CA2111921A1 - Formulated composition of pulp digesting assistant agent - Google Patents
Formulated composition of pulp digesting assistant agentInfo
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- CA2111921A1 CA2111921A1 CA 2111921 CA2111921A CA2111921A1 CA 2111921 A1 CA2111921 A1 CA 2111921A1 CA 2111921 CA2111921 CA 2111921 CA 2111921 A CA2111921 A CA 2111921A CA 2111921 A1 CA2111921 A1 CA 2111921A1
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Abstract
ABSTRACT OF THE DISCLOSURE
A formulated pulp digesting assistant agent is provided which allows particulate anthraquinone to be easily dispersed and dissolved in the pulp digesting liquid and precludes the harm otherwise done to the environmental hygiene by the powder as when it is drifted in a wind. This composition is obtained by mixing a particulate anthraquinone having an average particle diameter of not more than 10 µm and a maximum particle diameter of not more than 30 µm, 0.1 to 2% by weight, based on the amount of the particulate anthraquinone, of a nonionic surfactant mixture comprising an alkylene oxide adduct of a secondary alcohol, having an HLB value in the range of 12 to 16 and carbon numbers from 10 to 16 and an alkylene oxide adduct of an alkyl phenol having HLB value in the range of 12 to 16 and an alkyl group having carbon numbers from 6 to 12 at a weight ratio in the range of 5 : 1 to 1 : 5, and 5 to 30% by weight based on the amount of the formulated pulp digesting assistant agent of water and/or an alcohol having a molecular weight of not more than 200.
A formulated pulp digesting assistant agent is provided which allows particulate anthraquinone to be easily dispersed and dissolved in the pulp digesting liquid and precludes the harm otherwise done to the environmental hygiene by the powder as when it is drifted in a wind. This composition is obtained by mixing a particulate anthraquinone having an average particle diameter of not more than 10 µm and a maximum particle diameter of not more than 30 µm, 0.1 to 2% by weight, based on the amount of the particulate anthraquinone, of a nonionic surfactant mixture comprising an alkylene oxide adduct of a secondary alcohol, having an HLB value in the range of 12 to 16 and carbon numbers from 10 to 16 and an alkylene oxide adduct of an alkyl phenol having HLB value in the range of 12 to 16 and an alkyl group having carbon numbers from 6 to 12 at a weight ratio in the range of 5 : 1 to 1 : 5, and 5 to 30% by weight based on the amount of the formulated pulp digesting assistant agent of water and/or an alcohol having a molecular weight of not more than 200.
Description
FORMULATED COMPOSITION OF :
PULP DIGESTING ASSISTANT AGENT
BACKGROUND OF THE INVENTION
Field of the Invention:
This invention relates to a formulated composition of a powdery pulp digesting assistant agent. More particularly, it relates to a powdery readily dispersible formulated composition of pulp digesting assistant agent which comprises anthraquinone in a particulate form, two 10 kinds of speoific nonionic surfactants, water, and/or an alcohol having a molecular weight of not more than 200 and manifests a high digesting power.
Description of the Prior Art:
In recent years, it has been found that when 15 anthraquinones heretofore used prevalently in dyes and pigments are used as a pulp digesting assistant agent or a redox catalyst, they contribute in a great measure to ~;-increase the speed of digestion, lower the temperature of digestion and consequently save steam, economize chemical 20 agents to be used, shorten the time of digestion and consequently improve the rate of operation, exalt the quality of pulp, and increase the yield of pulp. As a result, the anthraquinones have been finding growing utility in the pulp digesting assistant agent.
The anthraquinones, however, are not soluble in -~
water. When powdery anthraquinone is added in its unformulated form to a pulp digesting liquid, therefore, the greater part of the powder floats on the surface of the digesting liquid and a considerably long time is required 30 for the powder to be thoroughly dispersed and dissolved in the digesting liquid. As a result, the powdery anthraquinone is at a disadvantage in failing to manifest amply the catalytic effect thereof because it is not fully dispersed or dissolved in the pulp digesting liquid within -~5 the ordinary digesting time.
As means to overcome the disadvantage, a method of v- , ,, ' ~ ,,,' : ~ .
using tetrahydroanthraquinone of a reduced form as diluted ~ in an aqueous alkali solution has been available. This j method indeed is fine in respect that tetrahydroanthraquinone is quickly dispersed and dissolved in the pulp digesting liquid. It is at a disadvantage, however, in requiring the entire aqueous alkali solution of tetrahydroanthraquinone to be covered with nitrogen gas while in transit and in use. Because, this solution is oxidized on exposure to the air, and entails separation of 10 crystals of anthraquinone. And the cost of transportation is expensive, because this solution is in a dilute form.
As another means to overcome the problem, a method which allows effective use of particulate anthraquinone in the pulp digesting liquid by having a surfactant, 15 particularly an anionic surfactant, deposited on the anthraquinone particles thereby facilitating the dispersion and dissolution of the particulate anthraquinone in the pulp digesting liquid is disclosed (JP-A-54-100,332). The method which involves deposition of an anionic surfactant among 20 other surfactants, however, has the disadvantage that since this deposition gives rise to a composition having the particulate anthraquinone kneaded in a pasty form with a ~olution of the ionic surfactant, this composition not only entails a high cost of transportation but also requires 25 consumption of the ionic surfactant in a large amount as compared with the particulate anthraquinone. In the detailed description of the invention which relates to the method under discussion, a mention is made to the effect that nonionic surfactants among other surfactants are not 30 fit for dispersion of particulate anthraquinone. From this statement, it is inferred that even if an anionic surfactant is managed to be uniformly mixed at its initial concentration of 100% with particulate anthraquinone, the resultant mixture placed in the pulp digesting liquid 35 induces the "phenomenon of gelation" which ought to be justly called a peculiar disposition owned by the nonionic ~.',,,`"'.-', .'`,,,',,':'i".' surfactant and, instead of fulfilling the function of a surfactant, rather covers the surface of anthraquinone particles with a jellylike coat and further obstructs dispersion and dissolution of anthraquinone in the pulp digesting liquid and, as a result, fails to produce any appreciable effect in the pulp digestion.
Canadian Patent No. 1,140,706 also discloses a method which similarly resorts to use of a surfactant. Even when an anionic surfactant is used as taught in the detailed 10 description of the invention relating to this method, this invention can be hardly called satisfactory because it still entails the problem of unduly heavy consumption of the anionic surfactant. Again in the case of this invention, the working examples cited in the specification invariably 15 represent cases of using an anionic surfactant. No mention is made anywhere of a nonionic surfactant regarding the structure, composition, or mode of use. The nonionic -~
surfactants which have many problems yet to be solved as to method of use and selection of species are not easily taken ~0 up as subjects of study. In the existing state of affairs, no method has yet been found for effective use of a nonionic surfactant as a digesting assistant agent.
