FI98224B - Method for bleaching of pulp - Google Patents

Abstract

Pulp is (a) cooked (b) treated wit EDTA, DTPA and/or acidified to remove heavy metals (c) delignified in at least 2 oxygen stages with no wash between them (d) bleached with O2, O3, ClO2 and/or H2O2 to give a bleached pulp prod. with at least ISO 80 brightness. Pulp bleaching with Cl2 free cpds. Cl2 and O3 use can be avoided. Brightness of prod. can be increased to ISO 90 if needed by using an O3 stage in place of H2O2. Pollution is lowered.

Description

98224

Method for bleaching pulp

The present invention relates to a process for bleaching pulp to at least a brightness of ISO 80 using at least two of the bleaching chemicals oxygen, ozone and hydrogen peroxide.

Due to, among other things, environmental considerations, efforts have been made to reduce the use of elemental chlorine used in the bleaching of cellulose pulp. The first attempts led to the use of chlorine dioxide, which is in a sense a better alternative to elemental chlorine in terms of environmental protection. In part, marketing factors are also leading the way in which the use of chlorine, both elemental chlorine and chloro-15 compounds, is being phased out altogether. Very many customers place great emphasis on the fact that no chlorine (TCF) has been used in the manufacture of the product they use. The minimum requirement is that no gaseous elemental chlorine (ECF) has been used in the manufacture of the products.

A few years ago, the development of medium-density ozone bleaching. to the form applicable on an industrial scale (cf.

* · FI advertisement publication 89516) most of the companies developing the processes and equipment in the pulp industry • · '···' 25 focused on developing ozone bleaching almost exclusively in a form that can be utilized in their own processes.

* ··. · · • · |

However, ozone has its own drawbacks. Of these, the 30 brands are likely to be expensive, largely due to: A: a more difficult manufacturing method. Another disadvantage of ozone is its high reactivity, which means that ozone-using • · · plants, like chlorine-using plants, must be kept absolutely gas-tight. For the same reason, ozone {* · .. 35 35 also easily damages the cellulose itself if its dosage is not exactly correct or the mixture is not efficient enough.

2,98224

For the above reasons, both peroxide steps and EOP steps have recently appeared in bleaching sequences, especially under pressure (cf. the article "Medium consistency pulp washer generates superior washing effi-5 ciency", TAPPI Journal, June 1990; PCT / FI92 / 00198; EP-pa - exam application 93301222; WO patent application PCT / FI93 / 00222). However, as can be seen from the above publications, it can be seen that ozone still plays a very important role in bleaching sequences.

10

The present invention seeks to take into account both the environmental values that divert development away from chlorine chemicals and also the economic considerations that at least to some extent oppose the use of ozone 15. The process according to the present invention has made it possible to bleach the pulp up to a brightness of 83-85 ISO, and even more, without the need to use more chlorine than ozone. However, if even higher brightness is desired, one peroxide step in the sequence according to the invention can be replaced by an ozone step, which easily achieves a brightness of ISO 90. Correspondingly, it is also possible to use significantly smaller amounts of chlorine dioxide to produce a fully bleached pulp.

‘···’ ’25 *» ·

The characteristic features of the method according to the invention are best apparent from the appended claims.

• · · • »· • · * •

In the following, the method according to the invention will be explained in more detail: ***: 30 with more reference to the accompanying figures, of which Figure 1 shows a batch of a bleaching sequence according to the invention. preferred embodiment.

Fig. 2 shows graphically a significant advantage to be achieved by the invention, Fig. 3 shows a preferred sub-process of the bleaching sequence according to the invention.

9322 ^

The bleaching sequence X / QO / O-EOP-P 2 Pj-P 1 according to the embodiment shown in Figure 1 is initiated by a known Q step for the removal of heavy metals from the cellulosic pulp using chelation (e.g. EDTA, DTPA or similar compounds) or acidification so as to that they would not interfere with subsequent peroxide steps (Pn). In the same step, it is also possible to treat the pulp with enzymes (described by the letter X) which expose the lignin for subsequent delignification steps. The oxygen step 0/0 following 10 actually consists of two pressurized oxygen delignification steps, or rather a step, between which no washing is carried out, as will be explained in more detail in connection with Figure 2. As a third step, separated from the 0/0 step by washing, the EOP step 15 (alkaline bleaching extraction step) has been previously described, for example, in "Medium consistency pulp washer generates superior washing efficiency", TAPPI Journal, June 1990. Similarly, the following, preferably pressurized , but also non-pressurized, peroxide steps (Pn) are disclosed, for example, in toilet patent application PCT / FI92 / 00198.

