NZ269362A - Recycling bleach plant filtrate from the oxidative extraction stage and the first chlorine dioxide bleaching stage - Google Patents

Description

New Zealand No. International No. 269362 TO BE ENTERED AFTER ACCEPTANCE AND PUBLICATION Priority dates: 27.06.1994 Complete Specification Filed: 27.06.1994 Classification^) D21C11/00// D21C9/14,147 Publication date: 28 July 1998 Journal No.: 1430 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Title of Invention: Improved process for recycling bleach plant filtrate Name, address and nationality of applicant(s) as in international application form: CHAMPION INTERNATIONAL CORPORATION, a Connecticut corporation of One Champion Plaza, Stamford, Connecticut 06921, United States of America 26 9 3 WO 96/00322 PCTAJS94/07450 1 IMPROVED PROCESS FOR RECYCLING BLEACH PLANT FILTRATE CROSS-REFERENCE TO RELATED APPLICATIONS FIELD OF THE INVENTION This invention relates to an improved method for recycling bleach filtrates. More particularly, this 5 invention relates to improvements in the bleaching process including a recycling process for reducing the environmental impact associated with the manufacture of bleached wood pulp.

* BACKGROUND OF THE INVENTION 10 The process of the present invention is applicable to any cellulosic fibrous material but is described with particular reference to the bleaching of wood pulp, preferably wood pulp produced by the Kraft process, i.e., wood pulp produced by digestion of wood 15 chips in the pulping liquor containing sodium hydroxide and sodium sulfide as the active pulping chemicals. Following the wood digestion process, pulp is separated from the spent pulping liquor. The spent pulping liquor is then recovered and regenerated for recycling. 20 The Kraft process wood pulp is then bleached and purified in a bleach plant operation. In the bleach, M2 Application No. 271075 08:53:09 269 WO 96/00322 PCTYUS94/07450 2 plant, pulp is first subjected to oxidizing chemicals such as chlorine and/or chlorine dioxide and followed by extraction with a suitable source of alkali such as sodium hydroxide. Depending on the desired pulp brightness, one 5 to three additional bleaching stages are employed with typically one being an alkali extraction stage and one or two stages using oxidizing chemicals. Following each bleaching stage, spent bleaching chemicals are removed from the pulp by washing with a suitable source of water; either 10 fresh water or previously used water from pulp washing or a combination of the two. Current state of the art requires that all wash water from the bleach plant along with spent bleaching chemicals be discharged to the sewer as effluents rather than being processed in the pulping liquor 15 regeneration operation noted above. Various concerns have prevented the recovery of these bleach plant effluents in the pulping liquor regeneration operation. One concern is the possible build-up of chlorides causing corrosion and operational problems. Another concern is the lack of 20 adequate systems for removing non-process metals, such as calcium, magnesium and manganese, which enter the bleach plant and are typically removed with wash water and spent bleach chemicals.

Further, the use of large volumes of water for 25 pulp washing in the bleach plant has also prevented recovery of bleach plant effluents due to the resulting high evaporator load. The environmental impact of these practices has been widely noted, but despite these serious N2 Application No. 271075 08:53:09 269 3 WO 96/00322 PCT/DS94/07450 3 concerns, the ability to overcome the problems associated with recovery as described above has riot been developed.

In the 1970's, the closed mill concept for recovering bleach plant effluents developed by Rapson, 5 United States Patent Ho., 3,698,995, and later improved by Reeve et al. in U.S. Patent 4,039,372 was tested at Great Lakes Papers in Thunder Bay, Ontario. The mill began operation in 1977 bat was abandoned in 1985. The mill attempted to reduce the discharge of the bleach plant 10 effluent by recycling the filtrates to the pulping liquor regeneration process. The bleaching process employed was (D/C)EDED. The process included a salt crystallization system as a means of purging sodium chloride. The chloride levels introduced into the pulping liquor 15 regeneration process were within the range of 90-100 lbs/adt pulp. With the crystallization process, the concentration in white liquor was equal to or in excess of 50 grams per liter before equilibrium was reached, i.e., chloride entering is equal to the amount of chloride 2 0 removed.

This process was unsuccessful in the recovery of the bleach plant filtrates. The reasons for this were related to continued concerns of corrosion, pulp quality, inadequate removal of non-process metals and high 25 evaporation requirements.

After the experience at Thunder Bay., . Reeve noted the following features as needing to be developed for the success of future effluent-free mills: low chloride NZ Application No. 271075 08:53:09 26 9 3 WO 96/00322 PCTAJS94/07450 4 concentrations in the recovery process; a chloride removal system employing minimal evaporation; low bleach filtrate flow to minimize evaporation requirements, a bleaching sequence that minimizes bleach chemical consumption due to 5 recycle of extracted organic components; and adequate systems to remove minor wood components such as potassium, calcium and pitch.

Substituting chlorine dioxide for chlorine and incorporating oxygen delignification in the bleach sequence 10 reduces the chloride content of the bleach effluent when compared to sequences without oxygen and chlorine dioxide. Use of the ODED sequence, referenced in United States Patent No. 4,039,372, for recovering bleach plant filtrates would reduce the sodium chloride input to the recovery 15 process by 73% over that experienced at Thunder Bay during closed mill operation. While use of the ODED bleach sequence would represent a significant reduction in chloride content of the bleach filtrate streams compared to Thunder Bay's closed mill experience, the resulting 20 chloride content of black liquor feeding the recovery boiler would cause operating problems. The chloride content of black liquor feeding the recovery boiler is a function not only of the quantity Df chloride introduced to the recovery process but also the process used to remove 25 chlorides. A significant fraction of the chloride feeding the recovery boiler is the result of chloride accumulation in the ash that is volatilized in the boiler, collected and returned to the boiler feed. Potassium, which also affects NZ Application No. 271075 08:53:09 26 9 3 WO 96/00322 PCTAJS94/07450 S recovery boiler operation, accumulates in the boiler ash in a similar manner. At Thunder Bay, sodium chloride was removed from the recovery process by evaporation and crystallization of sodium chloride from white liquor. This 5 chloride removal process not only represents a significant increase in the evaporation load of a mill, it also does not prevent the large cyclic flow of sodium chloride and potassium compounds contained in the recovery boiler ash which represents a significant fraction of the chloride and 10 potassium load to the recovery boiler.

