During mechanical pulping, fibre derived dissolved and colloidal substances (DCS) are released from wood into the process water, the quantity and the composition of the sub- stances depending on the wood raw material and the defibration method used. A consid- erably larger amount of DCS is dissolved from refiner mechanical pulp than from ground- wood, but the composition of the DCS in each is almost the same. 2 to 5% of wood mate- rial is released into the process water in mechanical pulping and the subsequent stages of treatment. Because there are no significant chemical changes, the same organic substances are found in the process water as in wood. More than 40% of the DCS released from unbleached spruce TMP are carbohydrates. In addition, lipophilic extracts (14%), water- soluble lignans (7%), and low molecular weight acids (2%) are released. The rest consists of, among others, lignin, bark derived phenols, proteins, colloidal fibre fines, and inorganic salts. The majority of carbohydrates dissolved from unbleached spruce TMP consists of acetylated galactoglucomannans (60%). In addition, smaller amounts of arabinogalactanes (11%) , arabinoglucuronoxylans (2%), and pectins (2%) are dissolved.

In traditional mechanical pulping methods, production lines are generally integrated with paper manufacture that uses, as process water, a water fraction that contains dissolved components and is obtained from the mechanical grinding process. Generally, the dis- solved components are not removed but they are recycled in the process water circulation.

Part of the DCS are removed from the process along with the paper, but part remains in the circulation water. In that case, they can react with paper chemicals and cause technical problems. When water circulation is closed, various DCS are enriched into the water in various ways. The substances with lowest solubility and those that are adsorbed by fibres the easiest are removed along with the paper. For example, the proportion of lignin and lipophilic extracts in the total amount of DCS decreases when the DCS level of the circu-

lating water increases, but the proportional part of carbohydrates, instead, increases. In the further treatment of fibres, it can be technically difficult to use process water that contains dissolved and colloidal components. Process water can reduce the runnability of the paper machine or increase the organic loading of the process, whereby external purification is needed. Such methods of purification include evaporation, deposition, clarification, flota- tion or some filtration methods. The pure water obtained from concentration can be re- turned to circulation. Evaporation is a common method in the pulp industry but not so much in paper processes yet. The treatment of process water containing polymeric carbo- hydrates by concentration is difficult because of colloidal substances and viscous proper- ties.

FI patent publication 85 041 suggests decomposition of ingredients dissolved or dispersed from paper pulp, with the aid of enzymes, by particularly adding enzymes that break down hemicellulose to the water circulation of a paper machine. The purpose was to improve infiltration from the pulp track formed on the wire and to improve the retention of fibres.

FI patent publication 954377 describes the use of enzymes, e. g., hemicellulases, in de- taching compounds derived from wood or coating which adhere to a moving member of the paper machine. FI patent publication 90 670 relates to hydrolyzing with pectinase the detrimental pectin dissolved from pulp during alkali treatment or peroxide bleaching, whereby the need to add cationic polymers is decreased. US patent publication 5,415, 735 suggests treatment of the glucomannans of the DCS by esterases to redeposit the gluco- mannans on the surface of the fibres and to reduce the concentration of dissolved sub- stances. FI patent publication 93 230 deals with depositing resinous substances onto a fibre by hydrolyzing with hemicellulases the carbohydrates that are on top of colloidal pitch droplets in the process water, whereby the stability of the pitch droplets deteriorates and the resinous substances are deposited onto the surface of the fibres. However, none of the publications mentioned above tries to solve the problem with concentration of the process waters derived from pulping.

Terho and Malinen (1996) (Wet-End Chemistry in Closed-Cycle Papermaking. Interna- tional Conference on New Available Techniques; 5th International Conference on New Available Techniques, 1. World Pulp and Paper Week (SPCI): 525 (1996; SPCI): Pa-

perchem AB 16849) and Gullichsen (1993) (Towards the Nonpolluting Pulp Mill; General Aspects, EUCEPA International Environmental Symposium: Pulp and Paper Technologies for a Cleaner World (EUCEPA), Session: Plenary Lectures: 27-34 (1993: CTP) Dialog File: 240 Paperchem AB6714168) deal with concentrating the process water from mechanical pulping by evaporation.

