MRI(§J REPORT ESTIMATES OF WASTE GENERATION BY THE PULP AND PAPER INDUSTRY Draft Report EPA Prime Contract No. 68-01-7287 Work Assignment No. 15 MRI Project No. 9015-L August 12, 1987 Prepare for: U.S. Environmental Protection Agency Office of Solid Waste 401 M Street, S.W. Washington, DC 20460 Attention: Mr. Benjamin P. Smith MIDWEST RESEARCH INSTITUTE 425 Volker Boulevard, Kansas City, MO 64110-2299 * (816) 753-7600 ------- MRI REPORT £M OKt ESTIMATES OF WASTE GENERATION BY THE PULP AND PAPER INDUSTRY EPA Prime Contract No. 68-01-7287 Work Assignment No. 15 MRI Project No. 9015-L August 12, 1987 U.S. Environmental Protection Agency Office of Solid Waste 401 M Street, S.W. Washington, DC 20460 Attention: Mr. Benjamin P. Smith Draft Report Prepare for: MIDWEST RESEARCH INSTITUTE 425 Volker Boulevard, Kansas City, MO 64110-2299 • (816) 753-7600 ------- PREFACE This draft report presents estimates of waste generation for the pulp and paper industry obtained by Midwest Research Institute (MRI) on MRI Project No. 9015-L. The personnel providing major contributions to this report were Ms. Jeannine Lehman, Mr. Ron Ramsey, Mr. Neal Frink, Mr. Rodney Gibson, and Dr. Tom Lapp. Approved for: MIDWEST RESEARCH INSTITUTE Thomas L. Ferguson Manager, Listing Support Program August 12, 1987 -ii- ------- CONTENTS Page Preface ii 3.0 Paper and Allied Products Industry Profile 1 3.1 Industry Overview 1 3.2 Industry Characterization 1 3.3 Industry structure 6 3.4 General Process Description, Waste Generation and Disposal 13 3.5 References 20 Appendix 21 -iii- ------- SECTION 3.0 PAPER'AND ALLIED PRODUCTS (SIC 26) 3.1 INDUSTRY OVERVIEW In 1982, the pulp and paper industry (SIC Major Group 26) consisted of 5,926 establishments with total shipments valued at approximately $80 trillion. The actual number of establishments may differ due to the complex and diverse nature of the industry. Approximately 72 percent of the pulp, paper, paperboard, and building board production occurs in companies which are integrated (EPA, 1980) yet waste quantities are often reported by process step. This makes it extremely difficult to estimate the impact. MRI estimates that the 5,400 facilities that are converters (SIC 264, 265) will not be adversely affected by the proposed regulation whereas the remaining 530 facilities will feel a major impact. The pulp and paper industry generates 6.7 x 109 MT/yr of wastewaters and 3.8 x 106 MT/yr of wastewater treatment sludges (EPA, 1980). MRI estimates that 4.8 x 10^ MT/yr of treated wastewater and 2.7 x 10^ MT/yr of wastewater treatment sludges have concentrations of chloroform, tetrachloroethylene, trichloroethylene and 2,4,6-trichlorophenol above the proposed regulatory levels. Additionally, MRI estimates that none of th'6 approximately 11.5 x 10^ MT/yr of process wastes will be regulated as hazardous. Table 3-1 presents a summary of the number of facilities, annual wastes generated, and potentially hazardous constituents in the pulp and paper industry. 3.2 INDUSTRY CHARACTERIZATION Paper and Allied Products (SIC Major Group 26) includes the manufacture of pulps from wood and other cellulose fibers, and from rags; the manufacture of paper and paperboard; and the manufacture of paper and -l- ------- TABLE 3-1 SIM4ARY OF NUMBER OF FACILITIES, ESTIMATED ANNUAL WASTE GENERATION, AND HAZARDOUS CONSTITUENTS IN THE PULP AND PAPER INDUSTRY NO. OF FACILITIES (Census of Manufactures, 1982) Total 5,926 Fewer than 20 employees 2,066 WASTES GENERATED ANNUALLY Total Waste Quantitv (MT/YR)6 Currently Hazardous Quantity (MR/YR) Quantity Currently Non- Hazardous (MT/YR)b Quantity Fai1ing TCLP (MT/yr)a Process Wastes -Wood Preparation 8.2 x 106 0 8.2 x 106 