United States Patent No. 4,039,372 by Reeve et al. shows that 1895 gallons per minute of bleach filtrate is recovered from a 500 T/D bleach plant and sent to the pulp mill/recovery operation. All liquor recovered from 15 the bleach plant must be evaporated. The flow of 1895 gallons per minute represents more than twice the normal volumetric flow needed for brown stock washing. According to United States Patent No. 4,039,372, a portion of the 1895 gallons per minute is used for diluting white liquor 20 that is concentrated during the sodium chloride removal operation. The net result is a nearly doubling of the evaporation load of the mill. The most significant factor contributing to the large filtrate flow from the bleach plant in United States Patent No. 4,039,372 is the use of 25 fresh water to wash pulp at two locations in the bleach plant.

Various metals such as calcium, magnesium, manganese and potassium enter the pulp mill with the wood NZ Application No. 271075 08:53:09 26 9 3 WO 96/00322 PCT/US94/D7450 6 supply. These xnetals if not adequately purged from the pulping and bleaching operations can cause operating problems. In current operations these metals aire released from the pulp in the first acidic stage of the bleach plant 5 due to the low pH (2-3) of operation and are purged to the sewer along with filtrate from this same first stage. Pulp is thoroughly washed as it leaves the first acidic stage of bleaching to prevent any entrained liquor containing solubilized metals from being carried into later stages of 10 bleaching. If not adequately removed in the first acidic stage of bleaching, manganese and iron can affect bleaching in the later stages by limiting brightness development and increasing chemical consumption.

In United States Patent No. 4,039,372, Reeve et 15 al. included a fresh water wash on the first acidic bleaching stage washer which prevents possible carryover of metals to the later stages of bleaching. A second fresh water wash volume was used after the final stage of bleaching. In this manner, two wash volumes of fresh water 20 must be evaporated as compared to evaporation of only one wash volume if bleach plant filtrates are not recovered. counter-current pulp washing with bleach filtrates can result in the accumulation of calcium and magnesium in the bleach plant/brown stock washing systems 25 due to adsorption of metals on pulp at high pH and re-dissolving at low pH. This accumulation of calcium and magnesium can result in the deposition of inorganic and organic matter on pulp and equipment which can increase NZ Application No. 271075 08:53:09 26 9 3 WO 96/00322 PCI7US94/07450 7 bleach chemical consumption and require down time for equipment cleaning. Reeve et al. described the problems of scaling and lignin deposition if calcium is not removed when practicing the art of recovering bieach filtrates. To 5 avoid this problem Reeve et al. used a portion of the filtrate from the first acidic stage of bleaching in the causticizing plant thereby purging from the bleach plant some of the dissolved metals. This method of purging metals is limited by the volume of filtrate that can be 10 used in causticizing. According to Reeve et al., approximately 325 gallons of the 1288 gallons of first acidic stage filtrate is purged " to the causticizing operation or about 25 percent. The remaining 75 percent of the filtrate from the first acidic bleaching stage is used 15 to wash pulp on the decker preceding the bleach plant allowing the possibility for metals to accumulate. Following the experience at Thunder Bay which incorporated this method of purging metals, Reeve noted that additional development would be needed to adequately purge metals for 20 the closed mill concept to be feasible.

When recovering bleach plant filtrates, it is not possible to remove all dissolved organic matter entrained in the pulp from counter-current displacement washing with bleach filtrates, before pulp enters the 25 bleach plant. This is particularly true if fresh water usage is to be limited to keep evaporation requirements "to a minimum. Reeve published laboratory results documenting the increased bleach chemical consumption that results as NZ Application No. 271075 08:53:09 26 9 3 6 WO 96/00322 FCT/US94/07450 8 the quantity of dissolved organic matter is increased in the first stage of bleaching of a D-CE • sequence at 70% chlorine dioxide substitution. This study showed that bleach chemical consumption increased as dissolved organic 5 matter, removed from pulp in the D-C stage, was re-introduced into the D-C stage, simulating the recovery of bleach plant filtrates. The same conclusions were reached when dissolved organic natter, removed from pulp during the extraction stage, was added to the D-C stage. 10 Bleach chemical consumption increased more for extraction stage organic matter compared to D-C stage organic matter. Competition exists for bleaching chemicals in the first acidic stage of bleaching between dissolved' organic matter and lignin within the pulp fibers. As the quantity of . 15 organic matter added increases, increasing amounts of bleach chemicals in the first stage are consumed non-productively by the dissolved organic matter. This results in less delignification of the pulp as measured by the pulp kappa number. Following the experience at Thunder 20 Bay, Reeve noted the need for developing a bleaching sequence that minimized bleach chemical consumption due to dissolved organic matter carried into the bleach plant as a result of counter-current displacement pulp washing.

Recently published investigations on recovering 25 chlorine-based bleach plant effluent have concluded that recovery of these effluents along with the pulping liquors in the conventional recovery process is not technically feasible. Others have published investigations on separate NZ Application No. 271075 08:53:09 269 3 WO 96/00322 PCT/US94/07450 9 recovery operations for pulping liquors and bleach plant effluent.

No process has since been developed that cones close to a substantial recovery of bleach plant filtrates.

In fact, based on a recent publication (Paper ja Puu -Paper and Timber; 5/89), several Pulp and Paper Research Institutes in Scandinavia concluded that closure of the bleach plant was not likely to be available technology for at least another decade and would be dependent upon 10 significant developments in both pulp bleaching and in chemical recovery.

It would therefore represent a notable advance in the state of the art if a new process for recovering chlorine-based bleach plant effluents in a conventional 15 pulping liquor recovery operation could be developed which provides very low chloride concentrations in the recovery process; little or no significant impact on evaporation requirements; more complete non-process metal removal; and negligible impact on bleach chemical consumption due to 20 recovery of bleach filtrate.

NZ Application No. 271075 08:53:09 26 9 3 WO 96/00322 PCT/DS94/07450 SUMMARY OF THE INVENTION The method of the present invention integrates advances in bleaching technology as well as in washing and recovery into a process that permits the substantial closure of the bleach plant while avoiding the problems previously encountered.

The process of the present invention provides for the bleaching of wood pulp and for the recycling and recovery of bleach filtrates in a manner that will allow for: 1) the production of pulp with acceptable brightness and quality; 2) the reduction of dissolved solids normally discharged with bleach effluents including chlorinated organic material; 3) minimal increase in the amount of water required to be evaporated; 4) no increased build-up of chlorides in the pulping liquor regeneration cycle; and 5) removal of non-process metals to prevent scale formation.

