AU652358B2

AU652358B2 - Process for processing waste paper with enzymatic removal of printing ink

Info

Publication number: AU652358B2
Application number: AU75430/91A
Authority: AU
Inventors: Hans-Peter Call
Original assignee: Individual
Current assignee: Individual
Priority date: 1990-03-20
Filing date: 1991-03-19
Publication date: 1994-08-25
Anticipated expiration: 2011-03-19
Also published as: RU2066720C1; NO180725C; AU7543091A; NO180725B; JPH05506275A; EP0447672B1; CA2078346A1; BR9106253A; NO923623L; HU9202981D0; HUT64118A; DE4008894A1; ATE119592T1; DE59008654D1; DE4008894C2; ES2072964T3; NO923623D0; DK0447672T3; WO1991014820A1; FI924168A0

Abstract

Process for processing waste paper with enzymatic removal of printing ink, in which a) the redox potential of a solution containing waste paper is adjusted to a value in the range of 200 to 500 mV by simultaneous dosing of oxidizing and reducing agents, b) a lignin-decomposing reaction is initiated by addition of lignolytic enzymes, c) the reaction is continued for approximately 10 minutes by adding 60 to 80 litres/hour of air per 1.5 litres of reaction volume at 40 DEG C, 0.8 to 2.5 % substance density and a stirrer speed of 1200 to 1600 rpm in a standard commercial flotation installation, and d) the reaction continues for 60 to 90 minutes with a reduced supply of air and at reduced stirrer speed.

Description

-7 OPT DATE 21/10/91 APPLN ID 75430 91 PCI' AOJP DATE 21/11/91 PCT NUMBER PCT/EP91/00539

INTERNATION.

INTERNATIONALE ZUSAMMENARBEIT AUF DEM GEBIET DES PATENTWESENS (PCI) (51) Internationale Patentklassirikation 5: (11) Internationale Ver~ffentlichungsnummer: WO 91/14820 D21C 5/02 Al (43) Internationales Ver~ffentlichungsdaunai: 3. Oktober 1991 (03.10.91) (21) Internationales Aktenzeichen: PCT/EP9 1/005391 Vrfetih Mit internalionalem Recherchenbericht.

(22) Internationales Anmeldedatum: 19. Miirz 1991 (19.03.9 1) Priorit~itsdaten: P 40 08 894.4 20. Miirz 1990 (20.03.90) DE (71X72) Anmelder lind Erd CALL, Hans-Peter [DE/DEI; b Heinsbergerstr. 14a, 0-5i12 Ubach-Palenberg (DE).

(74) Anwalt: FITZNER, Ulrich; Am Eichf6rstchen 2a, D-4030 Ratingen-Lintorf (DE).

(81) Bestimmungsstaaten: AT (europaisches Patent), AU, BE (europfiisches Patent), BR, CA, CH (europiiisches Patent), DE (europ~isches Patent), DK (europiiisches Patent), ES (europdisches Patent), FI, FR (europiiisches Patent), GB (europfiisches Patent), GR (europaisches Patent), HU, IT (europitisches Patent), JP, LU (europitisches Patent), NL (europiiisches Patent), NO, SE (europaiisches Patent), SU, US.

(54) Title: PROCESS FOR PROCESSING WASTE PAPER WITH ENZYMATIC REMOVAL OF PRINTING INK (54) Bezeichnung: VERFAHREN ZUR ALTPAPIERAUFBEREITUNG MIT ENZYMATISHER DRUCKFARBENENT-

FERNUNG

1 (57) Absti at Process for processing waste paper with enzymatic removal of printing ink, in which a) the redox potential of a solution containing waste paper is adjusted to a value in the range of 200 to 500 mV by simultaneous dosing of oxidizing and reducing agents, b) a lignin-decomposing reaction is initiated by addition of lignolytic enzymes, c) the reaction is continued for approximately 10 minutes by adding 60 to 80 litres/hour of air per 1.5 litres of reaction volume at 40' C, 0.8 to 2.5 substance density and a stirrer speed of 1200 to 1600 rpm in a standard commercial flotation installation, and d) the reaction continues for 60 to minutes with a reduced supply of air and at reduced stirrer speed.