• • 4 m »

Figure 1, on the other hand, shows a preferred way of arranging the washing liquid circulation in the bleaching sequence. In other words, zero water is used for washing after the last 25 bleaching steps, here P3. The filtrate obtained is passed over the pre-treatment step P2 to the scrubber washing liquid of step P3. Fresh, heated water with a temperature of about 75 ° C is introduced into the washing machine of step P2. The filtrate of step P2, or at least a portion of it, is passed to the scrubbing liquid following the EOP step as a scrubbing liquid, from which the filtrate is in turn passed to the scrubbing process following metal removal Q. In particular, the recycling of the filtrate from the P2 stage washing to the Q stage scrubber results in the peroxide entering the filtrate from the P2 stage being transported to the oxygen stage and enhancing its delignification reaction. If the process is considered further, it is possible that a peroxide-containing filtrate is passed from another scrubber of the bleaching stage, for example stage P, or P3, to the washing of the brown mass, whereby peroxide also passes through the delignification stages.

5 The reason for switching the two oxygen phases in succession as shown in Fig. 1 is shown in Fig. 2. The vertical axis shows the number of pieces and the horizontal axis the time used for the process. Graph a) shows the conventional process of the bleaching process. Unlike Salo soen, immediately after mixing the chemical, the Mass Number decreases very sharply to stabilize later to such an extent that increasing the time no longer produces a substantial change in the reaction result. There are, of course, many different reasons for this. First, the wear of the chemical slows the decrease in Chapter Number 15. Second, more and more reaction products are constantly being generated closest to the fibers in the suspension, so that the unreacted chemical still in the suspension does not easily reach the fibers. Thirdly, the amount of lignin in the fibers decreases, so that its release from the fibers 20 takes place in relation to the slower rate. And fourthly, because some gas is always present in the pulp, it tends to. natural gas in the form of microbubbles in the pulp after the mixer • ·. raised to accumulate into larger bubbles, which already • · · TI. * impede the transfer of substance in suspension. The new mixing step breaks the large bubbles into microbubbles, so that it is possible to think that the mixing alone will somewhat improve the processing result. Photographer b) shows what happens if • · «; the first reaction is kind of stopped at tx, a new dose of the chemical is fed into the suspension and Γ · ’: 30 is mixed into it efficiently and evenly. It is noted that the shape of graph b) is exactly the same as the shape of graph a) after the addition of the chemical. When comparing the time after tj, the graph • «· λ. en a) and b), it is observed that in the same time • m *; ** the procedure according to graph b) achieves a significantly lower Kappa value than the value of graph a) *: * · : in this case. Of course, it is conceivable that a chemical can also be added to the suspension a second time and an even lower Kappa value can be reached in the same time and with virtually the same use of chemicals.

Figure 3 shows in slightly more detail the implementation of the O / O phase of the sequence according to a preferred embodiment of the invention. At the far left, reference numeral 10 shows a scrubber for removing heavy metals from the pulp. The scrubber can be, for example, A. AHLSTRÖM CORPORATION1 in a so-called DD scrubber or a pressure diffuser from Kamyr Inc. After the scrubber 10, the pulp is fed to the steam mixer 12 to raise its temperature and from there further through an intermediate tank 14 by a pump 16 to the mixer 18, where the pulp is mixed with at least oxygen and sodium hydroxide to adjust the pH. If it is also desired to add some peroxide to this oxygen stage, it can also be mixed with the same mixer 18. Steam and / or magnesium, preferably magnesium sulphate, can also be mixed by means of a mixer 18. Said mixer 18 can also be replaced by one or more MC pumps with a chemical connection 20, whereby the pump 16 following the steam mixer 12 could also perform the functions of the mixer 18. One guideline for chemicals, especially • ·. [I for an oxygen mixture, a split ratio of 60/40 can be maintained, i.e. \\ Y, i.e. 60% of the total amount of oxygen is fed to the first stage and 40% to the second. More broadly, the co- • · · ··· '· overdose for the first oxygen stage is 5 to 20 kg02 / admt and if peroxide is to be fed to the first stage, the dosage is relatively low, only about 1-10 kg / admt. . The mass is discharged from the mixer 18 to a reaction temperature of 20 to 20, where the pH is kept in the range of 9 to 13, preferably in the range of 10 to 11.5, the temperature in the range of 75 to 110 ° C, preferably m #. between 85 and 95 ° C and a pressure between 2 and 15 bar, preferably between 3 and 10 bar. The residence time in the first reaction tower 20 is about 10 to 60 minutes, preferably between 25 and 50 minutes.

