WO2005054571A1 - Deinking system for carbonate pulping - Google Patents
Deinking system for carbonate pulping Download PDFInfo
- Publication number
- WO2005054571A1 WO2005054571A1 PCT/US2004/040154 US2004040154W WO2005054571A1 WO 2005054571 A1 WO2005054571 A1 WO 2005054571A1 US 2004040154 W US2004040154 W US 2004040154W WO 2005054571 A1 WO2005054571 A1 WO 2005054571A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fatty acid
- ink
- carbonate
- pulping
- surfactant
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/02—Working-up waste paper
- D21C5/025—De-inking
- D21C5/027—Chemicals therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Definitions
- a typical sodium hydroxide/hydrogen peroxide pulping regime operates at high pulper pH, e.g. about 8.5-1 1.0, and requires two separate bleaching stages to achieve the desired effect.
- Stage 1 bleaching takes place in the pulper and helps to offset alkali yellowing of the fiber before a floatation procedure removes ink from the system.
- Stage 2 bleaching is performed after the flotation procedure, but before the deinked pulp moves forward to a paper machine.
- the bleaching agents in stages 1 and 2 can be the same or different.
- the present invention is directed to deinking of sodium carbonate pulping systems which operate at near-neutral pulper pH, i.e. about 7.2 to 8.5, preferably about 7.5 to 8.0, and require only a single bleaching procedure (after flotation) to achieve the desired brightness effect.
- No sodium hydroxide, hydrogen peroxide or chelant are used during pulping.
- Deinking with carbonate pulping systems is disclosed in U.S. Pat. No. 5,882,476, the subject matter of which is incorporated herein by reference, of Solvay Minerals, Inc.
- the patent discloses the addition of a surfactant to the system.
- the only specific surfactant disclosed is DI-600 from Kao Japan.
- DI-600 is a difficult to classify mixture prepared by a manufacturing process in which tallow is broken down forming glycerin, half esters, and acids, etc. all of which are subsequently alkoxylated.
- the resulting surfactant composition has a cloud point of 45-48°C.
- U.S. Pat. No. 5,288,369 discloses the advantages of fatty acid enrichment during ink removal in a standard sodium hydroxide/peroxide pulping system. It does not disclose carbonate pulping systems as are used in the present invention.
- the prior art contains no recognition that in a carbonate pulping system of the present invention, unlike the sodium hydroxide/peroxide prior art systems, (i) there is an advantage to using high cloud point surfactants of improved detergency as the deinking agent and (ii) there is a need for rapid ink capture requiring the presence of a mixture of at least two fatty acid ink collectors. Moreover, it has unexpectedly been found that the enhanced ink collection system of the present invention reduces bleach demand and sheet dulling.
- the present invention is directed to a process of deinking paper being recycled by a carbonate pulping procedure that is performed in the absence of hydroxides and peroxides.
- the process entails pulping the paper in the presence of sodium carbonate (generally in combination with a minor amount of sodium silicate) in combination with a non-ionic, alkoxylated alcohol surfactant deinking agent having a cloud point of about 55 to about 85°C, preferably about 60 to about 70°C, and further in combination with two different ink collectors: the first being a C 16 to C20 fatty acid or a mixture of such acids, and the second being a C22 to C30 fatty acid or a mixture of such acids, the two ink collectors being used in a weight ratio of from about 98:2 to 70:30, preferably about 90: 10.
- the fatty acid ink collectors are normally fully hydrogenated (saturated), though for overall economic purposes up to about 25% by weight of the saturated fatty acid ink collectors may be substituted by one or more unsaturated fatty acids, particularly a mixture thereof such as tall oil fatty acids (TOFA).
- unsaturated fatty acids particularly a mixture thereof such as tall oil fatty acids (TOFA).
- Figure 1 is a graph of the Delta Brightness of ink collection systems evaluated in Example 2, including systems of the prior art (NaStearate, NaTallate), of the present invention (KStearate/KBehenate 9/1), and a comparison to the present invention (KStearate/KBehenate 4/1) versus time.
- Figure 2 is a graph of ERIC Number Reduction of the results of Example 2.
- the deinking of paper being recycled is performed by a carbonate pulping procedure in the substantial absence of hydroxides and peroxides.
- the process entails pulping of paper in the presence of sodium carbonate, sodium silicate, and optionally sodium sulfite, in combination with (a) a non-ionic, alkoxylated alcohol surfactant deinking agent having a cloud point of about 55 to about 85°C, preferably about 60 to about 70°C, most preferably about 65 to 68°C, and further in combination with (b) two different ink collectors -- one being a C16 to C20 fatty acid or a mixture thereof, and the other being a C22 to C30 fatty acid or a mixture thereof, the two ink collectors being used in a weight ratio of from about 98 :2 to 70:30.