No actual case of using a nonionic surfactant for the purpose under discussion has been reported to date. No 25 report has yet been published in literature as to the effectiveness of a nonionic surfactant in promoting dispersion and dissolution of anthraquinone in the pulp digesting liquid. Thi~ fact may well be regarded as reflecting the fact that this effectiveness of a nonionic 30 surfactant has not been uncovered to date.
I An object of this invention, therefore, is to provide a formulated pulp digesting assietant agent which allows anthraquinone used in a powdery form to be easily dispersed and dissolved in the pulp digesting liquid, 35 enables the anthraquinone to manifest thoroughly the effect thereof as a redox catalyst and, at the same time, precludes the harms which would be possibly done to the environmental hygiene by particulate anthraquinone when this powder is drifted in course of handling.
SUMMARY OF THE INVENTION
We have made a diligent study on formulated pulp digesting assistant agent with a view to accomplishing the object described above and consequently found that a formulated pulp digesting assistant agent which is perfectly free from the problsm mentioned above is obtained by 10 depositing on the surface of anthraquinone particles what is obtained by adding water and/or a low molecular water-soluble alcohol to a mixture of two kinds of specific nonionic surfactants. This invention has been perfected on the basis of this knowledge.
1~ The objects of this invention are accomplished by (1) a formulated pulp digesting assistant agent which comprises a particulate anthraquinone of an average particle diameter of not more than 10 ~m and a maximum particle diameter of not more than 30 ~m, 0.1 to 2% by weight, based 20 on the amount of the particulate anthraquinone, of a nonionic surfactant mixture comprising a first nonionic surfactant of an HLB value of 12 to 16 formed of a secondary alcohol having carbon numbers from 10 to 16 possessing an alkylene oxide adduct of 7 to 20 moles of ethylene oxide 25 added thereto and a second nonionic surfactant of an HLB
value of 12 to 16 formed of an alkyl phenol having the alkyl group carbon number from 6 to 12 possessing an alkylene oxide adduct having 8 to 15 moles of ethylene oxide added thereto, the weight ratio of the first to the second 30 nonionic surfactant being in the range of 5 : 1 to 1 : 5 and the total amount of the first and second nonionic surfactants being in the range of 0.1 to 2% by weight based on the amount of the particulate anthraquinone, and 5 to 30 by weight, based on 100% by weight of the formulated pulp 35 digesting assistant agent, of water and/or an alcohol of molecular weight of not more than 200.
:: .
The objects of this invention are further accomplished by (2) a formulated pulp digesting assistant agent set forth in (1) above, wherein the mixture of the first and second nonionic surfactants has an average HLB
6 value in the range of 13 to 15.
The objects of this invention are also accomplished by (3) a formulated pulp digesting assistant agent set forth in (1) above, wherein the total content of water and/or an alcohol of a molecular weight of not more than 200 is in the 10 range of 10 to 20% by weight based on 100% by weight of the formulated pulp digesting assistant agent.
EXPLANATION OF THE PREFERRED ENBODIMENT
Now, this invention will be described in detail below.
The particulate anthraquinone to be used in this invention has an average particle diameter of not more than 10 ~m, preferably not more than 7 ~m, and normally not less than 5~m. Generally, it has a maximum particle diameter of not more than 30 ~m, preferably not more than 20 ~m, and 20 normally not less than 18~m. If the average particle diameter exceeds 10 ~m, the undesirability arises that the particulate anthraquinone is not sufficiently dispersed or dissolved in the pulp digesting liquid within the ordinary span of digesting time because the speed of dispersion and 25 dissolution in the pulp digesting liquid is low and consequently the time for the dispersion and dissolution is proportionately large. If the maximum particle diameter exceeds 20 ~m, the disadvantage ensues that the speed of dispersion and dissolution is similarly low.
The first nonionic surfactant which is one of the two components of the mixture of two specific nonionic surfactants to be used in this invention is a nonionic surfactant of an HLB (hydrophile-lipophile balance) value in the range of 12 to 16, preferably 13 to 1~ formed of a 36 secondary alcohol having carbon numbers from 10 to 16, preferably 12 to 14, possessing an alkylene oxide adduct of .x.
. ~ , "
: . . . . : .: ~ : , ~ ;; . , . -: ~ : : . ... ; ; .
7 to 20, preferably 9 to 15 mols of ethylene oxide added thereto.
The second nonionic surfactant which is the other component is a nonionic surfactant of an HLB value in the range of 12 to 16, preferably 13 to 15, formed of an alkylphenol having the alkyl group carbon numbers from 6 to 12, preferably 8 to 9 possessing an alkylene oxide adduct having 8 to 16, preferably 10 to 14, mols of ethylene oxide added thereto.
The weight ratio of the first to the second nonionic surfactant to be used in this invention is such that the weight ratio of the secondary alcohol possessing the aforementioned alkylene oxide adduct (first nonionic surfactant) to the alkyl phenol possessing the 15 aforementioned alkylene oxide adduct (second nonionic -surfactant) is in the range of 5 : 1 to 1 : 5, preferably 3 : 1 to 1 : 3. If the weight ratio of the first to the second nonionic surfactant deviates from the range specified above, then the facilitation of dispersion and dissolution 20 of the particulate anthraquinone in the pulp digesting liquid is attained only with difficulty. This difficulty is -justified in the light of the fact that while a secondary alcohol possessing an alkylene oxide adduct generally i5 a surfactant widely known as excelling in permeating power and 25 thus is counted among the surfactants that exhibit the best ~
wetting power to hydrophobic fibers, this secondary alcohol ~-when used alone requires a long time in causing particulate anthraquinone to be dispersed and dissolved in the pulp digesting liquid. The facilitation of the dispersion and 30 dissolution of the particulate anthraquinone in the pulp digesting liquid is never attained unless the first and second nonionic surfactants are simultaneously used as~
combined at a weight ratio in the range specified above.
The total amount of the mixture of nonionic 35 surfactants is generally in the range of 0.1 to 2% by weight, preferably 0.2 to 1% by weight, based on the amount ' ' ~ ' '~' ' ' , . .' ' ' , ': ' ` .,' . .'; i ' '` . ' ' ` : : " , ` ' ` ' " .'. ' , of the particu]ate anthraquinone. If the total amount is less than 0.1% by weight based on the amount of the particulate anthraquinone, the mixture of nonionic surfactants fails to cover completely the surface of anthraquinone particles and the powder of anthraquinone added to the pulp digesting liquid cannot be thoroughly ~-dispersed or dissolved in the liquid because part of the powder floats on the surface of the liquid.
The average HLB of the mixture of the two specific 10 anionic surfactants is in the range of 12 to 16, preferably 13 to 15. The outstanding digesting effect obtained by this invention is never manifested unless this HLB falls in the range specified above in exactly the same manner as the weight ratio of the nonionic surfactants mentioned above.
1~The alcohol to be used in this invention has no particular restriction except for the requirement that the molecular weight thereof is generally not more than 200, preferably not more than 120. As typical examples of the alcohol which answers this description, lower monohydric 20 alcohols such as methanol, ethanol, propanol, and isopropanol and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, neopentyl glycol, and trihydric alcohols such as glycerol, 25 and etc. may be cited.
