JP2009275297A - Method for producing deinked pulp and deinking auxiliary used therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a deinked pulp having a high brightness, a small amount of residual ink and high qualities. <P>SOLUTION: In a process for producing the deinked pulp, a terpene compound is added to a pulp slurry having a pulp concentration of 0.5-2.0 wt.% at a position to excellently mix the pulp slurry with the compound ahead of a flotator. Consequently, ink removal performance from a pulp fiber as a raw material is improved and a deinked pulp having a high commercial value is obtained in a high yield. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a production method and a deinking aid for recovering high-quality DIP in a high yield in a process of producing deinked pulp (hereinafter also referred to as “DIP”) from used printed paper.

  In recent years, the use of waste paper pulp has been increasing from the viewpoint of resource saving and environmental protection. In recent years, this tendency has been strengthened, and it has become necessary to use low-quality wastepaper and difficult-to-deink wastepaper, which have been low in utilization rate, as raw materials. While there are an increasing number of users who handle environmentally friendly products such as products subject to the Green Purchasing Law and Eco Mark certified products, there are also increasing demands for the same quality as virgin pulp products. In the paper industry, efforts are being made to improve the quality and cost of DIP.

  In order to achieve high quality DIP and cost reduction, deinking treatment in the disaggregation process and the flotation process is regarded as important. Patent Document 1 (Japanese Patent Application Laid-Open No. 2006-169668) proposes a method of simultaneously adding two liquids, a higher alcohol deinking agent and a fatty acid deinking agent, as a deinking agent during the disaggregation step. In recent years, it has been difficult to adjust the foamability in the floatator according to diversification of used paper raw materials, deterioration of white water, changes in fillers and seasonal factors, and the adjustment work is complicated. Patent Document 2 (Japanese Patent Laid-Open No. 2007-119955) proposes a solution by improving the apparatus surface in the cleaning process. However, with this method, it is difficult to remove ink due to changes in waste paper due to the neutralization of newsprint paper, changes in the composition and properties of ink due to the spread of soybean oil ink and the appearance of UV ink. Waste paper has been increasing, and bubbles are generated during the deinking process due to the influence of binders and charcoal fillers in coated paper such as flyers, and fine ink accumulates in the finished pulp due to the closure of white water. However, there is a problem that the factors that cause the quality of the obtained DIP to deteriorate and the pulp recovery rate to decrease increase.

  Therefore, in the flotation process, it is important to adjust the bubbles to the optimum size in order to achieve both the ability to collect ink particles and the floatability of bubbles. However, the management of bubbles and foaming performance is complicated, and as a result, the whiteness of DIP and the pulp recovery rate are greatly affected.

  Until now, various methods of using terpene compounds such as terpene hydrocarbons, pine oil, terpene alcohols as deinking agents have been proposed. For example, in Patent Document 3 (International Publication No. 98/55683 pamphlet), a terpene hydrocarbon limonene is used as a solvent for a synthetic rubber used as a main component of a deinking agent. No. 4 (Japanese Patent Laid-Open No. 3-504523) has proposed a deinking agent prepared by mixing terpene hydrocarbons such as limonene and α-pinene with a highly foaming and low emulsifying surfactant. Yes. These are used only as solvents for dissolving synthetic rubber or ink, and are fundamentally different from terpene compounds for the purpose of adjusting foaming with the floatator of the present invention. These have terpene hydrocarbons acting as ink particle scavengers, but none has been specified for the location of the terpene compound addition, and both ink particle scavenging and air bubble floatability can be achieved. I could not.

  Further, in Patent Document 5 (Japanese Patent Laid-Open No. 58-215500), liquid soap obtained by mixing terpene alcohol and fatty acid soap is used as a deinking agent. Pine oil solubilizes fatty acid soap. It is only used for stabilization and high whiteness DIP cannot be obtained with high pulp recovery. Moreover, the addition place etc. are not specified.

  Patent Document 6 (Japanese Patent Application Laid-Open No. 2007-277768) proposes to add a terpene alcohol and a compound having a polyoxyalkylene group in combination or as a deinking agent. However, terpene alcohols are a combination with a compound having a polyoxyalkylene group, and the deinking agent is added in a disaggregation process which is a general addition site. Furthermore, in this prescription, since it is difficult to adjust the balance between foamability and foam breakability in the flotation process, it is insufficient to improve ink removability. For this reason, there is a problem that it is difficult to obtain a high whiteness DIP at a high pulp recovery rate.

In Patent Document 7 (Japanese Patent Laid-Open No. 2000-282383), the deinking aid is added in the flotation method at the concentration step after the disaggregation step, at the kneading step after the concentration step, at the aging step, and at the aging step. Although the time of the dilution process after the process is mentioned, it is not specified and terpene hydrocarbons or terpene alcohols are not used as a deinking aid.
JP 2006-169668 A JP 2007-119955 A International Publication No. 98/55683 Pamphlet Japanese Patent Laid-Open No. 3-504523 JP 58-215500 A JP 2007-277768 A JP 2000-282383 A

  An object of the present invention is to improve the free ink collection effect in a DIP production method by a flotation method, and to obtain a high-quality DIP having a high whiteness and a small amount of residual ink with a high pulp recovery rate. It is to provide a production method and a deinking aid.

The present invention is a method for producing deinked pulp by a flotation method including at least a disaggregation step, a dust removal step, and a flotation step, and the pulp concentration in the dust removal step and / or the flotation step is 0.5 to 2.0% by weight. The present invention relates to a method for producing a deinked pulp, wherein a terpene compound is added to a pulp slurry in the range of.
Here, the addition amount of the terpene compound is preferably 0.01 to 5.0% by weight with respect to the absolutely dry pulp.
The place where the terpene compound is added is preferably a place where the terpene compound is well mixed with the pulp slurry before the floater.
Furthermore, you may add a terpene compound to the conditioner tank provided before the flotation process.
The terpene compound preferably includes a terpene alcohol, and the terpene alcohol is at least one selected from the group consisting of terpineol, linalool, geraniol, myrcenol, dihydromyrcenol, menthol, and terpinene 4ol.
As the terpene compound, pine oil is more preferable.
The present invention also relates to a deinking aid characterized by containing a terpene compound as a main component in a method for producing deinked pulp by a flotation method.

