JP5168826B2 - Pitch control agent and pitch control method - Google Patents

Description

  The present invention relates to a pitch control agent and a pitch control method. More specifically, the present invention relates to a pitch control agent and a pitch control method capable of effectively suppressing and preventing pitch failure in a pulp or paper manufacturing process.

  What is said to be pitch in the pulp and paper manufacturing process is a natural resin or gum substance released from wood, pulp or paper, and organic substances derived from additive chemicals used in the pulp or paper manufacturing process. Is a water-insoluble adhesive substance. In general, pitch is dispersed in a colloidal manner during the pulp or paper manufacturing process, especially in white water, but some external action such as large shear force, rapid pH change, excessive addition of sulfuric acid band. For example, the colloidal state is destroyed and aggregated, and it is thought that it becomes enormous. Aggregated and enlarged pitch adheres to pulp and paper due to its adhesiveness, and also adheres to manufacturing equipment such as fan pumps, piping, chests, wires, felts and rolls. Furthermore, the pitch peels off later and reattaches to the pulp or paper, causing a pitch failure such as a deterioration in quality due to the occurrence of paper stains and defects, and a reduction in productivity and workability due to the occurrence of paper breaks. In recent years, as the number of chemicals used has increased due to diversification of paper and the water used in the process has been closed, the pitch obstacles have increased and become more complicated than before.

  Conventionally, various methods for pitch disturbance have been proposed. For example, as a method of reducing the cause of pitch, methods of reducing and removing the cause of pitch by seasoning wood and chips, strengthening washing of pulp, and cleaning of white water have been performed. However, since seasoning has its effects inserted over a long period of time, it used to take a seasoning period of 6 months to 1 year, but it requires a large site and increases production. This makes it difficult to secure and store logs and chips, and the seasoning period must be reduced to 3 to 5 months, and this method has its limitations. In addition, the enhancement of washing of pulp and the enhancement of cleansing of white water cannot be expected since further improvement is difficult because of the progress of closed water.

  JP-A-58-13795 discloses maleic acid or maleamic acid and isobutylene, diisobutylene or styrene as constituent units as a pitch adhesion inhibitor for papermaking that can effectively prevent pitch failure with a small addition amount. A paper pitch preventive agent containing a polymer containing and a nonionic surfactant has been proposed. As a method for reducing the deposition of pitch-like resin during the papermaking process, JP-A-57-149591 proposes a method in which a copolymer of diallyldimethylammonium chloride and acrylamide is added to a pulp slurry. Japanese Patent No. 57-149592 proposes a method of adding a copolymer of diallyldimethylammonium chloride, diallyldiethylammonium chloride, acrylamide and acrylate to a pulp slurry. Japanese Patent Application Laid-Open No. 55-80598 discloses a fatty acid ester in a pulp slurry during a papermaking process as a method of suppressing pitch failure that has a good pitch failure suppression effect and does not cause a decrease in fixing of foaming property and sizing agent. Japanese Patent Laid-Open No. 55-45857 proposes a method for suppressing pitch disturbance without adversely affecting the sizing degree. A method of adding a nonionic surfactant, which is an ethylene oxide adduct, is proposed. Furthermore, in Japanese Patent Application Laid-Open No. 2-182959, as a method for preventing the deposition of an adhesive material on a machine part such as a paper machine felt, an aqueous solution containing a cationic polymer and a nonionic or cationic surfactant are used in the machine part. A method of applying an aqueous solution containing it has been proposed. The method of dispersing the pitch with the surfactant is a simple and effective method, but the effect is lost by aggregating with substances having different ionicity. Further, since there is no decrease in the pitch amount in the system, there is always a risk that the pitch will suddenly occur due to a dispersion failure due to a change in the situation.

