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

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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

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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

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• 1. Introduction and Objectives (1)

60 60 61 61 60 65 65 65 65 66 67 56 58 60 62 64 66 68

Recovered paper utilization rate [%]

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006

Development of recovered paper utilization rate in Germany in the last 10 years

Source: VDP – Papier 2007

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• Fig. 4

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1 2 3 10 20 30 40 50 60 70 80 90 100

Recovered paper utilization rate [%] Relative contamination v

tN = 1

tN = 0.05

tN = 0.6 tN = 0.2

• 1. Introduction and Objectives (2)

The relative contamination of the produced paper as a function

• f recovered paper utilization rate and the transfer coefficient

tN = transfer coefficient

Source: Baumgarten, Großmann [1994]

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• Fig. 5

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• 1. Introduction and Objectives (3)

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.

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• Fig. 6

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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)

Further developments:

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• Fig. 7

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• 1. Introduction and Objectives (5)

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.

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• Fig. 8

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• 2. Sampling and Analysis (1)

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:

3 Tissue Papers 9 (Corrug. Board 5; Carton Board 2; Chip Board 2) Packaging Papers 3 Graphic Papers Number of investigated samples (mills) Paper Grade

Sampling directly at the reel drum on 10 consecutive days

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• Fig. 9

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• 2. Sampling and Analysis (2)

10 days mixed sample Daily samples from paper mills Grammage; Dry matter content Reducing in 1 cm x 1 cm - pieces Test on anti- microbial substances Test on bleeding (dye-stuffs,

• pt. brighteners)

Homogenization Cold water extract Direct determination

• f the paper sample

Extraction with

• rganic solvents

Chemical analysis

Procedures of sample preparation

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• Fig. 10

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• 2. Sampling and Analysis (3)

Analytical parameters Paper sample

Extraction with

• rganic solvents

Cold water extract

• Nickel
• Bromide, Chloride,

Fluoride, Nitrate, Phosphate, Sulphate

• Borate
• Water soluble halo-

genated organic compounds

• Prim. arom. amines
• Formaldehyde

Determination directly in the paper sample

• Halogenated organic

substances

• Bleeding of dye-stuffs
• Bleeding of optical

brightheners

• Releasing of anti-

microbial constituents

• PCP and other

chlorinated phenols

• PCB
• DIPN
• Phthalates
• Polycyclic

aromatic hydrocarbons

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• Fig. 11

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• 3. Results – Inorganic constituents (1)

Borates 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

Usage:

• Expanding agents for additives like starch, casein, animal glue
• Preservative effects
• Application: adjustment of starch viscosity in starch glue

processes of corrugated board

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• 3. Results – Inorganic constituents (2)

5 10 15 20 25 30 35 40 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15

Paper samples Code No. Borates in CWE (given as boron) in mg/kg dry paper Amounts 1991 Amounts 2005

• Corrug. Board

Carton Board Chip Board Tissue Papers Graphic Papers

<DL <DL <DL <DL <DL <DL <DL <DL

Amounts of borates in paper samples 1991 and 2005

DL

MV (1991): 6.9 mg/kg MV (2005): 6.8 mg/kg

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• 3. Results – Inorganic constituents (3)

Amounts of chlorides in paper samples 1991 and 2005

100 200 300 400 500 600 700 800 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15 Paper sample Code No. Chloride in CWE in mg/kg dry paper Amounts 1991 Amounts 2005

• Corrug. Board

Carton Board Chip Board Tissue Papers Graphic Papers

<DL

DL

MV (1991): 238 mg/kg MV (2005): 232 mg/kg

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• Fig. 14

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• 3. Results – Inorganic constituents (4)

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.

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1000 2000 3000 4000 5000 6000 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15 Paper sample Code No. Sulphate im CWE in mg/kg dry paper Amounts 1991 Amounts 2005

• Corrug. Board

Carton Board Chip Board Tissue Papers Graphic Papers

Amounts of sulphates in paper samples 1991 and 2005

• 3. Results – Inorganic constituents (5)

DL

MV (1991): 652 mg/kg MV (2005): 449 mg/kg

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• 3. Results – Organic constituents (1)

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.

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17 50 100 150 200 250 300 350 400 450 500 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15

Paper samples Code No.