  The present invention relates to a method for producing DIP by a flotation method, in a dust removal step and / or a flotation step, in a pulp slurry having a pulp concentration in the range of 0.5 to 2.0% by weight, specifically a terpene compound. Is added to the well mixed with the pulp slurry before the floatator and the conditioner tank before the floatator to adjust the particle size of the bubbles formed by the air blown into the floatator and optimize the surface area, It optimizes the flying speed of the ink particles peeled from the raw pulp fibers. Therefore, it is possible to balance both performances by adjusting the content of the terpene compound while exhibiting the effects of both the ink particle collection performance and the bubble floating performance. In the surface layer of the floatator, the bubbles are efficiently broken, and the selective sorting performance of ink particles and pulp fibers is improved, so that the recovery rate of the finished pulp obtained is improved and the residual ink amount of the pulp fibers is reduced. can do. That is, high-quality DIP with high whiteness can be obtained with a high pulp recovery rate, and the residence time of the raw material in the floatator can be shortened, so that the DIP production amount is expected to be improved.

  In addition, since the ink peeled from the pulp fiber that is the raw material can be effectively removed out of the system, when there is a bleaching step in the next step of the flotation step, the amount of bleach and alkali can be reduced. COD in the manufacturing system can be reduced. For this reason, there is an effect that the environmental load is reduced, and it is possible to further reduce the cost.

  Hereinafter, the present invention will be described in detail. In addition, this invention is not necessarily limited to the following embodiment, In the range which does not deviate from a claim, the structure can be changed suitably.

  Although there are a flotation method and a washing method in the production method of DIP, the present invention is made in the flotation method. As a result of the production of DIP, regardless of the quality such as whiteness of the finished pulp obtained, The present invention relates to a DIP manufacturing method including at least a disaggregation process, a dust removal process, and a flotation process. If desired, these steps may be a production step including a bleaching step, the order of each step, the equipment used in each step is not limited, the type of used waste paper or pulp slurry as a raw material, It can be appropriately changed depending on the amount of use or quality requirements such as the whiteness of DIP. The flotation method may be used in combination with the cleaning method.

  Here, examples of the raw paper raw material include newspaper / magazine paper, paperboard, cardboard base paper, sanitary paper, printing / information paper, etc. Newspaper waste paper DIP, high-quality waste paper DIP, newspaper / magazine that particularly require high whiteness. In the production of used paper high white DIP, the effects of the present invention can be exhibited.

  Although the embodiment in the manufacturing process of high whiteness newspaper waste paper DIP and high-quality waste paper DIP is illustrated below, it is not limited to this method.

The manufacturing process of DIP using newspaper waste paper as a raw material is further classified into a disaggregation process, a dust removal process, a dispersion process, a bleaching process, a flotation process, and a washing / dehydrating process.
General equipment in each process is as follows: disaggregation process: drum pulper, dust removal process: high-concentration cleaner, coarse selection hall screen, selective slit screen, first stage flotation process: flowator, dispersion process: kneader, bleaching process: reactor, Second stage flotation process: Flotator, washing / dehydration process: carefully selected slit screen, forward cleaner, reverse cleaner, disk filter, screw press, hot disperser, high speed belt filter.

Production of DIP using high-quality waste paper as a raw material is relatively easy because the quality of the raw material such as paper quality is stable.
The manufacturing process of DIP using high-quality waste paper as a raw material is roughly classified into a disaggregation process, a dust removal process, a flotation process, a washing process, and a bleaching process.
General equipment in each process is as follows: disaggregation process: high concentration pulper, dust removal process: high concentration cleaner, coarse selection slit screen, fine selection screen, forward cleaner, flotation process: floatator, bleaching process: kneader, hypo bleaching equipment Extractor, washing process: washing concentration machine.

  In the manufacturing process of DIP, a deinking agent is generally added in a disaggregation process and a dispersion process. A deinking agent is an agent that acts on the paper surface and pulp fibers, separates the ink adhering to the paper surface and pulp fibers, separates the pulp and ink, and releases the ink. Etc. are used. Deinking agents include fatty acid / fatty acid emulsions, fatty acid derivatives, oil and fat derivatives, higher alcohol derivatives, and the like. In general, many of the above derivatives have alkylene oxide added as a hydrophilic group, and the deinking agent used in the present invention is not particularly limited, but higher alcohol ethylene oxide, propylene oxide adduct, etc. may be used. That's fine.

  In the disaggregation process, a deinking agent is added to a disaggregator such as a high-concentration pulper or drum pulper together with an alkaline agent such as caustic soda and sodium silicate, and the ink particles are peeled off from the pulp fiber of the waste paper as a raw material, and the ink particles are refined. . The dispersion step is a step of peeling and dispersing the ink from the fiber with a kneader or a disperser, and a deinking agent is added immediately before the disperser treatment. As the deinking agent used in this step, a higher alcohol surfactant having excellent penetrating and peeling effects on the ink is used.

  In the flotation process required for the flotation method, the separated ink particles are collected on the surface of the bubbles formed by the air blown into the floatator, floated together with the bubbles, and discharged out of the system. The deinking agent that acts in this step is generally added to the dispersion step prior to the flotation step, and a fatty acid or fatty acid soap having a strong ink particle collecting property is often used.