(57) Zusammenfassung Die vorliegende Erfindung betrifft emn Verfahren zur Altpapieraufbereitung mit enzymatischer Druckfarbenentfernung, wobei a) unter gleichzeitiger Zudosierung von Oxidations- und Reduktionismitteln zu einer Altpapier enthaltenden L6sung emn Redoxpotential im Bereich von 200 bis 500 mV eingestellt, b) durch Zugabe von lignolytischen Enzymen eine ligninabbauende Reaktion gestartet und c) die Reaktion unter Zugabe von 60 bis 80 l/Std. Luft pro 1,51 Reaktionsvolumen bei 40 0,8 bis 2,5 Stoffdichte und einer Riihrergeschwindigkeit von 1200 bis 1600 rpm in handelsiiblicher Flotationsar!age for ca. 10 Min fortgefiihrt wird und d) die Reaktion unter verniinderter Zufuhr und reduzierter Rflhrergeschwindigkeit 60 bis 90 Minuten weiterl~uft.

_1 ~C1 -I "I -u March 18, 1991 Dr. Hans-Peter Call Heinsberger Strasse 14a D-5132 Uebach-Palenberg A Process for Scrap Paper Recycling with Enzymatical Printing Ink Removal The present invention concerns a process for scrap paper recycling with enzymatical printing ink removal.

In practical application, scrap paper recycling including printing ink removal ("deinking") is a chain of several partial processes. The selection of the apparatuses to be used and the design of the entire system must always be geared to the end product, taking into account the economic aspect of cost minimisation and the technological aspect of optimising the quality of the half-finished products. The objective of scrap paper recycling in a deinking process is the best possible quantitative removal of printing ink particles while losing only a minimum of those substances which are valuable for the subsequent paper production. Directly coupled with this objective is the desire to free the heterogeneous basic scrap paper substance of all substances, be they solids, solutes or colloidal solutes so that the paper production is not influenced negatively and the quality of the paper is not affected. It depends on the quality required of the end product which scrap/ paper ingredients are valuable for scrap paper production. Filling substances, for example, are valuable' components of newsprint paper within certain limits, but 4 i I: they are undesirable for the production of tissue papers. Accordingly, a variety of processes have been examined and recommended in prior art (Lausch, Ortner, iber den EinfluB der Druckfarbenzusammensetzung auf den DeinkingprozeB (The Influence of Printing Ink Composition on the Deinking Process) Wochenbl. f.

Papierf. 94 (1966), No. 5, pages 129 136; Berndt, W.: Druckfarben und Deinken (Printing Ink and Deinking) Wochenbl. f. Papierf. 104 (1976), No. 3, pages 95 98; Forester, Deinking of UV-cured Links Tappi J.

(1987), No. 5, 127 130; Deinkbarkeit von Flexodruck Tageszeitungen (Deinkability of Flexoprint Newsprint Paper) IFRA Special Report 1.3, Darmstadt, October 1987; Putz, Upcycling von Altpapier fUr den Einsatz in h6herwertigen graphischen Papieren durch chemisch-mechanische Aufbereitung (Deinken und Bleichen) (Upcycling of Scrap Paper for Use in High-grade Graphical Papers by Chemo-Mechanical Treatment Deinking and Bleaching) Thesis, Technical University of Darmstadt, 1987; Weidhass, Erfahrungen mit einer Deinking- Anlage zur Erzeugung von Zeitungspapier (Experience with a Deinking Apparatus for the Production of Newsprint Paper) Wochenbl. f. Papierf. 104 (1976), No. 22, pages 857 865; Lippert, Erfahrungen mit der Deinking- Anlage fUr Zeitungsdruckpapier der Leykam-MUrztaler AG im Werk Bruck (Experience with the Deinking Apparatus for Newsprint Paper of Leykam-Muerztaler AG at the Bruck Factory) Wochenbl. f. Papierf. 111 (1983), No. 15, 540- 542). All these processes work with physico-chemical methods. A process functioning biologically or enzymatically is not known from the prior art.

A process widely used today is the technology of flotation. A rectangular flotation cell with mechanical distribution of the flotation air was developed by Voit at the beginning of the sixties. In this cell, the suspension flows to a running wheel positioned at the bottom of the cell and propelled from above, which said wheel is surrounded by a concentrically positioned casing with holes. The cell is operated on a self-sucking basis. The running wheel effects the fine dispersion of air in the suspension as well as thrusts of the printing ink particles and the ink, and the distribution of the substances on the bottom of the cell. The accepts are withdrawn via an overflow, the foam is removed by means c a paddle.