  Japanese Patent Application Laid-Open No. 59-105842 discloses pulp pitch adsorption for papermaking in which a small amount of non-swellable mica powder is mixed with natural talc powder as a pulp pitch adsorbent for enhancing the adsorption performance of pitch components contained in pulp. JP-A-60-94687 discloses a paper-making pitch adsorbent that contains hydrotalcite as a paper-making pitch adsorbent for adsorbing the pitch generated in the paper-making process and taking it out of the system. Pitch adsorbents have been proposed. The method of adding talc, clay, and other porous inorganic substances is a method of adsorbing to pitch particles to reduce the stickiness and adhesion of the pitch, and further incorporating this into paper as an inorganic filler. Control has become mainstream. These porous inorganic materials are inexpensive, but the pitch adsorption is not always sufficient and the fixing to paper is low, which causes white water contamination and sludge deposition, as well as significant wire wear and damage, The improvement is desired.

  As a method for removing the pitch by dissolving and dispersing it, a method of adding a pitch-soluble organic solvent such as perchlorethane, trichloroethane, kerosene or the like has been proposed, but there are concerns in terms of environmental pollution and safety.

Further, Japanese Patent Publication No. 2003-517520 and US Pat. No. 5,139,616 propose a method of removing pitch from used paper using limonene, but it cannot be said that a sufficient effect is necessarily obtained.
JP 58-13795 A Japanese Patent Application Laid-Open No. 57-149591 JP-A-57-149592 Japanese Patent Laid-Open No. 55-80598 JP 55-45857 A JP-A-2-182959 JP 59-105842 A JP-A-60-94687 Special Table 2003-517520 US Pat. No. 5,139,616

  The present invention is applicable to a wide range of pulp or paper manufacturing processes regardless of pitch-causing substances and pitch occurrence conditions, and effectively prevents pitch obstacles such as paper stains, defects, paper breaks, and workability degradation. The object of the present invention is to provide a pitch control agent and a pitch control method that can be suppressed and prevented.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor effectively prevents pitch disturbance in the pulp or paper manufacturing process by using limonene, a nonionic surfactant and an alkaline compound. Based on this finding, the present invention has been completed.

That is, the present invention
(1) A pitch control agent containing limonene, a nonionic surfactant, and an alkali metal hydroxide,
(2) The pitch control agent according to (1), wherein the nonionic surfactant is a polyoxyalkylene alkyl ester,
(3) In the pulp or paper manufacturing process, 0.001 to 2 parts by weight of the pitch control agent according to (1) or (2) is added as an active ingredient to 100 parts by weight of pulp. Pitch control method,
(4) In the paper manufacturing process, the pitch control method according to (1) or (2) is sprayed on a manufacturing apparatus to which the pitch adheres;
Is to provide.

  According to the pitch control agent and the pitch control method of the present invention, by utilizing the synergistic effect between the three components of limonene, nonionic surfactant and alkaline compound, the pitch hindrance generated in the pulp or paper manufacturing process is effective. Can be prevented.

  The pitch control agent of the present invention contains limonene, a nonionic surfactant and an alkaline compound.

  Limonene used in the present invention is a natural substance mainly contained in plants such as citrus peel and mint, and is isolated by an extraction operation such as steam distillation. Limonene has d-form and l-form as optical isomers, both of which are applicable to the present invention, and a mixture thereof can also be used.

  The nonionic surfactant used in the present invention is not particularly limited, and examples thereof include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene styryl phenyl ether, polyoxyalkylene alkyl ester, sorbitan alkyl ester, and polyoxyalkylene sorbitan. Examples include alkyl esters and oxyethyleneoxypropylene block copolymers. Of these, polyoxyalkylene alkyl esters, particularly polyoxyethylene fatty acid esters are preferably used because of their excellent solubilizing power.

Examples of the alkali metal hydroxide used in the present invention include lithium hydroxide, sodium hydroxide and potassium hydroxide.

  In the present invention, by using it as a pitch control agent containing limonene, a nonionic surfactant and an alkaline compound, a remarkable synergistic effect is expressed among these three components, and the adhesion of pitch is effectively prevented. Can do. There are no particular restrictions on the blending ratio of limonene, nonionic surfactant and alkaline compound, but it is preferable that both limonene and nonionic surfactant are contained in an amount of 10% by weight or more of all active ingredients in the pitch control agent. . If the content of any component is less than 10% by weight of the total active ingredients, the synergistic effect of the three components may not be sufficiently exhibited.