The terpene compound of the present invention is added to a pulp slurry having a pulp concentration in the range of 0.5 to 2.0% by weight in the dust removal step and / or the flotation step. Furthermore, a pulp slurry of 0.5 to 1.5% by weight is more preferable. When the pulp concentration is less than 0.5% by weight, the production efficiency of DIP is poor, which is not economical. On the other hand, when the pulp concentration is more than 2.0% by weight, the terpene compound is poorly mixed, and the terpene compound penetrates into the pulp. The foaming performance in the rotator is not demonstrated. The dust removal step is a step of removing foreign substances in the raw material with a slit screen, a screen cleaner, or the like.
Here, when adding the terpene compound of the present invention in the dust removal step, it is preferable to add it to a place where it is well mixed with the pulp slurry before and after the screen, for example, near the suction part of the pump that sends the pulp slurry and the entrance of the screen cleaner It is more preferable to add to.

  Moreover, when adding the terpene compound of this invention in a flotation process, it is preferable to add to the place mixed well with the pulp slurry before a floatator, for example of the manufacturing process of DIP using, for example, newspaper waste paper as a raw material In some cases, it may be added to a place where it is well mixed with the pulp slurry before the first stage and / or the second stage. Moreover, it is more preferable to add to the suction part of the pump which sends a pulp slurry, and the vicinity of the inlet of a flowtater apparatus to the 1st stage | floatator and / or the 2nd stage | paragraph flowator.

  Furthermore, for example, in the case of DIP manufacturing process using high-quality waste paper as a raw material, as a place where it is well mixed with the pulp slurry before the floatator, near the suction part of the pump that sends the pulp slurry to the floatator and the inlet of the floatator device More preferably, it is added.

  Although the terpene compound of this invention is used together with a deinking agent, it adjusts the bubble in a floater and is not added to the same process as a deinking agent. In general, when a terpene compound is added to the disaggregation process and the dispersion process in which the deinking agent is added, the pulp concentration of the pulp slurry is higher than 2.0% by weight in the disaggregation process, so the mixing of the terpene compound is poor, and the floatator The foaming performance inside is not demonstrated. Moreover, since whitening will be inhibited when added to the dispersion step, the whiteness of the DIP is lowered.

  In the flotation process, when it is added to the floater, it is sufficient that the contact time with the pulp slurry is sufficiently secured. However, since the contact time with the pulp slurry is generally insufficient, Bubbles do not foam uniformly. When a terpene compound is added to the upper part of the tank in the above process, the foam on the surface disappears, and the selectivity of the ink particles and the pulp fibers is lost. Therefore, no improvement in whiteness is observed in the obtained DIP.

  However, if it is difficult to control the foaming property in the floatator due to differences in raw paper materials or differences in water temperature due to seasonal factors, the terpene compound is added to a place where it is well mixed with the pulp slurry before the floatator. Although it is preferable to add, adjustments such as adding the terpene compound directly from the upper part of the floatator tank may be performed while observing the state of foam.

Further, in the present invention, the conditioner tank is a device provided for managing the pH that varies depending on the type of used paper raw material, the water temperature that varies as a seasonal factor such as summer and winter, and foaming properties, and dilution. This is an apparatus for adjusting the pulp concentration, pH, and temperature with water and temperature control equipment, and sufficiently mixing the terpene compound of the present invention added to the apparatus and the raw material pulp slurry with an in-apparatus agitator. By providing the conditioner tank before the flotation step, it is possible to improve the ink particle trapping property and the bubble floating property in the flotator.
In addition, it is more preferable to install a scraping device at the upper part of the conditioner tank. The ink aggregates generated by the addition of the deinking agent and the terpene compound are discharged out of the system, and the load of the device in the next flowator is reduced. Can be reduced.

Next, the terpene compound used in the present invention will be described. The terpene compound is a generic name of compounds based on the isoprene rule of (C ₅ H ₈ ) _n , a compound having 10 carbon atoms with n = 2 is a monoterpene, a sesquiterpene having 15 carbon atoms with n = 3, and 20 carbon atoms. Diterpenes and polyterpenes having 30 or more carbon atoms. Terpene compounds include terpene hydrocarbons such as α-pinene, β-pinene and dipentene, terpene alcohols such as terpineol and linalool, and terpenes containing polar groups such as cineol and terpinyl acetate. Any product can be used.

  Examples of the terpene alcohols contained in the terpene compound of the present invention include monoterpenes having a hydroxyl group, such as terpineol, linalool, geraniol, myrcenol, dihydromyrsenol, menthol, terpinene 4ol, and the like, and natural products. Any of synthetic products can be used, and one or a combination selected from these groups can be used. It is preferable to use at least one of terpineol, linalool and dihydromyrsenol, which are relatively inexpensive and readily available.

  Terpene hydrocarbons include monoterpenes α-pinene, β-pinene, dipentene, limonene, ferrandlene, α-terpinene, γ-terpinene, terpinolene, myrcene, alloocimene, camphene, bornylene, paramenten-1, paramentene- 2, paramenten-3, paramentadienes, paramentane, 2-carene, 3-carene, tsujang and the like. Examples of sesquiterpenes include longifolene, caryophyllene, kazinene, tyuopsen, cedrene, cloben and longipinene. The terpene hydrocarbons include the above monoterpenes and sesquiterpenes, but are not limited to these, and any of natural products and synthetic products can be used, and one or a combination selected from these groups can be used. Can be used.

  Here, a method for synthesizing terpineol, linalool, dihydromyrcenol, and by-products and impurities will be described.