In order to improve the hydrodynamics of the cell, the flotation pipe cell was developed in 1978. Both the type of ventilation and the mechanical fine dispersion of the air were taken from the above-described flotation cell in this concept.

In 1982, the flotation pipe cell was reconstructed with the aim of energy reduction, improvement of the deinking effectiveness and increased safety. All that was kept was the shape of the pipe cell. The ventilation method was changed from mechanical ventilation to injector ventilation. The injector is operated on a self-sucking basis accordding to the Venturi principle and permits ventilation of up to 30 Removal of the foam is carried out automatically without the aid of a paddle.

In 1984, the compact flotation cell was introduced. Two factors are of decisive significance for flotation in this cell: 1) a suitable ventilation element in front of the cell, namely the step diffuser and 2) hydrodynamics of the cell which are favourable for the separation step. In four locations, the ventilated substance is guided tangentially to the round, upright cell. In contrast to all other flotation cells, the substance is fed in exclusively below the surface of the suspension.

Provided the mixture of air and suspension is optimal, 3 -1 the immediate double flow in the cell (air with printing ink particles upwards and accepts downwards) should prevent separation of the printing ink particles from the air bubbles.

A so-called "verticel" flotation cell consisting of two cylindrical vessels of different diameters which are positioned one over the other is also known. In this system, the substance is tangentially fed into the lower vessel by means of injectors. The substance-air-suspension stream rises and, over a separating wall, reaches the upper cylindrical vessel which has a larger diameter. While surmounting the separating wall the bubbles are captured by the foam suction means. The substance is led off tangentially downwards in the outer vessel and transported to a levelling bulb. The levelling bulb ensures a constant distance between the suspension level and the foam suction pipe so that control of the level is not reauired.

In addition to the flotation processes described above, there are other processes which will not be addressed in detail here. All these processes have in common that they work with chemicals which are harmful to the environment.

From U.S.-PS 4 687 745, 4 692 413 and 4 690 895 there is known that the enzymes produced by special mutants of the fungus Phanerochaete chrysosporium are suitable for bleaching materials containing cellulose which process, however, has nothing to do with a deinking process.

Also, such a process takes time (approx. 12 hours). Moreover, the enzymes can only be obtained from a specially bred strain of Phanerochaete chrysosporium.

The present invention has the object of providing a process for paper recycling by means of enzymatic deinking which does not have any of the disadvantages of the chemical and enzymatical processes described above.

According to the present invention there is provided a process for scrap paper recycling with enzymatic printing ink removal, comprising a) adjusting a redox potential in the range of 200 to 500 mV by carrying out a metered addition of oxidants and reductives to a reacting solution containing scrap paper; b) starting a lignin-decomposing reaction by adding lignolytic enzymes; and c) continuing the reaction in a commercial flotation unit for approximately 10 minutes to 40 C, 0.8 to 2.5% consistency and a stirring speed of **1,200 to 1,600 rpm, during which period 60 to 801 of air/h per 1.5 1 reaction volume is added, and 15 d) continuing the reaction for 60 to 90 minutes, during which period the addition of air and the stirring speed are reduced.

In a preferred embodiment step d) is carried out before step c).

S 20 In an alternative embodiment step d) is omitted altogether.

What is novel is the combination according to the invention of an enzyme system :..with the flotation processes known per se. This achieves that deinking is largely effected by lignolytical raw enzymes rather than by the conventional above-described flotation chemicals such as NaOH, H 2 0 2 or oleic acid. The actual decolouring jprocess in the process according to the invention is probably due to a loosening of the fibres caused as already mentioned above by the attack of the enzyme on the lignine. The effect is similar to the swelling effect of soda lye on the fibre in the conventional decolouring processes mentioned earlier. Therefore, the loosening by means of the enzymes results in a separation of the printing ink particles from the fibre. Owing to the loosened structure, the printing ink can be easily removed in the subsequent flotation process so that additional metered addition of a frothing reagent AY ,7 is only necessary in minimal concentrations.

4-e- V I MI Cupric sulphate, Mn(II)sulphate, Mn(II)acetate, Fe(II)sulphate, Ti(III)chloride, Ce(IV)ammonium nitrate and Ce(III)nitrate can additionally be used as redox mediators. Zinc, antimonial and lead salts are also suitable.

