J Mater Cycles Waste Manag (2004) 6:6472 DOI 10.

1007/s10163-003-0104-8

Springer-Verlag 2004

ORIGINAL ARTICLE

Masaya Koshikawa Akira Isogai

Analyses of incinerated ash of paper sludge: comparison with incinerated ash of municipal solid waste

Received: January 9, 2003 / Accepted: August 28, 2003

Abstract Fourteen paper sludge samples were collected at seven representative pulp and paper mills in Japan, and were analyzed to obtain fundamental data on the reuse of paper sludge-incinerated ash as papermaking material. For comparison, incinerated ashes of municipal solid waste (MSW) were collected at MSW incineration plants in Tokyo, and analyzed by similar methods. Elementary and X-ray diffraction analyses revealed that the predominant elements in paper sludge samples are calcium, silicon, aluminum, and magnesium, which are derived from paper llers, coating pigments, and coagulants used in papermaking and process efuent treatments. Similar results were also obtained for the MSW-incinerated ashes, indicating that major components in the collected MSW are paperrelated materials. Incineration of paper sludge around 800C is recommended in terms of high brightness of the incinerated ash, which has about 60% brightness. Calcium, silicon, and aluminum components in the paper sludge are fused or sintered by heating. Although paper-sludgeincinerated ashes have irregular shape and large particle size distributions, they may be used as papermaking materials after pulverization using a ball mill. The MSWincinerated ashes have 5%30% water-soluble fractions and low brightness, and thus incineration conditions must be changed to reuse the MSW-incinerated ash as a papermaking material. Key words Paper sludge Incineration Municipal solid waste Paper ller X-ray diffraction

Introduction
Paper and paper board are composed of pulp bers and some inorganic ne particles, which are used as paper llers and coating pigments in papermaking and coating processes, respectively. Paper and paper board production is now about 31 million tons per year in Japan, and about 60% of paper and paper board used is recycled and reused as secondary bers in papermaking. On the other hand, some pulp fractions and inorganic ne particles, which cannot be retained in paper or are rejected during recycling, transfer to paper sludge fractions by simple mechanical separation or coagulation treatments followed by sedimentation of suspended solids in efuents. Paper sludge also comes from deinking processes, in which ink fractions, deinking reagents, and extraneous materials are present. Paper sludge is generally dried in air, and subjected to incineration. The resulting ash is then disposed by landlling or is used by mixing in cement. The quantity of paper sludge produced is approximately 1.5 million tons per year in Japan, and about 0.6 million tons of incinerated ash is formed thereby.1 Thus, a large amount of paper sludge is formed in pulp and paper mills, and suitable methods to utilize the paper sludge have been examined. It is preferable to reuse inorganic compounds in paper sludge as papermaking materials, as 60% of pulp bers in waste paper are now reused in papermaking. Furthermore, some of the incinerated ash produced in plants that incinerate municipal solid waste (MSW) is good for reuse as papermaking materials if the MSW-incinerated ash components are partly derived from paper-related materials. Johnston and Wiseman2 studied mineral recovery from paper sludge formed in papermaking processes including deinking. In the case of incineration at 8001150C, fusion or sintering occurred among calcium, aluminum, and silicon components in the paper sludge, thus giving mullite (Al2O34/3SiO2), cristobalite (SiO2), or calcium silicate (CaSiO3), depending on the incineration temperature. On the other hand, the original paper ller components were recovered without fusion by hydrothermal oxidation of the

M. Koshikawa A. Isogai (*) Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan Tel. 81-3-5841-5538; Fax 81-3-5841-5271 e-mail: aisogai@mail.ecc.u-tokyo.ac.jp Part of this paper was presented at the 68th Research Conference of Japan Tappi, Tokyo, 2001

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paper sludge at 260C and 5 MPa conditions in which organic components such as pulp bers were converted to CO2. Moilanen et al.3 reported that precipitation of calcium carbonate on paper sludge-incinerated ash particles increased its brightness to more than 70%.Yamada and Fukui1 studied applications of paper sludge-incinerated ash to paper coating pigments, and relationships between the paper sludge incineration conditions and some properties of paper coated thereof were investigated.Also, the fates of some elements derived from some additives used in papermaking, efuent treatments, and others have been reported.4,5 However, analytical data on paper sludge samples are insufcient, and the number of samples used in previous reports is limited. More detailed analyses of paper sludge using multiple samples are, therefore, required for evaluations of reuse as resources of papermaking materials. In this study, 14 paper sludge samples were collected at seven pulp and paper mills in Japan, and their elements were determined using an X-ray uorescence analyzer. Two of the representative paper sludge samples were subjected to incineration, and changes in brightness, yield, X-ray diffraction patterns, morphologies, and distribution of elements were analyzed in terms of the incineration temperatures. This allowed the collection of fundamental data to examine the reuse of paper sludge-incinerated ash as papermaking material. The incineration temperature examined varied from 300 to 1000C, because uidized bed-type incinerators are generally used for paper sludge combustion in the temperature range of 600900C in pulp and paper mills. Incinerated ash samples were collected at ve MSW incineration plants in Tokyo and were investigated for comparison.