The total content of water and/or an alcohol of a molecular weight of not more than 200 to be used in the formulated pulp digesting assistant agent of this invention is generally in the range of 5 to 30% by weight, preferably 30 10 to 20% by weight, based on 100% by weight of the agent.
If this content is less than 5% by weight, based on 100~ by weight of the formulated pulp digesting assistant agent, the amount of water and/or the alcohol of a molecular weight of not more than 200 is unduly small relative to the amount of 35 the mixture of specific nonionic surfactants and consequently this mixture yields to the phenomenon of gelation and, as a result, the disadvantage arises that the nonionic surfactants are deposited in the state obstructed from producing the inherent functions thereof on the anthraquinone particles and, when the pulp digesting S assistant agent contacts the pulp digesting liquid, the surfactants fail to manifest their functions of facilitating dispersion and dissolution of anthraquinone in the pulp ~ -digesting liquid. If the content mentioned above exceeds 30% by weight based on 100% by weight of the formulated pulp 10 digesting assistant agent, the excess of the total amount of water andtor the alcohol of a molecular weight of not less than 200 prevents the nonionic surfactants from being deposited on the anthraquinone particles and consequently separates itself from the anthraquinone particles and 15 renders insufficient the thoroughness of dispersion and dissolution of the particulate anthraquinone in the pulp digesting liquid.
The formulated pulp digesting assistant agent o~
this invention is preferable to be homogeneously blended by 20 the use of a suitable mixing device or stirring device before it is placed and used in the pulp digesting liquid. ;
The pulp digesting liquid into which the pulp digesting assistant agent of this invention is thrown does not need to be particularly limited but may be any of the 25 digesting liquids in popular use. The composition may be added to an alkaline digesting liquid for the Kraft process or an acidic digesting liquid for the sulfurous acid process.
When the formulated pulp digesting assistant agent 30 is used as a dispersion in water1 viscosity of the ~
dispersion may be controlled by adding a thickener, if - `
necessary. As the typical thickener, there are carboxymethyl cellulose, starch, sodium polyarginate, sodium polyacrylate, (anhydrous) sodium methasilicate, xanthan gum, ~ -quar gum, carageenan and the like.
Now, this invention will be described more specifically b~low with reference to working examples.
Naturally, this invention is not limited to these working examples.
Example 1 In a rotary autoclave having an inner volume of 5 liters, 600 g of absolutely dry broadleaf tree chips, 0.3 g of a formulated pulp digesting assistant agent, and sodium hydroxide and sodium sulfide added thereto in such respective amounts as to account for an active alkali 10 content of 16% by weight (as reduced to Na20), a sulfidity of 25% by weight, and a liquid ratio of 3.6 liters/kg were together heated to 166C over a period of about 70 minutes and digested at 166C for 40 minutes.
The pulp consequently obtained was disintegrated and 15 then tested for kappa number and pulp yield. The results are shown in Table 1. Table 1 shows that the pulp had a kappa number of 16 and a pulp yie~d of 52.0% by weight.
The formulated pulp digesting assistant agent used in this example was obtained by mixing 80 parts by weight of 20 particulate anthraquinone having an average particle diameter of 5 ~m and a maximum particle diameter of 18 ~m, a mixture comprising a first nonionic surfactant of an HLB
value of 14.5 formed of a linear alkyl secondary alcohol having carbon numbers from 12 to 14 possessing an alkylene 25 oxide adduct of 12 mols of ethylene oxide added thereto (product of Nippon Shokubai Co., Ltd.; hereinafter referred to as "Softanol-120") and a second nonionic surfactant of an HLB value of 13.3 formed of an alkyl phenol having the alkyl group carbon numbers from 9 possessing an alkylene oxide 30 adduct of 10 mols of ethylene oxide added thereto (product of Sanyo Chemical Industries Co., Ltd.; hereinafter referred to as "Nonipol-100") at a weight ratio of 1 : 1, the total amount of the mixture of nonionic surfactants being 0.4% by weight based on the amount of the particulate anthraquinone, 3~ and 20% by weight, based on 100% by weight of the formulated pulp digesting agent composition, of water.
~"' '.'. ' ~'., . . . ` ... ..
Control 1 The procedure of Example 1 was repeated, except that the addition of the two specific nonionic surfactants was omitted. The pulp consequently obtained was tested for kappa number and pulp yield. The results are shown in Table 4. Table 4 shows that this pulp had a kappa number of 16 and a pulp yield of 50.8~ by weight.
In this experiment, the digestion was carried out at 166C for 52 minutes. In due consideration of the general 10 practice of comparing pulp yields on a common kappa number, the time of digestion in this case had to be adjusted to the value indicated above so as to equalize the kappa number, though approximately, with that of Example 1.
By the same token, in Examples 2 to 22 and Controls 15 2 to 9, the times of digestion at 166C were adjusted substantially to equalize the respective kappa numbers and the pulp yields found on these equalized kappa numbers were used for the purpose of comparison.
Examples 2 to 5 The procedure of Example 1 was repeated, except that the weight ratio of the two specific nonionic surfactants was varied as shown in Table 1~ The pulps consequently produced were tested for kappa number and pulp yield. The results were as shown in Table 1.
Table 1 -. .
Example 1 Z 3 ~ _ Softanol-120 0.16 0.256 0.192 0.128 0.064 tparts by weight) Nonipol-100 0.16 0.064 0.128 0.192 0.256 (parts by weight) Total amount used 0.32 0.32 0.32 0.32 0.32 (parts by weight) Kappa number 16 16 16 16 16 1 Pulp yield 52.0 51.7 52.0 52.0 51.8 (% by weight) I _ Controls 2 and 3 The procedure of Example 1 was repeated, except that the weight ratio of the two specific nonionic surfactants 20 was varied as shown in Table 2. The pulps consequently produced were tested for kappa number and pulp yield. The results were as shown in Table 2.
Table 2 26 Control 2 Control 3 _ Softanol~-120 0.32 0 (parts by weight) ..
Nonipol-100 0 0.32 (parts by weight) Total amount used 0.32 0.32 (parts by weight) _ Kappa number 16 16 Pulp yield 51.0 51.2 ( % by weight) Examples 6 to 9 The procedure of Example 1 was repeated, except that the total amount the two specific nonionic surfactants was varied as shown in Table 3. The pulps consequently produced 5 were tested for pulp yield. The results were as shown in Table 3.
In these experiments, the weight ratio of the two specific nonionic surfactants was invariably fixed at 1 Table 3 : ' Example 6 _ _ Total amount used 0. o8 o . 4 o . 8 1 . 6 - ~ -15 ( parts by weight) Kappa number 16 16 16 16 : :
Pulp yield 51.7 52.0 51.9 51.7 I
(% by weight) Note) The weight ratio of Softanol-120 to Nonipol-100 was invariably fixed at 1 : 1. -~ ~. ,' -Controls 4 and 5 The procedure of Example 1 was repeated, except that 25 the total amount of the two specific nonionic surfactants to be used was varied as indicated in Table 4. The pulps consequently produced were tested for pulp yield. The results of test were as shown in Table 4.
