of chlorine was adjusted to 6% by weight based on the absolute dry weight of the pulp. Thereafter, chlorine bleaching was performed at 50 ° C. for 60 minutes. Chlorine bleaching was carried out under the above conditions, and the amount of chlorine required for the Hunter whiteness of a pulp sheet having a water content of 45% to reach 52 was measured, and the chlorine reduction rate was determined by the following equation. Chlorine reduction rate = (B−S) × 100 / B B: Blank chlorine usage S: Chlorine usage in each test

Examples 1 to 15 and Comparative Examples 1 to 11 Water and caustic soda (addition amounts: 2% in terms of Na ₂ O per weight of absolutely dry pulp) and the bleaching aid (a1 to 5, b1-7) or a comparative bleaching aid (x1-7) was added to form a 12% by weight (vs. absolutely dry pulp) slurry, and kneaded in a kneader at room temperature for 10 minutes to prepare a pulp slurry for a bleaching test. did. This was put in an autoclave and, after sufficiently substituted with oxygen gas, an oxygen pressure of 5 kg /
Bleaching was performed for 30 minutes while maintaining the temperature at 90 ° C. and cm ² G. Immediately after the bleaching, the oxygen pressure was released, the pulp slurry was taken out of the autoclave, squeezed at the same temperature, and the squeezed liquid was collected. This was sufficiently washed with distilled water, filtered and dried to obtain oxygen bleached pulp. The squeezed liquid is subjected to a foaming test,
The dried pulp was subjected to measurement of copper value and pulp viscosity. Further, chlorine bleaching was performed using the dried oxygen bleached pulp. Table 1 shows the test results. Note that Comparative Example 11 was used as a blank. Comparative Example 12 Bleaching and various measurements were carried out in the same manner as in the above test example, except that the oxygen pressure during bleaching with oxygen gas was 10 kg / cm ² G, the temperature was 110 ° C., and the time was 120 minutes.

[0020]

[Table 1]

The structural formulas of the bleaching aids a1 to 5 and b1 to 7 of the present invention used in Examples 1 to 15 and Comparative Examples x1 to 7 are as follows. In the formula, X represents an alkyl-substituted phenol residue, EO represents ethylene oxide, PO represents propylene oxide, BO represents butylene oxide, SO represents styrene oxide, and the subscript on the right side of () represents the average number of moles added. / Indicates that the addition is performed in a random manner, and-indicates that the addition is performed in a block manner. a1: Tripropylene-X- (EO) ₁₂ -H a2: Diisobutylene-X- (EO) ₁₁ -H a3: 2-Ethylhexyl-X- (EO) ₁₀ -H a4: Isodecyl-X- (EO) ₁₃ -Ha5: di (isobutyl) -X-[(EO) ₁₅ // (P
O) _1] -H b1: tripropylene _{-X- (EO) 15 - (PO} ) 0.5
-H b2: tripropylene _{-X- (EO) 15 - (PO} ) 1 -
Hb3: diisobutylene-X-[(EO) ₁₅ // (PO)
_{1] - (PO) 0.5 -H} b4: isohexyl _{-X- (EO) 11 - (BO} ) 1 -H b5: n- octyl _{-X- (EO) 13 - (PO} ) 1 -H b6: n- dodecyl _{-X- (EO) 18 - (PO} ) 1 -H b7: tripropylene _{-X- (EO) 7 - (PO} ) 1 -
_{(EO) 7 - (PO)} 1 - Hx1: tripropylene _{-X- (EO) 3 -H x2:} 2- ethylhexyl -X- (EO) ₂₂ -H x3: diisobutylene -X - [(EO) ₁₀ / (PO)
_{3.5] - (PO) 1 -H} x4: isodecyl _{-X- (EO) 13 - (PO} ) 5 -H x5: heptadecyl _{-X- (EO) 19 -H x6:} t- butyl -O- (EO) ₉ -H x7: oleyl-O- (EO) _9- H

As shown in Table 1, the bleaching aid of the present invention (a
1 to 5, b1 to 7) and bleaching the pulp with oxygen gas (Examples 1 to 15), the remarkably excellent bleaching improvement effect and the chlorine usage in chlorine bleaching without lowering the pulp viscosity. Remarkable reduction effect is obtained. When the oxygen pressure, the bleaching temperature, and the bleaching time are increased without using the bleaching aid of the present invention (Comparative Example 12), the bleaching improvement effect and the effect of reducing the amount of chlorine used in chlorine bleaching are obtained, but the viscosity is significantly reduced To promote pulp deterioration. Furthermore, when the bleaching aid of the present invention is used, foaming is small and troubles due to foam in the process do not occur. In particular, when the bleaching aids (compound B) of b1 to b7 are used, the amount of the normally used antifoaming agent can be reduced because the foam suppressing effect is remarkable.