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The pulp 20 is discharged from the tower 20 by means of an unloader 22, which can, if desired, be equipped with an unloader capable of removing the above-mentioned gas problem (e.g. WO patent applications PCT / FI90 / 00085 and PCT / FI92 / 00216 disclose suitable unloaders) via a second mixer 24 28. Preferably, the feed to the reaction tower 28 is by means of a distributor 26 which ensures that the pulp column in the tower 28 rises evenly and that no channeling 10 takes place. Said dispenser is described, for example, in U.S. Pat. No. 4,964,950 and its use for the above-described purpose is discussed in FI patent application 924805. The chemical dosages in mixer 24 are as follows: 5-20 kgOj / admt and peroxide, preferably the entire peroxide dosage to this second stage, about 5-40 kg / admt . The pH is maintained in this second oxygen stage by means of a sodium hydroxide feed in the range from 9 to 13, preferably from 10 to 11.5, the temperature in the range from 75 to 110 ° C, preferably between 85 and 95 ° C and the pressure between 2 and 10 bar, preferably The residence time in the second reactor tower 26 is about 30 to 100 minutes, preferably between 45 and 90 minutes. From the tower 26, the mass is discharged from the unloader 28, if necessary gas • ♦. Ί separable, via a buffer tank 30, from which further • # by means of a pump 32 to a scrubber 34. If the gas is separated by means of a purge, it is advantageous to lead the gas to the buffer tank 30.

M »• · · · •» ·: In another aspect of the bleaching method according to the invention, V »; It is worth mentioning the bleaching sequence, which gives a pulp brightness of 90 ISO. In the described sequence, the first of the peroxy divides of the sequence of Figure 1 has been replaced by an ozone step. In other words .1. the sequence becomes 9 · «X / Q-O / O-EOP-Z-P-P.

9 - · • · • · · m 35 The alternative sequence is, of course, ·: ··: Q-O / O-EOP-Z-P-P, from which the 7 93224 enzyme treatment step is omitted.

The combination of medium-density ozone bleaching and pressurized peroxide step described in WO patent application PCT / FI92 / 00198, for example, can also be applied to the above sequence. In this case, the sequence becomes X / Q-O / O-EOP-ZP-P-P.

Excluding the enzyme treatment step, the sequence Q-O / O-EOP-ZP-P-P is obtained.

Other useful sequences specific to the method of the invention include e.g.

15-Q-O / O-Pn, which is started by oxygen delignification and continued with the sequence already described above. Among other things, it has been found in this sequence to have the significant advantage that one of the Pn filtrates of the peroxy-20 divages is passed to the washing step prior to oxygen delignification. It is also possible to add some peroxide to said oxygen delignification step. to make this more effective. This sequence achieves * «up to a brightness of approx. 85 ISO. If it is desired to reach i «25 brightness 90 ISO, the ♦ · · ozone phase can be added before the peroxide phase as follows: V 0-Q-0/0-z-Pn, or X 'OQO / OZ / Z-Pn, where Z / Z means more than one ozone bleaching step, as described, for example, in FI publication 89516. In practice, this is done by mixing the ozone into the pulp with several mixers, and from the mixer, in succession without intermediate washing of the pulp.