The purpose of the present invention is to eliminate the drawbacks of known technology and to provide a new kind of method to enhance the concentration of DCS in the process waters derived from mechanical pulping.

In the process according to the invention, the concentration of DCS can be enhanced by using enzymes, whereby a greater amount of recyclable water can be separated from the concentrate. In this case, the circulation water coming to the paper machine contains a smaller amount of detrimental substances. The purpose of the invention in particular is to decrease the amount of waste water from pulping processes and paper machine circulation waters.

It is well-known that the amount of waste water from pulping processes could be decreased by concentrating the process water. However, when process water is concentrated, the vis- cosity of the process water tends to go up so high that concentration cannot be continued.

By concentrating, a dry content of only 40% can be obtained, whereby it is not economic to bum the concentrate. In the process according to the invention, the increase in viscosity, when process water is concentrated, is prevented by using an enzymatic method or the vis- cosity of process water that has already been concentrated is reduced, whereby higher dry contents can be achieved as a consequence of concentration. With the aid of the process, dry contents of more than 40%, preferably more than 45%, more preferably more than 50%, and most preferably more than 60% can be achieved, whereby it is profitable to after- treat the concentrate by burning. Because their volumes decrease and their treatment either on dumping areas or by burning becomes easier, the process provides a more economic treatment for concentrates.

More specifically, the process according to the invention is mainly characterized in what is presented in the characterizing part of claims 1, 17,18, and 19.

The invention provides considerable advantages. Therefore, it is possible to modify the DCS of process water by using enzymatic methods so that the process water can be con- centrated by, for example, evaporating it into a high dry content without an increase in the viscosity of the process water, and the majority of the process water can be returned to circulation as pure water. After concentration, the dry content of the concentrate is prefera- bly more than 60%. Because of the reduction in the volume of the concentrate, it is easier to process further. The concentrate can be burned or taken to a dumping area.

In the following, the invention will be examined closer with the help of a detailed descrip- tion and some examples.

Fig. 1 is a diagrammatic presentation of the viscosity of TMP water as a function of a mannanase dosage. The effect of mannanase (50,200, and 500 nkat/g, 2h, 30°C, 150 rpm) on the viscosity of the TMP concentrate is shown at various rotation velocities.

Fig. 2 is a diagrammatic presentation of the viscosity of TMP water as a function of a dosage of an endoglucanase I preparation. The effect of endoglucanase (EG I) (10, 50, 200, and 500nkat/g, 2h, 30°C, 150rpm) on the viscosity of the TMP concentrate is shown at various rotation velocities.

Fig. 3 is a corresponding representation of the effect of an endoglucanase II preparation on the viscosity of TMP water. The effect of endoglucanase (EG II) (50,200, and 500nkat/g, 2h, 30°C, 150rpm) on the viscosity of the TMP concentrate is shown at various rotation velocities.

Fig. 4 shows the viscosity of TMP water as a function of a dosage of a commercial endo- glucanase preparation. The effect of endoglucanase (Econase) (20 and lOOnkat/g, 2h, 30°C, 150rpm) on the viscosity of the TMP concentrate is shown at various rotation ve- ; ives

Fig. 5 shows the effect of pectinase on viscosity. The effect of pectinase (Pectinex Ultra) (50 and lOOnkat/g, 2h, 30°C, 150rpm) on the viscosity of the TMP concentrate is shown at various rotation velocities.

Fig. 6 shows the effect of pectinase and pectinmethyl esterase on viscosity. The effect of pectinase and pectinmethyl esterase (200 and 500nkat/g, 2h, 30°C, 150rpm) on the viscosity of the TMP concentrate is shown at various rotation velocities.

