Overview of Chemical Recovery Processes in Pulp & Paper Mills

Figure 1

The kraft process is the dominant pulping process in the United States, accounting for approximately 85 percent of all domestic pulp production. The soda pulping process is similar to the kraft process, except that soda pulping is a non-sulfur process. One reason why the kraft process dominates the paper industry is because of the ability of the kraft chemical recovery process to recover approximately 95 percent of the pulping chemicals and at the same time produce energy in the form of steam. Other reasons for the dominance of the kraft process include its ability to handle a wide variety of wood species and the superior strength of its pulp.

The production of kraft and soda paper products from wood can be divided into three process areas:

1. Pulping of wood chips
2. Chemical recovery
3. Product forming (includes bleaching)

Figure 2

The relationship of the chemical recovery cycle to the pulping and product forming processes is shown in Figure 1. Process flow diagrams of the chemical recovery area at kraft and soda pulp mills are shown in Figures 1 and 2, respectively.

The purpose of the chemical recovery cycle is to recover cooking liquor chemicals from spent
cooking liquor. The process involves concentrating black liquor, combusting organic compounds, reducing inorganic compounds, and reconstituting cooking liquor.

Cooking liquor, which is referred to as "white liquor, is an aqueous solution of sodium hydroxide (Na01) and sodium sulfide (Na2S) that is used in the pulping area of the mill. In the pulping process, white liquor is introduced with wood chips into digesters, where the wood chips are "cooked" under pressure. The contents of the digester are then discharged to a blow tank, where the softened chips are disintegrated into fibers or "pulp. The pulp and spent cooking liquor are subsequently separated in a series of brown stock washers: Spent cooking liquor, referred to as "weak black liquor, from the brown stock washers is routed to the chemical recovery area. Weak black liquor is a dilute solution (approximately 12 to 15 percent solids) of wood lignins, organic materials, oxidized inorganic compounds (sodium sulfate (Na2SO4), sodium carbonate (Na2003)), and white liquor (Na2S and Na0H).

In the chemical recovery cycle, weak black liquor is first directed through a series of multiple-effect evaporators (MEE's) to increase the solids content to about 50 percent. The "strong. (or "heavy") black liquor from the MEE's is then either oxidized in the BLO system if it is further concentrated in a DCE or routed directly to a concentrator (NDCE). Oxidation of the black liquor prior to evaporation in a DCE reduces emissions of TRS compounds, which are stripped from the black liquor in the DCE when it contacts hot flue gases from the recovery furnace. The solids content of the black liquor following the final evaporator/concentrator typically averages 65 to 68 percent.

Concentrated black liquor is sprayed into the recovery furnace, where organic compounds are combusted, and the Na2SO4 is reduced to Na2S. The black liquor burned in the recovery furnace has a high energy content (13,500 to 15,400 kilojoules per kilogram (kJ/kg) of dry solids (5,800 to 6,600 British thermal units per pound {Btu/lb} of dry solids)), which is recovered as steam for process requirements, such as cooking wood chips, heating and evaporating black liquor, preheating combustion air, and drying the pulp or paper products. Particulate matter (PM) (primarily Na2SO4) exiting the furnace with the hot flue gases is collected in an electrostatic precipitator (ESP) and added to the black liquor to be fired in the recovery furnace. Additional makeup Na2SO4, or "saltcake," may also be added to the black liquor prior to firing.

Molten inorganic salts, referred to as "smelt," collect in a char bed at the bottom of the furnace. Smelt is drawn off and  dissolved in weak wash water in the SDT to form a solution of carbonate salts called "green liquor," which is primarily Na2S and Na2CO3. Green liquor also contains insoluble unburned carbon and inorganic Impurities, called dregs, which are removed in a series of clarification tanks.

Decanted green liquor is transferred to the causticizing area, where the Na2CO3 is converted to NaOH by the addition of lime (calcium oxide [Ca0]). The green liquor is first transferred to a slaker tank, where Ca0 from the lime kiln reacts with water to form calcium hydroxide (Ca(OH)2). From the slake, liquor flows through a series of agitated tanks, referred to as causticizers, that allow the causticizing reaction to go to completion (i.e., Ca(OH)2 reacts with Na2CO3 to form NaOH and CaCO3).