  Terpineol, which is a terpene alcohol of the present invention, is synthesized through a dehydration reaction using phosphoric acid, sulfuric acid, oxalic acid, etc., by adding an acid catalyst using α-pinene and water as raw materials to perform a hydrolysis reaction to form a hydrated terpene. The main component is α-terpineol, the by-products are β-terpineol, γ-terpineol, and borneol, isoborneol, fencor, terpinene 4 ol, 1,8-cineole, etc., terpene hydrocarbons such as dipentene, Δ3 Karen, camphene, terpinolene, α-terpinene, γ-terpinene, α-ferrandolene and the like are included.

  Linanol, which is a terpene alcohol of the present invention, can be synthesized by an acetone / acetylene method, an isobutene / acetone / formalin method, an isoprene method, a pinene method, and the like. For example, in the pinene method using β-pinene as a starting material, -It is obtained by thermally decomposing pinene to myrcene, adding hydrochloric acid, copper chloride, etc., and then hydrolyzing with sodium acetate, copper sulfate, and sodium hydroxide via linalyl chloride. Geraniol, nerol and the like can be produced as by-products. Moreover, the synthesis method using α-pinene as a starting material is obtained by thermal decomposition after first converting it to pinan by hydrogenation, converting it to 2-pinanol with sodium hydroxide and the like. Geraniol and nerol are also included as isomers. In addition, linanol synthesized by the pinene method includes α-pinene, β-pinene, pinane, myrcene, ocimene, dipentene, terpinolene, terpinene, and the like.

  Dihydromyrsenol, which is a terpene alcohol of the present invention, is pyrolyzed from α-pinene by hydrogenation and then synthesized via dihydromyrcene. Examples of impurities include α-pinene, pinane, and dihydromyrcene.

  The terpene alcohols of the present invention can be purified with high purity after being synthesized by the above reaction, and can be isolated after the synthesis, and commercially available products may be used. The terpene compound of the present invention preferably contains a terpene alcohol. The terpene alcohol synthesized by the above reaction is a mixture containing a terpene hydrocarbon as a by-product of the synthesis or impurities. The terpene alcohols may be mixed with terpene alcohols once purified to a high purity.

  The terpene compound of the present invention is more preferably pine oil, and the pine oil of the present invention may be an essential oil mainly composed of cyclic terpene alcohols such as terpineol, and contains terpene alcohols and terpene hydrocarbons. It is preferable to do.

Examples of the pine oil of the present invention include synthetic pine oil and natural pine oil.
Synthetic pine oil, for example, is obtained by subjecting terpene alcohols and terpene hydrocarbons to distillation by a distillation process after α-pinene obtained from wood turpentine, gum turpentine, and sulfate turpentine and water as raw materials and hydrated with an acid catalyst. It is obtained by separating the minutes. The terpene alcohols contained in the synthetic pine oil are mainly α-terpineol, and include β-terpineol, γ-terpineol, borneol, isoborneol, fencor, terpinene 4ol, 1,8-cineole and the like. Further, examples of the terpene hydrocarbons include dipentene, Δ3 carene, camphene, terpinolene, α-terpinene, γ-terpinene, α-ferrandylene, and the like, but the contained composition differs depending on the catalyst used for the hydration reaction. The purity of the terpene alcohols contained in the synthetic pine oil can be appropriately changed depending on the distillation purification conditions. Synthetic pine oil may be used because it is easy to obtain and adjust its composition. The synthetic pine oil is marketed by Yashara Chemical Co., Ltd. under the trade name “Pine Oil C # 30” (Turpineol purity 60%). Has been.
Natural pine oil is obtained, for example, by extracting from pine root with a solvent and water vapor.

  The terpene compound of the present invention preferably contains terpene alcohols, and a high whiteness DIP can be obtained. Terpene alcohols are appropriately selected and changed according to the type of waste paper used as the raw material, the concentration of pulp slurry, the required quality of DIP, etc., and in consideration of foaming adjustment and ink removal performance in the flotation process do it. Furthermore, it is preferable to contain terpene alcohol 5 to 95 weight%, and it is more preferable to contain 30 to 70 weight%. When the content of the terpene alcohol is increased, the foam particle size is small, and it takes time to foam, and it takes time to break the foam. On the other hand, when the content of the terpene alcohol is low, the foam particle size is large and the foaming property is high. However, since the foam breaking time is shortened, a stable foam cannot be formed.

  Since the terpene compound of the present invention changes the affinity for water and the surface tension used in the production of DIP depending on the content of terpene alcohols, for example, a solubility parameter (SP value) as an index of polarity proposed by Fedors et al. ), (Fedors. RF., Jet Propul. Lab. Quart. Tech. Rev, 3, 45, (1973).).

  Regarding the SP value of terpene alcohols, most of terpene alcohols are in the range of about 9.0 to 11.0, for example, terpineol is 10.4 and linanol is 9.6. Many SP values for terpene hydrocarbons are in the range of about 7.5 to 8.7, for example dipentene is 8.3. In the step of producing the DIP of the present invention, the terpene compound of the present invention has the effect that a highly hydrophilic terpene alcohol has a foaming performance, and conversely terpene hydrocarbons has a foam breaking performance. The content of terpene alcohols can be appropriately selected and used according to the type of used paper, the concentration of pulp slurry, the workability in the production process, the quality required for DIP, and the like.

  In the DIP production process, the terpene compound of the present invention is preferably added in an amount of 0.01 to 5.0% by weight, more preferably 0.02 to 0.1% by weight, based on the absolutely dry pulp. If the added amount is less than 0.01% by weight relative to the absolutely dry pulp, the effect of the present invention cannot be obtained, whereas if the added amount is more than 5.0% by weight, it is not economical.

  In addition to the terpene compound, other known auxiliary materials, deinking agents, foaming agents, antifoaming agents, pH adjusting agents, preservatives, flocculants and the like are used in the production of the DIP of the present invention. There is no limitation on the use of these in combination.

  Furthermore, the terpene compound used in the production of the DIP of the present invention can be used as a deinking aid.

