Investigation on the Behaviour of Undesirable Constituents Antje - PowerPoint PPT Presentation

Investigation on the Behaviour of Undesirable Constituents Antje Kersten, Udo Hamm, Samuel Schabel Chair of Paper Technology and Mechanical Process Engineering PMV, Technische Universität Darmstadt, Germany Hans-Jürgen Öller Papiertechnische Stiftung München, Germany TAPPI 8th Research Forum on Recycling 23-26th September 2007, Niagara Falls, Ontario Fig. 1 1 Fig.

CONTENT 1. Introduction and Objectives 2. Sampling and Analysis 3. Results 3.1 Inorganic constituents 3.2 Organic constituents 4. Conclusions 5. Acknowledgement Investigation on the Behaviour of Undesirable Constituents Fig. 2 2 Fig.

Development of recovered paper utilization rate in Germany in the last 10 years 68 67 66 Recovered paper utilization 65 65 65 65 66 64 rate [%] 61 61 62 60 60 60 60 58 56 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 Source: VDP – Papier 2007 1. Introduction and Objectives (1) Fig. 3 3 Fig.

The relative contamination of the produced paper as a function of recovered paper utilization rate and the transfer coefficient 3 t N = transfer coefficient Relative contamination v t N = 1 2 t N = 0.6 1 t N = 0.2 t N = 0.05 0 0 10 20 30 40 50 60 70 80 90 100 Recovered paper utilization rate [%] Source: Baumgarten, Großmann [1994 ] 1. Introduction and Objectives (2) Fig. 4 4 Fig.

Important developments in the last 15 years concerning the accumulation or removal of undesirable compounds � Production of virgin fibre pulps (chlorine free bleaching and bleaching with chlorine dioxide instead of chlorine bleaching, limited use of complexing agents), � Selection of chemical additives for paper producing, finishing and converting considering recyclability. 1. Introduction and Objectives (3) Fig. 5 5 Fig.

Further developments: � Optimization of recovered paper processing (for example multi-stage flotation and/or wash deinking systems in paper mills [graphic and tissue papers, respectively]), � Progressive closure of process water circuits with the possibility of accumulation of organic and inorganic constituents. 1. Introduction and Objectives (4) Fig. 6 6 Fig.

Target: Investigation and evaluation of the accumulation of harmful substances in paper and board made from recovered paper in 2005 in comparison to 1991 Assumptions: No relevant differences in the investigated paper mills regarding: - produced paper grade, - recovered paper processing, - grade and amount of recovered paper used as raw material, - white water circuit and white water management. 1. Introduction and Objectives (5) Fig. 7 7 Fig.

Sampling � Investigation 1991: 25 paper mills; 15 of 25 paper mills met the a. m. demands of no significant changes up to 2005 � Investigated paper grades: Paper Grade Number of investigated samples (mills) Graphic Papers 3 Packaging Papers 9 (Corrug. Board 5; Carton Board 2; Chip Board 2) Tissue Papers 3 � Sampling directly at the reel drum on 10 consecutive days 2. Sampling and Analysis (1) Fig. 8 8 Fig.

Procedures of sample preparation Daily samples from paper mills Grammage; Reducing in Test on anti- Test on bleeding Dry matter 1 cm x 1 cm - microbial (dye-stuffs, content pieces substances opt. brighteners) 10 days mixed sample Homogenization Cold water Direct determination Extraction with organic solvents extract of the paper sample Chemical analysis 2. Sampling and Analysis (2) Fig. 9 9 Fig.

Analytical parameters Paper sample Cold water Determination Extraction with extract directly in the paper organic solvents • Nickel sample • Bromide, Chloride, • PCP and other • Halogenated organic Fluoride, Nitrate, chlorinated phenols substances Phosphate, Sulphate • PCB • Bleeding of dye-stuffs • Borate • DIPN • Bleeding of optical • Water soluble halo- • Phthalates brightheners genated organic • Polycyclic • Releasing of anti- compounds aromatic microbial constituents • Prim. arom. amines hydrocarbons • Formaldehyde 2. Sampling and Analysis (3) Fig. 10 10 Fig.

Borates Usage: • Expanding agents for additives like starch, casein, animal glue • Preservative effects • Application: adjustment of starch viscosity in starch glue processes of corrugated board Limits for Application: Positive List of Recommendation XXXVI of BfR: • Borax as preserving agent for production of food contact paper; not exceeding 0.005 % relating to dry fiber pulp • Application of sodium silicate, stabilized by 0.42 % Borax, as dewatering accelerator 3. Results – Inorganic constituents (1) Fig. 11 11 Fig.