Again in this case, the weight ratio of the two 30 specific nonionic surfactants was invariably fixed at 1 : 1.
.
' '~' , ~'' Table 4 . _ Control 3 Control 4 Control 5 _ _ Total amount used O O . 04 3 . 2 (parts by weight) _ Kappa number 16 16 16 Pulp yield 50.8 51.4 51. 4 (% by weight) _ Note) The weight ratio of Softanol-120 to Nonipol-10Q to be used was invariably fixed at 1 :
1.
Example 10 The procedure of Example 1 was repeated, except that 15 a particulate anthraquinone having an average particle diameter of 3 ~m and a maximum particle diameter of 18 ~m was used instead. The pulp consequently produced was found to have a kappa number of 16 and a pulp yield of 52.2~ by weight.
The determination of the particle diameter was carried out by the use of a supercentrifugal automatic particle size testing device, CAPA-700 (produced by Horiba Seisakusho K.K.).
Control 6 2~ The procedure of Example 1 was repeated, except that a particulate anthraquinone having an average particle diameter of 30 ~m and a maximum particle diameter of 60 ~m was used instead. The pulp consequently produced was found to have a kappa number of 16 and a pulp yield of 50.7% by 30 weight.
Examples 11 to 15 The procedure of Example 1 was repeated, except that the amount of water added based on 80 parts by weight of anthraquinone was varied as indicated in Table 5. The pulps 3~ consequently produced were tested for pulp yield. The results were as shown in Table 5.
~. ,~;~ ~,; . : ; - . , . . :, ~ - .. ..... ~ -~ . . .
i~
Table 5 _ Example :
Total amount used 5 9 14 27 34 (parts by weight) Kappa number 16 16 16 16 16 : . ':
Pulp yield 51.6 51.9 52.0 51.9 51.7 10 (% by weight) ' . -Controls 7 to 9 The procedure of Example 1 was repeated, except thatthe amount of water added based on 80 parts by weight of 15 anthraquinone was varied as indicated in Table 6. The pulps consequently produced were tested for pulp yield. The ~-results were a~ indicated in Table 6.
Table 6 _ Control 7 IControl 8 IControl 9 _ Total amount used 0 2 43 (parts by weight) ~ -. ...
Kappa number 16 16 16 Pulp yield (% by 50.8 51.3 51.4 weight) , . .
Example 16 The procedure of Example 1 was repeated, except that 30 an aqueous solution containing 50% by weight of ethylene glycol was used in the place of water. The pulp consequently produced was disintegrated and then tested for kappa number and pulp yield. It was found to have a kappa number of 16 and a pulp yield of 52.0~ by weight.
3s Example 17 The procedure of Example 1 was repeated, except that an aqueous solution containing 40% by weight of diethylene glycol was used in the place of water. The pulp consequently produced was disintegrated and then tested for kappa number and pulp yield. It was found to have a kappa number of 16 and a pulp yield of 52.0~ by weight.
Examples 18 to 20 The procedure of Example 1 was repeated, except that nonionic sur~actants having ethylene oxide addition mol numbers indicated in Table 7 were used in the place of 10 Softanol-120 as the first nonionic surfactant. The pulps consequently produced showed pulp yields as indicated in Table 7.
Table 7 Example 18 _ _ Ethylene oxide 7 15 20 addition mol number Kappa number 16 16 1 16 Pulp yield 51.8 52.0 51.8 (% by weight) _ Example 21 and 22 The procedure of Example 1 was repeated, except that nonionic surfactants having ethylene oxide addition mol 25 numbers indicated in Table 8 were used in the place of Nonipol-100 as the second nonionic surfactant. The pulps consequently produced showed pulp yields indicated in T`ble 8. Table 8 30 Example 21 Example 22 _ Ethylene oxide 8 14 addition mol number .
Kappa number 16 16 35 Pulp yield 51.8 51.9 (% by weight) ......... .
The for~ulated pulp digesting assistant agent obtained in accordance with this invention can be used as an amply effective digestion assistant not only in the digestion by the kraft method, sulfurous acid method, and soda method but also in the digestion by the semi chemical method. They bring about decisively fine digesting effects as compared with a digesting assistant formed solely of anthraquinone. They produce a better digesting effect reduced to available anthraquinone content as compared with 10 an aqueous alkali solution of tetrahydroanthraquinone which is held to constitute an ideal form of use.
Further, in the formulated pulp digesting assistant agent of this invention, since two specific nonionic -~
surfactants are jointly used for the purpose of precluding 15 the possible occurrence of the "phenomenon of gelation" of a nonionic surfactant and, at the same time, these surfactants are incorporated in the composition in combination with a suitable amount of water and/or an alcohol having a molecular weight of not more than 200, these nonionic 20 surfactants are deposited in the state retaining their inherent functions intact on the anthraquinone particles.
When this agent is exposed to the pulp digesting liquid, therefore, the combined function of the surfactants is manifested at once in facilitating the dispersion and 25 dissolution of anthraquinone in the pulp digesting liquid.
Thus, the agents thoroughly manifest their effect as a redox catalyst for anthraquinone. --In the production of the formulated pulp digesting assistant agent, the conventional method which uses a 30 particulate anthraquinone having an average particle diameter in the neighborhood of 10 ~m is hardly practicable because the powder which is drifted about the site of-handling in a wind of such a low speed of about 2 m/sec.
poses a problem of environmental hygiene. In the formulated 35 pulp digesting assistant agent of this invention, the combined addition of the nonionic surfactants and water ~ -~
and/or an alcohol having a molecular weight of not more than 200 imparts a wet state to the agent and perfectly prevents the particulate anthraquinone from being drifted about in the form of dust.
Further, the formulated pulp digesting assistant agent of this invention can manifest an outstanding digesting effect even when trees and plants as well as conifers and broadleaf trees are used as pulpwood or chips.
This invention, therefore, is expected to lend itself 10 immensely to protection of environmental resources on a commercial scale and contribute extensively to the progress and prosperity of mankind.
PULP DIGESTING ASSISTANT AGENT
BACKGROUND OF THE INVENTION
Field of the Invention:
This invention relates to a formulated composition of a powdery pulp digesting assistant agent. More particularly, it relates to a powdery readily dispersible formulated composition of pulp digesting assistant agent which comprises anthraquinone in a particulate form, two 10 kinds of speoific nonionic surfactants, water, and/or an alcohol having a molecular weight of not more than 200 and manifests a high digesting power.
Description of the Prior Art:
In recent years, it has been found that when 15 anthraquinones heretofore used prevalently in dyes and pigments are used as a pulp digesting assistant agent or a redox catalyst, they contribute in a great measure to ~;-increase the speed of digestion, lower the temperature of digestion and consequently save steam, economize chemical 20 agents to be used, shorten the time of digestion and consequently improve the rate of operation, exalt the quality of pulp, and increase the yield of pulp. As a result, the anthraquinones have been finding growing utility in the pulp digesting assistant agent.