· / * If necessary, these ozone stages can be degassed, as disclosed in WO patent application PCT / FI92 / 00276 ··: so that the new ozone addition is proportional to the mass of the higher ozone dose. Of course, the sequences 8 98224 0-Q-0/0-ZP-PB, 0-Q-0/0-ZP-Pb, O-Q-O / O-ZP,

O-Q-O / O-Z / ZP and 5 O-Q-O / O-Z / ZP-PB

may come into question.

Example 1.

10 One pulp mill used a sequence

Do-O-EOP-Dj-E-D, where D generally describes the chlorine dioxide step. The normal dosage in such a case is about 40 kg of active chlorine / admt, i.e. about 15 kg of ClO 2 / admt. By replacing the oxygen phase O with a two-stage oxygen phase O / O, i.e. Do-O / O-EOP-D ^ E-Dj, the chlorine dose to the D0 phase could be reduced to 15 kg active chlorine / admt, i.e. to 5.7 kg ClO 2 / admt, i.e. more than 60%. The change in active chlorine consumption over the entire sequence is about 70 -> 45 kg Cl / admt, i.e. of the order of 35%. Often used as a measure of environmental impact, “AOX reduction is more than 50% i.e. <1.0 kg / admt. Peroxide can also be fed to phase 0/0 • «without worries, because phase D0 is • · '· 1 2 3 4 5 ·' 25 as such a very efficient heavy metal remover.

·· · • ·· 1 • · 1: V The following results have also been obtained for the number of pieces and * · 1 V · brightness at different stages.

30 D0 0 / 0p EOP Dj .’Ϊ ’. Chapter 16 3 3 <0.1

Brightness 50 83 90 • · v • · · m I »2 J · 3 ·; · 1 From the above results, it can be seen that the D0 phase can be converted to a heavy metal removal and lignin 5 activating phase alone, after which a preferred process of the invention can be converted. The 0/0 step according to the above embodiment, enhanced with peroxide, works very efficiently.

Example 2.

5

One pulp mill used the following bleaching sequence

Dt / 0-0 / 0-Eop-D2-E, 10 which achieved an ISO brightness of 90. However, since there were still two chlorine dioxide steps in the sequence, the plant wanted to-replace the use of chlorine with another chemical. It was decided to replace the second chlorine-using step D2 with one or more peroxide steps and the first chlorine-using step Dj with a lignin activating and heavy metal removal step X / Q using, for example, EDTA, DTPA or the like and enzymes (step X). Thus, the bleaching sequence became 20 X / Q-C / O-EOP-Pj-Pj-Pj.

Doses (kg / admt) in the experiment performed were as follows: • ·; according to Table 1. Table 2 shows the corresponding pro-. ·· *. sessiparametrit. The production in the experiment was 500 admt / d.

»··

Table 1 • · X / Q 0/0 EOP P1 P2 P3 • · · • ♦ ·

NaOH 25 5 11 7 • «·: 30 02 20 6 • · · V: H 2 O 2 5 7 40 5 21 H 2 SO 4 5 EDTA 3« · ./* DTPA 2 2 • JS MgSO 4 3 2 * Enzyme 5-10 SO2 3 10 98224

Table 2 Temperature 40 95 80 85 70 85

Delay 50 150 25 + 100 180 60 180

Kappa 15.2 <8 <5 <3 <2 5 Brightness 34 45 65 75 77> 83. pH 5.5 11 11

In the most successful test run, a brightness of> 85 ISO was achieved, which was significantly better than expected. The addition of peroxy-10 to the oxygen phase 0/0 significantly increased the brightness values, i.e. 45 -> 55 ISO. The number of pieces, in turn, decreased without 'peroxide addition 15 -> 5, but after peroxide addition 15' -> 4.

In general, using the dosages (kg / admt) in Table 3 below, a pulp with good results and low cost of preparation can be obtained using the bleaching sequence Q-O / O-EOP-P ^ Pj-Pj. Below each range, the dosage that has been shown to be particularly advantageous in our experiments is shown, but must, of course, be taken as an "approximate" value.

| Example 3 • m · ·. * · *. When performing experiments with pressurized peroxide bleaching «· · 25 it was found e.g. that the same bleaching result for both brightness and

With respect to the part number previously obtained without pressure with a treatment time of three hours, • ♦ · * was now obtained in one hour at a pressure of about 5 bar. In addition, experiments have shown that pressurized treatment also significantly improves the effect of chelating agents such as EDTA and DTPA, even to the extent that it would seem possible to dispense with even a separate separation of heavy metals. from the removal step and handles the chelation of heavy metals in conjunction with each * ΙΦ .. · deloxification / bleaching step using peroxide. • ·: 3 "5. Thus a very popular unpressurized *‘ sequence today

Q-P-Z-P

98224 11 »could be replaced by the sequence P-Z-P, in which the P steps are pressurized and in addition to them, or at least to the first, chelating agents would be added to bind ras-5 casmetals.

