Bleaching of wood pulp

Bleaching of wood pulp is the chemical processing carried out on various types of wood pulp to decrease the color of the pulp, so that it becomes whiter. The main use of wood pulp is to make paper where whiteness (similar to but not exactly the same as "brightness") is an important characteristic. [cite web|url=http://www.paperonweb.com/paperpro.htm#Brightness|title=PaperOnWeb discussion of brightness and whiteness|accessdate=2007-09-17] The processes and chemistry described in this article are also applicable to the bleaching of non-wood pulps, such as those made from bamboo or kenaf.

Brightness is a measure of how much light is reflected by paper under specified conditionscite book |last=Biermann |first=Christopher J. |authorlink= |coauthors= |title=Essentials of Pulping and Papermaking |year=1993 |publisher=Academic Press, Inc. |location=San Diego |isbn=0-12-097360-X |oclc=27173529] and is usually reported as a percentage of how much light is reflected, so a higher number represents a brighter or whiter paper. In the US, the TAPPI T 452 [http://www.tappi.org/s_tappi/doc_bookstore.asp?CID=7371&DID=517389] or T 525 standards are used. The international community uses ISO standards. The following table shows how the two systems rate high brightness papers, but there is no simple way to convert between the two systems because the test methods are so different [cite web|url=http://www.tappi.org/s_tappi/doc.asp?CID=13&DID=512204|title=TAPPI comparison of TAPPI and ISO brightness|accessdate=2007-09-15] . Note that the ISO rating is higher and can go above 100.

Newsprint ranges from 55-75 ISO brightness [cite journal |last=Ducey |first=Michael |authorlink= |coauthors= |year=2004 |month=June|title= Matching newsprint qualities to press technology|journal=The International Journal of Newspaper Technology |volume= |issue= |pages= |id= |url=http://www.newsandtech.com/issues/2004/06-04/nt/06-04_newsprint.htm|accessdate= 2007-09-15 |quote= ] . Writing and printer paper would typically be as bright as 104 ISO.

While the results are the same, the processes and fundamental chemistry involved in bleaching chemical pulps (like kraft or sulfite) are very different from those involved in bleaching mechanical pulps (like stoneground, thermomechanical or chemithermomechanical). Chemical pulps contain very little lignin while mechanical pulps contain most of the lignin which was present in the wood used to make the pulp. Lignin is the main source of color in pulp due to the presence of a variety of chromophores naturally present in the wood or created in the pulp mill.

Bleaching mechanical pulps

Mechanical pulps retain most of the lignin present in the wood used to make the pulp and thus contain almost as much lignin as they do cellulose and hemicellulose. It would be impractical to remove this much lignin by bleaching, and undesirable since one of the big advantages of mechanical pulp is the high yield of pulp based on wood used. Therefore the objective of bleaching mechanical pulp (also referred to as brightening) is to remove only the chromophores (color-causing groups). This is possible because the structures responsible for color are also more susceptible to oxidation or reduction.

Alkaline hydrogen peroxide is the most commonly used bleaching agent for mechanical pulp. The amount of base such as sodium hydroxide is less than that used in bleaching chemical pulps and the temperatures are lower. These conditions allow alkaline peroxide to selectively oxidize non-aromatic conjugated groups responsible for absorbing visible light. The decomposition of hydrogen peroxide is catalyzed by transition metals, and iron, manganese and copper are of particular importance in pulp bleaching. The use of chelating agents like EDTA to remove some of these metal ions from the pulp prior to adding peroxide allows the peroxide to be used more efficiently. Magnesium salts and sodium silicate are also added to improve bleaching with alkaline peroxide [cite web|url=http://www.pqcorp.com/applications/PulpandPaper_application.asp#topic01|title=Pulp bleaching chemicals information from PQ Corp.|accessdate=2007-09-17]

Sodium dithionite (Na₂S₂O₄), also known as sodium hydrosulfite, is the other main reagent used to brighten mechanical pulps. In contrast to hydrogen peroxide, which oxidizes the chromophores, dithionite reduces these color-causing groups. Dithionite reacts with oxygen, so efficient use of dithionite requires that oxygen exposure be minimized during its use.

Chelating agents can contribute to brightness gain by sequestering iron ions, for example as EDTA complexes, which are less colored than the complexes formed between iron and lignin.