The process of the present invention accomplishes the foregoing objectives by the following combination of sequences: A bleaching sequence which provides a minimal chloride content of the recovered filtrates is effected by minimizing first the requirements for molecular chlorine and secondly chlorine dioxide. This is accomplished preferably with the use of oxygen delignification of either softwood or-hardwood pulps obtained from the Kraft pulping process. After significant lignin reduction is achieved with the oxygen delignification system, the pulps are then NZ Application No. 271075 08:53:09 269 3 6 WO 96/00322 PCT/DS94/07450 . 11 treated successively with a chlorine dioxide (D) stage, a peroxide reinforced oxidative extraction (EOP) stage, and at least one final chlorine dioxide (D) stage. The first acidic bleach stage can be 100% chlorine dioxide, chlorine 5 dioxide with 10% or less nolecular chlorine added or ozone. The final treatment can be either one stage (preferably for the production of 80-88 brightness targets) or two stages (preferably for the production of 90+ brightness).

/ The first chlorine dioxide stage is preferably 10 operated at medium consistency; i.e., within the range of 8-14% and at a reduced pH of 2-2.5.

An acid treatment stage is preferably introduced after oxygen delignification. The acid treatment stage is preferably placed after oxygen delignification and before 15 the first chlorine dioxide stage. This stage is introduced for the purpose of removing non-process metals such as potassium, magnesium, calcium, manganese, iron, aluminum, and the like.

The pulp from the first chlorine dioxide stage 20 is neutralized by mixing with the extraction stage filtrate. This neutralization allows for the degassing of the pulp which enhances the effectiveness of the decker which follows it, thereby allowing for a more effective operation. Also, this neutralization effectively utilizes 25 residual alkali in the extraction stage filtrate and combines the filtrates from the first chlorine dioxide and extraction stages.

Recycling of the combined acid filtrate from the NZ Application No. 271075 08:53:09 269 3 WO 96/00322 PCT/DS94/07450 12 first chlorine dioxide stage and the caustic extraction stage filtrate is conducted in a countercurrent fashion back through post oxygen delignification and brown stock washing. The organic solids from these filtrates are 5 eventually processed in the mills' recovery boiler where they are destroyed through combustion. This recycling is accomplished with only an 8 to 10% increase in evaporator loading.

Removal . of sodium chloride from the recovery 10 boiler is accomplished preferably through the collection of the catch from the electrostatic precipitator followed by an aqueous leaching of this catch to allow for the separation of salt cake and sodium chloride. The salt cake is . recycled back to the black liquor feed and the 15 chloride-rich aqueous material is sewered.

By combining these various steps, the present invention allows for a significant reduction in color, AOX, BOD and solids discharged in the effluent associated with bleaching of chemical pulp to a degree that represents a 20 significant improvement relative to current practice.

Furthermore, the present invention accomplishes this in a manner that represents a significant improvement over previously developed techniques that attempted various approaches for bleach filtrate recovery.

NZ Application No. 271075 08:53:09 26 9 3 6 WO 96/00322 PCT/US94/07450 13 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of the overall pulp making and chemical recovery processes in 5 accordance with the present invention; and Figure 2 is a schematic illustration of the bleach plant operation including the filtrate recycling process of the present invention.

Figures 3 and 4 depict, in graphic form, the 10 percent removal of various metals from hardwood and softwood pulps as a function of the pH in the acid treatment stage, DETAILED DESCRIPTION OF THE INVENTION The process of the present invention overcomes 15 the previously encountered problems of high chloride concentration in the recovery process by maintaining chloride concentration at or near current, operating conditions of typical "inland mills". The process of the present invention achieves this low chloride concentration 20 in the recovery process by limiting chloride input to the recovery process with bleach plant filtrates and reducing the cyclic flow of chloride typically contained in the boiler ash.

Chloride input to the recovery process is limited 25 by reducing the amount of chlorine-baiisri bleach chemicals used in the bleach plant. In one instance, use of chlorine-based chemicals is reduced in the first chlorine NZ Application No. 271075 08:53:09 26 9 3 6 WO 96/00322 PCT/DS94/074S0 14 dioxide stage by incorporating stages of oxygen delignification, 100% chlorine dioxide substitution and hot oxidative extraction with peroxide into the process. Chloride input to the recovery process is also reduced by 5 recovering only the filtrates from the first chlorine dioxide stage and extraction stage in the OD(EOP)D bleaching sequence.

The present process recovers only the filtrates from the first chlorine dioxide stage and EOP stage. The 10 final chlorine dioxide stage filtrate is not recovered as this would more than double the quantity of chloride sent to the recovery process for only a 10% to 15% reduction in the environmental impact of the bleach plant effluent.

The final chlorine dioxide stage filtrate instead can be recovered by incorporating new cooking techniques such as extended modified continuous cooking or rapid displacement heating methods for batch cooking and enzyme prebleaching. By incorporating these techniques the total 20 chloride in all filtrates of the OxD(EOP)D bleaching sequence is reduced such that recovery of all filtrates can be achieved while maintaining chloride concentrations of current "inland" mills. Complete recovery of bleach plant filtrates can be accomplished by 25 replacing the hot wash water used on the (EOP) stage washer with filtrate.from the final chlorine dioxide stage washer.

Chlorides feeding the boiler and circulating in the liquor cycle are greatly reduced by incorporating a NZ Application No. 271075 08:53:09 26 9 3 (3 WO 96/00322 PCT/DS94/07450 system to remove chloride from the boiler ash. Sodium chloride has a significant vapor pressure at the operating temperatures of the boiler and as such chloride feeding the boiler is preferentially distributed in the boiler ash. 5 Ash, being re-dissolved in black liquor and fed to the boiler, creates a significant cyclic flow of chloride. The subject process avoids this cyclic flow of chloride by removing chloride from the ash before it is re-introduced to the boiler. The process also provides significant 10 benefit in the removal of potassium from the liquor cycle.

The removal of chloride and potassium provides significant benefit to the recovery boiler operation.

By limiting the amount of chlorine dioxide used in the bleach plant, which limits the chloride introduced 15 into the pulping liquor cycle, and avoiding the cyclic flow of chloride contained in the boiler ash, the chloride concentration in the pulping liquor cycle and feed to the recovery boiler is maintained at normal levels. Typical chloride concentrations in white liquor and feed to the 20 recovery boiler are contrasted in Table 1 for four mills. A typical "inland mill" is one that does not transport their wood supply via sea water. The "coastal mill" is one that does use sea water for wood supply transportation, such as some mills on the west coast of Canada. Results 25 from the Thunder Bay mill are reported literature values when that mill operated with the closed mill concept. The results for mills operating according to the present invention are calculated for an "inland mill" operating N2 Application No. 271075 08:53:09 269362 WO 96/00322 PCT/US94/07450 16 with the bleach filtrate recovery process shown in Figure 1 and Figure 2. As shown in Table 1, the process of the present invention reduces the chloride input to the liquor recovery operation by about 90% over that described by Reeve et al in U.S. Patent 4,039,372.