  In the first aspect of the pitch control method of the present invention, in the pulp or paper manufacturing process, the pitch control agent of the present invention is preferably 0.001 to 2 parts by weight, more preferably 100 parts by weight of pulp as an active ingredient. Is added in an amount of 0.05 to 1 part by weight. If the addition amount of the active ingredient of the pitch control agent is less than 0.001 part by weight with respect to 100 parts by weight of the pulp, the effect of preventing the adhesion of pitch may not be sufficiently exhibited. The amount of the pitch control agent added is 2 parts by weight or less as an active ingredient with respect to 100 parts by weight of the pulp, and a sufficient effect is obtained. Usually, the pitch control agent exceeds 2 parts by weight as the active ingredient with respect to 100 parts by weight of the pulp. There is no need to add.

  In the second aspect of the pitch control method of the present invention, the pitch control agent of the present invention is sprayed on a manufacturing apparatus to which the pitch adheres in the paper manufacturing process. Examples of the manufacturing apparatus to which the pitch is easily attached include a wire, a felt, and a roll. The pitch control agent is preferably sprayed as an aqueous solution. The method for spraying the pitch control agent is not particularly limited, but it is preferable to spray 10 to 1,000 ppm into the washing shower line.

  In the present invention, the mechanism by which the three components of limonene, nonionic surfactant, and alkaline compound exert a synergistic effect is not clear, but is estimated as follows.

  Limonene dissolves the pitch and the alkaline agent hydrolyzes the pitch. Hydrolysis is promoted by dissolving the hydrolyzed surface. Further, it is presumed that the alkaline compound and limonene penetrate into the inside by the action of the surfactant, promote dissolution and hydrolysis from the inside, and exhibit a synergistic effect.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

  In Examples and Comparative Examples, d-limonene (manufactured by Wako Pure Chemical Industries, Ltd.) as limonene, polyoxyethylene (10 mol addition) castor oil fatty acid ester (manufactured by Wako Pure Chemical Industries, Ltd.), alkaline as nonionic surfactant Sodium hydroxide [Wako Pure Chemical Industries, Ltd.] was used as the compound.

  Table 1 shows the composition of the pitch control agent used in the following examples and comparative examples.

〔洗浄試験〕
実施例１
段ボール古紙から中芯を製造している製造ラインより採取した付着物を採取して試料とした。この試料を、クロロホルム／ベンゼン＝１／１（容量比）の混合溶媒を用い、ソックスレー抽出し、抽出液から溶媒を蒸発させた抽出物をクロロホルム溶媒に再溶解して濃度３重量％のピッチ試料を調製した。

[Cleaning test]
Example 1
Deposits collected from a production line that produces cores from corrugated cardboard were collected as samples. This sample was subjected to Soxhlet extraction using a mixed solvent of chloroform / benzene = 1/1 (volume ratio), and the extract obtained by evaporating the solvent from the extract was redissolved in chloroform solvent to obtain a pitch sample having a concentration of 3% by weight. Was prepared.

  This pitch sample was applied on one side of a 50 mm × 240 mm × 0.05 mm stainless steel sheet so as to have a solid content of 0.12 g.

  The stainless steel sheet coated with the pitch sample was leaned against the wall surface of a beaker having a capacity of 500 mL so that the coated surface faced inward. 400 mL of pitch control agent A diluted with water so that the active ingredient was 2 w / v% was poured into a beaker, the liquid temperature was kept at 35 ° C., and the mixture was stirred at 500 rpm for 60 minutes using a magnetic stirrer.