- the fatty acid ink collectors are preferably saturated (fully hydrogenated).
- the saturated fatty acid ink collectors may be extended by up to about 25% by weight of one or more unsaturated fatty acids, e.g. a mixture such as tall oil fatty acids (TOFA).
- Suitable surfactants for use as deinking agents are non-ionic C 14 to C24 alcohol alkoxylates that have a cloud point of about 55 to 85°C, preferably about 60 to 70°C, most preferably about 65 to 68°C.
- the surfactant is generally used at a rate of about 1 to 10, preferably about 2 to 6, pounds per ton of paper. This corresponds to a rate of about 0.05 to 0.5, preferably about 0.1 to 0.3, % by weight of the paper being processed.
- the other critical component of the present invention is the ink collector system.
- Two different fatty acid ink collectors are used. The first is a C 16 to C20 fatty acid or a mixture of such fatty acids. The second is a C22 to C30 fatty acid or a mixture of such fatty acids.
- the ink collectors are used in a weight ratio of from about 98 :2 to 70:30.
- the fatty acid ink collectors are preferably fully hydrogenated (saturated). For economic purposes, up to 25% by weight of the combined saturated fatty acid ink collectors may be replaced by one or more unsaturated fatty acids.
- a mixture of unsaturated predominantly C 16 and C 18 fatty acids such as tall oil fatty acids (TOFA) is a suitable extender.
- TOFA tall oil fatty acids
- the fatty acid ink collectors are used in total amounts ranging from about 1 to 15 pounds per ton dry paper. Preferably about 2 to 10 pounds per ton are used. Most preferably about 4 to 6 pounds per ton are used.
- the chemicals normally present in a paper recycle system of the present invention using a carbonate pulping regime vs. those of a typical caustic pulping system (including the first bleaching stage) can be compared as follows:
- both systems require a post-pulping bleaching operation in which the following chemicals are used: POST-PULPING BLEACHING Hydrogen Peroxide yes no Sodium Hydrosulfite Optional yes Biocide Optional no Chelant yes Optional [0019] Normally all of the pulper and deinking chemicals are added into the pulper, though portions of the fatty acids and/or surfactant can be added by split addition, i.e. divided between the pulper and the feed to the flotation cell, as this may enhance ink capture.
- the sodium silicate and sodium carbonate are generally used at a ratio between about 95 to 5 and about 50 to 50 by weight with respect to each other.
- the sodium carbonate is used at a rate of about 2 to 20, preferably about 5 to 10, pounds per ton.
- the sodium silicate is used at a rate of about 10 to 30, preferably about 12.5 to 25, and most preferably about 15 to 20, pounds per ton.
- Sodium sulfite may also be added. When used it is added at a rate of about 2 to 8 pounds per ton.
- biocides are not needed in carbonate pulping systems, they may be added for simple microbial control if desired.
- chelants are necessary to help control transition metals in the stock that cause catalytic peroxide decomposition.
- Chelants are not required in the carbonate pulping systems of this invention, but can be used if so desired to increase the bleach response during post-pulping bleaching.
- Hyper-washing tests were run in order to assess the initial ink release during pulping, i.e., to assess if all available ink has been released from the fiber. This test is done usually after pulping, although it can be done at other times throughout the process whenever one wants to quantify the amount of free ink in the system.
- the hyper-washing test is conducted using a Britt filtration jar (approximately 1 liter capacity) whereby 10 g oven-dried pulped stock (furnish obtained after pulping) is washed with 5 liters of deionized (DI) water. The stock is placed in the Britt jar, diluted with wash water, and the agitation is turned on to about 1600 rpm.
- DI deionized
- the stock is stirred in this manner for one minute, and then the jar allowed to drain with the agitation still on. When the level approaches the agitator, the drain is closed and the cell refilled with DI wash water for another minute wash with agitation. The process is repeated until all 5 liters of DI wash water have been consumed. The stock is then filtered and made into a pad for ERIC and brightness measurements. The test has a repeatability of ⁇ +/- 10 to 15 ppm ERIC within a test series.
- Mill performance data clearly shows that the carbonate based deinking system gives satisfactory ink release during pulping and that the ink release is equivalent to that achieved using sodium hydroxide-based pulping regimes. This was true for Ponderay, Alabama River News Print, and Augusta News Print using Voith, Black Clawson and PDM deinking equipment respectively. The ink release was not influenced by equipment design.
- the fatty acid screening runs were conducted at low surfactant doses i.e., ⁇ 10.00% of the total combined FA/surfactant dose.
- the surfactant was used essentially as a hydrotrope to generate reliable data (at the same level of rejects) with no rejects/foam surging due to furnish changes.