Fig. 7 shows the effect of xylanase on viscosity. The effect of pure xylanase (I OOOnkat/g, 2h, 30°C, 150rpm) on the viscosity of the TMP concentrate is shown at various rotation velocities.

Fig. 8 shows the effect of lipase on viscosity. The effect of lipase (Resinase, Novo) (1000 and 5000nkat/g, 2h, 30°C, 150rpm) on the viscosity of the TMP concentrate is shown at various rotation velocities.

The carbohydrates that have dissolved into the process water from the wood consist of various hemicellulose compounds with molecular mass distributions within 3000 - 200 000. The majority consists of acetylated galactoglucomannan which, when concen- trated, forms viscose, gelatinous solutions. In addition, small amounts of xylans consisting of xylose, arabinose and methyl glucuronic acid units, glucans consisting of glucose, and pectins consisting of galacturonic acid units are dissolved. The process according to the invention makes it possible to modify the DCS in the process water by using enzymatic methods so that the viscosity of the concentrated process water is reduced. In the enzy- matic method, process water is treated with enzymes which have an effect on carbohy- drates and which break down carbohydrate polymers so that their molecular weight is re- duced. The released low-molecule water-soluble oligosaccharides no longer form viscose solutions. Typically, the enzymes that cause the desired effect are depolymerizing. Man- nanases and endoglucanases are particularly preferred hydrolytic enzymes in this inven- tion.

In the process according to the invention, enzymes are added in connection with concen- ration at either one or more stages before or during concentration. Due to the decrease in ">sity, concentration can be continued to attain a higher dry content than without en-

zyme treatment. Without enzyme treatment, process water can be concentrated to a dry content of about 40 to 50% maximum. By adding enzymes, concentration can be continued until burning the concentrate is economically profitable. According to the invention, the concentrate can be evaporated to a dry content of more than 40%, preferably more than 45%, more preferably more than 50%, and most preferably more than 60%.

In the present invention, "process water"refers to the process water used in mechanical or chemi-mechanical pulping, containing carbohydrates dissolved from the pulp. Mechanical and chemi-mechanical pulping includes, for example, refiner mechanical pulping (RMP), pressurized refiner mechanical pulping (PRMP), thermomechanical pulping (TMP), groundwood (GW) pulping, pressurized groundwood (PWG) pulping, and chemi- thermomechanical pulping (CTMP).

In addition to pulp prepared by the above-mentioned processes, the invention can be applied to the circulation waters of high yield chemical pulp, such as kraftliner.

Process water comprises the internal circulation of a mechanical or a chemi-mechanical pulping process. Typically, such circulation can be obtained from the"brown water"ob- tained in connection with the water elimination of refined pulp. Thus we can generally state that the process water to be treated comprises waste water formed by the processes that increase the dry content of the raw material, the waste water having been obtained by, for example, applying pressure or by filtering or precipitating. The process water can also come from the washing phase of refined pulp. Correspondingly, it is possible to treat a water flow, such as brown water or the waste water from washing which is led from the mechanical or chemi-mechanical pulping process to a paper or board machine.

The process according to the invention can be used to treat concentrated or unconcentrated process water by enzymes that influence carbohydrates. Surprisingly, we noticed in con- nection with this invention that mannanases and endoglucanases worked extremely well in

the process according to the invention. When conducting tests on pure enzymes, we ob- served that pure pectinase, xylanase or lipase did not cause a decrease in viscosity.

Enzyme preparations containing"mannanase and/or endoglucanase"refer to enzyme preparations containing enough mannanase and/or endoglucanase enzyme to reduce the viscosity of concentrated process water or to prevent the increase in viscosity when con- centrating process water. According to a preferred embodiment of the invention, process water has first been concentrated to a dry content of more than 30%. The viscosity of con- centrated process water can be reduced to one third, preferably to one fourth or as low as one tenth of the original viscosity of the concentrate. The amount of enzymes that is re- quired to lower the viscosity of the concentrate or to prevent the increase in viscosity when process water is further concentrated corresponds, when counted as mannanase or endo- glucanase activity, to 1-100000 nkat, preferably 20-1000 nkat/g, most preferably to 50-100 nkat/g of dry matter. By using the said amounts of enzyme, it is possible to prevent the increase in the viscosity of the concentrate to a dry content of 40-60%, preferably more than 60%, more preferably 60-70% or even higher, when concentrating process water.

