Nanotechnology in paper making

Written by Roxare on July 27th, 2008

The main reason for applying nanotechnology solutions is added value. Nanotechnology in papermaking can be applied in several areas. These include:

  • Water based coatings that are non-toxic, smoother and tougher
  • Surfaces that are smoother and have better printability
  • Enhanced sheet properties by adding nanoparticles such as silica
  • Developing grades that are stronger and lighter, use less fibre and are biodegradable
  • Closed looped water reuse with nano-filtration

In traditional paper making, nano-particle-based fillers, substituting for fibre, and combined with lower basis weights, are delivering significant savings to the industry. Also, wet end retention aids are another example of existing nanotechnology. Click to continue »



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A closed cycle kraft mill

Written by Roxare on June 14th, 2008

The Blue Ridge Paper Products (formerly Champion), Canton mill, NC, recycles both the Eop and D0 filtrates to meet strict permit requirements, for water use and effluent colour. As part of Champion International, the mill undertook an aggressive bleach filtrate recycle strategy (the BFR process). This strategy incorporates a metals removal process (MRP, i.e., based on ion-exchange technology) and a chloride/potassium removal process (CRP, i.e., based on evaporation-crystallization of ESP dust) into the recycling operation [1]. BFR uses oxygen delignification followed by three stages of post-oxygen washing and ECF medium consistency bleaching (OD0EopD), with recycle of bleach plant filtrate to the recovery system. To optimize bleach plant operation, the chlorine dioxide charge in the D0 stage was reduced from a kappa factor of 0.28 to between 0.18-0.22 before the recycle began [2]. Eop filtrate is recycled to the showers of the last post-oxygen washer, and D0 filtrate is processed through a metal removal process before being recycled to the D0 washer. A portion of the final D-stage filtrate is sewered, because of the minimal environmental effect and the higher chloride load that would have to be recovered. Click to continue »



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Trace elements in the recovery cycle

Written by Roxare on May 11th, 2008

Trace element (TE) distributions for As, Cd, Cr, Mn, Ni and Pb have been studied around the recovery boiler of a softwood kraft mill [1].The fate of these elements is of interest in closed cycle mills, where their toxicity could be an issue. An extensive sampling program was conducted in the mill, which had a production rate of 1700 adt/d, and used TCF bleaching. The black liquor was fired at 80%, and the capacity of the recovery boiler (RB) was 3000 t BLS/d. The lime kiln had a capacity of 500 t CaO/d; the lime was dried from 80% to 100% dry solids before burning. About 2% of the CaO used in the causticizing was added as make-up lime. Click to continue »



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Handling of non-process elements-Mill experience

Written by Roxare on April 11th, 2008

Effluents from the woodroom, the brownstock area and the evaporation plant have the highest toxic emission factor per COD unit, compared to the effluent from ECF or TCF bleaching [1]. Steps taken to reuse these effluents lead to high levels of non-process elements (NPEs) in the liquor cycle. The levels of NPEs for five Swedish mills were monitored for 7 years, and the data were used to evaluate the effect of increased mill closure, and to identify suitable methods to purge NPEs.  Click to continue »



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Spill Control

Written by Roxare on March 15th, 2008

Improved spill control is a cost effective way to reduce effluent discharge and lower the cost of waste water treatment.  The most significant spills in a mill occur from black, white and green liquors, and from paper coatings. Planned discharges include cooling water, boiler blow down, bleaching filtrates and wet debarking effluents. These discharges are generally, predictable and can be established by process simulation tools. Mills usually have spill containment systems for unplanned discharges such as leaks, tank overflows, and off-spec product dumps. In a modern mill with closed screening, O2 delignification and ECF bleaching, spills can account for up to half the colour in the final effluent, and up to a third of the operating cost of the waste treatment system [1]. Reducing spills will thus allow a mill to expand without expanding its effluent treatment system. 

Specific conductivity is the most widely used parameter for the continuous monitoring of black, white and green liquors, and soap spills. However, conductivity measurements will not detect paper coatings or turpentine spills. COD and colour are useful parameters for longer term assessment.  Spills have to be monitored instantaneously by conductivity or other real-time continuous sensors, at multiple points, to enable the appropriate corrective response. Most mills will consider pumping back an effluent stream with a conductivity of over 5000 ?mhos to the black liquor system. This corresponds to a black liquor concentration of about 0.5%.  At some mills, the set point is as low as 2500 ?mhos [1]. Low discharge of colour or COD is an indication of good spill control. As a rough guide, a mill with O2 delignification that has below 40 kg colour/t or 30 kg COD/t in its discharges before treatment would have good spill control [1]. 

