Method of bleaching cellulose pulp with ozone

Abstract: The present invention relates to a method of bleaching cellulose pulp with ozone. Ozone bleaching has been extensively studied in laboratory and pilot scale. It has been proved that at low consistencies, i.e. less than 5 %, ozone dissolves well in water and thus good transfer of substance between the ozone and the fibers in the water is achieved. On the other hand, it has been discovered that the ozone, being a gaseous substance, reacts well also directly with a fiber surface which, however, presupposes that the consistency of the suspension is over 25 %. Further, it has been discovered that in the intermediate range between said consistencies ozone cannot satisfactorily contact the fibers. However, both environmental and pumping factors determine the operation to be carried out at that particular intermediate consistency range of 5 to 25 %. A characteristic feature of the method of the present invention, which avoids the disadvantages of prior art methods and permits operation at the consistency range of 5 to 25 %, is that cellulose pulp is pumped with a high-­ consistency pump to a fluidizing mixer in which O₂/O₃ gas is introduced and mixed into the pulp so as to generate foam in which the fibers in the pulp and the ozone used as the bleaching agent are brought to contact with each other, and that the pulp is discharged from the mixer to a reaction vessel.

Description: The present invention relates to a method of bleaching cellulose pulp with ozone. Pulp for the paper and pulp industry must often be bleached in order to produce an end product of adequately high-quality. The most commonly used bleaching agents today are chlorine and oxygen. There is a tendency to avoid the use of chlorine or at least limit it to the minimum because of its damage to the environment. Oxygen is a good bleaching agent but its reaction selectivity is not always adequate whereby also other chemicals must be used. For these reasons, new bleaching agents have been sought. Ozone is one of these. Ozone bleaching has been extensively studied in laboratory and pilot scale. Ozone has proved to be a good bleaching agent but also expensive and difficult to use as the consistency of the pulp to be bleached has to be very low or very high because of the high reactivity of the ozone. For example, at low consistencies, i.e. below 5 %, ozone is dissolved in the water and thus good transfer of mass between the ozone and the fibers in the water is achieved as the ozone containing water can freely flow between the fibers. It has also been found out that ozone, being a gaseous substance, reacts well directly with a dry fiber surface which presupposes that the consistency is so high, in most cases over 30 %, that there is practically no water on the surface of the fiber or between the fibers. Now the ozone containing gas can freely flow between the fibers. On the other hand, for pumpability of the suspension, a certain amount of free water in the suspension must be accepted. For environmental and other reasons, it is desirable to keep this amount of water as small as possible. These factors define that the range which is optimal for both the apparatus and the environment and lies between 5 and 25%. However, ozone cannot contact the fibers in a satisfactory way in this particular consistency range as there is relatively little liquid in the suspension and it is bound in the spaces between the fibers and does not move freely in the suspension, and as ozone, being a gaseous substance, cannot move freely in the suspension because of the state of the suspension. In CA-A-1065105 of Sundman there is disclosed a method of bleaching pulp having a maximum consistency of 15% and being treated with an akaline solution and oxygen for removal of lignin from the cellulosic material at elevated temperature and pressure wherein the invention resides in transforming the pulp suspension into a stable foam in the presence of a foaming agent. In the specific description and examples there is only disclosed the use of oxygen and the introduction of such oxygen into the pulp upstream of a mixer which may be a defibrator with the foaming agent also being added upstream of said mixer to form the stable foam. There is only one brief mention in lines 4-6 of page 5 of the possibility of replacing oxygen with ozone although no detailed considerations nor examples are given in respect thereof and such is considered somewhat speculative and the specific requirements for the use of pure ozone are not considered. If pure ozone were introduced via pipeline 5 in Figs. 1 or 2 of Sundman, then the ozone would react in a number of seconds with the pulp to cause overbleaching and damage the pulp and also react with the simultaneously or previously introduced foaming agent to produce undesirable reaction products. Also, if the ozone is introduced into the pulp without the use of a mixer, only a small portion of the pulp would be in contact with the ozone. Due to the rapid reaction between ozone and everything it is in contact with said portion of pulp would, naturally, be