REPORT ON PAPTAC PULP BLEACHING COMMITTEES CHLORINE DIOXIDE GENERATOR SURVEY BY DENNIS OWEN

 

Introduction

The attached questionnaires were sent out to Pulp Bleaching committee members.  The responses to the survey are attached.  The responses are coded to protect the confidentiality of the mills.

 

Eighteen (19) mills reported on the operation of twenty (22) generators.  Of those, there were ten (10) R8, three (3) R10, one (1) SVP, one (1) SVP-SCW, three (5) Mathieson and two (2) Solvay generators.

 

Performance factors

Changes in rates of production, shutdowns, standby operation, boil outs, puffs and white outs reduce the plant yield.

 

Operating rate as a percent of designed rate varied from 0.5 to 1.8 times the design rate.

 

The frequency of rate changes range from zero (0) per week to ten (10) per week.

 

Standby operation on sub-atmospheric units is not an infrequent occurrence, two-three (2-3) per week being not uncommon.

 

In the sub atmospheric units, frequency of boil outs range from a low of twice (2) per year to twenty-six (26) times per year.

 

Maintenance shut downs range from annual, every six (6) months to once a month.  Reasons for shut down were preventative or corrective maintenance on all major items of equipment and instruments.

 

Puffing frequency

Several mills reported no puffs in the prior year.  Others reported up to three (3) puffs per week.  The predominant location of the puff was the generator and contaminants in the chemical feeds and sodium chlorate dissolving water as the source of the puffing.

 

Raw material specifications

Knowledge of the specification for the raw material was sparse.  It could be that specification is included in the purchase contract and was not readily available to the respondent.  Turbidity of sodium chlorate, colour and clarity of sulphuric acid and colour of methanol are quick qualitative assessment tools.

 

Sodium chlorate

Four (4) mills took delivery of sodium chlorate solution.  The mill’s hot water tank was the predominant source of sodium chlorate dissolving water.  This can become contaminated with extraneous mill process fluids, black liquor or other filtrates.

 

A few mills (4) filtered the water prior to its use to dissolve the sodium chlorate crystal.  Slightly more (5) filtered the sodium chlorate during the transfer from the unloading tank to the generator feed tank.

 

The filter elements used were 10 micron.  All mills filtered the sodium chlorate feed solution prior to its entry into the generator.  11% used 5 micron , 33% used 10 micron, 44% used 20 micron.  Two (2) mills still used porastone filter elements at 55 micron.

 

The change out frequency for sodium chlorate solution filter elements ranged from three (3) days to four (4) weeks.

 

The change out frequency for sodium chlorate feed filter elements ranged from two (2) days to eight (8) weeks.  Four (4) mills change on high pressure, low flow.

 

Sulphuric acid

Only four (4) mills reported filtering the sulphuric acid during the unloading. Seventeen (17) mills filtered the sulphuric acid prior to its injection into the generator.

 

The change out frequency for sulphuric acid unloading filter elements was weekly.  38% used 10 micron filters, five (5) mills used porostone filters.

 

The change out frequency for sulphuric acid feed filter elements ranged from two (2) to twenty-six (26) weeks and five (5) mills changed on low flow.

 

Methanol

Fifteen (15) of sixteen (16) methanol based units filtered the methanol feed.  54% 10 micron, 13% 20 micron, 33% 40 micron.  One (1) mill changed and therefore inspected the methanol quality every 12 months and another every 6-7 months.  45% of mills that diluted the methanol with water prior to entry into the generator room filtered that water.  The filter elements were 41% 10 micron, 20% 20 micron, 20% 40 micron.  One (1) mill used a stainless steel mesh screen.

 

Sub-atmospheric systems use hot water to flush slurry lines and wash the saltcake by-product.  Hot water tank was the major source of water.  Only five (5) mills filtered the water prior to its entry into the generator or filter process streams.

 

Sub-atmospheric generator operators reported problems with high pressure kick-outs and mills’ frequencies of six (6) and fourteen (14) per month were reported.

 

White outs are a potential problem in generators that use methanol and in R8 and R10 generators.  Several mills reported frequencies of three (3) and eight (8) per month.

 

Chemical usages

Seven (7) mills reported chemical usages that were superior to typical performance guarantees for the respective processes.

 

The lowest sodium chlorate usage for sub-atmospheric generator was 1.62 kg NaClO3/kg ClO2 (97% yield) and the atmospheric Mathieson was 1.65 kg NaClO3 (95% yield) and the Solvay 1.75 kg NaClO3/kg ClO2.(90% yield). 

 

The lowest methanol usage for sub-atmospheric generators was 0.15 kg CH3OH/kg ClO2.

 

The sulphur dioxide usage for Mathieson was 0.57 kg/kg ClO2.

 

There is significant room for improvement.  At 15.0 ton/day, a 1% improvement in yield could result in annual savings of $55,000/year, $110,000/year for a 30 ton/day plant and $165,000 for a 45 ton/day plant.

 

Emergency quench water

Sub-atmospheric generators use water to quench the reaction after a decomposition or puff or after an interlock has been activated.  The mill process water was the source of this emergency water.  Three (3) mills reported an emergency quench water tank as its back-up and three (3) mills had the mill’s fire water main as an emergency water source back-up.  Note.  Safety incident report on consequences of lack of back up.

 

Generator chemical targets and control

The range of targets for each process were significant.  The deviations from the set targets were reasonable.

 

Defoamer

Sixteen (16) mills used tributyl phosphate addition.  Nine (9) mills use small batch additions 25-75 mls once/twice/thrice/shift, nine (9) added it continuously through the methanol feed at concentrations ranging from 19 to 50 ppm.  Two (2) mills added as needed.

 

Saltcake filter operation

Only five (5) mills monitored the % NaClO3 lost in the cake.

 

Chlorine dioxide absorption tower

The water source for the towers in twelve (12) mills came from a chiller.  Four (4) took the water from the river and three (3) took its water from wells.  Only nine (9) mills had a back-up water supply.

 

Chlorine dioxide solution concentration

Four (4) mills were targeting a concentration ³12 gpl; seven (7) were 10 gpl and the remainder were at 8-9 gpl.

 

Chlorine dioxide solution storage

The capacity range from 3 hours for atmospheric units to 19 hours for one (1) sub-atmospheric unit.

 

Tail gas scrubber

It was vented to bleach plant scrubber in five (5) mills.

 

White liquor (2), caustic soda (2) and water were the scrubbing liquors of choice.