The best strategy is to prevent spills whenever possible. Appropriate instrumentation and knowledgeable mill staff are key factors. However, prevention is not always possible, and spill recovery sumps with automatic activation are required in critical areas [2]. A good spill control system provides operators with continuous, updated data on key parameters. The data must be understood by the operators, for them to be able to diagnose causes and take corrective action. Much of  the data required are the same as is needed to run an efficient operation; additional information, such as the levels of all major tanks, overflow alarms, and conductivity in floor drains, are also required. Continuous clean water discharges must be kept separate from the floor drains in areas covered by spill recovery. This is because the water dilutes the spills, and increases the black liquor evaporation load. 

1.       McCubbin, N., “Spill control: Assessing your situation”, Solutions!, 49-50, November, 2001.

2.     McCubbin, N., “Spill control, Part II: Reducing spills”, Solutions!, 36-37, December, 2001. 



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Managing Chloride and Potassium in a Kraft Mill

Written by Roxare on February 2nd, 2008

Chloride (Cl) and potassium (K) are the most problematic non-process elements in the kraft recovery cycle. Since the salts of these elements are very soluble, they build up in the recovery cycle, to an extent which depends on the amount of input, the degree of mill closure and the liquor sulphidity. Cl and K enter the mill with contaminated wood, chemical make-up and water. Depending on the type of wood, the K content can be high. As mills reduce water consumption, increase spill recovery or recycle bleach plant effluent to the recovery cycle, the level of Cl and K increases in the recovery cycle.

There are several methods employed in mills to combat this problem. Cl and K enrich in the electrostatic precipitator (ESP) dust, and most methods for removing them involve the treatment of the ESP dust. The simplest method is to discharge a portion of the dust and use relatively pure saltcake and caustic soda to replace the lost Na2SO4 and Na2CO3. This method incurs an operating cost, and may be problematic if the mill has limits on the effluent conductivity and flow. Other methods to treat ESP dust include: leaching, evaporation crystallization, cooling crystallization and ion exchange. The first three methods operate on the basis of differences in the solubility of alkali sulphate and alkali chloride salts. The ion exchange process uses ion retardation to separate chloride from sulphate.

Here are some examples of systems available:

Leaching: In this system the ESP dust is mixed with water to form a slurry. More Cl salts dissolve compared to sulphate salts and a filter or centrifuge is used to separate the solid sulphate. A leaching system was installed in a Brazilian mill in 2002 [1]; The Cl and K removal efficiencies were reported to be around 70%, with 80% recovery of Na and 85% recovery of S.

Evaporation Crystallization: This type of system (Chloride Removal Process or CRP) is offered by three manufacturers, each using different evaporator designs. As of 2004, there were six CRPs operating: three in North America, two in South America and one in Australia. Published data from one mill shows 95% Cl removal and 80% sulphate recovery. K removal varied between 50-85%, depending on the amount of K in the ESP dust and the balance between K removal, and Na and S recovery [1].

Cooling Crystallization: In this method a slurry of ESP dust is cooled to about 15 C, when Na2SO4 in solution re-crystallizes as Na2SO4.10 H2O. The crystals are then separated by decanting. The removal efficiency was reported as 90% for Cl and 75% for K, with 70% recovery for Na. There are six cooling crystallization systems installed in Japanese mills [1].

Ion Exchange: This system uses an amphoteric ion exchange resin to separate Cl from sulphate in an ESP dust solution. Pilot plant data provide a Cl removal efficiency of 97%, with minimal loss of Na, S and carbonate. However, the K removal efficiency is low (5%). One difference between ion exchange and other methods is that the purified sulphate is returned to the liquor cycle in the form of a solution and not as a slurry or as crystals. This requires extra capacity in black liquor evaporation. The addition point of sulphate solution to the evaporators is also critical, as a high concentration of sulphate could promote burkeite (2Na2SO4.Na2CO3) formation and scaling of the evaporators.

1. Tran, H. and Earl, P., Chloride and potassium removal processes for kraft pulp mills: a technical review, Inter. Chem. Rec. Conf., 2004.