Phenolic compounds are added to the reaction as enyzme protection substances. Especially suitable for this purpose are veratryl alcohols.

In addition to the above-mentioned chemicals other substances can be added to the reacting solution. These are sodium hypochlorite, polysaccharides such as glucanes or xanthanes, detergents, surface-active agents, fatty acids such as oleic acids, haeme compounds such as haemoglobin, and bleaching reagents such as sodium perborate. Conventional bleaching agents such as sodium hypochlorite, oxygen, chlorine dioxide, Ozone, H 2 0 2 and sodium dithionite can be used for after-bleaching of the decoloured paper.

Lignolytical enzymes such as phenol oxidases, laccases and lignine peroxidases are used as enzymes. These also include lignolytical enzymes obtained from the Phanerochaete chrysosporium fungus. However, it is not essential to employ the specific enzymes obtained in accordance with the U.S. patents mentioned above. According to the invention, it is not necessary to use enzymes in highly purified form or enzymes obtained by means of specially optimised mutants of micro-organisms. Rather, it is sufficient to use, for the process according to the invention, raw enzymes which are commercially available today. In addition to the lignolytical enzymes, pectinases and/or hemicellulases can also be used.

6 .1 The great advantage of the process according to the invention is based on the fact that a pre-treatment before the actual flotation process by means of the flotation chemicals mentioned above which could take up to minutes according to the prior art -is not necessary any more. Since lyes and similar substances are added to the process only in minimal quantities, the process according to the invention is characterised by waste products which are not harmful to the environment. In addition, it is possible to remove the lignine from the scrap paper by inserting a step either before or after the actual flotation process and thus to improve its mechanical properties. For example, the ripping length of the treated stuff can be improved by more than 30 at a lianine removal rate of 5 8 Besides, it should be mentioned that the use of surfaceactive agents is no longer essential in the process according to the invention. Presumably the polysaccharides present in the raw enzymes partially assume the frothing effect of the surface-active agents. This is because these surface-active agents as amphoteric substances with their hydrophobic molecules deposit on the originally hydrophobic printing ink particles in conventional flotation processes. Owing to the reaction with the hardening substances in the water they can deposit on the air bubbles that are present. The soap components which are not precipiatated by the waterhardening ions become active as frothing and dispersing agents.

In the following, the invention is illustrated in greater detail with the aid of an example: 12 g abs.dry (atro) substance (waste paper, newsprint paper) is torn into pieces of approx. 2 cm x 2 cm. Then 7 -8- 300 ml of water having an approximate calcium hardness of 2.5 mmol are added, homogenised by hand at approx. 400 C and then disintegrated in the disintegrator at 3,000 rpm for 5 minutes. Then disintegration is repeated for 2 minutes at a consistency of 3.5 and 3,000 rpm. Next, water at a temperature of 40 0 C is added until a volume of 1.5 1 is reached, and then the substance is filled into a 1.5 1 flotation cell.

0.1 1.5 H 2 0 2 based on abs.dry (atro) paper are added. 2 x 10 5 to 2 x 10 3 of VA based on abs.dry paper are also added. After addition of 500 to 5,000 IU of lignolytical enzymes (1 IU turnover of 1 nmol VA/min to veratryl aldehyde) the deinking flotation process is started with a stirring speed of 1,200 rpm, simultaneously adding 601 of air/h. At the same time, the addition of H 2 0 2 and the sodium bisulphite solution is metered in such a way by means of a submerged redox electrode connected to a pump control that an average redox potential of approx.

400 mV remains constant. The process is continued for 10 to 15 minutes at 40 C, and the contaminated substance is then skimmed off by means of a scraper.

otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.

S* e e I i t .940303,p:\oper\ee,75430caspe,8

Claims

1. A process for scrap paper recycling with enzymatic printing ink removal, comprising a) adjusting a redox potential in the range of 200 to 500 mV by carrying out a metered addition of oxidants and reductives to a reacting solution containing scrap paper; b) starting a lignin-decomposing reaction by adding lignolytic enzymes; and c) continuing the reaction in a commercial flotation unit for approximately 10 minutes to 40 0.8 to 2.5% consistency and a stirring speed of 1,200 to 1,600 rpm, during which period 60 to 801 of air/h per 1.5 1 reaction volume is added, and d) continuing the reaction for 60 to 90 minutes, during which period the addition of air and the stirring speed are reduced.