0 Wastes 1.1 x 10® -Pulping Wastes 0 1.1 x lof 0 -Papermaking Wastes 2.2 x 105 0 2.2 x 105 0 Waste Treatment Sludqes 3.8 x 105 0 3.8 x 10° 2.7 x 105 - Wastewaters 6.7 x 109 0 6.7 x 109 4.8 x 109 - Potentially Hazardous TCLP Constituents In Wastes 2,4,6-Trichlorophenol Chloroform Methylene Chloride Benzene Trichloroethylene Tetrachloroethylene ® MRI estimate b EPA, 1980 -2- ------- paperboard into converted products such as paper coated off the paper machine, paper bags, paper boxes, and envelopes. (Standard Industrial Classification Manual, 1972) This industry is further categorized as follows: 261 PULP MILLS 2611 Pulp Mills Establishments primarily engaged in manufacturing pulp from wood or from other materials such as rags, 1 inters, waste paper, and straw. Logging camps operated by pulp mills, and not separately reported, are also included in this industry. 262 PAPER MILLS, EXCEPT BUILDING PAPER MILLS 2621 Paper Mills, Except Building Paper Mills Establishments primarily engaged in manufacturing paper (except building paper Industry 2661) from wood pulp and other fibers, and which may also manufacture converted paper products. Pulp mills combined with paper mills, and not separately reported, are also included in this industry; where separately reported, they are classified in Industry 2611. 263 PAPERBOARD MILLS 2631 Paperboard Mills Establishments primarily engaged 1n manufacturing paperboard, including paperboard coated on the paperboard machine, from wood pulp and other fibers; and which may also manufacture converted, paperboard products. Pulp mills combined with paperboard mills, and not separately reported, are also included in this industry; where separately reported, they are classified in Industry 2611. -3- ------- 264 CONVERTED PAPER AND PAPERBOARD PRODUCTS, EXCEPT CONTAINERS AND BOXES 2641 Paper Coating and Glazing Establishments primarily engaged in manufacturing coated, glazed, or varnished paper from purchased paper. Also included are establishments primarily manufacturing pressure sensitive tape with backing of any material other than rubber. 2642 Envelopes Establishments primarily engaged in manufacturing envelopes of any description from purchased paper and paperboard. 2643 Bags, Except Textile Bags Establishments primarily engaged in manufacturing bags from purchased paper, cellophane, acetate, polyethylene, polypropylene, pliofilm, foil, and similar sheet or film materials. 2645 Die-Cut Paper and Paperboard and Cardboard Establishments primarily engaged in diecutting purchased paper and paperboard; and in manufacturing cardboard by laminating, lining, or surface coating paperboard. 2646 Pressed and Molded Pulp Goods Establishments primarily engaged in manufacturing all kinds of pressed and molded pulp goods, including papier-mache articles other than statuary and art goods (Industry 3299). 2647 Sanitary Paper Products Establishments primarily engaged in manufacturing, from purchased -4- ------- paper, sanitary paper products, such as facial tissues and handkerchiefs, table napkins, toilet paper, towels, disposable diapers, and sanitary napkins and tampons. 2648 Stationery, Tablets and Related Products Establishments primarily engaged in manufacturing stationery, tablets, looseleaf fillers, and related items from purchased paper. 2649 Converted Paper and Paperboard Products, Not Elsewhere Classified Establishments primarily engaged in manufacturing from purchased paper or paperboard miscellaneous converted paper or paperboard products, not elsewhere classified. 265 PAPERBOARD CONTAINERS AND BOXES 2651 Folding Paperboard Boxes Establishments primarily engaged in manufacturing set-up paperboard boxes from purchased paperboard. 