  In the DIP manufacturing method according to the present invention, by using the deinking aid and the deinking agent of the present invention in combination, in the DIP manufacturing process, not only the ink peeling, collecting and floating effects, but also within the flotation process. There is a synergistic effect of appropriately miniaturizing the bubbles and increasing the surface area of the bubbles.

The type, amount, and location of the deinking agent used in the present invention can be appropriately selected and used in consideration of the balance of the ink peeling performance and collection performance of the deinking agent. In view of the state of bubbles and foaming during the production process of the DIP of the invention, it is preferable to use in combination with the deinking aid containing the terpene compound of the present invention.
Here, examples of the deinking agent include fatty acid / fatty acid emulsions, fatty acid derivatives, oil and fat derivatives, higher alcohol derivatives, and the like. In general, many of the above derivatives have alkylene oxide added as a hydrophilic group, and the deinking agent used in the present invention is not particularly limited, but higher alcohol ethylene oxide, propylene oxide adduct, etc. may be used. That's fine. Specific examples of deinking agents include trade names “DI-767” and “DI-7020” manufactured by Kao Corporation, trade names “Neoscore FW-780” and “FW-795” manufactured by Toho Chemical Industries, Ltd. A trade name “Lipobright DP-810” manufactured by Kagaku Co., Ltd. may be mentioned.
The deinking agent is generally added in the disaggregation step and the dispersion step, and the deinking agent used in the disaggregation step is 0.3% by weight or less, preferably 0.1 to 0.2% by weight based on the absolutely dry pulp. What is necessary is just to add, and the deinking agent used at a dispersion | distribution process should just add 0.2 weight% or less with respect to an absolutely dry pulp, Preferably it may add 0.05 to 0.1 weight%.

  In addition to the above deinking agents, alkaline agents such as sodium hydroxide and sodium silicate, bleaching agents such as hydrogen peroxide and hypochlorite, foaming agents such as higher alcohol sulfates and alkylbenzene sulfonates, silicone oil Antifoaming agents such as oleic acid and mineral oil, antifoaming agents, pitch control agents, pH adjusting agents, preservatives, flocculants and the like may be used, and combinations of these are not limited.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the examples and comparative examples, “%” indicates wt%.
Further, the purity of the terpene compound was measured by gas chromatography (hereinafter abbreviated as “GC”) HP6890GCSYSTEM manufactured by HEWLETT PACKARD, column: HP-5 Crosslinked 5% PH ME Siloxane 30m, i. d. = 0.25 mm.

Preparation Example 1
[Pine oil terpineol purity adjustment]
250 g of α-pinene, 500 g of 38% sulfuric acid, and 0.5 g of a surfactant were charged into a 1 L four-necked flask equipped with a stir bar, a condenser, and a thermometer, and stirred at 20 ° C. for 11 hours. After allowing to stand and liquid separation, the oil phase was washed with water. An appropriate amount of an aqueous sodium carbonate solution was added to neutralize the reaction system, and concentrated sulfuric acid was further added until the pH of the reaction system reached 1, followed by stirring for 6.5 hours. The reaction solution was washed 3 times with 100 g of water to obtain 246 g of reaction oil. When the obtained water washing was analyzed by GC, the terpene alcohols terpineol and terpene hydrocarbons had a content (hereinafter referred to as “content”) of 45.6% and 52.5% on the basis of the GC peak area, respectively. Met.
This was distilled to separate terpineol and terpene hydrocarbons. The purity of the separated terpineol and terpene hydrocarbons was 99.5% and 99.7%, respectively. Using the separated terpineol and terpene hydrocarbons, they were prepared in the ratios shown in Table 1 and used as the terpene compound of Example 1.

Example 1
The deinking process was performed by the following procedures using newspaper-based waste paper.
1. Disaggregation process 2. Dust removal process First stage flotation process 4. 4. Concentration step Ink stripping process 6. 6. Bleaching / ripening process Second stage flotation process 8. Paper making

[Disaggregation process]
Waste paper raw material (newspaper / flyer weight ratio = 6/4) 75g dry weight 750cc water (pulp concentration 10%), 0.5% dry hydroxide sodium hydroxide, higher alcohol deinking agent (trade name) 0.2% of “DI-7255” (manufactured by Kao Corporation) was charged into a 2 L disaggregator and disaggregated for 15 minutes at 40 ± 2 ° C.

[Dust removal process]
After the pulp concentration was diluted to 1% with hot water at 40 ° C., dust removal was performed through a flat screen (screen plate 6 cuts) manufactured by Tozai Seiki.

[First stage flotation process]
4,000 g of pulp slurry having a pulp concentration of 1% was deinked for 10 minutes with an air supply of 15 NL / min and low-speed turbine rotation using an MT flowator manufactured by Ishikawajima Industrial Machinery.

[Concentration process]
Using a centrifuge, the pulp concentration was adjusted to about 20% by dewatering at 1,000 rpm for 3 minutes.

[Ink peeling process]
Sodium hydroxide 1.5%, No. 3 sodium silicate 1.5%, Hydrogen peroxide 1.5%, High alcohol alcohol deinking agent DI-7255 0.1% Then, the roll-housing was set to 0.5 mm by a PFI mill, and 500 rotations were performed with the total number of times.

[Bleaching and aging process]
Bleaching and aging were carried out in a thermostatic bath at 60 ° C. for 2.5 hours.

[Second stage flotation process]
0.1% of the terpene compound was added to 4,000 g of pulp slurry diluted to 1% with 40 ° C. hot water. Using an MT floatator manufactured by Ishikawajima Industrial Machinery, deinking treatment was performed for 10 minutes with an air supply of 15 NL / min and a low-speed rotation of the turbine.