The anthraquinones, however, are not soluble in -~
water. When powdery anthraquinone is added in its unformulated form to a pulp digesting liquid, therefore, the greater part of the powder floats on the surface of the digesting liquid and a considerably long time is required 30 for the powder to be thoroughly dispersed and dissolved in the digesting liquid. As a result, the powdery anthraquinone is at a disadvantage in failing to manifest amply the catalytic effect thereof because it is not fully dispersed or dissolved in the pulp digesting liquid within -~5 the ordinary digesting time.
As means to overcome the disadvantage, a method of v- , ,, ' ~ ,,,' : ~ .
using tetrahydroanthraquinone of a reduced form as diluted ~ in an aqueous alkali solution has been available. This j method indeed is fine in respect that tetrahydroanthraquinone is quickly dispersed and dissolved in the pulp digesting liquid. It is at a disadvantage, however, in requiring the entire aqueous alkali solution of tetrahydroanthraquinone to be covered with nitrogen gas while in transit and in use. Because, this solution is oxidized on exposure to the air, and entails separation of 10 crystals of anthraquinone. And the cost of transportation is expensive, because this solution is in a dilute form.
As another means to overcome the problem, a method which allows effective use of particulate anthraquinone in the pulp digesting liquid by having a surfactant, 15 particularly an anionic surfactant, deposited on the anthraquinone particles thereby facilitating the dispersion and dissolution of the particulate anthraquinone in the pulp digesting liquid is disclosed (JP-A-54-100,332). The method which involves deposition of an anionic surfactant among 20 other surfactants, however, has the disadvantage that since this deposition gives rise to a composition having the particulate anthraquinone kneaded in a pasty form with a ~olution of the ionic surfactant, this composition not only entails a high cost of transportation but also requires 25 consumption of the ionic surfactant in a large amount as compared with the particulate anthraquinone. In the detailed description of the invention which relates to the method under discussion, a mention is made to the effect that nonionic surfactants among other surfactants are not 30 fit for dispersion of particulate anthraquinone. From this statement, it is inferred that even if an anionic surfactant is managed to be uniformly mixed at its initial concentration of 100% with particulate anthraquinone, the resultant mixture placed in the pulp digesting liquid 35 induces the "phenomenon of gelation" which ought to be justly called a peculiar disposition owned by the nonionic ~.',,,`"'.-', .'`,,,',,':'i".' surfactant and, instead of fulfilling the function of a surfactant, rather covers the surface of anthraquinone particles with a jellylike coat and further obstructs dispersion and dissolution of anthraquinone in the pulp digesting liquid and, as a result, fails to produce any appreciable effect in the pulp digestion.
Canadian Patent No. 1,140,706 also discloses a method which similarly resorts to use of a surfactant. Even when an anionic surfactant is used as taught in the detailed 10 description of the invention relating to this method, this invention can be hardly called satisfactory because it still entails the problem of unduly heavy consumption of the anionic surfactant. Again in the case of this invention, the working examples cited in the specification invariably 15 represent cases of using an anionic surfactant. No mention is made anywhere of a nonionic surfactant regarding the structure, composition, or mode of use. The nonionic -~
surfactants which have many problems yet to be solved as to method of use and selection of species are not easily taken ~0 up as subjects of study. In the existing state of affairs, no method has yet been found for effective use of a nonionic surfactant as a digesting assistant agent.
No actual case of using a nonionic surfactant for the purpose under discussion has been reported to date. No 25 report has yet been published in literature as to the effectiveness of a nonionic surfactant in promoting dispersion and dissolution of anthraquinone in the pulp digesting liquid. Thi~ fact may well be regarded as reflecting the fact that this effectiveness of a nonionic 30 surfactant has not been uncovered to date.
I An object of this invention, therefore, is to provide a formulated pulp digesting assietant agent which allows anthraquinone used in a powdery form to be easily dispersed and dissolved in the pulp digesting liquid, 35 enables the anthraquinone to manifest thoroughly the effect thereof as a redox catalyst and, at the same time, precludes the harms which would be possibly done to the environmental hygiene by particulate anthraquinone when this powder is drifted in course of handling.
SUMMARY OF THE INVENTION
We have made a diligent study on formulated pulp digesting assistant agent with a view to accomplishing the object described above and consequently found that a formulated pulp digesting assistant agent which is perfectly free from the problsm mentioned above is obtained by 10 depositing on the surface of anthraquinone particles what is obtained by adding water and/or a low molecular water-soluble alcohol to a mixture of two kinds of specific nonionic surfactants. This invention has been perfected on the basis of this knowledge.
1~ The objects of this invention are accomplished by (1) a formulated pulp digesting assistant agent which comprises a particulate anthraquinone of an average particle diameter of not more than 10 ~m and a maximum particle diameter of not more than 30 ~m, 0.1 to 2% by weight, based 20 on the amount of the particulate anthraquinone, of a nonionic surfactant mixture comprising a first nonionic surfactant of an HLB value of 12 to 16 formed of a secondary alcohol having carbon numbers from 10 to 16 possessing an alkylene oxide adduct of 7 to 20 moles of ethylene oxide 25 added thereto and a second nonionic surfactant of an HLB
value of 12 to 16 formed of an alkyl phenol having the alkyl group carbon number from 6 to 12 possessing an alkylene oxide adduct having 8 to 15 moles of ethylene oxide added thereto, the weight ratio of the first to the second 30 nonionic surfactant being in the range of 5 : 1 to 1 : 5 and the total amount of the first and second nonionic surfactants being in the range of 0.1 to 2% by weight based on the amount of the particulate anthraquinone, and 5 to 30 by weight, based on 100% by weight of the formulated pulp 35 digesting assistant agent, of water and/or an alcohol of molecular weight of not more than 200.
:: .
The objects of this invention are further accomplished by (2) a formulated pulp digesting assistant agent set forth in (1) above, wherein the mixture of the first and second nonionic surfactants has an average HLB
6 value in the range of 13 to 15.
The objects of this invention are also accomplished by (3) a formulated pulp digesting assistant agent set forth in (1) above, wherein the total content of water and/or an alcohol of a molecular weight of not more than 200 is in the 10 range of 10 to 20% by weight based on 100% by weight of the formulated pulp digesting assistant agent.
EXPLANATION OF THE PREFERRED ENBODIMENT
Now, this invention will be described in detail below.
The particulate anthraquinone to be used in this invention has an average particle diameter of not more than 10 ~m, preferably not more than 7 ~m, and normally not less than 5~m. Generally, it has a maximum particle diameter of not more than 30 ~m, preferably not more than 20 ~m, and 20 normally not less than 18~m. If the average particle diameter exceeds 10 ~m, the undesirability arises that the particulate anthraquinone is not sufficiently dispersed or dissolved in the pulp digesting liquid within the ordinary span of digesting time because the speed of dispersion and 25 dissolution in the pulp digesting liquid is low and consequently the time for the dispersion and dissolution is proportionately large. If the maximum particle diameter exceeds 20 ~m, the disadvantage ensues that the speed of dispersion and dissolution is similarly low.