2653 Corrugated and Solid Fiber Boxes Establishments primarily engaged in manufacturing corrugated and solid fiber boxes and related products from purchased paperboard of fiber stock. Important products of this industry include corrugated and solid fiberboard boxes, pads, partitions, display items, pallets, single face products, and corrugated sheets. 2654 Sanitary Food Containers Establishments primarily engaged in manufacturing food containers from special food board. Important products of this industry -5- ------- include fluid milk containers; folding paraffined cartons for butter, margarine, and shortening, ice cream containers; frozen food containers; liquid tight' containers; round nested food containers; paper cups for hot or cold drinks; pails for food and ice cream; and stamped plates, dishes, spoons and similar products. 2655 Fiber Cans, Tubes, Drums, and Similar Products Establishments primarily engaged in manufacturing fiber cans, cones, drums,« and similar products from purchased materials, with or without metal ends, and vulcanized fiber boxes. 266 BUILDING PAPER AND BUILDING BOARD MILLS 2661 Building Paper and Building Board Mills Establishments primarily engaged in manufacturing building paper and building board from wood pulp and other fibrous materials. Pulp mills combined with building paper and building board mills, and not separately reported, are also included in this industry; where separately reported, they are classified in Industry 2611. 3.3 INDUSTRY STRUCTURE The geographical distribution, size, and value of shipments for establishments in the pulp and paper mill industry in 1982 are shown in Table 3-2. Paper mills, except building papers (SIC 262) constitute the largest portion of the industry (50% of the total establishments and 62% of the total value of shipments). Ninety-four (94%) percent of the industry employs 20 or more employees. -6- ------- TABLE 3-2 PULP AND PAPER INDUSTRY STATISTICS FOR SELECTED STATES (Census of Manufacturers, 1982) Industrial Group SIC and Code Geographic Area With 20 With < 20 Total Employees Employees (No.)a or more (No.)a (No.)d Value of Shipments (million dollars) 261 Pulp Mills 35 35 3,110.4 262 Alabama 2 2 0 (D) Alaska 2 2 0 (D) California 3 3 0 (0) Florida 3 3 0 (0) Georgia 4 4 0 549.5 Lou i s i ana 1 1 0 (D) Maine 3 3 0 (0) Mississippi 1 1 0 (0) North Carolina 3 3 0 (0) South Carolina 1 1 0 (D) Tennessee 3 3 0 (0) Washington 5 5 0 363.2 Wisconsin 4 4 0 (D) Paper Mills, Except Building Paper 289 273 16 20,994.6 Alabama 6 6 0 1,663.3 Arizona 3 2 1 (D) Arkansas 3 3 0 (D) California 9 8 1 (D) Connecticut 5 4 1 (0) Florida 2 2 0 (D) Georgia 6 5 1 (D) Kentucky 3 .3 0 (D) Louisiana 5 5 0 744.6 Maine 16 16 0 2,116.9 Maryland 1 1 0 (D) Massachusetts 30 30 0 638.9 Michigan 22 21 1 986.4 Minnesota 6 6 0 641.7 Mississippi 3 3 0 (D) -7- ------- TABLE 3-2 (CONTINUED) PULP AND PAPER INDUSTRY STATISTICS FOR SELECTED STATES (Census of Manufacturers, 1982) Industrial Group With 20 With < 20 SIC and Total Employees Employees Value of Shipments Code Geoqraphic Area (No.)a or more (No.)a (No.)a (mi 11 ion dollars) New Hampshire 13 12 1 281.5 New Jersey 8 6 2 303.9 New York 36 32 4 1,096.3 North Carolina 6 6 0 872.7 Ohio 16 14 2 883.8 Oregon 7 7 0 752.7 Pennsylvania 14 14 0 1,301.8 South Carolina 2 2 0 (0) Tennessee 4 4 0 614.8 Texas 4 4 0 (D) Vermont 7 6 1 (D) Virginia 3 3 0 (D) Washington 13 13 0 1,251.4 Wisconsin 36 35 1 2,960.7 263 Paperboard Mills 201 194 7 9,531.1 Alabama 8 8 0 758.6 Arkansas 4 4 0 687.2 California 18 17 1 391.7 Connecticut 7 7 0 (0) Florida 5 5 0 (D) Georgia 12 12 0 1,186.6 Idaho 1 1 0 (0) 111inois 7 7 0 104.6 Indiana 10 10 0 163.6 Louisiana 6 6 0 625.8 Massachusetts 