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Smelt Flow Problems

Written by Roxare on January 6th, 2008

Many mills experience smelt flow problems, which could lead to dissolving tank explosions and plugged smelt spouts. Liquor chemistry affects the smelt composition, causing changes in the smelt melting point and its viscosity. Higher melting point smelts tend to have higher viscosity at a given temperature. The sulphide content of the smelt has the most significant effect on the smelt’s melting point. The melting point and viscosity decrease as the sulphidity increases to about 40%, but increase rapidly when the sulphidity increases over 40%. Also, when the boiler is operating at very high reduction efficiencies (i.e., low Na2SO4 content in the smelt) the smelt melting point increases significantly.  K and Cl enrichment reduces the smelt melting point and the viscosity. 

Other factors, such as boiler operating conditions and design may also have an effect. Smelt spout feed water temperatures below BLRBAC guidelines (60-65 oC) can result in low smelt temperatures and high viscosity, or in the solidification of smelt in the spouts. High furnace drafts, and excessive air infiltration around the smelt spouts, could also cool the smelt, with the same result.  

Incomplete combustion of the BL organics, or firing a highly viscous BL, could lead to high carbon content in the smelt, raising the smelt melting temperature and viscosity. This can be verified by measuring the suspended solids in the unclarified green liquor. If the suspended solids are over 1200 ppm, this is an indication of unburned carbon or a dregs related problem [1]. Increased BL viscosity can result in the formation of larger droplets, that fall closer to the walls and increase the carbon or dregs content of the smelt. Other factors influencing smelt flow include bed temperature, excessive metals build-up in the smelt, a change in chemical makeup, upsets or control problems with practices that add Cl to the system, and a change of furnish. 

1.  Karidio, I, et al, A review of the conditions in chemical recovery boilers that result in poor-flowing smelt, 2004 Int. Chem. Rec. Conf.



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Sintering of recovery boiler dust

Written by Roxare on December 11th, 2007

Tough-to-remove deposits can form on the surfaces of recovery boiler (RB) tubes, even when the flue gas temperatures are too low to melt the dust.  Deposits formed from fume particles can begin to sinter and harden around 300o C, and the rate of sintering increases significantly with temperature.  The sintering tendency is affected by the dust’s composition and physical properties, and the RB operating conditions. 

The composition of the fume particles changes as they move through the upper furnace, reacting with sulphur oxides. However, beyond the superheater region, the composition does not change very much (as the SO2 levels are low) and the composition of the fume that deposits on the boiler bank tubes is the same as the ESP dust. Research has shown that the chloride content of the dust has a direct effect on sintering [1]. At Cl levels of less than 2 mole % (Cl/(Na+K)), the dust does not sinter well.  The effect of K becomes significant when the Cl content is more than 2 mole %.  The combination of high Cl and high K increases the sintering rate significantly. This is to be expected, as NaCl and KCl have a high vapour pressure relative to the other components of the dust, and they also decrease the first melting point temperature (FMT).  Rapid sintering takes place when the FMT is lowered. The FMT of RB dust without any Cl is very high (780o C). However, this is greatly reduced (<600o C) if a small amount of Cl is present. The FMT of dusts containing Cl will be affected mainly by K and, to a lower extent, by carbonate. Of the dust’s physical properties, an increase in un-compacted bulk density results in reduced sintering. This means that light dusts sinter more, while more dense dust (i.e., from the ash hopper) sinter less. The dust composition and particle size can be affected by the boiler’s operating conditions.  High solids firing, and increasing the firing load, result in hot beds and a low SO2 concentration in the flue gas. The light dust will contain more carbonate and Cl, and sinter more readily. 

SO2 at 1.0% concentration has been found to have a major impact, greatly increase the rate of sintering [2]. Since high levels of SO2 are not usually found in RB in the superheater section and beyond, SO2 is not usually a factor in the sintering of deposits. However, during upset conditions (i.e., a cold char bed) when the SO2 concentration is increased for a short time, sintering conditions are favoured.