The present invention also provides a method for removing metals. In one embodiment, the present process uses an acid treatment step to remove metals as illustrated in Figure 2. An alternate process for removing metals (not illustrated) utilizes sodium carbonate and/or sodium hydroxide and/or green liquor from the pulping liquor recovery process to cause metal carbonates and metal hydroxides to precipitate from a portion of the first acidic bleach stage filtrate.

According to Figure 2, an acid treatment stage 15 is located after post oxygen delignification washing. The entire pulp stream is first acidified to about 2 pH and then washed before it enters the chlorine dioxide stage of bleaching. Wash water from the acid treatment washing along with the solubilized raetals are discharged to the sewer. Figures 3 and 4 illustrate the percent removal of various metals from hardwood and softwood pulps at different pH values in the acid treatment stage. Nearly complete removal of troublesome metals such as calcium, magnesium and manganese is effected in this manner. With the acid treatment system, described above and. shown in Figure 2, metals are removed before filtrates are recycled thereby overcoming all of the problems associated with NZ Application No. 271075 08:53:09 269 WO 96/00322 PCT/US94/07450 17 metals noted previously. In addition, by using the acid treatment stage, the need for a fresh water wash on the first acidic bleach stage washer to prevent metals from being carried into later bleaching stages is eliminated.

Eliminating the need for a fresh water wash on this first acidic stage avoids additional evaporation requirements. Wash water used to wash the acid treated pulp is discharged to the sewer rather than being evaporated.

Location of the acid treatment stage after oxygen 10 delignification and post oxygen washing is critical in enhancing the recovery of spent chemicals and dissolved organic matter from the wood pulp. This improved recovery is illustrated in Table 2 which shows how sewer losses vary if the acid treatment process is located before 15 oxygen delignification versus after oxygen delignification. Percent metal removal is the same regardless of location. As shown in Table 2, nearly 25 times as much color and 40 times as much total organic carbon (TOC) is lost to the sewer if the acid treatment is placed before oxygen 20 delignification rather than after oxygen delignification. At high chlorine dioxide substitution the entire softwood bleach plant discharges about 50 to 60 #/T color. Placement of acid treatment before oxygen delignification would nearly negate the environmental benefit of recovering 25 bleach filtrates.

The process of the present invention is described here and shown in Figure 2 for medium consistency operation in the first chlorine dioxide stage of the NZ Application No. 271075 08:53:09 26 9 3 6 WO 96/00322 PCT/DS94/07450 18 OD(EOP)D sequence. The present process is equally applicable for low consistency operation in the first chlorine dioxide stage by removing the neutralization step shown in Figure 2 and recycling chlorine dioxide filtrate 5 from the first stage to the discharge of the high density storage tower as dilution to low consistency. In this case some extraction stage filtrate is used as a displacement wash on the first chlorine dioxide stage washer with the remaining extraction stage filtrate being used as 10 displacement wash on the last post oxygen stage washer.

Metals can also be removed by an alternate process which precipitates metals as carbonates and hydroxides. Metals, which enter the bleach plant absorbed to pulp at high pH, are dissolved in the low pH 5 aqueous 15 . solution of the first acidic bleaching stage. Any fraction of the aqueous filtrate from the first acidic stage of bleaching can be treated in the precipitation process; however, 25% is adequate to remove sufficient quantity of metals to prevent their detrimental effects on bleaching 20 and scale deposition.

In this metal precipitation embodiment a fraction of the first acidic filtrate is treated with sodium hydroxide and/or sodium carbonate, or green liquor from the pulping process, sufficient to raise the pH between 9 arid 25 11 and provide an amount of carbonate ion such that insoluble metal.carbonates and.hydroxides will -be.formed. The aqueous solution is maintained for 10 minutes at a temperature of from about 130°F to about 160°F. Under NZ Application No. 271075 08:53:09 t 26 9 3 6 2 WO 96/00322 PCI70SM/07450 19 these conditions, with adequate carbonate ions present, insoluble metal carbonates and hydroxides of calcium, magnesium, manganese and iron precipitate from the aqueous solution.

A suitable separation device, preferably a precoat filter or a clarifier, is used to separate the aqueous phase from the solid precipitate. The solid precipitate can then be disposed of by landfill or introduced into the pulping liquor cycle either with heavy 10 black liquor before combustion in the recovery boiler or with green liquor. If the precipitate is introduced into the pulping cycle, the non-process metals will be removed from the mill along with other non-process metals in the current practice of grits and dregs removal. 15 The aqueous phase from the separation device is then preferably reused in the bleaching operation. This aqueous phase is relatively free of metals and can be used in the first acidic bleach stage washer to displace entrained liquor containing metals. This method of washing 20 pulp with metal free filtrate reduces the quantity of metals carried into the extraction stage without the use of fresh water. Use of filtrate from the metal removal system is not limited to washing after the first acidic bleach stage. It can also be used for pulp dilution prior to the 25 high density storage or for washing pulp prior to bleaching..

Table 3 illustrates the results of a water balance around the bleach plant for a 500 T/D pulp mill NZ Application No. 271075 08:53:09 t 269362 WO 96/00322 PCT/US94/07450 incorporating the process illustrated in Figure 1. The recovered filtrate volume from the bleach plant is 515 gallons per minute (stream 40 in Figure 1) . This represents approximately an eight to fourteen percent 5 increase in evaporation load as compared to a 500 T/D pulp mill that does not recover bleach filtrates. The reduced evaporation load of the present process compared to the processes of the prior art is the result of less water usage in the bleach plant. The reduced water usage in the 10 present process results from the use of two 25 extraction stage washers and avoiding the need for fresh water on the chlorination stage washer to wash the pulp free of entrained metals. Use of two extraction stage washers allows a reduced shower flow to achieve the same degree of 15 washing.

In the present process, combined filtrates from the first chlorine dioxide stage and extraction stage are recycled counter-currently to pulp flow for the purpose of reducing the entrained black liquor from being carried into 20 the first chlorine dioxide stage (see Figure 2). While this placement washing process prevents black liquor from being carried into the first chlorine dioxide stage, organic matter from the combined filtrates, used to displace black liquor, are carried into the first chlorine 25 dioxide stage. Carryover of the combined bleach filtrates can be reduced by squeezing the pulp to high consistency and/or careful use of fresh water for pulp washing. Limiting the amount of organic matter carried into the NZ Application No. 271075 08:53:09 269 3 WO 96/00322 PCTAIS94/07450 21 first stage of bleaching will reduce the bleach chemical consumption by organic matter.