5 4 1 62.7 Michigan 13 11 2 290.6 Minnesota 1 1 0 (D) Mississippi 3 3 0 (0) Montana 1 1 0 (0) -8- ------- TABLE 3-2 (CONTINUED) PULP AND PAPER INDUSTRY STATISTICS FOR SELECTED STATES (Census of Manufacturers, 1982) SIC Code 264 Industrial Group With 20 With < 20 and Total Employees Employees Value of Shipments Geoqraphic Area (No.)a or more (No.)a (No.)a (million dollars) New Jersey 10 10 0 86.7 New York 11 9 2 (D) Ohio 18 18 0 305.1 Oklahoma 3 3 0 (D) Oregon 5 5 0 485.3 Pennsylvania 15 15 0 (D) South Carolina 6 5 1 421.0 Tennessee 7 7 0 (D) Texas 6 6 0 (D) Virginia 9 9 0 664.0 Washington 4 4 0 664.0 Wisconsin 6 6 0 (D) Converted Paper and Paperboard Products Except Containers and Boxes 2, 737 1,487 1,250 (D) Alabama 15 9 6 (0) Arizona 4 1 3 (D) Arkansas 23 20 3 (D) California 311 161 150 (0) Colorado 5 4 1 27.9 Connecticut 22 11 11 (D) Delaware 1 1 0 (D) District of Columbia 1 1 0 (0) Florida 80 37 43 (D) Georgia 87 52 35 (D) Idaho 2 2 0 (D) Illinois 229 123 106 (0) Indiana 78 48 30 (0) Iowa 26 15 11 295.3 Kansas 29 9 20 (D) -9- ------- TABLE 3-2 (COHTINUED) PULP AND PAPER INDUSTRY STATISTICS FOR SELECTED STATES (Census of Manufacturers, 1982) Industrial Group SIC and Code Geographic Area With 20 With < 20 Total Employees Employees (No.)a or more (No.)a (No.)a Value of Shipments (million dollars) Kentucky 13 Louisiana 10 Maine „ 4 Maryland 9 Massachusetts 152 Michigan 90 Minnesota 48 Mississippi 12 Missouri 66 Nebraska 5 New Hampshire 17 New Jersey 192 New York 387 North Carolina 71 Ohio 167 Oklahoma 9 Oregon 22 Pennsylvania 163 Rhode Island 15 South Carolina 16 Tennessee 46 Texas 121 Utah 2 Vermont 2 Virginia 34 Washington 37 West Virginia 9 Wisconsin 105 265 Paperboard Containers and Boxes 2,661 Alabama 34 Arizona 11 Arkansas 29 9 8 4 9 92 46 18 9 39 3 10 111 169 42 75 4 12 94 9 10 32 66 2 2 18 18 5 69 1,870 23 5 24 4 2 0 0 60 44 30 3 27 2 7 81 218 29 92 5 10 69 6 6 14 55 0 0 19 19 4 36 791 11 6 5 (0) 205.1 (D) (D) (D) (D) (D) (0) (D) (D) (0) 1,331.0 (D) (D) (0) (D) (0) (D) (D) (D) (0) (D) (0) (0) (D) (D) (D) 2841.7 19,145.6 (D) 39.4 D -10- ------- TABLE 3-2 (CONTINUED) PULP AND PAPER INDUSTRY STATISTICS FOR SELECTED STATES (Census of Manufacturers, 1982) Industrial Group With 20 With < 20 SIC and Total Employees Employees Value of Shipments Code Geoqraphic Area (No.)a or more (No.)a (No.)a (million dollars) California 241 166 75 2,202.3 Colorado 15 15 - (D) Connecticut 49 39 10 (D) Delaware 7 7 - (0) Florida 64 34 30 (0) Georgia 88 64 24 824.1 Idaho 3 3 - (D) Illinois 210 145 65 1,596.1 Indiana 86 64 22 (D) Iowa 18 16 2 (0) Kansas 11 10 1 212.7 Kentucky 30 25 5 (0) Louisiana 18 16 2 (D) Maine 5 5 - 45.0 Maryland 41 29 12 (D) Massachusetts 117 89 28 607.5 Michigan 104 63 41 (D) Minnesota 36 30 6 371.3 Mississippi 16 12 4 (D) Missouri 74 53 21 (0) Nebraska 9 8 1 (D) New Hampshire 7 6 1 (D) New Jersey 184 116 68 (0) New York 239 151 88 1,118.3 North Carolina 91 72 19 642.2 Ohio 196 127 69 1,167.9 Oklahoma 11 7 4 57.8 Oregon 12 10 2 (0) Pennsylvania 182 129 53 1,256.2 Rhode Island 35 22 13 (0) South Carolina 35 27 8 (D) Tennessee 70 56 14 467.7 Texas 122 76 46 821.8 Vermont 1 1 - (D) -11- ------- TABLE 3-2 (CONTINUED) PULP AND PAPER INDUSTRY STATISTICS FOR SELECTED STATES (Census of Manufacturers, 1982) Industrial Group With 20 With < 20 SIC and Total Employees Employees Value of Shipments Code Geographic Area (No.)a or more (No.)a (No.)a (million dollars) Virginia 47 32 15 (D) Washington 27 22 5 (D) West Virginia 8 7 1 (D) Wisconsin 78 64 14 (D) 266 Building Paper and Board Mills 3 1 2 366.1 Georgia 3 12 (D) TO] Withheld to avoid disclosing data for individual companies; data are included in higher level totals. a -SIC code totals reflect