The pressurized peroxide steps also make it possible to replace the above sequence Q-0/0-E0P-Pn with the sequence Q-0/0-Pn 10, which already achieves a brightness of ISO 85. if desired

to ISO 90, the peroxide phase can be replaced by a combined ozone and peroxide phase Q-O / O-ZP

15 Another experiment we performed also suggests that pressurization of the peroxide phase can completely eliminate the use of chelating agents. Namely, it has been found that the heavy metals are relatively slow-acting, so that by accelerating the reaction by pressurizing the peroxy-20 oi / subject or peroxide-exploiting step, the heavy metals are substantially prevented from adversely affecting the peroxide. In this case, it would be possible to • · ’remove all or substantially all of those described above. · · · Of the corresponding sequences Q-phase completely.

ψ · »· · 25

As can be seen from the above, a new environmentally friendly bleaching method has been developed which can * eliminate previously used bleaching steps using both elemental chlorine and chlorine compounds and also · * * 30 reduce the use of expensive ozone. It is to be noted, however, that only a few exemplary embodiments of the quenching method of the present invention have been described above. • * ·. ···. a form which is not intended to limit in any way our invention from what is set forth in the appended claims. Thus, for example, it is clear that even in those sequences in which the introduction of enzymes into the metal removal step is not shown separately, this can be done.

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Claims (28)