The enzymes that hydrolyze hemicellulose and/or cellulose: mannanase and endoglu- canase, can come from any micro-organisms capable of producing these enzymes, such as mould fungi, particularly the fungus genera of Trichoderma, Aspergillus, Penicillium, Pae- cilomyces, Sclerotium, Sporotrichum, Thielavia, Polyporus, Tyromyces or bacteria, such as Bacillus or Streptomyces. However, the invention is neither limited to these enzyme sources nor any certain isolation method, but the enzymes can also be obtained by other means.

The"enzyme preparation"in this application refers to an enzyme product that is, according to the invention, capable of preventing an increase in viscosity when process water is con- ontrated or causes a decrease in the viscosity of concentrated process water, when previ- concentrated process water is treated.

The term"enzyme preparation"in this application further refers to any product that con- tains at least one enzyme. Therefore, the enzyme preparation can be, for example, a cul- tured solution containing an enzyme or enzymes, an isolated enzyme or a mixture of two or more enzymes. "Mannanase"or"a mannanase enzyme preparation"or"endoglucanase"or "an endoglucanase preparation"refers to an enzyme preparation containing either one of the above-mentioned enzymes.

It is also possible to produce mannanase or endoglucanase by strains that have been geneti- cally improved to produce these proteins in particular, or by other genetically improved host organisms to which the genes that code these proteins have been transferred. When the genes of a desired protein have been cloned, the protein or part of it can be produced in a desired host organism. The desired host can be Trichoderma, preferably T. reesei mould, a yeast, another mould, such as one from the Aspergillus genus, a bacterium or any other micro-organism which has genetics that are sufficiently well known. The mannanase or endoglucanase preparation can be the cultured solution of a genetically improved produc- tion strain or an enzyme preparation that is taken from it by purifying.

The mannanase and endoglucanase enzyme preparations are also available commercially, for example, the ECONASE enzyme preparations (Rohm Enzyme Finland Oy, Nurmi- jarvi).

Process water is treated with mannanase and/or endoglucanase enzymes at a temperature of 20-90°C, preferably 30-60°C. The treatment time is 10 min to 24 hours, preferably 0.5-2 hours.

Treatment of process water is carried out in a pH of 5-8 and, generally, the pH does not need to be adjusted.

The following non-limiting examples illustrate the invention:

Example 1 Composition of process water of TMP pulp The chemical composition of the dry matter of process water used in thermomechanical pulping (TMP) of softwood was as follows: Gravimetric lignin 7.4% of dry matter <BR> <BR> <BR> <BR> <BR> Soluble lignin 3. 4" <BR> <BR> <BR> <BR> <BR> <BR> Lipophilic extracts 1. 2" <BR> <BR> <BR> <BR> <BR> <BR> Carbohydrates 34. 6" <BR> <BR> <BR> <BR> <BR> <BR> Lignans 4. 6" <BR> <BR> <BR> <BR> <BR> <BR> Ash 30. 5" The composition of the carbohydrate fraction was as follows: Xylan 0.8% of dry matter <BR> <BR> <BR> <BR> <BR> Glucomannan 20. 9" <BR> <BR> <BR> <BR> <BR> <BR> Pectin 0. 6" <BR> <BR> <BR> <BR> <BR> <BR> Cellulose 8. 5" <BR> <BR> <BR> <BR> <BR> <BR> Arabinogalactan 3. 8" Example 2 Treatment of concentrated TMP water with mannanase The dry content of TMP water concentrated by evaporation was 37% and the pH 5.8. The concentrate was treated with mannanase produced by the Trichoderma reesei mould (RUT-C-30) by using an enzyme dosage of 50-500nkat/g per dry matter of the concentrate by slightly agitating (150rpm) at 30°C for 2 hours. A reference sample was incubated without the enzyme. After incubation, the viscosity was immediately measured with a Bohlin Visco 88 BV viscosimeter (Bohlin Reologi AB, Sweden) at various rotation ve- locities. The volume of the sample was 17ml and the measuring head of the device C30.