Analyses Relative weight ratios of elements heavier than sodium in paper sludge and incinerated ash samples were measured by means of an X-ray uorescence analyzer using an attached determination program (Mesa 500, Horiba, Kyoto, Japan). About 1 g of a sample was put on a thin polyethylene lm, and X-rays generated at 15 kV and 500 A were irradiated onto the sample through the lm for 100 s under vacuum. Ash samples were pressed to pellet form using an apparatus for preparing KBr pellets in infrared (IR) measurements, and subjected to recording X-ray diffraction patterns on a Rigaku RINT 1000 (Kanagawa, Japan) with the reection mode at 40 kV and 40 mA. A data base system6 for X-ray diffraction patterns attached with the above X-ray diffractometer was used for assignment of diffraction peaks. Pyrolysis-gas chromatograms (Py-GC) of paper sludge samples were recorded on a Shimadzu GC14B (Shimadzu, Kyoto, Japan) attached with a vertical microfurnace-type pyrolyzer.7 The gas components formed from a 1-mg sludge sample pyrolyzed at 500C were directly analyzed by the GC equipped with a capillary OV-1 column (0.25 mm 30 m), whose initial temperature, nal temperature, and program rate were set at 150C, 300C, and 5C/min, respectively. Py-GC peaks were identied using pyrograms of pure cellulose, spruce wood meal, and typical deinking and sizing reagents. Distribution of elements in incinerated ash particles and their morphology were observed by a eld-emission-type scanning electron microscope (SEM: Hitachi S-4000, Tokyo, Japan) with an energy dispersive X-ray analyzer (EDX: Horiba EMAX 5770X, Kyoto, Japan) after platinum coating for 150 s.

Materials and methods

Materials Fourteen paper sludge samples were collected at seven representative pulp and paper mills in Japan. Detailed information about each paper sludge sample in terms of, for example, the original resources used for paper production as well as their weight ratios and deinking processes adopted are unknown. Talc (3MgO4SiO2H2O), kaolin clay (Al2O32SiO22H2O), titanium dioxide, and precipitated and ground calcium carbonates are commercial llers of papermaking grade. About 1 g of a dried paper sludge sample was set in a crucible, and heated at 3001000C for 1 h in the presence of air, using an electric mufe furnace (Eyela TMF 2000, Tokyo, Japan). Some incinerated ash samples were pulverized in a container with balls made of agate using a planetary ball mill (P-7, Fritsch, Kanagawa, Japan) for 3 min. MSW-incinerated ash samples were obtained from mixtures of bottom, grate, and y ashes at ve different MSW incineration plants in the Tokyo metropolitan area, whose MSW combustors were the continuous feed mass-red-type incinerators with re grates. The MSW incinerated ash samples were reuxed in boiling water for 1 h to remove watersoluble materials.

Results and discussion

Elements in paper sludge Figure 1 depicts the relative weight ratios of elements heavier than sodium in 14 paper sludge samples. The major three elements are silicon, calcium, and aluminum. Large uctuations of relative calcium content in the range from 6% to 42% are observed among the paper sludge samples. Mill efuents of alkaline papermaking and/or coating, where calcium carbonate is used as a ller and/or in coat-ing pigments, give paper sludge with higher calcium content than those of acidic papermaking. It is possible for silicon to mix in the paper sludge as kaolin clay (Al2O32SiO22H2O) or talc (3MgO4SiO2H2O) used as paper llers or coating pigments. Moreover, silicate ions are often present naturally in process water of paper mills. Sodium silicate is used as a stabilizer of hydrogen peroxide, which is used in the deinking process of secondary bers and for bleaching of mechanical pulps. These silicate ions present in efuents easily precipitate as aluminum silicates in the presence of water-soluble aluminum compounds such as aluminum sulfate and polyaluminum chloride, which are added to efuents as coagulants for suspended solids.8 Aluminum in Fig. 1 is derived from kaolin clay used as paper llers or coating pigments,