overbleached and thereby damaged. Pure ozone is also technically difficult to handle on an industrial scale. Ozone has to be handled at a low concentration in a carrier gas to make its industrial use possible. US Patent Specification 4,080, 249 (corresponding to FR-A-2353674) discloses ozone bleaching of a pulp slurry in a pressurised or unpressurised reaction vessel under agitation wherein the ozone containing gas is bubbled through the fibre suspension and reacts with the fibres in a few seconds and the residual gas leaves the reaction vessel continuously during the 10 to 20 minutes in which the ozone is fed into the batch type reactor provided with an agitator. The bleaching method disclosed is substantially independent of the total gas volume utilised and whilst a consistency of between and 1 and 10% is referred to, none of the twenty three examples actually discloses use of pulp with a consistency in excess of 2%. The problems described above have been solved in the method of the present invention the characterising features of which are disclosed by the appended patent claims. The invention provides a method for bleaching pulp with ozone at a consistency range of 5 to 25%. According to the invention, conditions for good mass transfer are created even if gas or water cannot move freely in the suspension. The invention is described below in detail with reference to the accompanying drawing figures of which: Fig. 1 illustrates a comparison of a state of the art ozone bleaching method and the ozone bleaching method of the present invention; Fig. 2 illustrates a method according to a preferred embodiment for carrying out the ozone bleaching process of the invention; and Fig. 3 illustrates another preferred embodiment of the ozone bleaching process. Figure 1 illustrates, as a function of pulp consistency, comparative reaction results of a conventional ozone bleaching process and an ozone bleaching process applying the method of the present invention. In Fig. 1, Curve A illustrates a typical result from ozone bleaching by a state of the art method. Curve A is based on the discovery by Carl-Anders Lindholm reported in Vol. 31987 of Paperi ja Puu that in previously known processes in the consistency range of 3-25%, the reactivity between ozone and pulp is quite low. Curve B illustrates the result achieved by ozone bleaching with the method of the invention. By conventional methods at low consistencies (0 to 3%) ozone dissolves in water and when the pulp-water mixture is agitated, good transfer of substance between the ozone and the fibers is achieved. Thus bleaching is effective in a dilute pulp suspension. At high consistencies (over 25%) ozone bleaching is carried out mostly as gas phase bleaching. Ozone in gaseous form reacts well with a fiber surface whereby good transfer of substance is gained between the ozone and the fibers. Gas moves freely between the fibers and bleaching proceeds well. At the consistency range of 5 to 25 %, good ozone bleaching requires special measures. The reason of the poor reaction is the somewhat solid nature of the pulp suspension at these consistencies. Water and air cannot readily move in the half-solid pulp. As illustrated by Fig. 1, curve B, the same bleaching result is achieved by using the method of the invention as by conventional bleaching at both low and high consistencies. A characteristic feature of the method of the invention is that in a pulp suspension of the consistency of 5 to 25%, conditions are created where ozone can contact the fibers. The simplest way of doing this has proved to be the mixing of ozone gas into the fiber suspension with an intensive high-shear mixer so as to generate foam comprising of wood fibers, water and 0 2 /0 3 gas. The intense agitation required by the method can be generated by e.g. a fluidizing mixer disclosed in Finnish patent application No. 870747 by A. Ahlstrom Corporation. This mixer typically brings as much mixing efficiency to a small space that fibers or fiber bundles move loose from each other which results in good mixing of chemicals in the fiber suspension. When gas is introduced to this kind of a mixing space, foam is produced. Table 1 presents the water and gas amounts used when ozone bleaching is performed at the consistency of 10%. When the consistency is 10% the pulp suspension contains one ton of fibers and nine tons of water. Approx. two tons of the water is absorbed in the walls of the fibers which leaves about seven tons of free water. The normal ozone dosage is around 1%, i.e. 10 kg 0 3 . The concentration of the ozone gas is 10% at the most, in other words the gas mixture contains 10 kg of 0 3 and 90 kg of 0 2 gas. As indicated by Table 1, the water/gas ratio varies between 1/10 and 1/1 depending on the pressure, which varies within the range of 1 to 10 bar, although the method of the invention only requires exceeding the lower pressure limit of one bar. 1 ton fibers 2 tons water in fibers 7 tons free water 7 m 3 7 m 3 7 m 3 1 % 0 3 , 10 kg 0 3 , 90 kg 02 70 m 3 14 m 3 7 m 3 Pressure 1 bar 5 bar 10 bar Water/gas ratio 1/10 1/2 1/1 The foam generated in a heavy-duty mixer is thus fairly light and the fiber material it contains makes the foam relatively stable. There is a good transfer of substance between the gas and the fibers in the foam which gives a good bleaching result even though the gas or the water cannot freely move among the fibers. Laboratory tests with a batch-type fluidizing mixer proved that large amounts of gas could be brought into the pulp suspensions. The tests were performed so that the gas and the pulp suspension were intensively mixed for a short time (approx. 