2. A process according to claim 1 wherein step d) is carried out before step c).

3. A process according to claim 1 wherein step d) is omitted. A process according to any one of claims 1 to 3 wherein the redox potential is in the range of 250 to 450 mV. i i

5. A process according to any one of claims 1 to 4, wherein at least one member of the group consisting of H 2 02, and ozone is used as the oxidant.

6. A process according to any one of claims 1 to 5, wherein at least one member of the group consisting of ascorbic acid, dithionite and sodium bisulphite is used as the reductive.

7. A process according to any one of claims 1 to 6, further comprising adding at Sleast one member of the group consisting of cupric sulphate, Mn(II)sulphate, S Mn(III)acetate, F(II)sulphate, Ti(llI)chloride, Ce(III)nitrate and/or 10 Ce(IV)ammonium nitrate to the reacting solution.

8. A process according to claim 7, wherein zinc salts, antimonial salts and lead salts are added to the reacting solution.

9. A Ii'ocess according to any one of claims 1 to 8, wherein phenolic compounds are added to the reacting solution. A process according to claim 9, wherein veratryl alcohol is used as the phenolic compound.

11. A process according to any one of claims 1 to 10, wherein at least one member of the group consisting of phenoloxidases, laccases and peroxidases are used as the lignolytic enzymes.

12. A process according to any one of claims 1 to 11, wherein pectinases and/or hemicellulases are used in addition to the lignolytic enzymes.

13. A process according to any one of claims 1 to 12, wherein only the prosthetic S 20 groups of the lignolytical enzymes are used. i ti

14. A process according to any one of claims 1 to 13, wherein the pH value is between 2 and i. 25 15. A process according to any one of claims 1 to 14, wherein the pH value is 3. 0

16. A process according to any one of claims 1 to 15, wherein sodium hypochlorite is added to the reacting solution.

17. A process according to any one of claims 1 to 16, wherein complexing agents are added to the reacting solution. 940303,p:\oper\ee,75430caLspe,10 11

18. A process according to claim 17, wherein ethylene diamine tetr'aacetic acid (EDTA) or diethylene triamine pentaacetic acid (DTPA) is used as complexing agent.

19. A process according to any one of claims 1 to 18, wherein polysaccharides are added to the reacting solution. A process according to claim 19, wherein glucanes or xanthane are used as polysaccharides.

21. A process according to any one of claims 1 to 20, wherein detergents are- added to the reacting solution.

22. A process according to any one of claims 1 to 21, wherein surface-active agents are added to the reacting solution.

23. A process according to any one of claims 1 to 22, wherein fatty acids are added to the reacting solution.

24. A process according to claim 23, wherein oleic acid is used as fatty acii, A process according to any one of claims 1 to 24, wherein haeme compounds are added to the reacting solution. 25 26. A process according to claim 25, wherein haemoglobin is used as haeme compound.

27. A process according to any one of claims 1 to 26, wherein perborate is added to the reacting solution. 940303,p: o 940303,p:\oper\ee,7543ca.Lspe,ll I I 12