- the results show a substantial advantage of hydrogenated/hard fatty acids (low iodine values ⁇ 10) as compared to TOFA (iodine value about 140) with respect to ink capture.
- the behenic acid blends with stearic acid show optimum performance at a 10/90 ratio of behenic acid/stearic acid respectively over all other combinations. Higher behenic ratios (40/60) show no improvement over the lower ratios and are substantially equivalent to stearic acid alone.
- the actual fatty acid deinking agent is the calcium salt of the fatty acids, made in-situ by the simple sodium or potassium/calcium exchange of the pre-neutralized fatty acid. Calcium water hardness is required to effectively complete this exchange. Most calcium salts are hydrophobic and have extremely low water solubility i.e. they readily accumulate at the air-water interface where ink collection takes place. The system was effective at a 50.0 ppm lower limit of calcium. Higher levels of calcium (>100 ppm) did not significantly improve the response.
- the fatty acids were pre- neutralized before use using sodium hydroxide, potassium hydroxide, or ammonium hydroxide in a conventional manner.
- the "fatty acid" used during these tests was the preferred 10/90 w/w mixture of behenic acid/stearic acid, sodium or potassium salt.
- the potassium salts are favored due to enhanced solubility in mill water.
- Each of the 4 different cloud point surfactants was an ethylene oxide/propylene oxide (EO/PO) alkoxylate on a C18 stearyl alcohol base, with varying ratios of EO to PO. Higher amounts of surfactant can be used in combination with the fatty acid up to a 1 : 1 ratio with no appreciable change in performance. In the interests of cost performance, surfactant use is minimized.
- EO/PO ethylene oxide/propylene oxide
- composition of the de-inked stock in a newsprint/maga-zine recycling operation is primarily mechanical pulp
- the harder-to-bleach chromophores still require the same application of hydrosulfite to drive the bleaching reaction for the harder-to-bleach species.
- What is unexpected is the response rate of the carbonate deinked stock.
- the easily bleached chromophores are still available for reaction, and a higher response is observed. This has not been the response of conventional alkaline- peroxide deinking systems as shown in Table 6.
- control deinking chemistry was: 0.82% hydrogen peroxide; 0.5% sodium hydroxide; 1.37% sodium silicate; 0.18% DTPA chelant; 0.18% alcohol
- the carbonate 1 deinking chemistry used 2.5% of a (Na CO 3 6-8 lb/ton solid, Na 2 SO 3 0-2 lb/ton solid, Na 2 SiO 3 (40°Be) 12.5 lb/ton as is); 0.6% fatty acid salt mixture (90%/10% K Stearate/K Behenate); and 0.06% of a C18 alcohol EO/PO alkoxylate surfactant of cloud point 66-68°C.
- Control deinking chemistry used was 1.0% hydrogen peroxide; 1.05% sodium hydroxide; 0.6% sodium silicate as is; 0.2% EDTA; 0.0575% alcohol EO/PO alkoxylate of cloud point 45-50°C surfactant; 0.0425% tall oil fatty acid blend (TOFA) extender fatty acid.
- the carbonate process of this invention also yielded a lower amount of fine ink particles with respect to the total release of ink particles. Ink particles that were ⁇ 0.04 square millimeter were arbitrarily considered to be adverse fine ink. [0048] Relating these effects to the standard brightness and ERIC measurements of the test pads after flotation made from the same/common flotation feed as described above, a number of conclusions were reached.
- the ink collector package of fatty acids and high cloud point surfactant is superior to the conventional collectors at removing fine inks ( ⁇ 0.04 square meters) as evidenced by the high brightness and improved bleach response of the stock after flotation. (See Table 8 "Spec Scan Analysis” and Table 9 - “Brightness Response Of Deinked Stock”)
- the deinked pulp of this invention has a greater/superior brightness gain than that exhibited by the conventional system.
- ERIC values of ⁇ 250ppm and preferably ⁇ 200ppm after flotation were previously believed required for a final pulp bleach response to be accept-able. i.e., to get a brightness gain of 2 or more points for the addition of 4 or more pounds/ton of sodium hydrosulfite before transferring the deinked pulp to the paper machine.
- ERIC # level of ERIC, a sufficient amount of fine ink is also removed to allow bleaching response of the deinked stock to approach that of virgin, unbleached mechanical pulp.
- the deinked stock of this invention exhibits this type of brightness response in the 250-300 ERIC range.