The first nonionic surfactant which is one of the two components of the mixture of two specific nonionic surfactants to be used in this invention is a nonionic surfactant of an HLB (hydrophile-lipophile balance) value in the range of 12 to 16, preferably 13 to 1~ formed of a 36 secondary alcohol having carbon numbers from 10 to 16, preferably 12 to 14, possessing an alkylene oxide adduct of .x.
. ~ , "
: . . . . : .: ~ : , ~ ;; . , . -: ~ : : . ... ; ; .
7 to 20, preferably 9 to 15 mols of ethylene oxide added thereto.
The second nonionic surfactant which is the other component is a nonionic surfactant of an HLB value in the range of 12 to 16, preferably 13 to 15, formed of an alkylphenol having the alkyl group carbon numbers from 6 to 12, preferably 8 to 9 possessing an alkylene oxide adduct having 8 to 16, preferably 10 to 14, mols of ethylene oxide added thereto.
The weight ratio of the first to the second nonionic surfactant to be used in this invention is such that the weight ratio of the secondary alcohol possessing the aforementioned alkylene oxide adduct (first nonionic surfactant) to the alkyl phenol possessing the 15 aforementioned alkylene oxide adduct (second nonionic -surfactant) is in the range of 5 : 1 to 1 : 5, preferably 3 : 1 to 1 : 3. If the weight ratio of the first to the second nonionic surfactant deviates from the range specified above, then the facilitation of dispersion and dissolution 20 of the particulate anthraquinone in the pulp digesting liquid is attained only with difficulty. This difficulty is -justified in the light of the fact that while a secondary alcohol possessing an alkylene oxide adduct generally i5 a surfactant widely known as excelling in permeating power and 25 thus is counted among the surfactants that exhibit the best ~
wetting power to hydrophobic fibers, this secondary alcohol ~-when used alone requires a long time in causing particulate anthraquinone to be dispersed and dissolved in the pulp digesting liquid. The facilitation of the dispersion and 30 dissolution of the particulate anthraquinone in the pulp digesting liquid is never attained unless the first and second nonionic surfactants are simultaneously used as~
combined at a weight ratio in the range specified above.
The total amount of the mixture of nonionic 35 surfactants is generally in the range of 0.1 to 2% by weight, preferably 0.2 to 1% by weight, based on the amount ' ' ~ ' '~' ' ' , . .' ' ' , ': ' ` .,' . .'; i ' '` . ' ' ` : : " , ` ' ` ' " .'. ' , of the particu]ate anthraquinone. If the total amount is less than 0.1% by weight based on the amount of the particulate anthraquinone, the mixture of nonionic surfactants fails to cover completely the surface of anthraquinone particles and the powder of anthraquinone added to the pulp digesting liquid cannot be thoroughly ~-dispersed or dissolved in the liquid because part of the powder floats on the surface of the liquid.
The average HLB of the mixture of the two specific 10 anionic surfactants is in the range of 12 to 16, preferably 13 to 15. The outstanding digesting effect obtained by this invention is never manifested unless this HLB falls in the range specified above in exactly the same manner as the weight ratio of the nonionic surfactants mentioned above.
1~The alcohol to be used in this invention has no particular restriction except for the requirement that the molecular weight thereof is generally not more than 200, preferably not more than 120. As typical examples of the alcohol which answers this description, lower monohydric 20 alcohols such as methanol, ethanol, propanol, and isopropanol and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, neopentyl glycol, and trihydric alcohols such as glycerol, 25 and etc. may be cited.
The total content of water and/or an alcohol of a molecular weight of not more than 200 to be used in the formulated pulp digesting assistant agent of this invention is generally in the range of 5 to 30% by weight, preferably 30 10 to 20% by weight, based on 100% by weight of the agent.
If this content is less than 5% by weight, based on 100~ by weight of the formulated pulp digesting assistant agent, the amount of water and/or the alcohol of a molecular weight of not more than 200 is unduly small relative to the amount of 35 the mixture of specific nonionic surfactants and consequently this mixture yields to the phenomenon of gelation and, as a result, the disadvantage arises that the nonionic surfactants are deposited in the state obstructed from producing the inherent functions thereof on the anthraquinone particles and, when the pulp digesting S assistant agent contacts the pulp digesting liquid, the surfactants fail to manifest their functions of facilitating dispersion and dissolution of anthraquinone in the pulp ~ -digesting liquid. If the content mentioned above exceeds 30% by weight based on 100% by weight of the formulated pulp 10 digesting assistant agent, the excess of the total amount of water andtor the alcohol of a molecular weight of not less than 200 prevents the nonionic surfactants from being deposited on the anthraquinone particles and consequently separates itself from the anthraquinone particles and 15 renders insufficient the thoroughness of dispersion and dissolution of the particulate anthraquinone in the pulp digesting liquid.
The formulated pulp digesting assistant agent o~
this invention is preferable to be homogeneously blended by 20 the use of a suitable mixing device or stirring device before it is placed and used in the pulp digesting liquid. ;
The pulp digesting liquid into which the pulp digesting assistant agent of this invention is thrown does not need to be particularly limited but may be any of the 25 digesting liquids in popular use. The composition may be added to an alkaline digesting liquid for the Kraft process or an acidic digesting liquid for the sulfurous acid process.
When the formulated pulp digesting assistant agent 30 is used as a dispersion in water1 viscosity of the ~
dispersion may be controlled by adding a thickener, if - `
necessary. As the typical thickener, there are carboxymethyl cellulose, starch, sodium polyarginate, sodium polyacrylate, (anhydrous) sodium methasilicate, xanthan gum, ~ -quar gum, carageenan and the like.
Now, this invention will be described more specifically b~low with reference to working examples.
Naturally, this invention is not limited to these working examples.
Example 1 In a rotary autoclave having an inner volume of 5 liters, 600 g of absolutely dry broadleaf tree chips, 0.3 g of a formulated pulp digesting assistant agent, and sodium hydroxide and sodium sulfide added thereto in such respective amounts as to account for an active alkali 10 content of 16% by weight (as reduced to Na20), a sulfidity of 25% by weight, and a liquid ratio of 3.6 liters/kg were together heated to 166C over a period of about 70 minutes and digested at 166C for 40 minutes.
The pulp consequently obtained was disintegrated and 15 then tested for kappa number and pulp yield. The results are shown in Table 1. Table 1 shows that the pulp had a kappa number of 16 and a pulp yie~d of 52.0% by weight.