When organic matter from the combined filtrate (DlOO + EO) of the present process is added to the first 5 chlorine dioxide stage a small amount of chlorine dioxide is consumed by the dissolved organic matter. This results in reduced delignification in the first chlorine dioxide stage as shown in Table 4 by the increased kappa number as the amount of added organic matter increases. However this 10 loss of delignification in the first chlorine dioxide stage may be corrected by oxygen in the oxidative extraction stage as evidenced by the constant extracted kappa numbers shown in Table 4. Bleach chemical consumption by carryover of dissolved organic matter in the 15 first acidic bleacL stage is further reduced by complete substitution of chlorine dioxide for chlorine. Also contributing to the low chemical consumption in the first acidic stage of bleaching, by dissolved organic matter, is the highly oxidized nature of the organic matter having 20 been exposed to oxygen and peroxide in the extraction stage. This means that for a given extracted kappa number, carryover of organic matter from the combined filtrate (D+EOP) of the present process into the first chlorine dioxide stage will not increase bleach 5 chemical 25 consumption.

The present process thereby avoids any increase in bleach chemical consumption due to the presence of dissolved organics by incorporating oxygen and/or peroxide NZ Application No. 271075 08:53:09 269 WO 96/00322 PCT/US94/07450 22 in the extraction stage of the bleach plant. In this manner one of the difficulties encountered while practicing the art of recovering bleach plant filtrates, as described in United States Patent No. 4,039,372, is unexpectedly 5 avoided.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to Figure 1, Southern Pine Softwood (hardwood) Chips 10 are screened (not shown) to remove oversized and undersized chips, then cooked in a digester 10 12 using the Kraft pulping process with a white liquor 14 charge of from about 15 to 22%, and preferably 18%, active alkali and about 20 to 40%, preferably about 30%, sulfidity under cooking conditions of about 310" to about 350°F, and preferably about 344°F, and from about 80 psi to about 140 15 psi, and preferably about 110 psi.

The resulting pulp having a Kappa number ranging from about 25 to about 35, and preferably about 30, is discharged under pressure into a blow tank (not shown), then screened to remove uncooked knots (not shown). After 20 removal of knots, the brown stock 16 is washed successively with from two to four stages, and preferably three stages of washing. After washing, pulp is screened 20 to remove rejects and the resulting pulp 22 is then charged to the oxygen delignification stage 32.

As best shown in Figure .2, the pulp, after brown stock washing and screening, is shown entering the last wash stage 26 prior to entering the oxygen delignification NZ Application No. 271075 08:53:09 1 269 3 6 2 WO 96/00322 PCT/DS94/07450 23 stage 32, wherein it is admixed with oxygen 28 and oxidized white liquor 3 0 and then further delignified in an oxygen delignification stage 32 to a Kappa number ranging from about 14 to about 20, and preferably about 16, 5 corresponding to about 30 •to about 55%, and preferably about 45%, delignification. The oxygen delignification stage 32 is run under conditions of temperature (180°—210°F) and pressure (90-100 psi) with alkali supplied in the form of the oxidized white liquor 30. 10 Following oxygen delignification, the pulp .is again washed successively with from 2 to 4 stages of washing (shown as 34 and 38) to remove the lignin and inorganic materials. The wash water 35 is derived from the washings from the next subsequent wash stage 38. The final 15 wash is derived from filtrate 40 obtained from the decker 42 after the first bleach stage as described hereinbelow. The resulting washed pulp is then stored in a high density (10-12%) storage vessel 44.

The filtrates from the post oxygen 20 delignification washers, 34 and 38, are recycled back counter currently as wash water through the pre-oxygen delignification washer 26 as best seen in Figure 2. All of the organic and inorganic materials are eventually concentrated through a train of black liquor evaporators 46 25 and sent to the recovery boiler 48 for combustion, as shown in Figure l; As best seen in Figure l, the inorganic salts, recovered as smelt 50, are dissolved in water to form green NZ Application No. 271075 08:53:09 269 3 WO 96/00322 FCT/DS94/07450 24 liquor in liquid preparations 52, which in turn is treated with calcium oxide to regenerate the white liquor 14 fed to the digester 12. The calcium carbonate by product is burned in a kiln (not shown) expelling carbon dioxide and 5 regenerating calcium oxide which is used to regenerate the white liquor.

Throughout the pulping (including oxygen delignification), washing and recovery processes, no organic or inorganic materials are intentionally discharged 10 and/or disposed of, with the exception of the small amount of dregs that settle out in the green liquor clarifier and grits from the green liquor shaker (not shown).

Returning now to Figure 2, the pulp from high density storage 44 is then subjected to an acidification 15 treatment in tank 54 equipped with mixer 57. The pulp can be treated with sulfuric acid, hydrochloric acid, nitric acid or the like to a pH within the range of from about 2 to about 3 entering tank 54 through a line 59. The primary function of the acidification treatment is to solubilize 20 the non process metals that come in with the wood supply and which must be purged from the process. In the past, this typically w?.s done in the first acidic bleaching stage where the filtrate was discharged to the sewer. By adding an acidic stage with no ability to delignify, the metals 25 can be removed and thereby allow the first acidic bleaching stage with its .content of solids (.color,-BOD, etc.,) .to be recovered. By acid treating the pulp from the high density storage not only are the metals removed but most of the NZ Application No. 271075 08:53:09 26 9 3 WO 96/00322 PCT/US94/074S0 dissolved organics associated with the pulp slurry will be precipitated onto the fibers and will be carried into the. first bleaching stage rather than discharged with the metals to the sewer. This is preferred to significantly reduce the discharge of dissolved organics. Accordingly, it can be seen that the acidification treatment step prevents the build-up of metals within the brownstock washing/bleach plant cycle which would otherwise limit the viability of the process.

After acidification, the pulp is washed in washer 58 with fresh water to remove the acidic wash and the non-process metals. This wash, which is low in environmental impact since no bleaching or delignification is effected, is discharged to the sewer at 60.

After the acid treatment and wash, chlorine dioxide or a mixture of chlorine dioxide and chlorine is added to the pulp at an application rate of about 2.0 to 3.4%, preferably about 2.6%, calculated as active chlorine. The pulp is treated with the chlorine dioxide or a mixture of chlorine dioxide and chlorine solution in the first bleaching stage 62 under conditions of 10-12% consistency, a reaction time ranging from about 30 to about 90 minutes, preferably about 60 minutes, and a temperature ranging from about 100 to about 160°F, preferably about 140°F. Although chlorine can be added along with the chlorine dioxide in the first bleaching stag&, it is considered important in achieving a bleaching stage with minimal chloride residuals to limit the use of chlorine to less NZ Application No. 271075 08:53:09 t 269 3 6 2 WO 96/00322 PCT/US94/07450 26 than about 10%, or completely eliminate the use of molecular chlorine.