The brightness gains achieved in bleaching mechanical pulps are temporary since almost all of the lignin present in the wood is still present in the pulp. Exposure to air and light can produce new chromophores from this residual lignin.cite book
author= E. Sjöström
title= Wood Chemistry: Fundamentals and Applications
publisher= Academic Press
year= 1993
isbn= 012647480X
oclc= 58509724 7461039] This is why newspaper yellows as it ages.

Bleaching chemical pulps

Chemical pulps, such as those from the kraft process or sulfite pulping, contain much less lignin than mechanical pulps, (<5% compared to approximately 40%). The goal in bleaching chemical pulps is to remove essentially all of the residual lignin, hence the process is often referred to as delignification. Sodium hypochlorite (household bleach) was initially used to bleach chemical pulps, but was largely replaced in the 1930s by chlorine. Concerns about the release of organochlorine compounds into the environment prompted the development of Elemental Chlorine Free (ECF) and Totally Chlorine Free (TCF) bleaching processes.

Delignification of chemical pulps is rarely a single step process and is frequently comprised of four or more discrete steps. These steps are given a letter designation [cite web|url=http://www.paperonweb.com/bleach.htm|title=PaperOnWeb description of bleaching sequences|accessdate=2007-09-17] , and these are given in the following table:

A bleaching sequence from the 1950s could look like: CEHEH . The pulp would have been exposed to chlorine, extracted (washed) with a sodium hydroxide solution to remove lignin fragmented by the chlorination, treated with sodium hypochlorite, washed with sodium hydroxide again and given a final treatment with hypochlorite. An example of a modern totally chlorine-free (TCF) sequence is OZEPY where the pulp would be treated with oxygen, then ozone, washed with sodium hydroxide then treated in sequence with alkaline peroxide and sodium dithionite.

Chlorine and hypochlorite

Chlorine replaces hydrogen on the aromatic rings of lignin via aromatic substitution, oxidizes pendant groups to carboxylic acids and adds across carbon carbon double bonds in the lignin sidechains. Chlorine also attacks cellulose, but this reaction occurs predominantely at pH 7, where un-ionized hypochlorous acid, HClO, is the main chlorine species in solution.cite journal |last=Fair |first=G. M. |authorlink= |coauthors=J. C. Morris, S. L. Chang, I. Weil, and R. P. Burden |year=1948 |month= |title=The behavior of chlorine as a water disinfectant
journal=J. Am. Water Works Assoc. |volume=40 |issue= |pages=1051–1061 |id= |url= |accessdate= 2007-09-17 ] To avoid excessive cellulose degradation, chlorination is carried out at pH <1.5.

: Cl₂ + H₂O unicode| H⁺ + Cl^- + HClO

At pH >8 the dominant species is hypochlorite, ClO^-, which is also useful for lignin removal. Sodium hypochlorite can be purchased or generated "in situ" by reacting chlorine with sodium hydroxide.

: 2 NaOH + Cl₂ unicode| NaOCl + NaCl + H₂O

The main objection to the use of chlorine for bleaching pulp is the large amounts of soluble organochlorine compounds produced and released into the environment.

Chlorine dioxide

Chlorine dioxide, ClO₂ is an unstable gas with moderate solubility in water. It is usually generated in an aqueous solution and used immediately because it decomposes and is explosive in higher concentrations. It is produced by reacting sodium chlorate with a reducing agent like sulfur dioxide.

: 2 NaClO₃ + H₂SO₄ + SO₂ → 2 ClO₂ + 2 NaHSO₄

Chlorine dioxide is sometimes used in combination with chlorine, but it is used alone in ECF (elemental chlorine-free) bleaching sequences. It is used at moderately acidic pH (3.5 to 6). The use of chlorine dioxide minimizes the amount of organochlorine compounds produced.