The formulated pulp digesting assistant agent used in this example was obtained by mixing 80 parts by weight of 20 particulate anthraquinone having an average particle diameter of 5 ~m and a maximum particle diameter of 18 ~m, a mixture comprising a first nonionic surfactant of an HLB
value of 14.5 formed of a linear alkyl secondary alcohol having carbon numbers from 12 to 14 possessing an alkylene 25 oxide adduct of 12 mols of ethylene oxide added thereto (product of Nippon Shokubai Co., Ltd.; hereinafter referred to as "Softanol-120") and a second nonionic surfactant of an HLB value of 13.3 formed of an alkyl phenol having the alkyl group carbon numbers from 9 possessing an alkylene oxide 30 adduct of 10 mols of ethylene oxide added thereto (product of Sanyo Chemical Industries Co., Ltd.; hereinafter referred to as "Nonipol-100") at a weight ratio of 1 : 1, the total amount of the mixture of nonionic surfactants being 0.4% by weight based on the amount of the particulate anthraquinone, 3~ and 20% by weight, based on 100% by weight of the formulated pulp digesting agent composition, of water.
~"' '.'. ' ~'., . . . ` ... ..
Control 1 The procedure of Example 1 was repeated, except that the addition of the two specific nonionic surfactants was omitted. The pulp consequently obtained was tested for kappa number and pulp yield. The results are shown in Table 4. Table 4 shows that this pulp had a kappa number of 16 and a pulp yield of 50.8~ by weight.
In this experiment, the digestion was carried out at 166C for 52 minutes. In due consideration of the general 10 practice of comparing pulp yields on a common kappa number, the time of digestion in this case had to be adjusted to the value indicated above so as to equalize the kappa number, though approximately, with that of Example 1.
By the same token, in Examples 2 to 22 and Controls 15 2 to 9, the times of digestion at 166C were adjusted substantially to equalize the respective kappa numbers and the pulp yields found on these equalized kappa numbers were used for the purpose of comparison.
Examples 2 to 5 The procedure of Example 1 was repeated, except that the weight ratio of the two specific nonionic surfactants was varied as shown in Table 1~ The pulps consequently produced were tested for kappa number and pulp yield. The results were as shown in Table 1.
Table 1 -. .
Example 1 Z 3 ~ _ Softanol-120 0.16 0.256 0.192 0.128 0.064 tparts by weight) Nonipol-100 0.16 0.064 0.128 0.192 0.256 (parts by weight) Total amount used 0.32 0.32 0.32 0.32 0.32 (parts by weight) Kappa number 16 16 16 16 16 1 Pulp yield 52.0 51.7 52.0 52.0 51.8 (% by weight) I _ Controls 2 and 3 The procedure of Example 1 was repeated, except that the weight ratio of the two specific nonionic surfactants 20 was varied as shown in Table 2. The pulps consequently produced were tested for kappa number and pulp yield. The results were as shown in Table 2.
Table 2 26 Control 2 Control 3 _ Softanol~-120 0.32 0 (parts by weight) ..
Nonipol-100 0 0.32 (parts by weight) Total amount used 0.32 0.32 (parts by weight) _ Kappa number 16 16 Pulp yield 51.0 51.2 ( % by weight) Examples 6 to 9 The procedure of Example 1 was repeated, except that the total amount the two specific nonionic surfactants was varied as shown in Table 3. The pulps consequently produced 5 were tested for pulp yield. The results were as shown in Table 3.
In these experiments, the weight ratio of the two specific nonionic surfactants was invariably fixed at 1 Table 3 : ' Example 6 _ _ Total amount used 0. o8 o . 4 o . 8 1 . 6 - ~ -15 ( parts by weight) Kappa number 16 16 16 16 : :
Pulp yield 51.7 52.0 51.9 51.7 I
(% by weight) Note) The weight ratio of Softanol-120 to Nonipol-100 was invariably fixed at 1 : 1. -~ ~. ,' -Controls 4 and 5 The procedure of Example 1 was repeated, except that 25 the total amount of the two specific nonionic surfactants to be used was varied as indicated in Table 4. The pulps consequently produced were tested for pulp yield. The results of test were as shown in Table 4.
Again in this case, the weight ratio of the two 30 specific nonionic surfactants was invariably fixed at 1 : 1.
.
' '~' , ~'' Table 4 . _ Control 3 Control 4 Control 5 _ _ Total amount used O O . 04 3 . 2 (parts by weight) _ Kappa number 16 16 16 Pulp yield 50.8 51.4 51. 4 (% by weight) _ Note) The weight ratio of Softanol-120 to Nonipol-10Q to be used was invariably fixed at 1 :
1.
Example 10 The procedure of Example 1 was repeated, except that 15 a particulate anthraquinone having an average particle diameter of 3 ~m and a maximum particle diameter of 18 ~m was used instead. The pulp consequently produced was found to have a kappa number of 16 and a pulp yield of 52.2~ by weight.
The determination of the particle diameter was carried out by the use of a supercentrifugal automatic particle size testing device, CAPA-700 (produced by Horiba Seisakusho K.K.).
Control 6 2~ The procedure of Example 1 was repeated, except that a particulate anthraquinone having an average particle diameter of 30 ~m and a maximum particle diameter of 60 ~m was used instead. The pulp consequently produced was found to have a kappa number of 16 and a pulp yield of 50.7% by 30 weight.
Examples 11 to 15 The procedure of Example 1 was repeated, except that the amount of water added based on 80 parts by weight of anthraquinone was varied as indicated in Table 5. The pulps 3~ consequently produced were tested for pulp yield. The results were as shown in Table 5.
~. ,~;~ ~,; . : ; - . , . . :, ~ - .. ..... ~ -~ . . .
i~
Table 5 _ Example :
Total amount used 5 9 14 27 34 (parts by weight) Kappa number 16 16 16 16 16 : . ':
Pulp yield 51.6 51.9 52.0 51.9 51.7 10 (% by weight) ' . -Controls 7 to 9 The procedure of Example 1 was repeated, except thatthe amount of water added based on 80 parts by weight of 15 anthraquinone was varied as indicated in Table 6. The pulps consequently produced were tested for pulp yield. The ~-results were a~ indicated in Table 6.
Table 6 _ Control 7 IControl 8 IControl 9 _ Total amount used 0 2 43 (parts by weight) ~ -. ...
Kappa number 16 16 16 Pulp yield (% by 50.8 51.3 51.4 weight) , . .
Example 16 The procedure of Example 1 was repeated, except that 30 an aqueous solution containing 50% by weight of ethylene glycol was used in the place of water. The pulp consequently produced was disintegrated and then tested for kappa number and pulp yield. It was found to have a kappa number of 16 and a pulp yield of 52.0~ by weight.
3s Example 17 The procedure of Example 1 was repeated, except that an aqueous solution containing 40% by weight of diethylene glycol was used in the place of water. The pulp consequently produced was disintegrated and then tested for kappa number and pulp yield. It was found to have a kappa number of 16 and a pulp yield of 52.0~ by weight.
Examples 18 to 20 The procedure of Example 1 was repeated, except that nonionic sur~actants having ethylene oxide addition mol numbers indicated in Table 7 were used in the place of 10 Softanol-120 as the first nonionic surfactant. The pulps consequently produced showed pulp yields as indicated in Table 7.