After the first bleaching stage, the pulp is then discharged into a mixing tank 64 for partial neutralization 5 to a pH ranging from about 5 to about 7, and preferably to about 7, using the alkaline filtrate 66 from the first oxidative extraction stage 68 with some caustic make-up in the form of oxidized white liquor 65, generally less than 1% on pulp. The pulp is then thickened by passage over 10 decker 42 and oxidized white liquor is added at an application rate of about 1 to about 2%. Hydrogen peroxide is then introduced to the stream from the decker and oxygen is added to the pulp through high intensity mixer 70. Additional delignification is thus accomplished in 15 oxidative extraction stage 68 thereby producing a pulp with a Kappa number ranging from about 2 to about 6, and preferably about 4. The pulp is then diluted at the oxidative extraction tower discharge using a portion of the filtrate 66 from the first post extraction stage washer 72. 20 Following the oxidative extraction stage 68, the pulp is washed successively on two conventional rotary drum washers 72 and 73. The pulp is then heated by steam in a steam mixer 74 and chlorine dioxide is added in a high intensity mixer 76 and allowed to react in the chlorine dioxide 25 bleaching tower 78 at a temperature ranging from about 150° to about 180°F, and preferably about 160°F, for from . about two to about four hours, and preferably for about three hours.

NZ Application No. 271075 08:53:09 i ^ © WO 96/00322 PCT/US94/07450 27 The bleached pulp is then washed using paper machine white water with a portion of the filtrate being sewered at 80 and not recovered within the process. The remaining portion of the filtrate can be recycled to the 5 chlorine dioxide bleaching tower 78 for pulp dilution. Thus, from the bleach plant 24, the only intentional discharges are flows from the acid pretreatment stage at 60 and from the final wash applied to the fully bleached pulp at F,o.

Filtrate, from washing pulp exiting the oxidative extraction stage 68, is used, in part, for discharge dilution of the pulp from the oxidative extraction tower 68 by way of line 66, and in part, is used for neutralization of the pulp exiting the first bleaching stage 62 in 15 neutralization stage 64. Addition of fresh water to wash the pulp after the extraction stage is reduced by using two stages of washing and as such is preferred to reduce, if not eliminate, additional evaporator requirements. Thus two stages of washing after the oxidative extraction stage 20 is an important element to the viability of this process.

As shown in Figure 2, filtrate 40 is produced when decker 42 thickens the pulp received from the neutralization stage 64. Filtrate 40, which is a combination of filtrate from the first chlorine dioxide 25 stage and extraction stage, is used as wash water in the last post-oxygen delignification washer 38. The filtrate 35 from the last post oxygen delignification washer 38 is, as discussed, hereinabove, recycled counter-current to pulp 9 3 6 2 NZ Application No. 271075 08:53:09 I '69352 WO 96/00322 PCT/DS94/07450 28 71 through washers 34 and 26 via lines 35 and 33. As shown in Figure 1, filtrate 31 from washer 26 flows counter-current to pulp through screening 20 and brown stock washing 18. In this way, chlorides, spent bleaching 5 chemicals and organic matter removed during bleaching are combined with spent pulping liquor and evaporated producing strong black liquor 84. chloride from the bleach plant, contained in black liquor 84 feeding the recovery boiler 48, is 10 partially volatilized in the recovery boiler and carried to the electrostatic precipitator 86 where it is collected and removed with salt cake in the precipitator ash. This ash is dissolved with water in the salt leaching process at a temperature ranging from about 80° to about 120°F, and 15 . preferably about 100°F, to separate out sodium sulfate from sodium chloride. The aqueous sodium chloride solution is sewered at 90 and the solid sodium sulfate 88, with some residual chloride is recycled back to the mix tank 89. The leaching process prevents the build up of chloride 20 concentration in the liquor cycle and maintains the concentration of sodium chloride in the white liquor at less than 5 grams per liter.

The leaching process as described herein operates at greater than 95% efficiency in terms of salt cake 25 recovery.

Moreover, and most importantly, the improved process of the present invention wherein the filtrate from the peroxide reinforced oxidative extraction (EOP) stage is NZ Application No. 271075 08:53:09 269 3 6 2 WO 96/00322 PCT/DS94/07450 29 recycled counter currently through the bleach plant and brown stock washing and most preferably, wherein additionally, the filtrate from the first chlorine dioxide bleaching stage (D) is also recycled counter currently 5 through the brown stock washing, significantly reduces the color, AOX and BOD in the bleach plant effluent as shown in Table 5 wherein the effects of chlorine dioxide substitution for molecular chlorine and the effect of the filtrate recycle in accordance with the present invention 10 are shown.

NZ Application No. 271075 08:53:09 26 9 3 6 WO 96/003Z2 TABLE 1 COMPARISON OF TYPICAL CHLORIDE CONCENTRATIONS FOR VARIOUS MILLS NaCl in White liquor, grains NaCl/liter NaCl to Recovery Boiler, % of B.L. Solids INLAND COASTAL HILL HILL 3.6 -50 0.2-0.5 6.1 THUNDER PRESENT BAY MILL HILL 50 6.0 4.5 0.45 NaCl to Recovery process, pounds NaCl per ton pulp 1-3 11-36 115 -12 TABLE 2 COMPARISON OF SEVER DISCHARGE FROH ACID TREATMENT OF SOFTWOOD PULP BEFORE AND AFTER OXYGEN DELIGNIFICATION BEFORE OXYGEN DELIGNIFICATION AFTER OXYGEN DELIGNIFICATION h2Xso4 TO SEWER H TOC Color if/T #/T H^so, pH TO SEWER TOC Color #/T #/T 9.1 2.1 41.2 48.8 2.0 2.3 0.9 2.0 NZ Application No. 271075 08:53:09 26 9 3 6 2 31 HATER BALANCE 500 T/D BLEACH PLANT WITH BLEACH FILTRATE RECOVERY (FIG. 1) I Stream No. Flow /gpml 40 515 41 148 60 826 63 1561 67 735 69 41 71 104 80 804 82 557 TABLE 4 EFFECT ON CBLOR1NATXON AND EXTRACTED KAPPA NUMBERS WHEN ORGANIC MATTER 18 ADDED TO THE CHLORINATION 8TATE (combined Filtrate (Dloo + EO) From Bleach Filtrate Recovery Added To First D Stage Of OD (EO)B sequence) Added Organic D100 Kappa Extracted Kappa Matter % TOC On Pulp 4.1 4.0 4.3 4.2 0 0.145 0.29 0.44 6.3 6.6 7.0 7.1 NZ Application No. 271075 08:53:09 2 6 9 3 6 2 WO 96/00322 PCT/US94/07450 32 BLEACH PLANT EFFLUENT CHARACTERISTICS BLEACH SEOUENCE COLOR AOX BODj O(C+D,0) (EO) D 120 8 O(DS0/c) (EO) D 90 4 OD(EO)D 50 2 Recycle OD(EO)D 1 OD(EO)D 1 0.1 2 All values in lbs/ton NZ Application No. 271075 08:53:09 • • • ft •ft) .