28. A process according to claim 1 substantially as hereinbefore described with reference to the example. DATED this 3rd day of March, 1994. HANS-PETER CALL By His Patent Attorneys DAVIES COLLISON CAVE Ii -i -I 940303,p:\oper\ee,743Ocatpe,12 March 13, 1991 Summary The present invention concerns a process for scrap paper recycling with enzymatic printing ink removal wherein a) a redox potential in the range of 200 to 500 mV is adjusted while metered addition of oxidants and reduc- tives to a solution containing scrap paper takes place simultaneously, b) a lignine-decomposing reaction is started by adding lignolytical enzymes, c) the reaction is continued in a commercial flotation unit for approxi- mately 10 minutes at 40 0 C, 0.8 to 2.5 consistency and a stirring speed of 1,200 to 1,600 rpm, during which period 60 to 80 1 of air/h per 1.5 1 reaction volume is added, and d) the reaction is continued for 60 to minutes during which period the addition and the stir- ring speed are reduced. i |If *W i Li I INTERNATIONAL SEARCH REPORT International Application No PCT/EP 91/00539 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, Indicate all) According to International Patent Classificat!gn (IPC) or to both National Classification and IPC Int. C1. 5 D 21 C 5/02 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System j Classification Symbols Int. C1. 5 D 21 C Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched a Ill. DOCUMENTS CONSIDERED TO BE RELEVANT' Category Citation of Document, 11 with Indication, where appropriate, of the relevant passages 12 Relovant to Claim No. 13 Y WO, A, 8803190 (CALL, 5 May 1988, see page 3, lines 21 28, see page 4, lines 13 claims 1-20 A 4,6,7, 9-12,14-16 Y ABSTRACT BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY, volume 59, No. 3, September 1988, APPLETON US page 373 Nomura, Shoji, S.: "Elimination of ink from reclaimed paper." see abstract JP-63059494 (Oji Paper Mfg. Co.) P,A PAPIER DAS. volume 44, No. 10A, October 1990, 1,5,9-11, DARMSTADT DE pages V33 V41; Call, H.P. et al.: 14,15, "Einsatz von lignolytischen Enzymen bei der 23-25 Zellstoff- und Papierherstellung (Biopulping, Biobleaching)." see page Vn40 V41 Special categories of cited documents: 10 later document published after the International filing date document defining the general state of the art which is not or priority date and not In conflict with the application but considered to be of particular relevance inventonderstand the principle or theory underlying the earlier document but published on or after the international document of particular relevance; the claimed Invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or Involve an inventive step which Is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- othermeans ments, such combination being obvious to a person skilled document published prior to the international filing date but In the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Serrch Report 27 June 1991 (27.06.91) 10 July 1991 (10.07.91) International Searching Authority Signature of Authorized Officer European Patent Office Form PCT/ISA/210 (second sheet) (January 1985) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 9100539 SA 45711 This annex lists thle patent family miembers relating to the patent documents cited in the above-mentioned international search report. The memhers arc as contained in the European Patent Office EDP File on The European Patent Office is in no way liable for these particulars which are merely given for the purpose or information. 27/06/91 Patent document Publication Patent family Publication cited in search report date member(s) date WO-A-8803 190 05-05-88 DE-A- 3636208 AU-B- 605215 AU-A- 8230387 EP-A- 0327576 ~JP-T- 2500990 05-05-88 10-01-9 1 25-05-88 16-08-89 05-04-90 W& -63059494 None FW or more details about this annex see Official Journal of the European Patcnt 0ffice, No. 12/82 r INTFERNATIONALER RECHERCHENBERICI4r Intereationales Aktenzeichen PCT/EP 91/00539 I. KLASSIFIKATION DES ANMELDUNGSGEGENSTANDS (bel mehrercn Kiassiflkationssymboten sled alle anzugeben) 6 Nach der Internatlonalen Patent klassllkation (WC) oder nach der vationaien Vlasslflkation und der IPC Int.K1. 5 021C5/02 HI. RECIIERCI1ERTE SACIIGEBIETE Recherchierter Nllndestprilfstoff 7 Recherchiertc dcli? sum Mindcstprltfstoff gehorcode Vcritffentllchungcn, sowei thdese enter die recherchierten Sachgebicte fallen a~ Ill. EINSCIILAGIGE VFROFFENTICIIUNGEN 9 Art.* Kcnnzelchnung der VerfiffentlichungI soweit erforderlich enter Angabe dcr mangeblichen Telie 1 2 fletr. Anspruch Nr.1 3 Y WO,A,8803190 (CALL,H.P.) 05 Mai 1988 1, siehe Seite 3, Zeilen 21 28 siehe Seite 4, Zeilen 13 20; AnsprUche 1-20 A 4, 6, 7, 9-12, 14-16 y ABST RACT BULLETIN OF THE INSTITUTE OF PAPER 1, CHEMISTRY. vol. 59, no. 3, September 1988. APPLETON US Seite 373 Nomura,Y.; Shoji,S.: "Elimination of ink from reclaimed paper." siehe Zusammenfassung &JP-63059494 (Oji Paper Mfg. Co.) 0 Besondere Kategarien Yon angegebenen Vorliffentllchungen t0 Vertfifentlichung, die den ailgemeinen Stand der Technlk IT. Sp~tere Vertiffentllchung, die each 8cm Internatiocalen An- definiert, aber nicht ais besenders bedeuteare anzusehen let meldedatum oder dent Priorili~sdalum verllffentlicht worden IE fibtres Doktument, das jedoch erst am oder each dem interna- let und mit dcr Anmeidueg nichi koilidleri, sonderi, cur zumn tionalen Ancieldedatum verllffentllcht worijen isl Verstfndnls des der Erfindeeg zu grendetiegenden Prinzips IV' Vertiffenflichung, die geeligel 1st, cicoe Prirliltsacspruch oder 8er lhr zugrundellegendcc Theorle aegegeben Ist zwelfelhaft erscheinen zu lassen, oder dorch die das Verbf- Vertlffentlchung von besonderer Bedeutung, die beanspruch- fentiichuegsdatum eicer anderec Ici Rectierchenbercht ge- te Erflndung kann niebt ale neu oder auf erfinderiecher Titig. annien Vezltffentiichucg betegi werdec soil ode, die aes eem hell beruhtend beiractitet werden aderen besonderen Creed angeglebec ist (wie susgefutirt) I' Verfiffentlichung von besoederer Bedeutun die beans rech- Vetbffentlichung, die sich auf em. citindliche Offeeliarung, te Erfindung kane nicbt ais auf elnderisc er ftet be. ein Benizrig eie Asstllug oer ndee M~namenrulheed betractitel werden, wenn di e Verttfcnliichung mit deieot7uleeeA stlu 8r deeMinbe ener oder Inenrerce anderen Ver6 (ecIichuegen di, -er Kte. bezehtgonle In Verblndung gobractit wird end diese Verbindung fur P Verbffentlicheng, die v'or den tnteationalen Anuneldeda. cinen Fachmniac naheltegend let turn, aber nach dcct beanspruchten Pronfltftsdatumn vertiffect- W Vertffentilehung, die Mitlled derselbec Patentfaille ist lichI worden let IV. RESCIIEJNIGUNC Datum des Abschlusss 8cr lelercatlonaice Recherche Absendedatum des Intcrationalen Recherchenbericts 27.JUNI 1991 10JUL 194'. Internatioeale Recberchenhehlrde Uterschrft des be'olrIchtlgtcc iledienstelen EUROPAISCIIES PATENTAMT BERNARDO NORI EGA F. ~AY..J Famblatt PCTIISA/21O (cit 21 (Jmu. 19115) r PCT/EP 91/00539 Tnterflationalest Aktcnzelchen