Extraction or washing

All bleaching agents used to delignify chemical pulp, with the exception of sodium dithionite, break lignin down into smaller, oxygen-containing molecules. These breakdown products are generally soluble in water, especially if the pH is greater than 7 (many of the products are carboxylic acids). These materials must be removed between bleaching stages to avoid excessive use of bleaching chemicals since many of these smaller molecules are still susceptible to oxidation. The need to minimize water use in modern pulp mills has driven the development of equipment and techniques for the efficient use of available water. [cite paper |last=Sillanpää |first=Mervi |authorlink= |title=Studies on washing in kraft pulp bleaching |version= |publisher=Faculty of Technology University of Oulu, Finland|date=2005 |url=http://herkules.oulu.fi/isbn9514278771/isbn9514278771.pdf |format=Thesis |id= |accessdate=2007-09-19 ]

Oxygen

Oxygen exists as a ground state triplet state which is relatively unreactive and needs free radicals or very electron-rich substrates such as deprotonated lignin phenolic groups. The production of these phenoxide groups requires that delignification with oxygen be carried out under very basic conditions (pH >12). The reactions involved are primarily single electron (radical) reactions. [cite book |last=Starnes |first=W.H. |authorlink= |coauthors= |title=Chemistry of Delignification with Oxygen, Ozone and Peroxides |year=1991 |publisher=UMI Out-of-print Books on Demand |location=Ann Arbor, MI |isbn= ] [cite book |last=Singh |first=R.P. |authorlink= |coauthors= |title=The Bleaching of Pulp, 3rd ed. |year=1979 |publisher=TAPPI Press |location=Atlanta |isbn= ] Oxygen opens rings and cleaves sidechains giving a complex mixture of small oxygenated molecules. Transition metal compounds, particularly those of
iron, manganese and copper, which have multiple oxidation states, facilitate many radical reactions and impact oxygen delignification.cite journal |last=McDonough |first=Thomas Joseph |authorlink= |coauthors= |year=1983 |month=Jan |title=Oxygen bleaching processes : an overview |journal=IPC technical paper series |volume=132 |issue= |pages= |id= |url=http://www.smartech.gatech.edu/bitstream/1853/2685/1/tps-132.pdf |accessdate= 2007-09-19 |quote= ] [cite conference |first=E. |last=Johansson |authorlink= |coauthors=S. Ljunggren |title=The reactivity of lignin model compounds and the influence of metal ions during bleaching with oxygen and hydrogen peroxide |booktitle=Proceedings of the Seventh International Symposium on Wood and Pulping Chemistry vol. I|pages=180–187 |publisher= |date=1991 |location=Beijing, PR China |url= |accessdate= |id= ] While the radical reactions are largely responsible for delignification, they are detrimental to cellulose.Oxygen-based radicals, especially hydroxyl radicals, HO•, can oxidize hydroxyl groups in the cellulose chains to ketones, and under the strongly basic conditions used in oxygen delignification, these compounds undergo reverse aldol reactions leading to cleavage of cellulose chains. Magnesium salts are added to oxygen delignification to help preserve the cellulose chains, but mechanism of this protection has not been confirmed.

Hydrogen peroxide

Using hydrogen peroxide to delignify chemical pulp requires more vigorous conditions than for brightening mechanical pulp. Both pH and temperature are higher when treating chemical pulp. The chemistry is very similar to that involved in oxygen delignification, in terms of the radical species involved and the products produced. [cite conference |first=H.U. |last=Suss |authorlink= |coauthors=N.F. Nimmerfroh |title=Peroxide Bleaching _ Technology Review |booktitle=Workshop on Emerging Pulping and Chlorine-free Bleaching Technologies |pages= |publisher= |date=1993 |location=Raleigh, N.C. |url= |accessdate= |id= ] Hydrogen peroxide is sometimes used with oxygen in the same bleaching stage and this is give the letter designation Op in bleaching sequences. Metal ions, particularly manganese catalyze the decomposition of hydrogen peroxide, so some improvement in the efficiency of peroxide bleaching can be achieved if the metal levels are controlled.

Ozone

Ozone is a very powerful oxidizing agent and the biggest challenge in using it to bleach wood pulp is to get sufficient selectivity so that the desirable cellulose is not degraded. Ozone reacts with the carbon carbon double bonds in lignin, including those within aromatic rings. In the 1990s ozone was touted as good reagent to allow pulp to be bleached without any chlorine-containing chemicals (totally chlorine-free, TCF). The emphasis has changed and ozone is seen as an adjunct to chlorine dioxide in bleaching sequences not using any elemental chlorine (elemental chlorine-free, ECF). Over twenty-five pulp mills worldwide have installed equipment to generate and use ozone. [cite web|url=http://www.ca.airliquide.com/en/business/industry/pulp_paper/applications/ozone_bleaching.asp|title=Use of Ozone from web page by Air Liquide|accessdate=2007-09-19]