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20040812624 EP1689930A1 (en) | 2003-12-01 | 2004-12-01 | Deinking system for carbonate pulping |
AU2004295711A AU2004295711A1 (en) | 2003-12-01 | 2004-12-01 | Deinking system for carbonate pulping |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US52635903P | 2003-12-01 | 2003-12-01 | |
US60/526,359 | 2003-12-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005054571A1 true WO2005054571A1 (en) | 2005-06-16 |
Family
ID=34619658
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/040154 WO2005054571A1 (en) | 2003-12-01 | 2004-12-01 | Deinking system for carbonate pulping |
Country Status (5)
Country | Link |
---|---|
US (1) | US20050133172A1 (en) |
EP (1) | EP1689930A1 (en) |
AU (1) | AU2004295711A1 (en) |
CA (1) | CA2488670A1 (en) |
WO (1) | WO2005054571A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7862685B2 (en) * | 2006-01-09 | 2011-01-04 | Kemira Chemicals, Inc. | Method for deinking pulp using premixed hydrophobically modified calcium carbonate particles |
US7897010B2 (en) * | 2006-01-09 | 2011-03-01 | Kemira Chemicals, Inc. | Method for deinking pulp using premixed hydrophobically modified calcium carbonate particles |
US8815051B2 (en) | 2006-06-12 | 2014-08-26 | Thiele Kaolin Company | Deinking of waste paper |
US8052837B2 (en) * | 2006-06-12 | 2011-11-08 | Thiele Kaolin Company | Deinking of waste paper |
US8317973B2 (en) | 2009-11-11 | 2012-11-27 | Kemira Chemical, Inc. | Polyester surfactants for deinking |
US11447914B2 (en) | 2017-12-07 | 2022-09-20 | Thiele Kaolin Company | Removal of stickies in the recycling of paper and paperboard |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4231841A (en) * | 1977-10-20 | 1980-11-04 | Montedison S.P.A. | Process for the de-inking of printed waste paper |
US5288369A (en) * | 1990-12-28 | 1994-02-22 | Kao Corporation | Deinking method and deinking composition |
EP0741203A1 (en) * | 1995-05-05 | 1996-11-06 | SOLVAY MINERALS, Inc. | Method of deinking wastepaper |
US5672244A (en) * | 1994-05-10 | 1997-09-30 | Kao Corporation | High temperature deinking method using an alkylene oxide adduct |
US6241849B1 (en) * | 1998-09-17 | 2001-06-05 | Novo Nordisk Biochem North America, Inc. | Methods for deinking and decolorizing printed paper |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
LU76021A1 (en) * | 1976-10-15 | 1978-05-16 | ||
IT1155310B (en) * | 1982-04-19 | 1987-01-28 | Jean Marie Clement | PROCESS FOR THE RECYCLING PROCESS OF PAPER PRINTED FROM MACERO |
US5417808A (en) * | 1991-08-30 | 1995-05-23 | Lion Corporation | Deinking composition for flotation and deinking method |
JP2627043B2 (en) * | 1993-02-26 | 1997-07-02 | ライオン株式会社 | Deinking agent and deinking method by flotation using the deinking agent |
US5718801A (en) * | 1994-08-11 | 1998-02-17 | Ppg Industries, Inc. | Method for controlling froth and reducing stickies in the flotation process for deinking waste paper using a froth moderating agent |
US5837097A (en) * | 1995-12-20 | 1998-11-17 | Lion Corporation | Deinking agent for regenerating waste paper and method for deinking waste paper |
JP4233867B2 (en) * | 2000-08-07 | 2009-03-04 | 花王株式会社 | Flotation deinking method |
-
2004
- 2004-11-29 US US10/999,196 patent/US20050133172A1/en not_active Abandoned
- 2004-11-30 CA CA 2488670 patent/CA2488670A1/en not_active Abandoned
- 2004-12-01 AU AU2004295711A patent/AU2004295711A1/en not_active Abandoned
- 2004-12-01 EP EP20040812624 patent/EP1689930A1/en not_active Withdrawn
- 2004-12-01 WO PCT/US2004/040154 patent/WO2005054571A1/en not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4231841A (en) * | 1977-10-20 | 1980-11-04 | Montedison S.P.A. | Process for the de-inking of printed waste paper |
US5288369A (en) * | 1990-12-28 | 1994-02-22 | Kao Corporation | Deinking method and deinking composition |
US5672244A (en) * | 1994-05-10 | 1997-09-30 | Kao Corporation | High temperature deinking method using an alkylene oxide adduct |
EP0741203A1 (en) * | 1995-05-05 | 1996-11-06 | SOLVAY MINERALS, Inc. | Method of deinking wastepaper |
US6241849B1 (en) * | 1998-09-17 | 2001-06-05 | Novo Nordisk Biochem North America, Inc. | Methods for deinking and decolorizing printed paper |
Also Published As
Publication number | Publication date |
---|---|
US20050133172A1 (en) | 2005-06-23 |
CA2488670A1 (en) | 2005-06-01 |
EP1689930A1 (en) | 2006-08-16 |
AU2004295711A1 (en) | 2005-06-16 |
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