The causticizing product is then routed to the white liquor clarifier, which removes CaCO3 precipitate, referred to as "lime mud." The lime mud, along with dregs from the green liquor clarifier, is washed in the mud washer to remove the last traces of sodium. The mud from the mud washer is then dried and calcined in a lime kiln to produce "reburned" lime, which is reintroduced to the slaker. The mud washer filtrate, known as weak wash, is used in the SDT to dissolve recovery furnace smelt. The white liquor (NaOH and Na2S) from the clarifier is recycled to the digesters in the pulping area of the mill.

At about 7 percent of kraft mills, neutral sulfite semi-chemical (NSSC) pulping is also practiced. The NSSC process involves pulping wood chips in a solution of sodium sulfite and sodium bicarbonate, followed by mechanical de-fibrating. The NSSC and kraft processes often overlap in the chemical recovery loop, when the spent NSSC liquor, referred to as "pink liquor," is mixed with kraft black liquor and burned in the recovery furnace. In such cases, the NSSC chemicals replace most or all of the makeup chemicals. For Federal regulatory purposes, if the weight percentage of pink liquor solids exceeds 7 percent of the total mixture of solids fired and the sulfidity of the resultant green liquor exceeds 28 percent, the recovery furnace is classified as a "cross-recovery furnace.'" Because the pink liquor adds additional sulfur to the black liquor, TRS emissions from cross recovery furnaces tend to be higher than from straight kraft black liquor recovery furnaces.

Industrial Inline Refractometers for Sucrose, Fructose and Dextrose

The Electron Machine MPR E-Scan is perfectly suited for sugar applications. The refractometer directly measures dissolved solids, which can be easily converted to Brix.

In sugar refineries, the MPR E-Scan can be used to monitor and control Brix measurement from the beginning of the evaporation stages up to the seed point of crystallization.

The suggested adapter for most installations is either a 316S/S in-line type adapter or a 316S/S vacuum pan adapter. If coating may be an issue, a steam or hot water wash nozzle can be provided.

Sanitary-type adapters designed and manufactured to appropriate 3-A Sanitary Standards are also available if needed.

Refractometer for Food & Beverage Industries from Electron Machine Corporation

Industrial Refractometers in Action: Pulp & Paper Mill

This video below highlights various applications for inline refractometers in a pulp and paper mill.

The Electron Machine Corporation pioneered the use of refractometers to accurately measure black liquor dissolved solids nearly 50 years ago. Our long history with this application has resulted in numerous design features that specifically address problems associated with this harsh process measurement. Electron Machine refractometers have been accurately measuring green liquor solids in the paper industry for more than 30 years.

For more information visit http://www.electronmachine.com or call 352-669-3101.

Introduction to Industrial Instrumentation

Engineer adjusting a
process controller measuring 
the refractive index of a process.

Instrumentation is the science of automated measurement and control. Applications of this science abound in modern research, industry, and everyday living. From automobile engine control systems to home thermostats to aircraft autopilots to the manufacture of pharmaceutical drugs, automation surrounds us. This chapter explains some of the fundamental principles of industrial instrumentation.

The first step, naturally, is measurement. If we can’t measure something, it is really pointless to try to control it. This “something” usually takes one of the following forms in industry:

• Fluid pressure
• Fluid flow rate
• The temperature of an object
• Fluid volume stored in a vessel
• Chemical concentration
• Machine position, motion, or acceleration
• Physical dimension(s) of an object
• Count (inventory) of objects
• Electrical voltage, current, or resistance
• Refractive Index

Once we measure the quantity we are interested in, we usually transmit a signal representing this quantity to an indicating or computing device where either human or automated action then takes place. If the controlling action is automated, the computer sends a signal to a final controlling device which then influences the quantity being measured.

This final control device usually takes one of the following forms:

• Control valve (for throttling the flow rate of a fluid)
• Electric motor
• Electric heater

Both the measurement device and the final control device connect to some physical system which we call the process. To show this as a general block diagram:

Process control loop

The common home thermostat is an example of a measurement and control system, with the home’s internal air temperature being the “process” under control. In this example, the thermostat usually serves two functions: sensing and control, while the home’s heater adds heat to the home to increase temperature, and/or the home’s air conditioner extracts heat from the home to decrease temperature. The job of this control system is to maintain air temperature at some comfortable level, with the heater or air conditioner taking action to correct temperature if it strays too far from the desired value (called the setpoint).

Industrial measurement and control systems have their own unique terms and standards. Here are some common instrumentation terms and their definitions:

Process: The physical system we are attempting to control or measure. Examples: water filtration system, molten metal casting system, steam boiler, oil refinery unit, power generation unit.