Amounts of borates in paper samples 1991 and 2005 40 Corrug. Board Borates in CWE (given as boron) 35 30 in mg/kg dry paper 25 Amounts 1991 20 Amounts 2005 Carton Chip 15 Board Board 10 Tissue Papers Graphic 5 Papers <DL DL <DL <DL <DL <DL <DL <DL <DL 0 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15 Paper samples Code No. MV (1991): 6.9 mg/kg MV (2005): 6.8 mg/kg 3. Results – Inorganic constituents (2) Fig. 12 12 Fig.

Amounts of chlorides in paper samples 1991 and 2005 800 Chip Board Tissue Papers Chloride in CWE in mg/kg dry paper 700 600 Corrug. Board Carton Board 500 Graphic Amounts 1991 Papers 400 Amounts 2005 300 200 100 <DL DL 0 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15 MV (1991): 238 mg/kg Paper sample Code No. MV (2005): 232 mg/kg 3. Results – Inorganic constituents (3) Fig. 13 13 Fig.

Sulphates Usage: � Aluminium sulphate • additive for resin sizing, dewatering and retention agents, pH adjustment, • precipitation agents in mechanic chemical waste water treatment. � Sulfuric acid • pH adjustment, • bleaching processes and • producing of parchment paper. 3. Results – Inorganic constituents (4) Fig. 14 14 Fig.

Amounts of sulphates in paper samples 1991 and 2005 6000 Chip Board Sulphate im CWE in mg/kg dry paper 5000 4000 Amounts 1991 Amounts 2005 3000 Graphic Papers 2000 Corrug. Board Carton Tissue Board Papers 1000 DL 0 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15 MV (1991): 652 mg/kg Paper sample Code No. MV (2005): 449 mg/kg 3. Results – Inorganic constituents (5) Fig. 15 15 Fig.

Halogenated organic compounds Important Sources � chlorine bleached pulp, � wet strength agents based on epichlorhydrine, � chlorine treated industrial water and � in colour printed papers: yellow pigments (diaryl pigments) as constituents of printing inks. 3. Results – Organic constituents (1) Fig. 16 16 Fig.

Amounts of halogenated organic compounds in paper samples 1991 and 2005 500 Tissue Papers 450 Amount of halogenated organic compounds in mg/kg dry paper Chip Carton Amounts 1991 400 Board Board Corrug. Board Amounts 2005 350 Graphic 300 Papers 250 200 150 100 50 DL 0 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15 Paper samples Code No. MV (1991): 260 mg/kg MV (2005): 103 mg/kg 3. Results – Organic constituents (2) Fig. 17 17 Fig.

Pentachlorophenol (PCP) Usage: � Widely used in the past due to ist fungicide and bactericide properties especially as wood preservative agent in the agriculture and forestry, in the building and furniture industry. � Slimicide in the German Pulp and Paper Industry till 1971. � Persistent and toxic → Law to ban the use of PCP and its salts in Germany 1989. Limit: � 150 µg/kg dry paper for food contact paper and all paper grades with the Environmental label „Blue Angel“ 3. Results – Organic constituents (3) Fig. 18 18 Fig.

Amounts of PCP in paper samples 1991 and 2005 300 PCP amount in µg/kg dry paper 250 Chip Amounts 1991 Board 200 Amounts 2005 Limit 2005 150 100 Carton Corrug. Board Tissue Papers Board Graphic 50 Papers DL 0 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15 Paper samples Code No. 3. Results – Organic constituents (4) Fig. 19 19 Fig.

Diisopropylnaphthalene (DIPN) Usage: � Solvent for colour creating substances in the capsules of carbonless copy paper since the 1980´s as alternative to the former used PCBs and chlorinated paraffines. � Due to recycling of fibers DIPN enters the paper manufacturing process again. � Migration by direct and/or indirect contact via gas phase into food. � No evidence of risk to human health . 3. Results – Organic constituents (5) Fig. 20 20 Fig.

Amounts of DIPN in paper samples 1991 and 2005 100 Chip Board 90 DIPN amount in mg/kg dry paper Carton 80 Board 70 Corrug. Board Amounts 1991 60 Amounts 2005 50 40 Graphic 30 Papers Tissue 20 Papers 10 <DL <DL DL <DL <DL 0 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15 Paper samples Code No. MV (1991): 29.5 mg/kg MV (2005): 31.9 mg/kg 3. Results – Organic constituents (6) Fig. 21 21 Fig.

Polycyclic aromatic hydrocarbons (PAH) � Source: Constituents of mineral oils in printing inks and carbon black pigments. � Majority of PAH very carcinogenic. � Migration tests are required for wet and fatty foodstuffs (limit: 0.01 mg/kg foodstuffs). � Formation of PAH in paper production process nearly impossible (imperfect combustion). 3. Results – Organic constituents (7) Fig. 22 22 Fig.