Table 7 Example 18 _ _ Ethylene oxide 7 15 20 addition mol number Kappa number 16 16 1 16 Pulp yield 51.8 52.0 51.8 (% by weight) _ Example 21 and 22 The procedure of Example 1 was repeated, except that nonionic surfactants having ethylene oxide addition mol 25 numbers indicated in Table 8 were used in the place of Nonipol-100 as the second nonionic surfactant. The pulps consequently produced showed pulp yields indicated in T`ble 8. Table 8 30 Example 21 Example 22 _ Ethylene oxide 8 14 addition mol number .
Kappa number 16 16 35 Pulp yield 51.8 51.9 (% by weight) ......... .
The for~ulated pulp digesting assistant agent obtained in accordance with this invention can be used as an amply effective digestion assistant not only in the digestion by the kraft method, sulfurous acid method, and soda method but also in the digestion by the semi chemical method. They bring about decisively fine digesting effects as compared with a digesting assistant formed solely of anthraquinone. They produce a better digesting effect reduced to available anthraquinone content as compared with 10 an aqueous alkali solution of tetrahydroanthraquinone which is held to constitute an ideal form of use.
Further, in the formulated pulp digesting assistant agent of this invention, since two specific nonionic -~
surfactants are jointly used for the purpose of precluding 15 the possible occurrence of the "phenomenon of gelation" of a nonionic surfactant and, at the same time, these surfactants are incorporated in the composition in combination with a suitable amount of water and/or an alcohol having a molecular weight of not more than 200, these nonionic 20 surfactants are deposited in the state retaining their inherent functions intact on the anthraquinone particles.
When this agent is exposed to the pulp digesting liquid, therefore, the combined function of the surfactants is manifested at once in facilitating the dispersion and 25 dissolution of anthraquinone in the pulp digesting liquid.
Thus, the agents thoroughly manifest their effect as a redox catalyst for anthraquinone. --In the production of the formulated pulp digesting assistant agent, the conventional method which uses a 30 particulate anthraquinone having an average particle diameter in the neighborhood of 10 ~m is hardly practicable because the powder which is drifted about the site of-handling in a wind of such a low speed of about 2 m/sec.
poses a problem of environmental hygiene. In the formulated 35 pulp digesting assistant agent of this invention, the combined addition of the nonionic surfactants and water ~ -~
and/or an alcohol having a molecular weight of not more than 200 imparts a wet state to the agent and perfectly prevents the particulate anthraquinone from being drifted about in the form of dust.
Further, the formulated pulp digesting assistant agent of this invention can manifest an outstanding digesting effect even when trees and plants as well as conifers and broadleaf trees are used as pulpwood or chips.
This invention, therefore, is expected to lend itself 10 immensely to protection of environmental resources on a commercial scale and contribute extensively to the progress and prosperity of mankind.
Claims (9)
1. A formulated pulp digesting assistant agent which comprises a particulate anthraquinone of an average particle diameter of not more than 10 µm and a maximum particle diameter of not more than 30 µm, 0.1 to 2% by weight, based on the amount of said particulate anthraquinone, of a nonionic surfactant mixture comprising a first nonionic surfactant of an HLB value of 12 to 16 formed of a secondary alcohol having carbon numbers from 10 to 16 possessing an alkylene oxide adduct having 7 to 20 mols of ethylene oxide added thereto and a second nonionic surfactant of an HLB value of 12 to 16 formed of an alkyl phenol having the alkyl group carbon numbers from 6 to 12 possessing an alkylene oxide adduct having 8 to 15 mols of ethylene oxide added thereto, the weight ratio of said first to said second nonionic surfactant being in the range of 5 :
1 to 1 : 5 and the total amount of said first and second nonionic surfactants being in the range of 0.1 to 2% by weight based on the amount of said particulate anthraquinone, and 5 to 30% by weight, based on 100% by weight of said formulated pulp digesting assistant agent, of water and/or an alcohol of a molecular weight of not more than 200.
1 to 1 : 5 and the total amount of said first and second nonionic surfactants being in the range of 0.1 to 2% by weight based on the amount of said particulate anthraquinone, and 5 to 30% by weight, based on 100% by weight of said formulated pulp digesting assistant agent, of water and/or an alcohol of a molecular weight of not more than 200.
2. An agent according to claim 1, wherein the average HLB value of said mixture of first and second nonionic surfactants is in the range of 13 to 15.
3. An agent according to claim 1, wherein the total content of said water and/or alcohol having a molecular weight of not more than 200 is in the range of 10 to 20% by weight, based on 100% by weight of said formulated pulp digesting assistant agent.
4. An agent according to claim 1, wherein the number of mols of ethylene oxide added in said first nonionic surfactant is in the range of 9 to 15 and the number of mols of ethylene oxide added in said second nonionic surfactant is in the range of 10 to 14.
5. An agent according to claim l, wherein the weight ratio of said first nonionic surfactant to said second nonionic surfactant is in the range of 3 : 1 to 1 :
3.
3.
6. An agent according to claim 1, wherein the total amount of said first and second nonionic surfactants to be used is in the range of 0.2 to 1% by weight, based on the amount of said particulate anthraquinone.
7. An agent according to claim 1, wherein said alcohol is an alcohol having a molecular weight of not more than 120.
8. An agent according to claim 1, wherein the content of said water and/or alcohol is in the range of 10 to 20% by weight based on the amount of said formulated pulp digesting assistant agent.
9. An agent according to claim 1, wherein the average particle diameter of said particular anthraquinone is not more than 10 µm and the maximum particle diameter thereof is not more than 30 µm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34070492A JP3304145B2 (en) | 1992-05-18 | 1992-12-21 | Pulp cooking aid composition |
| JP4-340704 | 1992-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2111921A1 true CA2111921A1 (en) | 1994-06-22 |
Family
ID=18339522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2111921 Abandoned CA2111921A1 (en) | 1992-12-21 | 1993-12-20 | Formulated composition of pulp digesting assistant agent |
Country Status (4)
| Country | Link |
|---|---|
| AU (1) | AU666788B2 (en) |
| BR (1) | BR9305171A (en) |
| CA (1) | CA2111921A1 (en) |
| FI (1) | FI935782A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2827111A1 (en) * | 1978-06-21 | 1980-01-10 | Bayer Ag | AGENTS FOR USE IN CELL PROCESSING |
| DE3905311C2 (en) * | 1989-02-21 | 1994-09-29 | Bayer Ag | Process for the preparation of anthraquinone / surfactant mixtures and use of these mixtures |
-
1993
- 1993-12-20 CA CA 2111921 patent/CA2111921A1/en not_active Abandoned
- 1993-12-21 FI FI935782A patent/FI935782A/en unknown
- 1993-12-21 AU AU52547/93A patent/AU666788B2/en not_active Ceased
- 1993-12-21 BR BR9305171A patent/BR9305171A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BR9305171A (en) | 1994-10-25 |
| AU5254793A (en) | 1994-06-30 |
| FI935782A0 (en) | 1993-12-21 |
| FI935782A (en) | 1994-06-22 |
| AU666788B2 (en) | 1996-02-22 |
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