Process Variable, or PV: The specific quantity we are measuring in a process. Examples: pressure, level, temperature, flow, electrical conductivity, pH, position, speed, vibration.

Setpoint, or SP: The value at which we desire the process variable to be maintained at. In other words, the “target” value for the process variable.

Primary Sensing Element, or PSE: A device directly sensing the process variable and translating that sensed quantity into an analog representation (electrical voltage, current, resistance; mechanical force, motion, etc.). Examples: thermocouple, thermistor, bourdon tube, microphone, potentiometer, electrochemical cell, accelerometer.

Example of a transducer.
In this case, a
Refractive Index transducer.

Transducer: A device converting one standardized instrumentation signal into another standardized
instrumentation signal, and/or performing some sort of processing on that signal. Often referred to as a converter and sometimes as a “relay.” Examples: I/P converter (converts 4- 20 mA electric signal into 3-15 PSI pneumatic signal), P/I converter (converts 3-15 PSI pneumatic signal into 4-20 mA electric signal), square-root extractor (calculates the square root of the input signal).
Note: in general science parlance, a “transducer” is any device converting one form of energy into another, such as a microphone or a thermocouple. In industrial instrumentation, however, we generally use “primary sensing element” to describe this concept and reserve the word “transducer” to specifically refer to a conversion device for standardized instrumentation signals.

Transmitter: A device translating the signal produced by a primary sensing element (PSE) into a standardized instrumentation signal such as 3-15 PSI air pressure, 4-20 mA DC electric current, Fieldbus digital signal packet, etc., which may then be conveyed to an indicating device, a controlling device, or both.

Example of a transmitter and/or
controller. In this case, refractive
index signal conditioning electronics
to modify the transducer signal,
and optionally, provide a control
output to a final control element.

Lower- and Upper-range values, abbreviated LRV and URV, respectively: the values of process ^oC and its URV would be 500 ^oC.
measurement deemed to be 0% and 100% of a transmitter’s calibrated range. For example, if a temperature transmitter is calibrated to measure a range of temperature starting at 300 degrees Celsius and ending at 500 degrees Celsius, its LRV would be 300

Zero and Span: alternative descriptions to LRV and URV for the 0% and 100% points of an instrument’s calibrated range. “Zero” refers to the beginning-point of an instrument’s range (equivalent to LRV), while “span” refers to the width of its range (URV − LRV). For example, if a temperature transmitter is calibrated to measure a range of temperature starting at 300 degrees Celsius and ending at 500 degrees Celsius, its zero would be 300 ^oC and its span would be 200 ^oC.

Controller: A device receiving a process variable (PV) signal from a primary sensing element (PSE) or transmitter, comparing that signal to the desired value (called the setpoint) for that process variable, and calculating an appropriate output signal value to be sent to a final control element (FCE) such as an electric motor or control valve.

Final Control Element, or FCE: A device receiving the signal output by a controller to directly influence the process. Examples: variable-speed electric motor, control valve, electric heater.

Manipulated Variable, or MV: The quantity in a process we adjust or otherwise manipulate in order to influence the process variable (PV). Also used to describe the output signal generated by a controller; i.e. the signal commanding (“manipulating”) the final control element to influence the process.

Reprinted from Lessons In Industrial Instrumentation by Tony R. Kuphaldt under the terms and conditions of the Creative Commons Attribution 4.0 International Public License.

Chemical Recovery in Black Liquor Processing for Pulp and Paper Production

Pulp and paper mill.

For economic and environmental reasons, pulp mills employ chemical recovery processes to reclaim spent cooking chemicals from the pulping process. At kraft and soda pulp mills, spent cooking liquor (referred to as weak black liquor), from the brown stock washers is routed to the chemical recovery area.

The chemical recovery process involves concentrating weak black liquor, combusting organic compounds, reducing inorganic compounds, and reconstituting the cooking liquor.

Residual weak black liquor from the pulping process is a dilute solution (approximately 12 to 15 percent solids) of wood lignin, organic materials, oxidized inorganic compounds (Na2SO4, Na2CO3), and white liquor (Na2S and NaOH). The weak black liquor is first directed through a series of multiple-effect evaporators to increase the solids content to about 50 percent to form “strong black liquor.”

Monitoring percent solids in black liquor
is an important part of chemical recovery.