The weight of the solid content remaining on the stainless sheet after the test was measured, and the washing rate was calculated based on the following formula. As a result, it was 75%.
Washing rate (%) = 100− (0.12 g−residual solid weight) /0.12 g × 100
Example 2
The same operation as in Example 1 was performed except that pitch control agent B was used as the pitch control agent. The cleaning rate was 50%.
Example 3
The same operation as in Example 1 was performed except that pitch control agent C was used as the pitch control agent. The cleaning rate was 70%.
Example 4
The same operation as in Example 1 was performed except that the pitch control agent D was used as the pitch control agent. The cleaning rate was 70%.
Example 5
The same operation as in Example 1 was performed except that pitch control agent E was used as the pitch control agent. The cleaning rate was 60%.
Example 6
The same operation as in Example 1 was performed except that pitch control agent F was used as the pitch control agent. The cleaning rate was 55%.
Comparative Example 1
The same operation as in Example 1 was performed except that 400 mL of water was used instead of the diluted pitch control agent. The cleaning rate was 4%.
Comparative Example 2
The same operation as in Example 1 was performed except that the pitch control agent G was used as the pitch control agent. The washing rate was 23%.
Comparative Example 3
The same operation as in Example 1 was performed except that the pitch control agent H was used as the pitch control agent. The washing rate was 42%.
Comparative Example 4
The same operation as in Example 1 was performed except that the pitch control agent I was used as the pitch control agent. The washing rate was 40%.
Comparative Example 5
The same operation as in Example 1 was performed except that pitch control agent J was used as the pitch control agent. The washing rate was 37%.

  Table 2 shows the results of Examples 1 to 6 and Comparative Examples 1 to 5.

表２に見られるように、ｄ−リモネン、ポリオキシエチレン（１０モル付加）ひまし油脂肪酸エステル及び水酸化ナトリウムを含有する本発明のピッチコントロール剤を用いた実施例１〜６では、ピッチコントロール剤を用いなかった比較例１に比べて、顕著に高い洗浄率を示した。これに対して、上記３成分のうちいずれかが含まれていないピッチコントロール剤を用いた比較例２〜５では一定程度の洗浄効果は認められるものの、十分に高い洗浄率は得られなかった。この結果から、ｄ−リモネン、ポリオキシエチレン（１０モル付加）ひまし油脂肪酸エステル及び水酸化ナトリウムの３成分の間に特異的な相乗効果が現れ、ピッチの付着が効果的に防止されることが分かる。
〔起泡試験〕
実施例７
ピッチコントロール剤Ａ〜Ｆを有効成分濃度が５００ｐｐｍとなるように希釈して得た液体１Ｌを、直径約７ｃｍ、容積約２Ｌのガラス製円筒状容器に注入した。ポンプにより、底部から当該液体を抜き、上記容器の上部から同液体を容器内部へ落下させることにより液体を循環落下させた。循環の速度は約１５Ｌ／分とし、５分後の泡の高さを測定した。
比較例６
ピッチコントロール剤を希釈したものの替わりに水１Ｌを用いた以外は、実施例１と同じ操作を行った。
比較例７
ピッチコントロール剤Ｇ〜Ｊを用いた以外は実施例７と同様の操作を行った。

As can be seen in Table 2, in Examples 1 to 6 using the pitch control agent of the present invention containing d-limonene, polyoxyethylene (10 mol addition) castor oil fatty acid ester and sodium hydroxide, the pitch control agent was Compared with Comparative Example 1 that was not used, the cleaning rate was significantly higher. On the other hand, in Comparative Examples 2 to 5 using a pitch control agent that does not contain any of the above three components, a certain degree of cleaning effect was recognized, but a sufficiently high cleaning rate was not obtained. From this result, it can be seen that a specific synergistic effect appears between the three components of d-limonene, polyoxyethylene (10 mol addition) castor oil fatty acid ester and sodium hydroxide, and the adhesion of pitch is effectively prevented. .
[Foaming test]
Example 7
1 L of a liquid obtained by diluting the pitch control agents A to F so that the active ingredient concentration becomes 500 ppm was poured into a glass cylindrical container having a diameter of about 7 cm and a volume of about 2 L. The liquid was circulated and dropped by removing the liquid from the bottom with a pump and dropping the liquid into the container from the top of the container. The speed of circulation was about 15 L / min, and the height of the foam after 5 minutes was measured.
Comparative Example 6
The same operation as in Example 1 was performed except that 1 L of water was used instead of the diluted pitch control agent.
Comparative Example 7
The same operation as in Example 7 was performed except that the pitch control agents G to J were used.