TABLE 6 ACID LEACHING OF OXYGEN DELIGNIFIED PULPS 9\ N > *o *2. o* Q> i—>• O* 3 M -si o -vl en o 00 01 co o CO As Is After leaching % Removed Metals in Softwood Pulp, ppm Na K Mg Ca Mn Fe Ai 2765 273 572 1358 66 11 26 124 32 29 66 4 6 9 95 88 94 95 93 54 65 Metals in Hardwood Pulp, ppm Na K Mg Ca Mn Fe Al I CO LP \ 6498 667 382 2529 88 16 22 180 30 15 97 4 7 5 97 96 96 96 95 56 77 * PO 05 CO Osf CD PO 269362 WO 96/00322 PCTAJS94/07450 34 TABLE 7 laboratory Bleaohing of Oxygen Salignified Softwood Pulp With and Without Bleaoh Plant Filtrat* Recycle Kappa number after oxygen delignification 14.2; Viscosity 15.1 cp.

Without Recycle With Recycle First Chlorine Dioxide State Chlorine dioxide, % as active chlorine 3.13 3.13 Chlorine dioxide, % as chlorine dioxide 1.19 1.19 Final pH 1.9 1.8 Oxidative Extraction State Sodiun Hydroxide applied, % 1.3 1.8 Final pH 11.2 11.3 CEK No. 2.1 2.1 Brightness 52.4 51.1 Viscosity, cp 14.4 14.0 Second Chlorine Dioxide Stage Chlorine Dioxide, % as chlorine dioxide 1.0 1.25 Final H 3.2 3.1 Brightness1 86 86 Viscosity, cp 12,7 13.1 1 Chlorine dioxide requirement to achieve 86 brightness interpolated from several bleaching experiments.

NZ Application No. 271075 08:53:09 269 3 6 2 WO 96/00322 PCT/US94/07450 A laboratory simulation of the bleaching sequence with filtrate recycle as depicted in Figure 2 was . conducted. A mill softwood pulp (Kappa 14.2) taken from the second stage of post oxygen washing, similar to washer 5 38 in Figure 2, was bleached using the scheme in Figure 2. In these runs sodium hydroxide was substituted for oxidized white liquor. Fresh mill pulp from the second post oxygen washer was bleached in repeated runs. Filtrates from each run were saved and applied in the manner shown in Figure 2 10 during the succeeding run. This was continued until equilibrium dissolved solids were established in the recycling filtrates. chlorine dioxide was completely substituted for molecular chlorine in these runs.

Results of metal removal in the acid treatment 15 stage are shown in Table 6. The acid treatment stage was conducted at pH 2. More than 90% of the sodium, magnesium, calcium, and manganese present in the oxygen delignified and washed pulp was removed during acid treatment. Removal of potassium, iron and aluminum was 20 lower, about 88% for potassium, 54% for iron and 65% for aluminum.

Bleach chemicals demand and final brightness achieved during these recycle procedures are shown in Table 7 and are compared to lab bleaching of the same 25 softwood pulp without filtrate recycle. A modest increase in both sodium hydroxide, 0.5%, and chlorine dioxide, 0.25%, was observed for the case of filtrate recycle compared to no filtrate recycle. Targeted NZ Application No. 271075 08:53:09 « 269 36 2 WO 96/00322 PCT/US94/074S0 . 36 brightness of 86 was achieved in both cases viscosity was similar.

The above-mentioned patents are hereby incorporated by reference.

Many variations of the present invention will suggest themselves to those of ordinary skill in the art in light of the above-detailed description. All such obvious modifications are within the full intended scope of the appended claims.

NZ Application No. 271075 08:53:09

Claims (12)

What is Claimed is: 37

1. A process for bleaching Kraft wood pulp after brown stock washing comprising the following steps conducted in sequence: an oxygen delignification stage; a washing sequence; a first acidic bleaching stage; partial neutralization with a filtrate from a subsequent oxidative extraction stage; an oxidative extraction stage; and a washing stage to remove bleach solids; and said process further comprising: subjecting said pulp to an acid wash after said washing sequence and prior to said first bleaching stage to remove all or a portion of non-process metals contained in said pulp; passing all or a portion of the filtrate from said first acidic bleaching stage and all or a portion of the filtrate from said oxidative extraction stage counter-currently through the washing sequence and the brown stock washing which constitutes a weak black liquor; passing said weak black liquor to a black liquor evaporation stage to produce a strong black liquor; combusting said strong black liquor to produce a smelt stream and a flue gas, said flue gas comprising particulates wl i (b) chloride and/or potassium salts, and separating said smelt sHrgatij^dSSfil flue Dcr.FlVPD and ;as; 2693 treating said flue gas to separate said particulates as ash, and treating said ash to form a component comprising sulfate salts and a component comprising chloride salts and/or potassium salts; recycling said component comprising sulfate salts to said strong black liquor and discharging said component comprising chloride salts and/or potassium salts; and recycling said smelt to a causticizing stage to regenerate a pulping liquor.

2. Process of claim 1, wherein said first acidic bleaching stage comprises bleaching with (a) chlorine dioxide, or (b) chlorine dioxide and elemental chlorine wherein the elemental chlorine is less than 10% by weight of the chlorine dioxide.