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Fig. 1. Relative weight ratios of elements in 14 paper sludge samples collected at 7 Japanese pulp and paper mills

and from aluminum sulfate or polyaluminum compounds used as retention aids in papermaking or coagulants for efuents. Magnesium and titanium in the paper sludge originate from talc or magnesium carbonate and titanium dioxide, respectively, used as paper llers. Paper sludge samples A and B in Fig. 1 are selected as representatives having high and low calcium contents, respectively, for the successive incineration treatments. Because the paper sludge sample A is dark gray (brightness ca. 10%), it contains carbon black and other ink components, which may be formed in deinking of waste paper. On the other hand, the paper sludge sample B, which has brightness of about 40%, may be from efuents of papermaking without any deinking processes.

Fig. 2. Yields and brightness of paper sludge samples A and B heated at various temperatures. Paper sludge A contains Ca Si Al Mg, whereas paper sludge B contains Si Mg Al Ca (see Fig. 1)

Incineration of paper sludge The selected paper sludge samples were heated at 3001000C for 1 h, and changes in yield and brightness of the residues were measured (Fig. 2). Both paper sludge samples have similar yield patterns with increasing heating temperature, and the patterns consist of three different phases: the rst phase at 20400C, the second phase at 400700C, and the third plateau phase at 7001000C. The difference in yield between the two paper sludge samples are caused by different content of burnable organic compounds such as pulp bers, which are rejected during the screening and drainage processes of papermaking. Cellulose, which is the main component in pulp bers, starts to decompose at 200270C and ignites at 390400C. Thus, cellulose and other organic compounds such as hemicellulose and lignin in the paper sludge are thermally decomposed and ignite in the rst phase. The inorganic hydrates present in the paper sludge are probably partly dehydrated in the second phase. Calcium carbonate is decomposed together with decrystallization to calcium oxide at about 800C, when heated as

a single component or even in the presence of burnable cellulose. The paper sludge sample A certainly contains calcium carbonate, as described in the following section. However, no such yield decrease was observed around 800C. This result indicates that calcium carbonate turns to some compounds other than calcium oxide during heating in the presence of aluminum and/or silicon compounds below 600C by sintering or fusion. In fact, when the heated product of the paper sludge sample A was treated with boiling water for 1 h, almost no weight loss was observed; if calcium oxide is formed by heating, it becomes partly watersoluble Ca(OH)2 and this brings about some yield loss by the boiling-water treatment. It is unlikely that the burning temperature of the paper sludge in the crucible exceeded the setting temperature of the mufe furnace. This is because neither weight decrease nor decrystallization of calcium carbonate occurred at 400700C, when calcium carbonate or a mixture of calcium carbonate and cellulose powder was heated at 400700C. Brightness of the heated products increased with increasing heating temperature up to about 600C, and then a rough plateau level was observed at 6001000C. Unburned carbon residues entrapped inside the heated products probably burn up to 600C. The maximum brightness values are about 65% and 57% for paper sludge samples A and B, respectively. These values are lower than those of commercial paper llers, which have brightness values of more than 80%. However, these incinerated ashes may be used as paper llers for producing some particular papers, which require recycling of paper sludge but do not require high brightness levels. Considering the incineration temperature forming dioxin,9 incineration of paper sludge at around 800C may be suitable. Figure 3 shows the Py-GC of the original paper sludge samples A and B and their heated products at 300, 500,

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gasied and/or carbonized below 300C, and then completely burn by 600C, forming CO2.

X-ray diffraction analysis of paper sludge X-ray diffraction patterns of the paper sludge samples heated at 4001000C are illustrated in Fig. 4. The original paper sludge sample A, whose predominant elements are calcium, silicon, and aluminum, has a relatively simple pattern, which is composed of clear diffraction peaks due to cellulose (broad peaks around 2 16 and 22), talc, kaolin clay, and calcium carbonate. The diffraction peaks due to kaolin clay disappeared at 600C by converting to amorphous metakaolin, and that due to talc disappeared at 1000C. The diffraction peak due to calcium carbonate at 2 29.5 disappeared at 600C, indicating that calcium carbonate in the paper sludge turned to some compounds with aluminum and/or silicon other than calcium oxide. As described in the previous section, when calcium carbonate or a mixture of calcium carbonate and cellulose were heated at 600C, neither yield reduction nor decrystallization of calcium carbonate occurred. Almost all diffraction peaks present in the original paper sludge disappear for the product heated at 1000C, and quite small peaks, which are not due to calcium silicate (wollastonite)2 but probably due to anorthite (CaAl2Si2O8) and gehlenite (Ca2Al2SiO7), are detected at 2 of 28.2 and 31.7, respectively.6 The paper sludge sample B has a similar X-ray diffraction pattern, but has no peak due to calcium carbonate. The sharp peak was observed at 32.9, which may be due to MgCO3 used as a paper ller. Diffraction peaks of mullite (2Al2O34/3SiO2), cristobalite (SiO2), and woolastonite (CaSiO3)2 were not detected in the X-ray diffraction patterns of the paper sludge-incinerated ashes.