Amount of halogenated organic compounds in mg/kg dry paper

Amounts 1991 Amounts 2005

• Corrug. Board

Carton Board Chip Board Tissue Papers Graphic Papers

• 3. Results – Organic constituents (2)

Amounts of halogenated organic compounds in paper samples 1991 and 2005

DL

MV (1991): 260 mg/kg MV (2005): 103 mg/kg

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• 3. Results – Organic constituents (3)

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“

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• 3. Results – Organic constituents (4)

Amounts of PCP in paper samples 1991 and 2005

50 100 150 200 250 300 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15

Paper samples Code No. PCP amount in µg/kg dry paper Amounts 1991 Amounts 2005

• Corrug. Board

Carton Board Chip Board Tissue Papers Graphic Papers

DL

Limit 2005

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• 3. Results – Organic constituents (5)

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.

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• 3. Results – Organic constituents (6)

Amounts of DIPN in paper samples 1991 and 2005

10 20 30 40 50 60 70 80 90 100 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15

Paper samples Code No. DIPN amount in mg/kg dry paper Amounts 1991 Amounts 2005

• Corrug. Board

Carton Board Chip Board Tissue Papers Graphic Papers

<DL <DL <DL <DL

DL

MV (1991): 29.5 mg/kg MV (2005): 31.9 mg/kg

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• 3. Results – Organic constituents (7)

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).

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• 3. Results – Organic constituents (8)

Amounts of PAH (Sum of 23 single substances) in paper samples 1991 and 2005

200 400 600 800 1000 1200 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15

Paper samples Code No. Σ PAH in µg/kg dry paper Amounts 1991 Amounts 2005

• Corrug. Board

Carton Board Chip Board Tissue Papers Graphic Papers

DL

MV (1991): 603 µg/kg MV (2005): 424 µg/kg

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• Fig. 24

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• 3. Results – Organic constituents (9)

Amounts of Phenanthrene in paper samples 1991 and 2005

50 100 150 200 250 300 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15

Paper samples Code No. Phenanthrene amounts in µg/kg dry paper Amounts 1991 Amounts 2005

• Corrug. Board

Carton Board Chip Board Graphic Papers Tissue Papers DL

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• 3. Results – Organic constituents (10)

Phthalates Source: Plasticizers as parts of recipes for adhesive agents and additives for paper converting (printing inks, glues, especially dispersion adhesives). Not chemically bound to the polymer → readily released by elution, migration and evaporation. Some compounds: mutagenic and negative effects on the fertility. Deinking stages are very efficient to remove phthalates from the fibres.

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• 3. Results – Organic constituents (11)

Amounts of Di-n-butylphthalate (DBP) in paper samples 1991 and 2005

20 40 60 80 100 120 140 160 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15 Paper samples Code No. DBP amounts in mg/kg dry paper Amounts 1991 Amounts 2005

• Corrug. Board

Carton Board Chip Board Tissue Papers Graphic Papers

<DL <DL <DL <DL <DL <DL <DL <DL <DL <DL <DL

DL

MV (1991): 39.9 mg/kg MV (2005): 8.5 mg/kg

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• 3. Results – Organic constituents (12)

Amounts of Di-iso-butylphthalate (DIBP) in paper samples 1991 and 2005

20 40 60 80 100 120 140 160 180 23 24 25 16 18 26 12 10 19 4 11 14 6 7 15 Paper samples Code No. DIBP amounts in mg/kg dry paper Amounts 1991 Amounts 2005 Corrug. Board Carton Board Chip Board Tissue Papers Graphic Papers

MV (1991): 26.3 mg/kg MV (2005): 64.5 mg/kg

DL

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• 4. Conclusions (1)

Conclusions

Amounts of harmful inorganic and organic constituents did not increase in spite of the increased use of recovered paper in the period from 1991 to 2005. Borates and Chlorides on a constant level, amounts

• f sulphates in recycling papers significantly

decreased in the last 15 years. Current paper and board with a lower amount of halogenated organic compounds (only 40 % in 2005 in comparison to 1991).

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• 4. Conclusions (2)

Conclusions

All investigated paper and board samples clearly fulfill the fixed limit for Pentachlorophenol in spite

• f increasing amount in some papers.

For the other unhalogenated organic compounds no increasing amounts due to the raised recovered paper utilization rate. The deinking stages may remove up to 60 % of the

• rganic hydrophobic compounds of the used

recovered paper.

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Acknowledgement Special thanks to the Committee for Research and Technology of the Association of the German Pulp and Paper Industry for their support of the project INFOR 73 in 2005.

• 5. Acknowledgement