 1.             The sintering tendency of recovery boiler precipitator dust, Duhamel, M., et al, 2002 Tappi Fall Conf. & Trade Fair

2.             Effect of gas composition on fume sintering rates, Lien, S.J., et al, 2004 Int. Chem. Rec. Conf.



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Plugging of kraft recovery boilers

Written by Roxare on November 18th, 2007

Plugging problems in kraft recovery boilers (RB) are caused by a combination of factors. These are: the particle quantity, particle composition (e.g., stickiness), recovery boiler operating conditions and sootblowing efficiency.  The concentration of soluble elements such as Cl and K increases in the recovery cycle when mills reduce water consumption and liquor losses, and/or recycle bleaching effluent.  Cl and K lower the melting point and decrease the sticky temperature of the deposits formed on the tube surfaces.  Deposits include carryover (0.01-3 mm), fume (0.1-1 ?m) and intermediate size particle [1]. 

Carryover particles are partially oxidized smelt or partially burnt black liquor (BL) droplets, and they deposit mostly on the superheater tubes. Fume particles form by condensation of the vapours of Na/K compounds, and mostly deposit on the generating bank and economizer tubes.  The quantity of carryover particles increases when the firing load is increased, when the proportion of smaller liquor droplets increases (i.e., from firing low viscosity liquors), and when the flue gas velocity is high. The quantity of fume particles is determined by the vapourization rate of Na/K compounds from the char bed, and the rate of Na/K release during liquor pyrolysis.  Therefore, operating the boiler with a hot bed (i.e., high solids firing) will generate more fumes in the upper furnace. High solids firing will also produce larger droplets, lower the quantity of particles and reduce fouling by carryover.  

The particles formed in the RB have to be sticky to adhere to the tube surfaces. The stickiness of the particles depends on their liquid content when they impact the tube surface. The liquid content depends on the particle composition and temperature. It has been shown that particles with a liquid content of over 15% are sticky. The sticky temperature can be estimated if the particle’s composition is known [2]. However, this is not usually possible, as the composition changes continuously when carryover particles are being formed and deposited.  Laboratory and field tests indicate that the Cl content of carryover particles is around 30% of the Cl in the feed BL, and the K content is about 80% that of the feed BL [3].  Two factors appear to be responsible for the depletion of Cl in the carryover with time: one is the vapourization of Na/KCl, and the other is the sulphation of Na/KCl by SO2 in the flue gas, that releases HCl.  

2Na/KCl +SO2+O2+H2OàK2/Na2SO4+2HCl? 

Higher bed temperature leads to greater depletion of Cl and K, higher sticky temperatures and reduced deposition of carryover. However, greater depletion of Cl and K in carryover leads to greater enrichment of these elements in the fume.  Field studies have shown that there is a linear correlation between the K and Cl contents of the as-fired BL, the smelt, the carryover deposits and the ESP dust [3]. This linear correlation is not expected to hold if there is excess sulphur in the flue gas. Simple approximation can be used to estimate the composition and sticky temperature of carryover in a RB. This approximation is based on the above- mentioned linear relationship. Chemical analysis of the as-fired BL and ESP dust is all that is required for the calculation of the sticky temperature. First of all, Cl and K enrichment factors are calculated for the ESP dust.  The enrichment factor for Cl can then be plotted versus that of K. The linear graph is extrapolated to estimate the Cl and K content in the carryover, using a Cl enrichment factor of about 0.4 and a K enrichment factor of about 0.88 [3]. The sticky temperature can then be predicted for a range of carryover, using available graphical data [2].

1.                   Tran, H.N. et al, Fouling of tube surfaces in kraft recovery boilers, 40th anniversary, Int. Rec. boilers conf., Porvoo, Finland. March 12-14 (2004).

2.                   Tran, H.N. et al, The sticky temperature of recovery boiler fireside deposits, Pulp & Paper Canada, 103:9, P.29-33 (2002).

3.                   Khalaj, A. et al, Composition of carry over particles in recovery boilers, Chem. Rec. Conf. Charleston, SC, USA, June 6-10 (2004).



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Water and Energy Benchmarking

Written by Roxare on October 28th, 2007

I have been asked by some of the readers of this website to comment on water and energy benchmarking and to provide some data. Benchmarking is the comparison of a mill’s water and energy consumptions with reference to its competitors or to a model mill with modern technology. This provides opportunities for optimizing water and steam consumption in a mill. Water and energy reduction strategies have been studied by the research community and practiced by mills for the past several years. Factors driving these measures are usually economics and/or regulatory compliance.