Chelant wash

The effect of transition metals on some of the bleaching stages has already been mentioned. Sometimes it is beneficial to remove some of these metal ions from the pulp by washing the pulp with a chelating agent such as EDTA or DTPA. This is more common in TCF bleaching sequences for two reasons: the acidic chlorine or chlorine dioxide stages tend to remove metal ions (metal ions usually being more soluble at lower pH) and TCF stages rely more heavily on oxygen-based bleaching agents which are more susceptible to the detrimental effects of these metal ions. Chelant washes are usually carried out at or near pH 7. Lower pH solutions are more effective at removing transition metals, but also remove more of the beneficial metal ions, especially magnesium [cite web|url=http://www.prochem.ch/html/forum/versene/VERSENE%20for%20Ion%20control%20in%20pulp%|title=Dow Chem. data presented at 1994 and 1996 International Pulp Bleaching Conferences |accessdate=2007-09-19]

Other bleaching agents

A variety of more exotic bleaching agents have been used on chemical pulps. They include peroxyacetic acidcite journal |last=Ragauskas |first=A.J. |authorlink= |coauthors=K.M. Poll and A.J. Cesternino |year=1993 |month=April |title=Effect of Xylanase Pretreatment Procedures for Nonchlorine Bleaching |journal=IPST Technical Paper Series,Institute of Paper Science Atlanta, Georgiaand Technology |volume=NUMBER 482 |issue= |pages= |id= |url=http://smartech.gatech.edu/bitstream/1853/2037/1/tps-482.pdf |accessdate= 2007-09-20 |quote= ] , peroxyformic acid, potassium peroxymonosulfate (Oxone), dimethyldioxirane [cite journal |last=Bouchard |first=J. |authorlink= |coauthors=C. Maine, R.M. Berry, and D.S. Argyropoulos |year=1996 |month= |title=Kraft pulp bleaching using dimethyldioxirane: stability of the oxidants |journal=Can. J. Chem. |volume=74 |issue=2 |pages=232–237 |id= |url=http://article.pubs.nrc-cnrc.gc.ca/ppv/RPViewDoc?issn=1480-3291&volume=74&issue=2&startPage=232 |accessdate= 2007-09-20 |quote=|doi=10.1139/v96-026 ] , which is generated "in situ" from acetone and potassium peroxymonosulfate, and peroxymonophosphoric acid [cite journal |last=Springer |first=E.L. |authorlink= |coauthors= |year=1997 |month=December |title=Delignification of Wood and Kraft Pulp with Peroxymonophosphoric Acid |journal=Journal of Pulp andPaper Science |volume=23 |issue=12 |pages=582–584 |id= |url= |accessdate= 2007-09-20 |quote= ]

Enzymes like xylanase have been used in pulp bleaching to increase the efficiency of other bleaching chemicals. It is believed that xylanase does this by cleaving lignin-xylan bonds to make lignin more accessible to other reagents. It is possible that other enzymes such as those found in fungi that degrade lignin may be useful in pulp bleaching. [cite journal |last=Harazono |first=Koicho |authorlink= |coauthors=Ryuichiro Kondo and Kokki Sak |year=1996 |month=Mar |title=Bleaching of Hardwood Kraft Pulp with Manganese Peroxidase from Phanerochaete sordida YK-624 without Addition of MnSO4 |journal=Applied and Environmental Microbiology |volume=62 |issue=3 |pages= 913–917|id= |url=http://aem.asm.org/cgi/reprint/62/3/913.pdf |accessdate= 2007-09-20 |quote= ]

Environmental considerations

Bleaching mechanical pulp is not a major cause for environmental concern since most of the organic material is retained in the pulp, and the chemicals used (hydrogen peroxide and sodium dithionite) produce benign byproducts (water and sodium sulfate (finally), respectively).

Delignification of chemical pulps releases considerable amounts of organic material into the environment, particularly into rivers or lakes. Pulp mills are almost always located near large bodies of water because of they require substantial quantites of water for their processes.