[Paper making]
Sulfuric acid band was added to 10% dry pulp and hand-made with a TAPPI standard machine at a basis weight of 100 g / m ² (band method).

[Evaluation]
Foaming and foam breaking properties:
300ml of 150g pulp slurry before deinking used in the second stage flotation process
Take it in a tall beaker, send 500 ML / min of air using a diffuser stone, the time until the foam height reaches 11 cm (foaming), and the time until the liquid level is visible after the air supply is stopped (breaking) Foamability) was measured.
Pulp recovery rate:
The floss generated in the second stage flotation process was collected and suction filtered using a pre-weighted filter paper, and the pulp recovery rate was calculated from the absolute dry weight of the floss. In addition, in the process which manufactures DIP, floss mainly means the ink, pulp fiber, filler, etc. which are isolate | separated from a pulp fiber with a foam with the floatator which removes the ink adhering to waste paper.
Pulp recovery rate (%) = (1-A / B) × 100
A: Absolute dry weight of floss (g)
B: 30 (g), the weight of the absolutely dry pulp used in the second stage flotation step Whiteness (%):
Using the obtained paper sheet, the whiteness was measured using a spectroscopic whiteness meter (manufactured by Nippon Denshoku Industries Co., Ltd.).
Residual ink amount:
Using the obtained paper sheet, the remaining ink amount was measured using Color Touch Eric 950 (Technidyne).
The evaluation results of Example 1 are shown in Table 1.

  In the deinking test of DIP using newspaper newspapers, terpene compounds containing terpeneol, a terpene alcohol, were added, and as a result of observing effervescence and foam breakage, etc. Therefore, it took a long time to foam, and when the ratio of terpene hydrocarbons was high, the foam tended to be broken.

  Hereinafter, using old newspaper paper, confirmation was made of foaming properties and foam breaking properties depending on the type and amount of the terpene compound.

Example 2
The terpene compound was changed to “Pine Oil C # 30” (terpineol purity 60%) manufactured by Yasuhara Chemical Co., Ltd., and 0.1% was added to the second stage flotation step, and the same procedure as in Example 1 was performed.

Example 3
The terpene compound was changed to a terpene compound containing 65% linalool and 35% terpene hydrocarbon, and 0.1% was added to the second stage flotation step, and the same procedure as in Example 1 was performed.

Example 4
The terpene compound was changed to a terpene compound containing 60% dihydromyrsenol and 40% terpene hydrocarbon, and 0.1% was added to the second stage flotation step, and the same procedure as in Example 1 was performed.

Example 5
The terpene compound was changed to a terpene compound containing 50% of milsenol and 50% of terpene hydrocarbon, and 0.1% was added to the second stage flotation step, and the same procedure as in Example 1 was performed.

Example 6
The terpene compound was changed to a terpene compound containing 55% geraniol and 45% terpene hydrocarbon, and 0.1% was added to the second stage flotation step, and the same procedure as in Example 1 was performed.

Example 7
The terpene compound was changed to a terpene compound containing 45% menthol and 55% terpene hydrocarbon, and 0.1% was added to the second stage flotation step, and the same procedure as in Example 1 was performed.

Example 8
The terpene compound was changed to a terpene compound containing 62% terpinene 4ol and 38% terpene hydrocarbon, and 0.1% was added to the second stage flotation step, and the same procedure as in Example 1 was performed.

Example 9
The terpene compound was changed to “Pine Oil C # 30”, and 0.01% was added to the second stage flotation step, and the same procedure as in Example 1 was performed.

Example 10
The terpene compound was changed to “Pine Oil C # 30” and 1.5% was added to the second stage flotation step, and the same procedure as in Example 1 was performed.

Example 11
The terpene compound was changed to “Pine Oil C # 30” and 5.0% was added to the second stage flotation step, and the same procedure as in Example 1 was performed.

Comparative Example 1
The same procedure as in Example 1 was performed without adding the terpene compound to the second stage flotation step.

Comparative Example 2
The terpene compound was changed to “Pine Oil C # 30”, and 0.005% was added to the second stage flotation step, and the same procedure as in Example 1 was performed.

Comparative Example 3
The terpene compound was changed to “Pine Oil C # 30”, and 15% was added to the second stage flotation step.

The evaluation results of Examples 2 to 11 and Comparative Examples 1 to 3 are shown in Table 2.

  As a result of adding a terpene compound in a DIP deinking test using newspaper-based waste paper, the whiteness and residual ink amount showed good results.

Next, the whiteness and residual ink amount were evaluated according to the location where the terpene compound was added.
When changing the place of addition, the operating times of the first and second stage floatators were adjusted so that the pulp recovery rate was about 91%.

Example 12
In Example 1, the terpene compound was changed to “Pine Oil C # 30”, and the addition location was changed before the first stage flotator, and 0.1% was added. The operation time of the first-stage floatator was 6 minutes, the operation time of the second-stage floatator was 10 minutes, and the pulp recovery rate was 91.4%.

Example 13
In Example 1, the terpene compound was “Pine Oil C # 30”, and the addition location was changed to a dust removal process using a flat screen, and 0.1% was added. The operation time of the first-stage floatator was 7 minutes, the operation time of the second-stage floatator was 10 minutes, and the pulp recovery rate was 91.6%.

Example 14
In Example 1, the terpene compound was “Pine Oil C # 30”, and the place of addition was changed to two locations before the first-stage floatator and before the second-stage floatator. %)added. The operation time of the first-stage floatator was 9.5 minutes, the operation time of the second-stage floatator was 9.5 minutes, and the pulp recovery rate was 91.0%.

Example 15
In Example 1, the terpene compound was “Pine Oil C # 30”, and the addition location was changed to dripping into bubbles generated at the top of the apparatus during the operation of the second stage floatator, and 0.1% was added. The operation time of the first-stage floatator was 10 minutes, the operation time of the second-stage floatator was 10 minutes, and the pulp recovery rate was 91.4%.

