Chemical Reactions and Catalysts Quiz

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Questions and Answers

What is the purpose of oil in the reactor system?

  • To provide a cooling effect to the reactor
  • To increase the temperature of the reaction
  • To enhance chemical reactions within the system
  • To prevent the gel from sticking to internal reactor parts (correct)

What type of reactors are used in the Plaquemine plant?

  • Continuous flow reactors
  • Stirred tank reactors
  • Tube reactors with electro-polished coatings (correct)
  • Batch reactors

Which of the following is an example of a reducing agent?

  • Mohr Salt
  • TBHP
  • Sodium Hypophosphite
  • MBS (correct)

What happens when oxidizing and reducing catalysts are mixed together?

<p>A violent chemical reaction can occur (D)</p> Signup and view all the answers

What is the color designated for crosslinkers in the polymerization table?

<p>Yellow (C)</p> Signup and view all the answers

Which of the following categories does Ammonium Persulfate belong to?

<p>Oxidizers (A)</p> Signup and view all the answers

What is the consequence of mixing oxidizers with reducers outside of the reactor?

<p>An explosion can occur (B)</p> Signup and view all the answers

What is one of the main consequences of inadequate housekeeping while handling catalysts?

<p>Serious bodily injury (B)</p> Signup and view all the answers

Which catalyst is primarily used as a reducer in redox reactions?

<p>Mohr’s Salt (C)</p> Signup and view all the answers

In the Dissolution Tank to Reactor Draw Down diagram, what is the role of the flow meter?

<p>To measure the flow rate (D)</p> Signup and view all the answers

What must be done to thermal catalysts to maintain their stability?

<p>Store in cold storage (A)</p> Signup and view all the answers

What happens when thermal catalysts degrade?

<p>They form free radicals (C)</p> Signup and view all the answers

Which step of polymerization involves creating a free radical on the end of a polymer chain?

<p>Initiation (D)</p> Signup and view all the answers

What is the role of chain transfer agents in polymerization?

<p>Terminate growing polymer chains and create new free radicals (D)</p> Signup and view all the answers

What is a byproduct of the degradation of Vazo64?

<p>Tetramethylsuccinonitrile (TMSN) (D)</p> Signup and view all the answers

Which of the following steps in polymerization directly follows initiation?

<p>Propagation (D)</p> Signup and view all the answers

What happens if the sparge pressure or flow-rate is too low?

<p>Inadequate mixing of catalysts occurs. (A)</p> Signup and view all the answers

What is one consequence of a high sparge rate?

<p>Poor catalyst mixing. (D)</p> Signup and view all the answers

What phenomenon may occur if there are leaks in the nitrogen lines?

<p>Air is pulled into the sparge lines. (A)</p> Signup and view all the answers

At what oxygen concentration level might convulsive movements occur?

<p>6-10% oxygen. (C)</p> Signup and view all the answers

Which of the following is a symptom of oxygen levels between 10-14%?

<p>Emotional upset. (B)</p> Signup and view all the answers

What is the most significant risk indicated for nitrogen exposure?

<p>Asphyxiation due to oxygen displacement. (B)</p> Signup and view all the answers

Which of the following is NOT a symptom of nitrogen over-exposure?

<p>Enhanced appetite. (B)</p> Signup and view all the answers

What effect can poor ventilation in a space lead to when nitrogen is released?

<p>Oxygen-deficient environment. (D)</p> Signup and view all the answers

What is the primary purpose of pre-grinding?

<p>To tear the gel into smaller pieces (D)</p> Signup and view all the answers

Which gel characteristics affect the pre-grinding process?

<p>The gel's temperature and product type (A)</p> Signup and view all the answers

What can happen if the feed to the granulator is inconsistent?

<p>Non-uniform drying may happen (C)</p> Signup and view all the answers

What is added to the gel to make it easier to cut during pre-grinding?

<p>Lubrhophos PK455 (A)</p> Signup and view all the answers

What happens when the gel is dumped into the pre-grinder?

<p>The screws must be turning forward (A)</p> Signup and view all the answers

Which product types could be more difficult to grind?

<p>Low UL products and cationic products (D)</p> Signup and view all the answers

What could indicate a problem with the gel during pre-grinding?

<p>If a normally easy product does not grind (D)</p> Signup and view all the answers

What could occur if too much surfactant is added during pre-grinding?

<p>The granulator and fan may plug (B)</p> Signup and view all the answers

What is the main function of a centrifugal fan?

<p>To build pressure using centrifugal force (B)</p> Signup and view all the answers

Which type of impeller can move both air and powder/gel?

<p>Open impeller (D)</p> Signup and view all the answers

What could cause a centrifugal fan to be out of balance?

<p>Accumulation of product on the impeller (B)</p> Signup and view all the answers

What is a key feature of closed impellers?

<p>They have a plate on both sides of the blades (B)</p> Signup and view all the answers

Which type of fan is specifically used to convey product from the granulator to the dryer?

<p>Granulator fan (B)</p> Signup and view all the answers

What impact does a worn impeller have on a centrifugal fan?

<p>Causes excessive vibration (C)</p> Signup and view all the answers

What is necessary for maintaining good suction in a fan?