1 second) and then the bleaching reaction was allowed to happen without intensive mixing. The gas had, however, a tendency to separate, and therefore a better bleaching result in the laboratory batch mixer was achieved when the gaseous chemicals first were intensively mixed into the fiber suspension which is in a fluidized state and the resulting gas-water-fiber foam or mixture was lightly agitated in order to prevent separation of gas. Figure 2 illustrates one possible way of carrying out the ozone bleaching stage. Pulp 7 is pumped with a medium-consistency pump 1 to an intensive mixer 2 into which ozone gas 5 is introduced. From the mixer, the pulp 7 is transferred in a foam-like condition to a reaction vessel 3 and therefrom to gas separation 4. After the reaction, residual gas 6, which is mainly the oxygen added to the pulp with the ozone 5, must be separated from the pulp. From the gas separation 4 the pulp flows on to further treatment. It is sometimes necessary to arrange light agitation in the reaction vessel 3 to prevent the foam or mixture formed in the mixer 2 from collapsing. The agitation can be accomplished by an agitator or by arranging proper flow conditions in the vessel 3. Figure 3 is a flow diagram of an alternative embodiment illustrating ozone bleaching stage with a plurality of ozone feed steps (only two illustrated) since the amount of the ozone to be introduced to the process may be so large that it is not advantageous to add all the gas at the same time. Thus the method illustrated in Fig. 3 may be employed. Pulp 18 is pumped with a medium consistency pump 11 (preferably a fluidizing centrifugal pump by A. Ahlstrom Corporation) to a mixer 12 into which gas containing ozone 19 is introduced to form a foam. Pulp 18 flows via reaction vessel 13 to gas removal, for example to a gas-removing medium -consistency pump 14 (preferably a fluidizing, gas-separating centrifugal pump by A. Ahlstrom Corporation). Residual gas 21 is removed. From the medium consistency pump 14 the pulp flows to a second mixer 15, into which ozone is introduced. After reaction vessel 16 and gas removal 17 the pulp flows on for a further treatment stage. Again the reaction vessels 13 and 16 may be equipped with some kind of agitation. It is clear that more that two bleaching steps can be carried out in the corresponding way. The stages/steps are pressurized. The density of the produced foam can be regulated by choosing a desired pressure. Pilot tests were performed according to the embodiment of Fig. 2. Due to practical reasons it was not possible to use ozone gas but normal air. The object of the tests was to study mixing of large amounts of gas into fiber suspensions. The reaction vessel 3 was partly replaced by a plexiglass pipe where the formed foam or mixture could be inspected. The foam or mixture varied much according to the surface tension of the water suspension, the type of fiber, and the amount of gas. In some tests the foam or mixture looked much like a snowstorm where bundles of fibres flew in a gas like snow flakes in air but in the gas there also flew water drops and free single fibers. It is clear that high mixing intensity is needed to form a foam or mixture like this from the original somewhat solid fiber suspension of the consistency of about 10%. It is also clear that some light agitation or special flow conditions are needed to prevent the foam or mixture from collapsing. Other tests with soap added to reduce surface tension produced more milk-like foams. The residual gas 6, 21, 22 produced by the reaction can be used in many ways. The typical ozone gas contains 9 parts oxygen per each part ozone. The residual gas is thus mainly oxygen as oxygen, because of its lower reactivity, does not have enough time to react. The residual oxygen gas can be used in any other stage of the pulp production process, for example as an additional ahemical elsewhere in the bleaching plant or as combustion gas e.g. in a soda recovery boiler or in a lime sludge reburning kiln. Example 1 In a laboratory test, pulp was bleached with the sequence OZDED instead of the conventional OCEDED (O = oxygen, Z = ozone, E = alkaline extraction, D = chlorine dioxide). All bleaching stages were performed at the consistency of 10%. The goal was to verify that Z can replace CE and that the Z stage can be performed at the consistency of 10 %. With an ozone dosage of about 0.9 %, the kappa number after the oxygen stage could be reduced to 8 - 9 in ozone stage without damaging the fibers. With a conventional CE stage, the kappa number is reduced to about 