the summation of totals for individual states and may differ from Census of Manufactures totals. Individual state data is provided by Census of Manufactures (1982). -12- ------- 3.4 GENERAL PROCESS DESCRIPTION, WASTE GENERATION AND DISPOSAL The production of pulp, paper and paperboard involves several standard manufacturing processes including 'raw material preparation, pulping, bleaching and papermaking. These processes are described in the following sections and are illustrated schematically in Figure 3-1. Refer to Table 3-3 for waste summary. Raw material preparation. Wood preparation includes log washing, bark removal, chipping and screening. Bark from whole logs is removed prior to chipping and removal can be accomplished by dry or wet methods. In some cases, water is used as a presoak to soften bonds between the wood and bark prior to barking. Coarse screens are then used to remove large pieces of bark and wood slivers. Barking wastewater is passed through fine screens with the screenings combined with the coarse screening materials. The combined screenings can be dewatered in a press and burned in a bark boiler. This eliminates a source of solid waste while generating power. Approximately 8.2 x 10® MT/yr of bark and wood wastes are generated and approximately 5.3 x 10® MT/yr of that will be burned for fuel (EPA, 1980). MRI estimates that of the remaining 2.9 x 10® MT/yr, none will be deemed hazardous. Pulping and Recovery. Pulping involves the reduction of cellulosic raw material into pulp suitable for further processing. Pulping processes vary from simple mechanical action, as in groundwood pulping, to complex chemical digesting sequences, such as in the alkaline (soda or kraft), sulfite, or semi-chemical (NSCC) processes. Wastes from mechanical pulping include screening dirt and slivers and wastewater that is either recycled or discharged to the treatment system. Wastes from chemical pulping vary greatly due to the type of chemical pulping process employed. Basically there are three chemical pulping processes used most frequently. They are the kraft, sulfite, and semi- chemical processes. The kraft process produces a stronger pulp and is currently the dominant pulping process worldwide. Kraft pulp now accounts for over 80% of the chemical pulp produced in this country. -13- ------- TABLE 3-3 PROCESS HASTE TYPE TOTAL QUANTITY PRODUCED (KTAR) WASTE GENERATION FOR THE PULP AND PAPER INDUSTRY ESTIMATED CONSTITUENTS OF CONCERN0 QUANTITY FAILING (HT/YR) CONSTITUENT ESTIMATED RANGE (ppm) POINT ESTIMATE (PP«) None None None None None None Phenol 0.006-1.4 0.11 (130) 2,4-D1chlorophenol 2,4,6-Trlchlorophenol Pentachlorophenol Chloroform Tetrachloroethylene B1s(2-ethylhexyl) phthalate Dl-n-butyl phthalate Toluene Chromium Lead Mercury N0-0.22 0.006-0.4 N0-0.05 0.001-9.7 ND-0.18 N0-0.2 ND-0.03 ND-0.4 0.001-18 0.005-0.0018 0.001-9 0.1 (39) 0.03 (60) 0.007 (26) 0.5 (84) 0.014 (12) 0.025 (111) 0.004 (54) 0.015 (79) 0.06 (142) 0.18 (130) 0.0005 (142) TREATMENT/DISPOSAL Process Wastes -Wood Preparation -Pulping -Paper-making Wastewater treatment Waste Wood and Bark Kraft Chemical Recovery Wastes Sulfite Chemical Recovery Wastes Pulping Rejects Cellulostc Fines Wastepaper Rejects Wastewater 8.2xl06b 594,OOOb 20,000b 460,000b unknown 2.2 x 10' 6b 6.7x10 9b Oa 0a 0a 4.8x10 9a - 65% recycled for fuel - 35% landfllledb - Inc Inerated'5 - Landfllledb - 80% recovered15 - 203C landf 11 ledb - Recycledb - Landf11ledb - Recycled*1 - Landf11ledb - NPDES d1scharged ------- TABLE 3-3 (CONTINUED) WASTE GENERATION FOR THE PULP AND PAPER INDUSTRY TOTAL ESTIMATED CONSTITUENTS OF CONCERN0 QUANTITY QUANTITY ESTIMATED POINT WASTE PROOUCED FAILING RANGE ESTIMATE PROCESS