The measuring temperature varied within 23.4 - 24. 5°C. On the smallest enzyme dosage, 50nkat/g, the viscosity decreased to less than half of the original, and on a dosage of 200nkat/g to one fifth (25 M Pas) (Fig. 1).

Example 3 Treatment of concentrated TMP water with endoglucanase I In accordance with Example 1, TMP concentrate was treated with an endoglucanase I preparation (EG I) produced by the Trichoderma reesei mould. EG I was efficient in re- ducing the viscosity. As small an amount as 50nkat/g of endoglucanase reduced the vis- cosity to one fourth (29 M Pas) (Fig. 2).

Example 4 Treatment of concentrated TMP water with endoglucanase II In accordance with Example 1, TMP concentrate was treated with an endoglucanase II preparation (EG II) produced by the Trichoderma reesei mould. A tenfold amount of the EG II (500nkat/g) enzyme was needed compared to EG I to achieve the same reduction in viscosity (Fig 3).

Example 5 Treatment of concentrated TMP water with an industrial cellulase enzyme In accordance with Example 1, TMP concentrate was treated with a commercial industrial enzyme (Econase CE, Rohm Enzyme Finland Oy, Nurmijarvi) suitable for breaking down cellulose and hemicellulose. Because Econase contained endoglucanase and mannanase, the viscosity of the concentrate was reduced to one fourth with even a small amount of enzyme (lOOnkat/g) , as counted according to endoglucanase activity (Fig. 4).

Example 6 reatment of concentrated TMP water with industrial pectinase enzyme

In accordance with Example 1, TMP concentrate was treated with a commercial pectinase preparation (Pectinex Ultra SP-L, Novo) which, in addition to endopolygalacturonase, also contained endoglucanase and mannanase. The enzyme dosage (100nkat/g), as counted on the basis of endopolygalacturonase activity decreased the viscosity of the concentrate to nearly a third (Fig. 5).

Example 7 Treatment of concentrated TMP water with pure pectinase enzyme In accordance with Example 1, TMP concentrate was treated with a mixture of endo- polygalacturonase (MegaZyme) that had been isolated from the Aspergillus niger mould and purified and pectinmethylic esterase (P 5400, Sigma), the mixture breaking pectin down into smaller oligosaccharides. Pure pectinase had no effect on the viscosity of TMP water; therefore, pectin is not a compound that increases the viscosity of this process water (Fig. 8).

Example 8 Treatment of concentrated TMP water with pure xylanase In accordance with Example 1, TMP concentrate was treated with xylanase that had been isolated from the Trichoderma reesei mould and purified, and that decomposes xylan into smaller oligosaccharides. Pure xylanase had no effect on the viscosity of TMP water; therefore, xylan is not a compound that increases the viscosity of this process water (Fig.

7).

Example 9 Treatment of concentrated TMP water with lipase enzyme In accordance with Example 1, TMP concentrate was treated with commercial lipase (Resinase A, Novo) that decomposes the triglycerides contained by extracts into free fatty acids and glycerol. The lipase had no effect on the viscosity of TMP water; therefore, the triglycerides of the extracts are not compounds that increase the viscosity of this process "ter (Fig. 8).

Example 10 Effect of enzyme treatment on viscosity in concentration of TMP process water Untreated TMP process water and TPM process water that had been pre-treated with man- nanase and endoglucanase were concentrated into various dry contents. Water treated with an enzyme could be concentrated into higher dry contents than untreated water. The vis- cosity of the enzyme-treated water did not increase to a level that impedes concentration.