3. Process of claim 1 wherein said first acidic bleaching stage comprises bleaching with ozone.

4. Process of claim 1 which further comprises at least one additional acidic bleaching stage after said washing stage.

5. Process of claim 4 which further comprises passing counter-currently through said washing sequence and said brown stock washing all or a portion of said filtrates from said partial neutralization; from said washing stage; and from said at least one additional acidic bleaching stage. INTELLECTUAL PrSTOFFTCT OF N.2. 18 KAY 1933 39 — u _ p * /i '-J f; ^ A 1" A fc o 9 »4 h J

6. A Process for bleaching Kraft wood pulp after brown stock washing comprising the following steps conducted in sequence: an oxygen delignification stage; a washing sequence; a first acidic bleaching stage; an oxidative extraction stage; and a washing stage to remove bleach solids; and said process further comprising: treating all or a portion of filtrate from said first acidic bleaching stage to remove all or a portion of non-process metals from said filtrate to form treated filtrate; passing all or a portion of said treated filtrate from said first acidic bleaching stage and all or a portion of filtrate from said oxidative extraction stage counter-currently through the washing sequence and the brown stock washing which constitutes a weak black liquor; passing said weak black liquor to a black liquor evaporation stage to produce a strong black liquor; combusting said strong black liquor to produce a smelt stream and a flue gas, said flue gas comprising particulates which include (a) sulfate salts and (b) chloride and/or potassium salts, and separating said smelt stream and said flue gas; treating said flue gas to separate said particulates as ash, and treating said ash to form a component comprisi comprising chloride salts and/or potassium salts; ^HllflMUiSaltgoi^i^'^gpponent 18 MAY 1SS3 RECEIVED 2693 recycling said component comprising sulfate salts to said strong black liquor and discharging said component comprising chloride salts and/or potassium salts; and recycling said smelt to a causticizing stage to regenerate a pulping liquor.

7. Process of claim 6, wherein said acidic bleaching stages comprise bleaching with (a) chlorine dioxide, or (b) chlorine dioxide and elemental chlorine wherein the elemental chlorine is less than 10% by weight of the chlorine dioxide.

8. Process of claim 6 which further comprises at least one additional acidic bleaching stage after said washing stage.

9. Process of claim 6 wherein said first acidic bleaching stage comprises bleaching with ozone.

10. Process of claim 8 which further comprises passing counter-currently through said washing sequence and said brown stock washing all or a portion of said filtrates from said at least one additional acidic bleaching stage.

11. Process of claim 1 for bleaching Kraft wood pulp comprising subjecting the wood pulp after a brown stock washing stage to the following steps: ______ oxygen delignifying said wood pi and base followed by at least one post oxygen v delignified pulp; intellectual p r o p e r ty"* off/c i lp in the jSMfefence of oxygen 18 WAV 1323 ashing stage to form o>{; RECEI^f? 0 ygen 41 subjecting the oxygen delignified pulp to an acid treatment to remove all or a portion of non-process metals to form treated pulp, and washing the treated pulp with water to form washed treated pulp; bleaching the washed treated pulp in a first chlorine dioxide bleaching stage to form a first bleached pulp; subjecting the first bleached pulp to an extraction stage in the presence of base to form extracted pulp; washing the extracted pulp from said extraction stage with water on at least one post extraction washing "tn rr:,tn form vrn nh r-rtrnrtrri pulp; OF N.z. ' 8 MAY 1998 I RECEIVED 1 subjecting said washed extracted pulp to one or more additional chlorine dioxide bleaching stages and washing pulp after each stage; discharging the filtrate from said washings after one or more of said one or more additional chlorine dioxide bleaching stages, passing counter currently all or a portion of said filtrate from said washing after said one or more of additional chloride dioxide bleaching stages to said extraction stage as wash water; recycling counter currently filtrate from said washing stage to the last post oxygen stage as wash water; recovering filtrate from said last post oxygen washing stage in the cooking liquor recovery process by recycling said filtrate counter currently through the brownstock washing stage constituting a weak black liquor which is evaporated to produce a strong black liquor; combusting said strong black liquor in a recovery boiler to produce a smelt and a flue gas such that chloride salts from the counter currently recycled filtrates from one or more of the chlorine dioxide bleaching stages is enriched in the flue gas from combustion; collecting particulates containing potassium, chloride and sulfate salts in said flue gas as ash; removing chloride and potassium salts from said ash to produce a component comprising sulfate salts and a Q^pnrP"* i 7^o/^OFncil chloride and potassium salts; / x J 8 MAY 1998 HECElvpft 269 i*3 discharging the component comprising chloride and potassium salts; mixing said component comprising sulfate salts with said strong black liquor prior to combustion of said liquor in said recovery boiler; and dissolving said recovery boiler smelt in water to form green liquor and converting the green liquor to pulping liquor in the causticizing process.

12. Process of claim 6 for bleaching Kraft wood pulp comprising subjecting the wood pulp after brown stock washing stage to the following steps: oxygen delignifying said wood pulp in the presence of oxygen and base followed by at least one post oxygen washing stages to form oxygen delignified pulp; bleaching the oxygen delignified pulp in a first chlorine dioxide bleaching stage to form first bleached pulp; thickening said first bleached pulp from said first chlorine dioxide bleaching stage to form thickened pulp and extracting said thickened pulp in an extraction stage in the presence of base to form extracted pulp; washing said extracted pulp in a washing stage to form washed extracted pulp; ^ULkuiUAL propStT ' OF NZ Y 18 MAY 1998 PECFfl/pp 44 ' bleaching said washed extracted pulp in one or more additional chlorine dioxide bleaching stages and washing pulp after said one or more additional chlorine dioxide bleaching stages to form a washed bleached pulp; discharging the filtrate from said washings after said one or more additional chlorine dioxide bleaching stages, recycling all or a portion of said filtrate from said washings after said one or more additional chlorine dioxide bleaching stages to said washing stage as wash water; treating all or a portion of said filtrate from said thickening stage to remove all or a portion of non-process metals that enter the process with the wood fiber to form a filtrate having reduced non-process metal content and using the filtrate having reduced non-process metal content to wash pulp in the first chlorine dioxide bleaching stage to prevent the carryover of metals to the extraction stage whereby all or a portion of dissolved solids entering or generated in the first chlorine dioxide bleaching stage either pass to the extraction stage with the pulp or disposed of with the remove metals or a combination thereof; recycling filtrate from said washing stage as wash water to counter currently wash pulp beginning with a last post oxygen washing stage and continuing through a brownstock washing stage which constitutes a weak black liquor; I 18 Mr t$23 ■ -SgCE/l/rp j evaporating said weak black liquor to produce a strong black liquor; combusting said strong black liquor in a recovery boiler to produce a smelt and a flue gas whereby chloride salts from the counter currently recycled filtrate from one or more of the chlorine dioxide bleaching stages is enriched in the flue gas from combustion; collecting particles containing potassium, chloride and sulfate salts in said flue gas as ash; removing chloride and potassium salts from said ash to produce a component comprising sulfate salts and a component comprising chloride and potassium salts; discharging the component comprising chloride and potassium salts; mixing said component comprising sulfate salts with said strong black liquor prior to combustion of said liquor in said recovery boiler; and dissolving said recovery boiler smelt in water to form green liquor and converting the green liquor to pulping liquor in the causticizing process. intellectual pno^rftofrcn of n.z. * 18 (>!A7 KS3 Received end of claims