The strong black liquor from the multiple-effect evaporator system is either oxidized in the black liquor oxidation system, or routed directly to a non-direct contact evaporator (also called a concentrator). Oxidation of the black liquor prior to evaporation in a direct contact evaporator reduces emissions of odorous total reduced sulfur compounds. 

The solids content of the black liquor following the final evaporator/ concentrator typically averages 65 to 68 percent. The soda chemical recovery process is similar to the kraft process, except that the soda process does not require black liquor oxidation systems, since it is a non-sulfur process that does not result in total reduced sulfur emissions.

The concentrated black liquor is then sprayed into the recovery furnace, where organic compounds are combusted, and the Na2SO4 is reduced to Na2S. The black liquor burned in the recovery furnace has a high energy content which is recovered as steam for process requirements, such as cooking wood chips, heating and evaporating black liquor, preheating combustion air, and drying the pulp or paper products. 

The process steam from the recovery furnace is often supplemented with fossil fuel-fired and/or wood-fired power boilers. Particulate matter (primarily Na2SO4) exiting the furnace with the hot flue gases is collected in an electrostatic precipitator and added to the black liquor to be fired in the recovery furnace.

Refractometer for black liquor measurement.

The process of chemical recovery must be carefully managed. Process variables such as temperature, pressure, flow and level require robust instruments to ensure safety and accuracy. The measurement of black liquor solids content has relied upon the use of industrial inline refractometers for many decades. The Electron Machine Corporation, with it's ruggedly designed MPR E-Scan,  has established itself as the leader in this process. Incorporating a ruggedly designed sensing head with a 2205 S/S prism holder, sapphire prism, LED light source, and very sturdy electronics, the Electron Machine device delivers on it's claim as the "world's most rugged process refractometer".  Since the refractometer is specifically designed for the very harsh environment of a pulp mill, it promises years of low-maintenance and very reliable operation. 

For more information about inline process refractometers for black liquor processes visit this link or contact Electron Machine at 352-669-3101. 

Happy Fourth of July from Electron Machine

"We hold these truths to be self-evident, that all men are created equal, that they are endowed by their Creator with certain unalienable Rights, that among these are Life, Liberty and the pursuit of Happiness. — That to secure these rights, Governments are instituted among Men, deriving their just powers from the consent of the governed, — That whenever any Form of Government becomes destructive of these ends, it is the Right of the People to alter or to abolish it, and to institute new Government, laying its foundation on such principles and organizing its powers in such form, as to them shall seem most likely to effect their Safety and Happiness."

THOMAS JEFFERSON, Declaration of Independence

Inline Refractometers for the Production of Jams and Jellies

Refractometers are used to maintain
standards of jams and jellies.

The quality and uniformity of a food product is paramount to the sales of that product. Assuring that standards are maintained is key to quality and consistency.  Jams, jellies, marmalades, conserves and fruit butters are characterized by concentration of fruit components and sugars. Attention to solids content, pH, and sweetness is essential, and controlling these variables in a production environment requires the proper systems, instruments, and automation.

Jams, jellies, marmalades, conserves and fruit butters are made by boiling fruit and sugar together to give a high solids product, and are characterized by concentration of their fruit components and sugars.

Inline refractometer for jam and jelly production.

Accordingly, standards of identity have been enacted to require specific amounts of the comparatively expensive fruit ingredient. Without these guides, producers could substitute flavored and colored pectin and sugars in place of real fruit.

Definitions:

• Jam – a product containing both soluble and insoluble fruit constituents.
• Conserve or preserve – large pieces of fruit are present.
• Butter - a smooth, semisolid fruit mixture with no fruit pieces or peel. May be spiced
• Marmalade – are made from citrus fruits and contain some peel.
• Jelly – is made from filtered fruit juice, no pieces of fruit or insoluble solids present.

In the U.S. jams and jelly products are graded as follows:

• Fancy  - 50 parts fruit to 50 parts sugar 
• Standard  - 45 parts fruit to 55 parts sugar 
• Imitation - 35 parts fruit to 65 parts sugar
• Fruit butters - At least 5 parts fruit to 2 parts sugar

Standards of identity can be easily formulated with the aid of a refractometer - and instrument that the sugar/solids content by the angle that the solution refracts or bends light. Refractometers are the preferred method of determining of measuring soluble solids and sugars in many food products.

In large scale commercial food production environments, inline process refractometers provide real-time sugar and solids measurement allowing plant operators tight control of product variables so that product uniformity and quality is maintained.