Example 16
In Example 1, the addition method was changed supposing a conditioner tank. After the bleaching / ripening step, the pulp slurry was diluted with hot water at 40 ° C. to a concentration of 1%, and then the terpene compound was added as pine oil C # 30 to 0.1% of the absolutely dry pulp. This was stirred with a three-one motor at 300 rpm for 5 minutes to uniformly disperse, and then charged into the second stage flowator. The operation time of the first-stage floatator was 10 minutes, the operation time of the second-stage floatator was 10 minutes, and the pulp recovery rate was 92.0%.

Comparative Example 4
In Example 1, the terpene compound was “Pine Oil C # 30”, and the addition location was changed to a disaggregation step with a pulp concentration of 10%, and 0.1% was added. The operation time of the first-stage floatator was 8 minutes, the operation time of the second-stage floatator was 10 minutes, and the pulp recovery rate was 91.5%.

Comparative Example 5
In Example 1, the terpene compound was changed to “Pine Oil C # 30”, and the place of addition was changed to an ink peeling process with a pulp concentration of 20%, and 0.1% was added. The operation time of the first-stage floatator was 10 minutes, the operation time of the second-stage floatator was 17 minutes, and the pulp recovery rate was 92.1%.

Comparative Example 6
In Example 1, it evaluated without adding a terpene compound. The operation time of the first-stage floatator was 10 minutes, the operation time of the second-stage floatator was 19 minutes, and the pulp recovery rate was 91.2%.

The evaluation results of Examples 12 to 16 and Comparative Examples 4 to 6 are shown in Table 3. In addition, the state of the foam in the second stage floatator was visually confirmed.

  In the deinking test of DIP using newspaper waste paper, the pulp recovery rate, whiteness, and residual ink amount are good when added to a dust removal process with a low pulp concentration of 1%, the first stage flowator and the second stage flowator Results are shown. When a terpene compound is added at a place where the pulp concentration is high, such as a disaggregation process with a pulp concentration of 10% and an ink peeling process with 20%, mixing with the terpene compound is poor, and foamability in the floater cannot be obtained. High whiteness was not obtained.

Example 17
Using high-quality waste paper, deinking treatment was performed in the following one-stage flotation process.
1. Disaggregation process 2. Dust removal process Concentration step 4. 4. Ink peeling process Bleaching / ripening process Flotation process 7. Washing / concentration process Paper making

[Disaggregation process]
750 cc water (pulp concentration 10%), anti-dry pulp 0.5% sodium hydroxide, higher alcohol deinking agent (trade name “DI-7255”, manufactured by Kao Corporation) 0 2% was charged into a 2 L disaggregator and disaggregated for 15 minutes at 40 ± 2 ° C.

[Dust removal process]
After the pulp concentration was diluted to 1% with hot water at 40 ° C., dust removal was performed through a flat screen (screen plate 6 cuts) manufactured by Tozai Seiki.

[Concentration process]
Using a centrifuge, the pulp concentration was adjusted to about 20% by dewatering at 1,000 rpm for 3 minutes.

[Ink peeling process]
Add 1.5% sodium hydroxide, 1.5% sodium silicate, 1.5% hydrogen peroxide, 0.1% of "DI-7255" made by Kao Co. to PB mill Then, the distance between the roll and the housing was set to 0.5 mm, and 5,000 rotation processing was performed with the total number of times.

[Bleaching and aging process]
Bleaching and aging were carried out in a thermostatic bath at 60 ° C. for 2.5 hours.

[Flotation process]
After diluting the pulp concentration to 1% with hot water at 40 ° C, 0.1% of "Pine Oil C # 30" (terpineol purity 60%) manufactured by Yashara Chemical Co., Ltd. is added to the absolutely dry pulp as a terpene compound. Using a manufactured MT flowator, deinking treatment was performed for 5 minutes with an air supply of 15 NL / min and a low-speed rotation of the turbine.

[Washing / concentration process]
A 100-fold amount of water was added to the absolutely dried pulp, diluted and washed, and then centrifuged at 1,000 rpm for 3 minutes to remove fine ink and ash.

[Paper making]
A 10% sulfuric acid band was added to the dried pulp, and paper was made with a TAPPI standard machine at a basis weight of 100 g / m ² (band method).
[Evaluation]
Pulp recovery rate:
The floss generated in the flotation process was collected and suction filtered using a filter paper whose weight was measured in advance, and the pulp recovery rate was calculated from the absolute dry weight of the floss.
Pulp recovery rate (%) = (1-A / B) × 100
A: Absolute dry weight of floss (g)
B: 30 (g), weight of the absolutely dry pulp used in the flotation process Whiteness (%):
Using the obtained paper sheet, the whiteness was measured using a spectroscopic whiteness meter (manufactured by Nippon Denshoku Industries Co., Ltd.).
Residual ink amount:
Using the obtained paper sheet, the remaining ink amount was measured using Color Touch Eric 950 (Technidyne).
Foam condition:
The state of the foam on the floatator was visually evaluated.

  When the raw paper was changed, the operation time of the floatator was changed so that the pulp recovery rate was about 85%.

Example 18
In Example 17, the terpene compound was a terpene compound containing 54% of terpene alcohols terpineol and 46% of terpene hydrocarbons, and 0.08% was added before the floater. The operating time of the flotator was 6 minutes, and the pulp recovery rate was 85.5%.

Comparative Example 7
In Example 17, it evaluated without adding a terpene compound. The operating time of the flotator was 16 minutes, and the pulp recovery rate was 84.8%.

The evaluation results of Examples 17 and 18 and Comparative Example 7 are shown in Table 4.