96224 PATENT CLAIM ET A process for bleaching cooked pulp with chlorine-free chemicals to at least ISO 80 using at least two of the bleaching chemicals oxygen, ozone, peroxide, characterized by the steps of a) subjecting the pulp to a heavy metal removal treatment by at least one of the following treatments; acidification and chelation, b) treating the pulp in an oxygen step in an oxygen reactor at an oxygen dose of 5-20 kg / admt, preferably about 15 kg / admt, with a peroxide dose of 0-10 kg / admt at a pH in the range of 9-13 and a temperature in the range of 75-110 ° C, and c) bleaching the pulp in at least one pressurized peroxide utilization bleaching step to which peroxide of 5-40 kg / admt is metered. Process according to Claim 1, characterized in that before step a) the pulp is delignified in a separate oxygen step. Process according to Claim 1, characterized in that step b) also comprises a second oxygen reactor, in which the chemical dosages are from 5 to 20 kgO 2 / admt, preferably • · · ···. about 10 kg / admt and 5 to 40 kgH 2 O 2 / admt, preferably 15 kg / admt, and conditions pH 9 to 13 and a temperature of 75 to 110 ° C. * ···· • * · • · · Process according to Claim 1 or 3, characterized in that the oxygen phase of step b) is pressurized and two-stage (OOp) without intermediate washing. A method according to claim 1, characterized in. ; that the pressure in step b) is 2 to 15 bar, preferably 3 to 35 bar. v t Process according to Claim 3, characterized in that the pressure in the second reactor of step b) is 2 to 10 bar, preferably 3 to 5 bar. Process according to Claim 1, characterized in that there is an ozone step between steps b) and c). Process according to Claim 3 or 4, characterized in that the pulp is treated before step c) in a bleaching alkaline extraction step (EOP) fed with 2-8 kg / admt of oxygen, preferably about 6 kg / admt and 0-10 kg / admt, preferably about 7 kg / admt. Process according to Claim 1, characterized in that oxygen is added to step c) in an amount of 5 to 20 kg / admt, preferably 10 kg / admt, at a pH of 9 to 13 and a temperature of 75 to 110 ° C. Method according to Claim 9, characterized in that the pressure in step b) is 2 to 15 bar, preferably 3 to 10 bar, and in step c) 2 to 10 bar, preferably 3 to 5 bar. Method according to Claim 9, characterized in. that the pulp is treated after step (c) or «I»:. 25 in a refractory alkaline extraction step fed with an oxygen of 2-8 kg / admt, preferably 4-6 kg / admt, and peroxide "! 1-10 kg / admt, preferably 5-7 kg / admt. • M · A method according to claims 8 and 11, characterized in that the bleaching sequence used is Q-OOp-E0P-Pn, where Q represents metal removal, o oxygen step, EOP bleaching. alkaline extraction step and Pn in general one or more peroxide steps, in addition to the marking corresponding to washing between steps. «M A method according to claim 12, characterized in that at least one of said peroxide utilizing steps is replaced by an ozone step to achieve a higher final brightness, wherein the sequence is either Q-OOp-EOP-zPP or Q-00p-E0P-ZP-P, where Z represents ozone bleaching. 5 Method according to Claims 8 and 11, characterized in that one of the following bleaching sequences Q-00p-Pn is used, 10 Q-00p-ZP, 0-Q-00P-Pn, 0-Q-00P-Z-P n; 0-Q-00P-Z / Z-P ", 0-Q-00p-ZP-Pn, 15 0-Q-00p-ZP, 0-Q-00p-Z / ZP, OQ-OOp-Z / ZP-Pn, where 0 denotes a single-stage oxygen delignification step, Q denotes a metal removal step using chelating agents or acidification, OOp a two-step oxygen delignification step, Z / Z two-stage or multi-stage ozone bleaching, one or more successive peroxide steps. • · · • · · • ·:. A method according to any one of the preceding claims. method, characterized in that at least a part of the filtrate obtained from the washing following one peroxide step is passed to the washing preceding the oxygen step in order to retain the residual peroxide to enhance the oxygen step. ; 30 Process according to Claim 11, characterized in that magnesium, preferably MgSO 4, EDTA or DTPA is added to the EOP step. Process according to Claim 1, characterized in that magnesium, preferably MgSO 4, EDTA or DTPA is added to the oxygen step b). • · • ♦ · * · · • · 98224 A method according to claim 1, characterized in that chelating agents are added to the first pressurized peroxide-exploiting step of the sequence. 5 Process according to Claim 3, characterized in that the bleaching sequence is Q-OOp-EOP-P1-P2-P3, at the end of which the pulp has a piece number <2.0 and a brightness> 83. Process according to Claim 3, characterized in that the bleaching sequence is Q-OOp-EOP-Pj-Pj-Pj, at the end of which the pulp has a piece number <2 and a brightness> 8.5. Process according to Claim 19 or 20, characterized in that a total of 25 to 110 kg / admt, preferably about 60 kg / admt, of peroxide is added to the P-steps. Process according to Claim 19 or 20, characterized in that the peroxide is added to the Pi step from 10 to 40 kg / admt, preferably about 30 kg / admt. Process according to Claim 19 or 20, characterized in that the peroxide is added to the P2 stage from 5 to 30 kg / admt, preferably about 10 kg / admt. : 25 «· ·’ ···. Process according to Claim 19 or 20, characterized in that the peroxide is added to the P3 step from 10 to 40 kg / admt, preferably about 20 kg / admt. A method according to claim 12, 14, 19 or 20, characterized in that at least one of said P-steps is pressurized. • · · 0 · · • · ·. · '; Process according to Claim 2, 4 or 25, characterized in that chelating agents, such as EDTA, DTPA, are added to at least one of said pressurized peroxide-using steps. m · • · · • · · • 98224 A method according to claim 7, characterized in that steps a) and b) are combined, wherein the sequence becomes QOp-Z-P. Process according to one of the preceding claims, characterized in that the Q-step is combined with a lignin activation treatment with the enzyme (X). • · • · * · • · I «•« «·» «* · •« · • 0 · • · ♦ · »· ·» • I * 4 • «» • · · »• · # · * • · »• · Μ · • * *: ·: • · • * ·:::» * • · 9 · »#« · »e» · • # · · mm ·· • ♦ * Φ M · · * m · ··· »« · · · · · · · · ··· · · · · · · · · · · ··· * ·· • · · · · · · · · ·· · • * 98224