Water:

A survey done in 1996 for US and Canadian mills provided data on total water consumption for different types of mills, giving a range of 47-142 m3/adt for bleached kraft mills [1]. Since then a lot of measures have been employed to reduce water consumption. In 1999, the approximate flow of effluent from a modern ECF mill was estimated to be between 13 to 22 m3/adt (10-15 m3/adt from bleaching), whereas that of a TCF mill was between 8 to 17 m3/adt (5-10 m3/adt from bleaching). The main difference is that the alkaline filtrates are more frequently recovered from TCF mills. These low effluent flows indicate that the cooling water and process water are segregated in these mills. The first effluent-free bleach plant based on the evaporation of Q-stage filtrate started in 1997 in Sweden. In this case, the recovery boiler was used to burn the concentrate.

A model reference mill (using best available technologies in the year 2000) was projected to have a total effluent flow of 15 m3/adt, of which 11 m3/adt was attributed to the bleach plant [3]. This mill has dry debarking, continuous cooking, 80% black liquor solids to the recovery boiler, two-stage oxygen delignification, extensive washing, a bleaching sequence of Q(OP)(DQ)(PO) (or TCF alternative of Q(OP)(ZQ)(PO)), and alkaline filtrate recycle to brownstock washing. These measures, taken to reduce water consumption in the pulp mill, generally increase the solids loading of the recovery boiler. Future mills, in which the filtrates are evaporated and the condensates are re-used, will have a total effluent flow of 2 to 7 m3/adt.

Energy:
Data regarding energy consumption are collected based on purchased, self generated and sold energy, as well as the mill’s pulp and paper production. The energy intensity of a mill is the total energy consumed divided by the total production. In order to identify opportunities for energy savings, benchmarking should be done for specific process areas in a mill. For example, a mill producing kraft pulp will have process and energy conversion areas. Process areas cover wood room, pulping, bleaching, evaporation, recausticizing, pulp machine and effluent treatment. Energy conversion areas include power and recovery boilers, turbines and deaerators.

Technology descriptors are defined to account for energy use by different technologies. For example, in kraft pulping, the energy use varies with the pulping method (i.e., continuous, batch or M&D digesters). In a 2006 paper [4], data were collected from 49 mills on fibre and energy inputs and outputs. These were then allocated to the process and energy conversion areas. These data showed that, for bleached kraft market pulp, the fuel consumption (including spent pulping liquor and fossil fuel) was between 22-42.5 GJ/adt and the thermal energy (defined as steam used less condensate returned) consumption varied between 13.7-24.1 GJ/adt. For the production of newsprint from TMP, the electricity consumption was about 2.3-3.0 MWh/adt and the net thermal energy consumption was about 1.9-7.4 GJ/adt.

In terms of selected process areas in kraft pulping, the median thermal energy consumption was 2.43 GJ/odt for continuous digesters, 5.03 GJ/odt for indirect contact evaporators and 2.57 GJ/odt for softwood bleaching. Median thermal energy consumption for the paper machine varied according to the product: 5.36 GJ/adt for newsprint, 6.21 GJ/adt for uncoated GW, and 9.10 GJ/adt for kraft papers.

To start benchmarking, a database of water and energy consumption information from similar mills is required. A mill wide water and energy (steam generation and distribution) audit can be used to construct a base case material and energy balance for a specific mill. This is important, as measures taken to reduce water could impact energy balances and vice versa. Once a model is validated with the mill data, it is easy to study what-if scenarios to see, for example, what can be done to decrease water consumption in a specific area, and what the effect may be on steam use. Pinch analysis is used to optimize steam consumption.

References:

1. Bryant, P.S., et al, Pulp and paper mill water use in North America, Tappi 1996 International Environmental Conference, Orlando, FL, Book 2, pp. 451-460, (1996).
2. Henricson, K., et al, Steps towards minimum impact mill – Mill case examples, 27th EUCEPA Conference – Crossing the millennium frontier, emerging technical and scientific challenges, Grenoble, France, pp. 143-148, (1999).

3. Axegard, P., The Ecocyclic pulp mill- Prospects for closure and energy efficiency, 2000 Japan Tappi annual meeting and Pan Pacific Conference Proceedings, Tokyo, pp. 129-134, (2000).

4.        Francis, B., et al, Benchmarking energy use in pulp and paper operations, PAPTAC, 92nd Annual meeting reprints, Book A. pp. 55-61, (2006).



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