  In the deinking test of DIP using high-quality waste paper, the terpene alcohols of the terpene compound of the present invention were higher in foamability in the flotator than the newspaper waste paper due to the influence of filler, latex, etc. contained in the raw waste paper By optimizing the content, foaming in the flotation was suppressed, and the whiteness and residual ink amount were good.

Example 19
The implementation of the present invention was performed using a deinked pulp manufacturing facility of Notsumachi, Chuoka Pulp Co., Ltd. Takaoka Factory.
1. Disaggregation process 2. Dust removal process First stage flotation process 4. 4. Washing and concentration process 5. Bleaching / dispersing / aging process 6. Second stage flotation process Bleaching and washing process 8. Complete

  Wastepaper, flyers, and wastepaper mainly containing office wastepaper are fed into a pulper, the raw material concentration is 15%, higher alcohol deinking agent ("DI-7255" manufactured by Kao) 0.2% (for pulp), sodium hydroxide 0 Disintegration was performed at a disaggregation temperature of 40 ° C. at a disaggregation time of 15 minutes and a pulp slurry was obtained. The pulp slurry was dedusted with a screen, adjusted to a raw material concentration of 1%, and then treated with a first-stage flowator. After the first stage flotation step, pulp was produced in the order of washing / concentration, bleaching, ink dispersion, and second stage floatator treatment. The bleaching conditions were: hydrogen peroxide 1.5% (vs. pulp), sodium silicate 1.5% (vs. pulp), sodium hydroxide 1.5% (vs. pulp), raw material concentration 30%, bleaching time 3 hours, bleaching The temperature was 60 ° C. The second stage floatator conditions are: special fatty acid derivative deinking agent ("DI-1120" manufactured by Kao Corporation) 0.07% (vs. pulp), floater treatment concentration 1%, treatment temperature 40 ° C ± 2, floatator feed Pine oil ("Pine oil C # 30" manufactured by Yashara Chemical Co., Ltd., terpineol purity 60%) 0.1% (vs. pulp) was added from the suction part of the pump, and flotation treatment was performed to obtain deinked pulp. The obtained deinked pulp was added with 10% sulfuric acid band (absolute dry pulp) by the band method, and paper was made with a TAPPI standard machine. In addition, 200 times the amount of tap water was added on a 150-mesh net by a complete washing method, and the ink and ash were washed and removed, and then paper was made to evaluate the whiteness and the residual ink amount.

[Evaluation]
Whiteness (%):
Using the obtained paper sheet, the whiteness was measured using a spectroscopic whiteness meter (manufactured by Nippon Denshoku Industries Co., Ltd.).
Residual ink amount:
Using the obtained paper sheet, the remaining ink amount was measured using Color Touch Eric 950 (Technidyne).
Number of microorganisms:
In order to confirm the antiseptic properties, the number of bacteria / yeast and the number of molds were measured using a deinked pulp slurry. The number of bacteria and yeast was cultured in an incubator at a temperature of 35 ° C. for 3 days, and the number of molds was cultured in an incubator at a temperature of 28 ° C. for 7 days.

Example 20
In Example 19, 0.1% of pine oil was added from the suction portion of the second-stage floatator feed pump, and the amount was changed to 0.07% to obtain deinked pulp.

Comparative Example 8
In Example 19, it evaluated without adding pine oil, and the deinked pulp was obtained.

Example 21
In Example 19, 0.1% of pine oil was added from the suction part of the second stage floatator feed pump, changed to 0.03%, and further, the whiteness equal to that of Comparative Example 8 was obtained. The pulp recovery rate was controlled to obtain deinked pulp.

The evaluation results of Examples 19 to 21 and Comparative Example 8 are shown in Table 5.

  When the pulp recovery rate was the same, when the terpene compound was added, the improvement in whiteness was recognized in all cases. Moreover, when the whiteness was the same, the improvement of the pulp recovery rate was recognized by adding a terpene compound. Furthermore, by adding a terpene compound, the effect of suppressing the generation of microorganisms was confirmed.

The present invention relates to a method for producing DIP and a deinking aid, and a terpene compound performs foaming adjustment in a flotation process. In addition, the present invention can also be applied to cleaning stains such as ink and organic solvent compounds. In addition, since the terpene compound has an antibacterial action, it also has an effect of suppressing the generation of bacteria in the DIP production process system, and the preservative can be reduced. Furthermore, it can be used in the papermaking related technical fields such as recycled pulp manufacturing and recycled paper manufacturing.

Claims (8)

  At least the pulp concentration in the dust removal step and / or the flotation step is in the range of 0.5 to 2.0% by weight in the method for producing deinked pulp by the flotation method including the disaggregation step, the dust removal step, and the flotation step. A method for producing deinked pulp, comprising adding a terpene compound to a pulp slurry.   The method for producing a deinked pulp according to claim 1, wherein the addition amount of the terpene compound is 0.01 to 5.0% by weight with respect to the absolutely dry pulp.   The method for producing deinked pulp according to claim 1 or 2, wherein the place where the terpene compound is added is a place where the terpene compound is well mixed with the pulp slurry before the flotator.   The manufacturing method of the deinking pulp of any one of Claims 1-3 which adds a terpene compound to the conditioner tank provided before the flotation process.   The manufacturing method of the deinked pulp of any one of Claims 1-4 in which a terpene compound contains terpene alcohols.   The terpene alcohol is at least one selected from the group consisting of terpineol, linalool, geraniol, myrcenol, dihydromyrcenol, menthol, and terpinene 4ol. 6. The deinked pulp according to any one of claims 1 to 5. Production method.   The method for producing a deinked pulp according to any one of claims 1 to 6, wherein the terpene compound is pine oil. A deinking aid comprising a terpene compound as a main component in a method for producing deinked pulp by a flotation method.