TYPE (HT/YR) (MT/YR) CONSTITUENT (ppm) (ppm) TREATMENT/DISPOSAL Wastewater Nickel 0.002-0.02 0.018 (136) Treatment (cont). * Methylene Chloride ND-2.5 0.03 (70) * Benzene ND-0.15 *0.007 (23) Ethylbenzene ND-0.08 0.008 (16) * Trlchloroethylene NO-0.85 0.074 (20) 1,1,1,-Tr1chloroethane ND-2.0 1.3 (20) Wastewater 3.8 x 106b 2.7 x 109a Phenol 9.93 -Biological treatment^ Sludge 2,4-Dlchlorophenol 45.1 * 2,4,6-Trlchlorophenol 20.0 Pentachlorophenol 21.6 * Chloroform 352 * Tetrachloroethylene 16.3 , B1s(2-ethylhexyl) 1.0xl0J phthalate Dl-n-butyl phthalate 9.88 Toluene 8.98 * Chromium 106 1 ~— Lead 317 Ul 1 * Mercury 0.882 Nickel 31.7 * Methylene Chloride 3.08 * Benzene 1.50 Ethylbenzene 7.10 * Trlchloroethylene 63.6 , 1,1,1,-Trlchloroethane 3.67x10 ? MR I estimate b EPA, 1980 •j EPA, 1981 - Numbers In parentheses represent number of points d EPA. 1981 e Sludge concentrations estimated using Organic Leachate Model (OLM) for organic constItutents, and assuming worst case senarlo of 100X precipitation for metals. ------- GENERAL FLOW SHEET PULPING AND PAPERMAKING PROCESS HAW MATtWULS rUMQtMtirrA\. MOCIM PreD. RAW vooo VTERIAL ftcnaiTMi nam ¦CMPOatTiOW LOM acto auiprrt Liouoa UJULItl M>ATt I *»1*T) nuTtAL oviprrt PULPING (MOMnCH "" iwrewvvw CMIH i i L'*J" . ¦ »] PVLPia* - : uooo« ~ I I I ItV»»< E12I11 10« FUM utiti iciata* COOO** WATI* MID WATT* M» iirtm vooo »««Tieut* AMD IUTIK IA«OU«T tuifru. cauot kum rut* L-l. taianoH )t N(AT ncm At a ®t* rtooucT IKUT1* mi ateov. eoattaim »l«ClT TANK c»ia«io« imc kils cait«io« tCCOYCKT FUftAACt CHIttlOH rM»o«ATioa tuurrrt i*trr LltUQft ILM PIT COULXCTCO •»tn« COVQCKiATt MI tl VASMIH4 »U9 ftMul ACID »UA*r UITK ittiouct vaitc VATCB ntSN MTU ¦mntri vatci < •(vts Mm icicouM 3LEACHING I TUKtllltl UK OTNII KUIUtT CMCMtCtUI 'APER - ..aKING paean urn < •ATI! tint m.LtM " OTC : •IZf AhUM ITAICM kUI "Tj- -J=l unuicm W 1 (U«0 IMT1 rite* piaca Plica • TOCI pwwatioi coat in* »«mcwra unwaim MMI ¦ACMIBC ¦«« at um um rinuiM ui | nwtrrm etc**- up una WBITI «4TCa CIS*¦ * UP iua lATCa HIT STOCS V1U4 piica PILLCai •ion IMII csatiiii Pima i a hhi pinvcra Source: Proposed Development Document for Effluent Limitations Guidelines for the Pulp, Paper and Paperboard; and the Builders Paper and Board Mills. ------- (EPA, 1980). Waste quantities generated from pulp manufacture are greatly dependent on the process used and on whether chemical recovery is practiced. In mechanical pulping, no chemicals are used and little or none of the wood material is dissolved. However, in sulfite pulping with lime and sulfurous acid, half of the wood is dissolved and both the dissolved wood and the chemical are discharged to the wastewater treatment stream, creating large quantities of waste. In kraft pulping, sodium hydroxide and sulfide0 (from sulfate) are used to dissolve, about hair or the wood but the chemicals are recovered. In recovery the dissolved wood material is burned as a fuel. Semi-chemical pulping dissolves less of the wood material and consequently smaller waste quantities would be expected if recovery were practiced. However, recovery is not generally practiced. Pulping process wastes include pulp rejects (460,000 MT/yr), cellulosic fines, Whitewater and chemical recovery wastes (614,000 MT/yr). Currently, all of these wastes except chemical recovery wastes are managed in the wastewater treatment system and are expected to settle out with the primary or secondary treatment sludge. Some mills clarify wash waters of the pulping operations to recover and reuse cellulosic fines and pulping rejects. In this case, these wastes would be considered non- hazardous (EPA, 1980). Dissolved pulp including pulp rejects and cellulosic fines is expected to