<p>Ensuring belts are tight (D)</p> Signup and view all the answers

Which factor does NOT contribute to a fan plugging?

<p>Excessive lubrication (C)</p> Signup and view all the answers

What is the purpose of using a belt tensioner after installing belts?

<p>To ensure proper tension according to manufacturer’s specifications (B)</p> Signup and view all the answers

What should be included in the safe permit’s scope of work regarding belt replacement?

<p>Replace belts and check alignment and tension with special tools (B)</p> Signup and view all the answers

Why is it important to witness maintenance tasks being performed?

<p>To improve job knowledge and ensure correct procedures (D)</p> Signup and view all the answers

What equipment should laser alignment be used on?

<p>All equipment that has pulleys (C)</p> Signup and view all the answers

What role does water play in polymerization?

<p>It helps absorb the exothermic heat of reaction (B)</p> Signup and view all the answers

Where does the majority of the water in the acrylamide solution originate from?

<p>Raw materials and direct addition (D)</p> Signup and view all the answers

Why is dry acrylamide not typically used?

<p>It sublimates to vapors and is more hazardous to handle (C)</p> Signup and view all the answers

What can happen if water is not added during polymerization?

<p>The batch would boil out of the reactor (B)</p> Signup and view all the answers

Flashcards

What type of reactor is used at the Plaquemine plant?

Tube reactors are used at the Plaquemine plant for polyacrylamide production. These reactors have a smooth, electro-polished interior coating.

What is the purpose of oil in reactors before drawdown?

Oil is crucial in reactors before drawdown. It prevents the gel from sticking to the reactor parts, reducing contamination. It also speeds up draining and reduces equipment strain.

Describe the role of the dissolution tank in the drawdown process.

The dissolution tank supplies glycol to the reactor during the drawdown process. Glycol flows from the dissolution tank to the reactor through a line with a flow meter.

What is the function of reducers in polymerization?

Reducers are chemical additives that control the rate of polymerization. They reduce the speed of the reaction.

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What role do oxidizers play in polymerization?

Oxidizers are chemicals that initiate the polymerization reaction. They are needed to start the process.

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What is the purpose of Chain Transfer Agents (CTAs) in polymerization?

Chain Transfer Agents (CTAs) help regulate the length of the polymer chains. They control how long the chains grow.

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What safety precautions must be taken when handling catalysts?

Mixing oxidizing and reducing catalysts can cause a violent chemical reaction leading to serious injuries. Therefore, extreme care and high housekeeping standards are crucial when handling catalysts.

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What effect do crosslinkers have on polymers?

Crosslinkers create bridges between polymer chains, enhancing its strength and stability.

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Catalyst

A substance that speeds up a chemical reaction by lowering the activation energy needed for the reaction to occur.

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Redox Reactions

Chemical reactions that involve the transfer of electrons between reactants.

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Reducer

A substance that causes a reduction in another substance, donating electrons.

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Oxidizer

A substance that causes an oxidation in another substance, accepting electrons.

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Polymerization

A chemical process that involves the joining of monomers (small molecules) to form polymers (large molecules).

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Thermal Catalysts

Chemical compounds that initiate the polymerization process by creating free radicals.

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Initiation

A stage in polymerization where a monomer molecule is attacked by a free radical, forming a new free radical with a single monomer added to it.

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Propagation

A stage in polymerization where the newly formed free radical in the polymer chain continues to add more monomers.

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What happens if sparge pressure or flow rate is too low?

If the sparge pressure or flow rate is too low, not enough oxygen will be removed from the reaction. This can make the reaction slow to start or erratic, resulting in poor product quality.

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What happens if the sparge rate is too high?

Excessive sparge rate leads to poor mixing of catalysts, causing inconsistent reaction rates and off-spec product.

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What happens if there are leaks in the nitrogen lines?

Leaks in nitrogen lines allow air to enter the sparge lines, introducing oxygen into the reaction. This causes a slow start or even a completely failed batch.

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What is the Venturi effect?

The Venturi effect happens when a restriction in the nitrogen line causes air to be pulled into the sparge lines due to a pressure drop.

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What is the main hazard associated with nitrogen?

Nitrogen is a colorless, odorless gas, making it undetectable. Its primary hazard is asphyxiation, as it displaces oxygen.

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What are the symptoms of mild oxygen deficiency?

Low levels of oxygen (12-16%) can cause breathing and pulse rate to increase, and slight coordination issues.

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What are the symptoms of severe oxygen deficiency?

In extreme cases of oxygen deficiency (below 6%), individuals may experience convulsions, respiratory collapse, and even death.

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Why are tight fittings around sparges important?

It is crucial to ensure a tight fit around the sparges to prevent leaks and ensure proper nitrogen flow during the reaction.

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Centrifugal Fans

Air enters the front of the fan and exits at a 90 degree angle through the top.

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Axial Flow Fan

Air is moved through the fan by turning pitched blades.

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How do Centrifugal Fans work?

An impeller pulls air into the fan and the housing creates pressure through centrifugal force.

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Closed Impellers

Have a plate on either side of the blades for moveing air only.