  Table 3 shows the results of Example 7 and Comparative Examples 6-7.

表３に見られるように、ｄ−リモネン、ポリオキシエチレン（１０モル付加）ひまし油脂肪酸エステル及び水酸化ナトリウムを含有する本発明のピッチコントロール剤を用いた実施例７では、ピッチコントロール剤を用いなかった比較例６及び、界面活性剤が配合されていないピッチコントロール剤Ｇ及びＩを用いた場合に比べて、若干の起泡が認められた。一方、界面活性剤が配合されているピッチコントロール剤Ｈ及びＪを用いた場合と実施例とを比べると、泡泡が顕著に抑制されていることが分かる。
実施例８
某製紙工場の抄紙機プレス工程における１番プレスフェルトのフェルト洗浄用高圧シャワー水（約２０ｋｇ／ｃｍ²の水圧）にピッチコントロール剤Ａを有効成分の濃度が０．０２重量％となるように連続注入し、３ヶ月間操業後、使用済みフェルトの一部を採取し、フェルトに付着したピッチ量を測定した。なお、ここでいうピッチ量とはフェルトの重量に対するピッチ重量の比（％）である。
実施例９
ピッチコントロール剤Ｂを用いたこと以外は実施例８と同様の操作を行った。
比較例８
ピッチコントロール剤を用いなかったこと以外は実施例８と同様の操作を行った。
比較例９
ピッチコントロール剤Ｈを用いたこと以外は実施例８と同様の操作を行った。

As seen in Table 3, in Example 7 using the pitch control agent of the present invention containing d-limonene, polyoxyethylene (10 mol addition) castor oil fatty acid ester and sodium hydroxide, no pitch control agent was used. Some foaming was recognized compared with the comparative example 6 and the case where the pitch control agents G and I which are not containing surfactant were used. On the other hand, when the pitch control agents H and J in which the surfactant is blended are used and the examples are compared, it can be seen that the foam is remarkably suppressed.
Example 8
Pitch control agent A is continuously added to high pressure shower water (water pressure of about 20 kg / cm ² ) for felt washing of No. 1 press felt in a paper machine press process at a paper mill at a concentration of 0.02% by weight. After injecting and operating for 3 months, a portion of the used felt was collected and the amount of pitch attached to the felt was measured. Here, the pitch amount is the ratio (%) of the pitch weight to the weight of the felt.
Example 9
The same operation as in Example 8 was performed except that the pitch control agent B was used.
Comparative Example 8
The same operation as in Example 8 was performed except that the pitch control agent was not used.
Comparative Example 9
The same operation as in Example 8 was performed except that the pitch control agent H was used.

  Table 4 shows the results of Example 8 and Comparative Examples 8-9.

表４に見られるように、ｄ−リモネン、ポリオキシエチレン（１０モル付加）ひまし油脂肪酸エステル及び水酸化ナトリウムを含有する本発明のピッチコントロール剤を用いた実施例８では、ピッチコントロール剤を用いなかった比較例８及び、水酸化ナトリウムが配合されていないピッチコントロール剤Ｈを用いた場合に比べて、ピッチ量が顕著に減少したことが分かる。

As seen in Table 4, in Example 8 using the pitch control agent of the present invention containing d-limonene, polyoxyethylene (10 mol addition) castor oil fatty acid ester and sodium hydroxide, no pitch control agent was used. It can be seen that the pitch amount was significantly reduced as compared with Comparative Example 8 and the case where the pitch control agent H not containing sodium hydroxide was used.

Claims (4)

A pitch control agent containing limonene, a nonionic surfactant, and an alkali metal hydroxide. The pitch control agent according to claim 1, wherein the nonionic surfactant is a polyoxyalkylene alkyl ester. In the pulp or paper manufacturing process, 0.001 to 2 parts by weight of the pitch control agent according to claim 1 or 2 as an active ingredient is added to 100 parts by weight of pulp. A pitch control method comprising spraying the pitch control agent according to claim 1 or 2 onto a manufacturing apparatus to which pitch adheres in a paper manufacturing process.