Fig. 3. Pyrolysis-gas chromatograms of paper sludge samples A and B heated at various temperatures. Peaks due to pyrolyzed products originating from cellulose, lignin, deinking reagents, and sizing chemicals (alkylketene dimers) are marked as C, L, D, and S, respectively

SEM-EDX analysis Scanning electron micrographs of paper sludge sample A and the product heated at 800C are shown in Fig. 5, together with the corresponding distribution of elements. In the original paper sludge, aluminum and silicon are present in the same particles but calcium is not in most cases, because the former two elements are present as kaolin clay and the latter as calcium carbonate. In some particles, the three elements seem to coexist. This may be due to either physical adsorption of calcium carbonate particles on kaolin clay particles or low EDX resolution among the three elements. After heating at 800C, calcium, aluminum, and silicon are all present in the same particles, suggesting that sintering or fusion occurs among these elements. In the case of paper sludge sample B, some particles have both magnesium and silicon but others have magnesium only, suggesting that the former is due to talc and the latter is due to magnesium carbonate (Fig. 6). Because the diffraction peak due to MgCO3 in paper sludge sample B disappears together with kaolin clay after heating at 600C (Fig. 3), these two components have the opportunity to

and 900C. Levoglucosan formed from cellulose by thermal degradation is detected at a retention time of 25 min in the Py-GC patterns of the paper sludge samples. This result shows that wood pulp is the predominant organic component in the paper sludge. Peaks due to pyrolyzed products originating from cellulose, deinking reagents, sizing chemicals (alkylketene dimers), and lignin in mechanical pulp are marked in Py-GC patterns of the paper sludge samples in Fig. 3. When the paper sludge samples are heated at 300C, almost no organic compounds are detected in the Py-GC patterns, because the peaks at 1, 18, and 22 min are due to some compounds adsorbed on the glass wool used for the pyrolysis. In fact, these Py-GC patterns are almost identical to those of the paper sludge heated at 500C and 900C. Thus, most organic compounds present in paper sludge are

68 Fig. 4. X-ray diffraction patterns of paper sludge samples A and B heated at various temperatures. Paper sludge A contains Ca Si Al Mg, whereas paper sludge B contains Si Mg Al Ca (see Fig. 1). T, Talc; K, kaolin clay; C, calcium carbonate; M, magnesium carbonate; A, anorthite; G, gehlenite

Fig. 5. Scanning electron micrographs of paper sludge A and its heated product at 800C for 1 h, and the corresponding distribution of Al, Ca and Si. Bar 10 m

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Fig. 6. Scanning electron micrographs of paper sludge B and its heated product at 800C for 1 h, and the corresponding distribution of Al, Mg and Si. Bar 10 m

Fig. 7. Scanning electron micrographs of the paper sludge A and B, their ashes incinerated at 800C for 1 h, and the same ashes after ball milling for 3 min. Bar 0.1 mm

sinter together. However, there are no particles having both magnesium and aluminum in the heated product in Fig. 6. Thus, magnesium and aluminum do not appear to fuse together even after heating. Because the paper sludge-incinerated ashes have irregular-shapes and heterogeneous distributions of particle

size, it is difcult to reuse them as paper llers. On the other hand, the ashes are convertible to ne powder by pulverization using a ball mill (Fig. 7), and these ne particles are able to be used as recycled paper llers or coating pigments in papermaking and coating processes. Many pulp bers are present in the original paper sludge, and disappear in the

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Fig. 9. Yields of incinerated ash of municipal solid waste after boilingwater extraction for 1 h

Fig. 8. Relative weight ratios of elements in incinerated ash samples collected at ve incineration centers of municipal solid waste in Tokyo before and after boiling-water extraction for 1 h

heated residues. Thus, reuse of paper sludge as papermaking material may be feasible for particular cases by incineration of paper sludge at around 800C and the successive pulverization of the incinerated ash.