5 - 6 or somewhat lower than in the Z stage. However, the reduction in the Z stage is big enough to enable final bleaching with DED. It is thus possible to completely replace the chlorine with ozone by using medium consistency (10 %) ozone bleaching. This is a significant improvement as the severe environmental problems connected with chlorine are thus avoided. The ozone stage performed at the consistency of 10 % was also compared with ozone stages performed at the consistencies of 1 % and 30 %. It turned out that ozone bleaching performed at the consistencies of 1 % and 10 % gave approximately the same result. This is probably due to good mass transfer in a very dilute agitated solution and in a foam-type mixture. The bleaching performed at the consistency of 30 % gave somewhat worse results. This in probably due to the fact that in a pulp of the consistency of 30 %, there are always fairly big flakes of fibers into the inside of which the ozone cannot reach properly, with the result that the surface of the falkes becomes overbleached and the inside unbleached. Example 2 A mill feasibility study was performed to evaluate the size of the machinery needed for ozone bleaching at the consistencies of 1 %, 10 %, and 30 %. At 1 %, a reaction vessel provided with agitation and operating at 1 % fiber-water suspension was needed into which oxygen-ozone gas was added. A residual gas collecting system was needed as well as a filter machine which after the bleaching raised the consistency of 10 - 15 % before the next process step. At 10 %, only one mixer with high shearing capacity was needed, and a small reaction vessel with light agitation created by an agitator or flow conditions. No filter was needed but only a small gas separator before the next process step. At 30 %, a press was needed before the reaction tower to raise the consistency. Additionally, a high-consistency mixer was needed, and a reaction tower capable of handling solid-gas reactions and provided with some type of intermediate bottoms. After the reaction tower, a dilution, gas separation and discharge system was needed. It was obvious that the machinery needed for bleaching at the consistency of 10 % was by far the cheapest and simplest. As can be comprehended from the above description, a new method avoiding the disadvantages of the prior art ozone bleaching methods has been developed. Only two preferred applications of the method have been described above which in no way intend to limit the invention from what has been presented in the appended patent claims which alone define the scope of protection and coverage of the invention. Thus, although only a few bleaching agents have been mentioned in the above examples, also the other bleaching stages may in addition use any conceivable bleaching agent, e.g. chlorine, ozone, peroxide, chlorine dioxide, sodium hydroxide or enzymes.

Claims: A method of bleaching cellulose pulp with ozone serving as a bleaching agent comprising introducing the pulp having a consistency of 5 to 25% into a fluidizing mixer, introducing a mixture of oxygen and ozone gas into the mixer, mixing said ozone containing gas with the pulp for approximately 1 second under intense agitation and under a pressurized state of 1 to 10 bar thereby forming a fluidized mixture, and discharging the mixture into a reaction vessel. A method according to claim 1 wherein the bleaching is performed in at least two steps such that residual gas is removed after the previous step in a reaction vessel, and additional ozone containing gas is added in the further step. The method according to claim 1 or 2, wherein the ozone content in said ozone containing gas is 10% by weight. The method according to claim 1 or 2, wherein the residual gas is separated from the pulp after the bleaching stage. The method according to claim 4, wherein the residual gas is separated by a gas removing pump used for pumping the pulp for further treatment. The method according to any of the claims 1 to 5, wherein the pulp is introduced into the bleaching process by means of a medium consistency pump. The method according to claim 5 or 6, wherein the pump is mainly used for gas separation and the actual flow is kept up by said medium consistency pump. The method according to claim 4 or 5, wherein the residual gas is fed to another stage of the process, preferably to serve as an additional chemical in the bleaching plant or as combustion gas in a soda recovery boiler or a lime sludge burning kiln. The method according to any of the claims 1 to 8, wherein the ozone bleaching forms a bleaching stage which is part of a larger bleaching plant where the other bleaching stages are performed at a consistency of 5 to 25 %. The method according to claim 9, wherein the other bleaching stages use at least one of the following bleaching agents: chlorine, ozone, peroxide, chlorine dioxide, sodium hydroxide, or enzymes.

Inventors: HENRICSON, LAXEN TOROLF, PELTONEN JUHANI, LAXEN, TOROLF, PELTONEN, JUHANI
Applicants: AHLSTROEM OY, A. AHLSTROM CORPORATION
Application year: 1990
Main classification: D21C9
IPC codes: B01D19, D21C9, D21D5