contain phenol levels in the interstitial water of the wastes. Phenol is generated during chemical and mechanical pulping when lignins and resins are separated from the cellulosic fibers. Whitewater fines are expected to contain chlorophenol and chloroform levels above the proposed regulatory level. Bleaching. Following pulping, the unbleached pulp is brown or deeply colored due to the presence of Hgnins and resins or because of inefficient washing of the spent cooking liquor from the pulp. Bleaching is required to produce a light colored or white product. Bleaching is generally performed in several different stages. Some of the stages (abbreviations in parenthesis) are: -L6- ------- chlorination (C) caustic extraction (E) hypochlorite (H) chlorine dioxide (D) oxygen (0) etc. C-E-D-E-D is a common sequence in kraft bleaching, and C-E-H in sulfite bleaching. Almost all sulfite pulps are bleached. Secondary fibers are also often ^bleached (i.e., wastepaper that has been de-inked). Wastes from the bleaching step include wastewaters with chlorophenol and chloroform above the current regulatory levels and waste fiber which will be landfilled. Chlorophenols and chloroform are generated during the bleaching process when chlorine bleaching agents are used. Additionally, given the presence of pentachlorophenols and alkali conditions in sulfate bleaching, there exists a potential for generation of dioxins. Dioxins generated in the sulfate bleaching step may persist through other steps of the process and into the wastewater treatment system. Papermakinq. Once pulps have been prepared, they are further mixed, blended, and non-cellulosic materials added to make the "furnish" for papermaking. This stock preparation step could involve dyeing, sizing, and starching. A dilute water suspension of pulp is prepared from the "furnish" and from this, a layer of fiber is deposited on a fine screen. This layer is then removed, pressed, dried and when desired, coated to form the final product. Titanium, zinc sulphide, and lithopone pigments are generally used in paper-making (Masselli, 1970). Sizing of paper is done to increase resistance to penetration by liquids, particularly water. Rosin is typically used when sizing is required but natural waxes, starches, sodium silicate, glues, casein, synthetic resins, rubber latex and various hydrocarbons are also used (Masselli, 1970). Starching may be done to paper, however, its retention is difficult since it forms colloidal solutions and readily passes off with the filtered water. Coating of paper is designed to solve the problems of permeability and -17- ------- printability. Chemicals which may be used as binders or coatings are polyvinylidine chloride, polypropylene, "saran" lacquer, rubber, acrylic latex, styrene-butadiene latex, polyvinyl acetate, polyvinyl alcohol, and carboxymethyl cellulose (Masselli, 1970). Papermaking wastes include process wastewaters, which are handled in the wastewater treatment system, and other process wastes which are incinerated when they have sufficiently high organic content and landfilled or managed in the wastewater treatment system otherwise. The solid wastes from papermaking include 2.2 x 10® MT/yr of wastepaper rejects and some fillers and wasted fiber which are landfilled (EPA, 1980). MRI estimates that, none of the solid wastes will be deemed hazardous as a result of the proposed regulatory levels. Wastewater Treatment. The pulp, paper,and paperboard industry employs many types of wastewater treatment systems to reduce the levels of pollutants contained in mill effluents. Biological treatment systems are used extensively by the industry. Aerated stabilization is the most common