Analysis of incinerated ash of municipal solid waste Differences between paper sludge-incinerated ashes discussed in the previous sections and MSW-incinerated ashes were investigated. Figure 8 shows the relative weight ratios of elements heavier than sodium present in the MSWincinerated ash samples. Because only about 1 g of ash sample collected from huge ash heaps are subjected to the elemental analysis, the ratios may have large uctuations even among samples collected at the same incineration plant. However, when the relative weight ratios are compared among the ve MSW-incinerated ash samples, similar trends are observed. The major three elements are calcium, silicon, and aluminum, and these three components occupy about 75% in the detectable elements of the ash samples. A part of calcium must be derived from garbage bags containing calcium carbonate ller, which is incinerated together. Because some water-soluble inorganic compounds may remain in the MSW-incinerated ashes, they were treated

with boiling water to remove the water-soluble fractions. Consequently the relative weight ratios of elements became quite similar among the ash samples (Fig. 8). Yields after the boiling-water treatment are shown in Fig. 9; about 5%30% of the MSW-incinerated ash is water soluble. Although relative calcium content in these samples are higher than those of paper sludge, the predominant elements are the same between the MSW-incinerated ash and paper sludge. This similarity of the predominant elements indicates that paper-related materials are the major components in the collected MSW. Figure 10 illustrates X-ray diffraction patterns of MSWincinerated ash samples before and after the boiling-water treatment. Consequently, similar X-ray diffraction patterns were obtained for the ve MSW-incinerated ashes. The diffraction peaks at about 29.6 and 31.6 may be due to calcium silicate (Ca8Si5O18)6 that is formed by incineration. These two peaks are not detected in the X-ray diffraction patterns of paper sludge-incinerated ashes, indicating that this calcium silicate may be formed from calcium carbonate and some silicate compounds under particular incineration conditions used in the MSW incineration plants. All the MSW-incinerated ashes collected were dark gray, clearly having black carbon particles, probably because these ashes were produced by incomplete combustion. Brightness of these MSW-incinerated ashes were less than 10% but increased up to 40% by heating the ashes again at 800C for 1 h. Thus, the rst incineration temperature of MSW is signicant in order to increase brightness of MSWincinerated ash. There are some common points between paper sludgeincinerated ash and MSW-incinerated ash, and thus both paper sludge and MSW collected at municipal incineration plants have potential to be used as papermaking materials by incineration under suitable conditions. However, MSWincinerated ash, once produced under conventional procedures, has lower brightness and some water-soluble fractions, compared with paper sludge-incinerated ash.

71 Fig. 10. X-ray diffraction patterns of incinerated ash of municipal solid waste before and after boiling-water extraction for 1 h. Arrowheads, peaks at 29.6 and 31.6 may be attributed to calcium silicate formed during incineration

Moreover, although trace elements present in paper sludgeincinerated ash and MSW-incinerated ash samples were disregarded in this study, they may have some negative effects on reuse and recycling processes.

be changed to reuse the MSW-incinerated ash as papermaking materials.

Acknowledgments The authors thank Dr. Norio Matsukura of Nippon Paper (now of Japan Pulp and Paper Research Institute), Mr. Yuzo Igarashi of Nippon Paper, Dr. Tokiya Yaguchi of Oji Paper, Dr. Tohru Katsura of Mitsubishi Paper, and Mr. Michitaka Kubota of Daishowa Paper for kindly providing paper sludge samples. Mr. Takafumi Watanabe of the Environment Bureau of the Tokyo Metropolitan Government arranged sampling opportunities for MSW-incinerated ash samples. This research was supported by a Grant-in-Aid for Scientic Research (Grant number 12556025) from Japan Society for the Promotion of Science.

Conclusions
This study reveals the feasibility of paper sludge for reuse as papermaking materials. The predominant elements in paper sludge samples are calcium, silicon, aluminum, and magnesium, which are derived from paper llers, coating pigments, and coagulants. Incineration of paper sludge at around 800C is recommended in terms of brightness of the incinerated ash. When the paper sludge is incinerated at 800C, the residues contain talc and amorphous fused or sintered compounds. Although paper sludge-incinerated ashes have irregular shapes and large particle size distributions, they may possibly be used as papermaking materials by pulverization through ball milling. The predominant elements in MSW-incinerated ashes are the same as those of paper sludge, indicating that major components in the collected MSW are paper-related materials. However, the MSWincinerated ashes have 5%30% water-soluble fractions and low brightness, and thus incineration conditions must

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