Example 16 and Comparative Example 13 Hardwood pulp after digestion (kappa number: 18.3) was pulp concentration 15%, ozone concentration 1.8% by weight, ozone flow rate 4L / min, bleaching temperature 20 ° C, bleaching. Time 30 minutes, pH7
At each condition, no additives and (b8): tripropylene -X- (EO) ₁₄ - (P
O) _O.6- H was added to 0.8% by weight of pulp and ozone bleached. When the bleaching aid (b8) was added to the Kappa number after bleaching of 7.8 in the case of no addition (Comparative Example 13) (Example 1)
The copper value after bleaching of 6) was 4.5. The pulp viscosity after bleaching was equivalent. From this, it is apparent that the above-mentioned bleaching aid greatly improves the degree of bleaching even in ozone bleaching.

Example 17 and Comparative Example 14 Softwood pulp (whiteness 36, Kappa number 32) was used instead of hardwood pulp, and the pulp concentration was 10% by weight and the concentration of hydrogen peroxide was 0.51% by weight (vs. absolutely dry pulp). , Bleaching temperature 60
° C., at the conditions of the bleaching time 120 minutes, no additives and (b8): tripropylene _{-X- (EO) 14 - (PO} )
Hydrogen peroxide bleaching was carried out by adding 0.8% by weight of _0.6- H to pulp. Brightness 7 after bleaching without additive (Comparative Example 14)
When the above bleaching aid was added to 0.9 (Example 17), the whiteness after bleaching was 77.1. From this, it is clear that the above-mentioned bleaching aid greatly improves the degree of bleaching even in hydrogen peroxide bleaching.

[0025]

The bleaching method using the pulp bleaching aid comprising the compound (A) and / or (B) of the present invention has the following effects. (1) Bleaching degree is remarkably improved without adversely affecting cellulose strength. (2) It is excellent in foam suppression effect and does not cause process trouble due to foam. From the above effects, the method of the present invention is a very useful method that can reduce or completely eliminate the use of chlorine, which is a starting material for harmful substances such as dioxin, which is a serious problem in the human living environment. It is obvious that this is a practical technique.

Claims (9)

(57) [Claims] 1. A compound (A) represented by the following general formula (1) or a compound (B) represented by the following general formula (3)
A bleaching aid for bleaching oxygen gas or peroxide in a cellulose pulp alkaline water slurry, characterized by comprising: Formula ^{_{(R 1) t -X - [}} (C 2 H 4 O) m / (AO) n] -H (1) ( wherein ^{R 1} is a hydrogen atom, a methyl group, an ethyl group or a carbon number from 3 to 12 T is an integer from 1 to 5;
X is a phenol residue; m is an average number of added moles of 4 to 20;
A represents a propylene group, a butylene group or a phenylethylene group; n represents an average number of added moles of 0 to 4; The addition format in [] is a random shape or a block shape. ) General formula ^{_{(R 5) t -X - [}} (C 2 H 4 O) p / (AO) q] - (AO) r -H (3) ( wherein ^{R 5} is a hydrogen atom, a methyl group, an ethyl group Or a linear or branched alkyl group having 3 to 12 carbon atoms; t is an integer of 1 to 5; X is a phenol residue; p is an average addition mole number of 4 to 20; A is a propylene group, butylene group or phenylethylene; Group; q is an average addition mole number of 0 to 3.9; r is an average addition mole number of 0.1 to 4; [] indicates that the addition form is random or block.) 2. The bleaching aid for cellulose pulp according to claim 1, wherein R ¹ of the compound (A) or R ⁵ of the compound (B) is a branched alkyl group represented by the following general formula (2). (In the formula, R ² represents a methyl group, an ethyl group, a propyl group or a butyl group; R ³ represents a linear or branched alkyl group having 1 to 9 carbon atoms; and R ⁴ represents an alkylene group having 1 or 2 carbon atoms.) 3. The compound (A) or the compound (B)
The bleaching aid according to claim 1 or 2, which has a cloud point of 40C to 110C in a 2% aqueous solution. 4. A bleaching aid for oxygen gas bleaching for cellulose pulp, comprising the compound (A) or the compound (B) according to claim 1. 5. A method for bleaching cellulose pulp, comprising treating with oxygen gas or peroxide in the presence of the bleaching aid according to any one of claims 1 to 4. 6. A method for bleaching cellulose pulp in which oxygen bleaching is carried out in the presence of the bleaching aid according to claim 1. 7. A method for bleaching cellulose pulp which is treated with a peroxide selected from the group consisting of hydrogen peroxide, chlorine dioxide, peracid and ozone in the presence of the bleaching aid according to claim 1. . 8. The method for bleaching cellulose pulp according to claim 1, wherein said cellulose pulp is unbleached chemical pulp or unbleached mechanical pulp. 9. The method for bleaching cellulose pulp according to claim 1, wherein said cellulose pulp is unbleached chemical pulp.