111. EINSCIILAGIGE VFROFFENTIICIUNGEN (rortsetzung von Bliatt 2) Art 7 F Kern7eichnung der Verdilkntlichung, sotwcit erforderlich tinter Angabe der inageblichen TcBefltr. Arispruch Nr. P,A PAPIER, DAS. vol. 44, no. IOA, Oktober 1990, DARMSTADT DE Seiten V33 V41; Call,H-.P. et al.: 'Einsatz von lignolytischen Enzymen bei der Zelistoff- und Papierherstellung (Biopulping, Biobleaching)." siehe Seite Vn40 V41 1, 9-11, 14, 23 Formiat PCTIISAI21O (7".IzbOtefl) (J201U 1985) ANHANG ZUM INTERNATIONALEN RECHERCHENBERiCHT OBER DIE INTERNATIONALE PATENTANMELDUNG NR. EP 9100539 SA 45711 In diesemn Anhang sind die Mitglieder der Patentfamilicn der im ohcngcnanntcn internationalen Recherchenhericht angertlhirten Patentdokumente angegehen. Die Angaben uhber die Familienmitglieder entspreehen dem Stand der Datei des Europflischen Patentnmts am Diese Angahen dienen nur zur Unterrichtung tind erfolgen ohne Gewsihr. 27/06/91 ImRecherchenbericht Datum der Nlitglicd(er) der Datum der 1 angefuhrtes Patentdokument Ver~flentlichung Patentramilie Ver~ffentlichung WO-A-8803 190 05-05-88 DE-A- AU-B- AU-A- EP-A- ~JP-T- 3636208 605215 8230387 0327576 2500990 05-05-88 10-01-91 25-05-88 16-08-89 05-04-90 63059494 Keine L Mir nihere Einzeiheiten diesem Anhang :.iehe Amtshlatt des Europlischen Patentamt, Nr.12/S2