Bleaching with chlorine produced large amounts of organochlorine compounds, including dioxinscite web |url=http://www.hc-sc.gc.ca/ewh-semt/pubs/contaminants/psl1-lsp1/pulp_mill_effluents_pate_blanchie/index_e.html |title=Effluents from Pulp Mills using Bleaching - PSL1 |accessdate=2007-09-21 |last= |first= |coauthors= |date=1991 |work=ISBN 0-662-18734-2 DSS |publisher=Health Canada] . Increased public awareness of environmental issues, as evidenced by the formation of organizations like Greenpeace, influenced the pulping industry and governments to address the release of these materials into the environment [cite conference |first=David A. |last=Sonnenfeld |authorlink= |coauthors= |title=Social Movements and Ecological Modernization: The Transformation of Pulp and Paper Manufacturing, Paper: WP00-6-Sonnenfeld
booktitle= Berkeley Workshop on Environmental Politics |pages= |publisher=Institute of International Studies (University of California, Berkeley) |date=1999 |location=Berkeley,CA |url=http://repositories.cdlib.org/cgi/viewcontent.cgi?article=1005&context=iis |accessdate=2007-09-20 |id= ] . The amount of dioxin has been reduced by replacing some or all of the chlorine with chlorine dioxide [cite web |url=http://www.aet.org/epp/ecf_brochure.pdf |title=ECF: The Sustainable Technology |accessdate=2007-09-19 |last= |first= |coauthors= |date= |work= |publisher=Alliance for Environmental Technology] . The use of elemental chlorine has declined significantly and as of 2005 was used to bleach 19-20% of all kraft pulp. ECF (elemental chlorine-free) pulping using chlorine dioxide is now the dominant technology worldwide (with the exception of Finland and Sweden), accounting for 75% of bleached kraft pulp globally.

The promise of complete removal of chlorine chemistry from bleaching processes to give a TCF (totally chlorine-free) process, which peaked in the mid-1990s, did not become realitycite web |url=http://www.gunnspulpmill.com.au/factsheets/BleachingByCSIRO.pdf |title= Frequently Asked Questions on Kraft Pulp Mills|accessdate=2007-09-21 |last= |first= |coauthors= |date=2005-03-04 |work= |publisher=Ensis/CSIRO (Australia) joint research [http://www.csiro.au/org/psq3.html] ] . The economic disadvantages of TCF [cite web |url=http://aet.org/reports/technical/fact.html |title=TCF and ECF: Separating Fact From Fiction |accessdate=2007-09-21 |last= |first= |coauthors= |date=September, 1994 |work= |publisher=The Alliance for Environmental Technology] , the lack of stricter government regulation and consumer demand meant that EFC has not been replaced by TCF. As of 2005 only 5-6% of bleached kraft is made using TCF sequences, mainly in Finland and Sweden. Thispulp and paper goes to the German market, where regulations and consumer demand for TCF pulp and paper makes it viable.

A study based on EPA data demonstrated that TCF processes reduce the amount of chlorinated material released into the environment, relative to ECF bleaching processes which do not use oxygen delignification. The same study concluded that "Studies of effluents from mills that use oxygen delignification and extended delignification to produce ECF and TCF pulps suggest that the environmental effects of these processes are low and similar." cite web |url=http://www.environmentaldefense.org/documents/1626_WP5.pdf |title= ENVIRONMENTAL COMPARISON OF BLEACHED KRAFT PULP MANUFACTURING |accessdate=2007-11-18 |last= |first= |coauthors= Duke University, Environmental Defense Fund, Johnson&Johnson |date= December, 1995 |work= |publisher= Environmental Defense Fund [http://www.environmentaldefense.org/documents/1626_WP5.pdf] ] The energy needed to produce the bleaching chemicals for an ECF process not using oxygen delignification is about twice that needed for ECF with oxygen delignification or ECF processes. The environmental impact differences between TCF and ECF process however are not fully understood.Dubious|date=March 2008 Some recent studies have pointed out that no difference in acute or chronic toxicity is to be found when comparing well-treated ECF and TCF effluents breaking the paradigm that TCF is the most environmental friendly process. In fact some relevant analysis in field have been pointing out that mills which previously ran with TCF and migrated to ECF have reduced significantly their NOx air emissions.Dubious|date=March 2008cite web |url=http://aet.org/reports/technical/ecf2.html |title= ECF and TCF: Toxicity An Analysis of Recent Published Data |accessdate=2007-10-26 |last= |first= |coauthors= |date= October, 1994 |work= |publisher= The Alliance forEnvironmental Technology (International Association) joint research [http://aet.org/epp/brochure_0806.pdf] ]

References