treatment process employed at mills discharging directly to a receiving' water. Primary treatment only is employed at a relatively large number of plants. Primary treatment involves sedimentation, flotation, or filtration using mechanical clarifiers or sedimentation lagoons. Approximately 3.8 x 106 MT/yr of wastewater treatment sludge is generated (EPA, 1980). Primary and secondary treatment sludges are expected to have concentrations of chlorophenols, chloroform, trichloroethylene, methylene chloride, benzene and tetrachloroethylene above the proposed regulatory level." These constituents are all present in the interstitial water of the sludges above the regulatory levels. Sludges from bleached kraft, sulfite, and de-inking processes exhibit the. highest levels of these constituents, with average chloroform levels estimated to be over 1 ppm. MRI estimates that 2.7 x 10® MT/yr of waste water treatment sludges from these processes are expected to be regulated as hazardous. Approximately 6.7 x 10^ MT/yr (EPA, 1980) of wastewater is generated from -18- ------- the pulp and paper mill industry. Of this amount, 4.8 x 10^ MT/yr of wastewater generated by mills manufacturing bleach kraft pulp, bleached sulfite pulp or de-inked pulp with high levels of trichloroethylene, chlorophenols, chloroform and tetrachloroethylene are expected to be regulated as hazardous (MRI estimate). -19- ------- 3.6 REFERENCES U.S. Department of Commerce, Bureau of the Census, 1982 Census of Manufactures, Industry Series. 1985, Washington, D.C. U.S. Government Printing Office, Office of Management and Budget, Standard Industrial Classification Manual. 1972, Washington, D.C. U.S. Environmental Protection Agency, Environmental Pollution Control, Pulp and Paper Industry-Part I Air, October, 1976, Washington, D.C. Brown, K.W., and Associates, Inc., Characteristics of Hazardous Waste Streams, December 1982, Cincinnati, OH. U.S. Environmental Protection Agency, Treatability Manual, Vol II and III, September 1981, Washington, D.C. U.S. Environmental Protection Agency, Subtitle D Study Phase I Report, October 1986, Washington, D.C. U.S. Environmental Protection Agency, Development Document for Proposed Effluent Limitations Guidelines New Source Performance Standards and Pretreatment Standards for the Pulp, Paper and Paperboard and the Builders' Paper and Board Mills Point Source Categories, December 1980, Washington, D.C. Sterling, Doreen, Background Information on Pulp and Paper Industry, June 1987, Washington, D.C. Austin, George, Shreve's Chemical Process Industries, Fifth Edition, 1984, New York, NY. U.S. Environmental Protection Agency, Disposal practices for Selected Industrial Solid Wastes, May 1980, Washington, O.C. K1rk-0thmer, Encyclopedia of Chemical Technology, Third Edition, 1984, Washington, D.C. Illinois Environmental Protection Agency, Industrial Waste Survey Data Summary, October 1980, Springfield, IL. Research Triangle Institute, Review of Public Comments on the Proposed Toxicity Characteristic, November 1986, Research Triangle Park, NC. -20- ------- APPENDIX Summary of Assumptions and Calculations for Pulp and Paper Industry (SIC 26) Parameters No. of Facilities 1 Total Value of Shipments 1 Total Process Solid Waste^ Wood Preparation Wood and Bark Wastes'- Kraft Pulping Chemical Recovery Wastes2 Sulfite Pulping Chemical Recovery Wastes" Pulping Rejects2 Cellulosic Fines2 Papermaking Wastepaper Rejects2 Wastewater2 Wastewater Treatment Sludges2 Totals 5,926 $79,895.1 x 106/yr 11.5 x 106 MT/yr 8.2 x 106 MT/yr 594,000 MT/yr 20,000 MT/yr 460,000 MT/yr Unknown 2.2 x 106 MT/yr 6.7 x 109 MT/yr 3.8 x 106 MT/yr \ Census of Manufactures, 1982 2 EPA, 1980 -21- ------- |