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Open Impellers

Have one plate and can move both air and powder/gel.

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Fan Balancing

Fans must be properly balanced to avoid shaking.

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Fan Bearing Maintenance

Bearings need to be securely mounted to the housing to prevent issues.

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Fan Impeller Wear

Worn impellers can vibrate and cause damage.

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What is pre-grinding?

The process of breaking down gel into smaller pieces using screws. This ensures a consistent feed to the granulator, leading to uniform drying.

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How does the pre-grinder work?

The weight of the gel presses against rotating screws, which tear the gel apart. Hot gel grinds easier than cold gel.

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How does the product type affect pre-grinding?

Products like 934SH and 923SH grind easily. Low UL products (VLM, BPM) are harder to grind. Highly cationic products are sticky and difficult to grind.

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What is the role of Lubrhophos PK455?

Lubrhophos PK455 is added to make the gel easier to cut. Half of the surfactant is added to the screws before dumping the gel, and the other half after the gel has been ground.

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How is the gel dumped into the pre-grinder?

The gel is dumped into the pre-grinder from the reactors after it has reacted and reached its peak. The process uses hydraulic cylinders or pressure for dumping, depending on the reactor type.

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Why is the screw direction important during dumping?

The screws should be turning forward during gel dumping. This helps pull the gel out and reduces strain on the gear motors.

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Describe the grinding process.

The gel is ground for 20 minutes forward and then reversed to pull it back for further treatment.

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What are the key points regarding surfactant?

Surfactant levels vary depending on the product and plant. Too much surfactant can make the gel too fine, clogging the granulator and fan.

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Belt Tensioner

The tensioner is used after a belt replacement to ensure the belt is tightened to the manufacturer's specifications. Tightening a belt too much or too little can cause damage to the equipment.

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Laser Alignment Tool

Laser alignment tools ensure proper alignment of pulleys on equipment, reducing wear and tear. This reduces the chances of premature belt failure.

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Why is water added during polymerization?

Water is added to the polymerization process to absorb the heat released, preventing the mixture from boiling over.

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Where does the water in polymerization come from?

Water is added to the polymerization process directly, and it's also a component of the raw materials, like acrylamide solution.

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Why is dry acrylamide not used?

Acrylamide is not used in its dry form because it sublimates (turns directly from solid to gas) and becomes hazardous.

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Operator's role in belt replacement.

If a belt replacement has been performed, the operator should witness the tensioner and alignment tools being used to ensure correct installation.

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What to do if proper tools are not used?

If craftsmen are not using the proper tools for belt replacement tasks, the supervisor must investigate and ensure correct tools are employed.

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Requirements for belt replacement work orders.

A work order should clearly state the requirements for using the tensioner and laser alignment tool for belt replacement tasks.

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Study Notes

Outside Operator Training

  • Walking out the job is the responsibility of both the permit writer (usually an operator) and permit approver (usually the shift supervisor)
  • If a job scope changes, the permit writer must get approval from the permit acceptor before permitting the work
  • A review of the job, LOTO, and permit must be completed before scope changes
  • Board operators should not write permits for jobs in the field that another operator is responsible for
  • Permit approvers (not permit writers) are ultimately responsible for the permit being sufficient for the work

PPE Matrix

  • This is a table that lists the required personal protective equipment (PPE) for various tasks in a powder plant
  • It includes a variety of PPE, including respirators, eye protection, body protection, hand protection, and foot protection
  • The table allows users to quickly determine the appropriate protection for a given task
  • Safety data is provided in a matrix format

Plant Safety - Slips

  • Emphasize the slipperiness of the product when it comes in contact with water
  • Avoid puddles and walk on the driest surface possible
  • Address wet spots quickly to prevent accidents
  • Be aware that gratings can be slippery and step over them
  • Keep shoes clean to prevent slipping hazards, especially on surfaces with moisture

Plant Safety - Slips (One Point Lesson)

  • Five SNF operators and one Emulsions employee, and one contract employee fell in February 2020 due to areas with residual PAM powder and that had gotten wet.
  • Barricade tape and overspray should cover the affected areas
  • Workers need to avoid the area when wet and should use safety observers
  • Use of safety procedures for slip prevention is vital.

Working in Liquids

  • Notify Supervisor if you need to work in a liquid environment.
  • Ensure the area is properly barricaded and required precautions are taken
  • Chemical boots are required, not leather shoes
  • Clean boots after completing the work.

Barricade Tapes

  • Yellow caution tape indicates a low-degree safety concern, such as hoses, noise, heavy equipment, etc.
  • Red danger tape indicates an immediate or high-risk safety concern, such as overhead loads, work at heights, etc.

LOTO and Barricade Tags

  • Safety department has tags for LOTO and barricades.
  • Barrier tag gives context about the reason for the barricade and who to contact if needed.
  • Tags help with task-specific LOTO

Quarterly Inspection Color Code

  • Colored tape or tie wraps indicate inspection requirements for specific equipment at the beginning of each quarter
  • Items such as GFCI's, portable equipment, rigging and slinging equipment, ladders, hoists, power strips, and welding leads are examples checked.
  • Color codes are used to differentiate inspection by quarter.

Dissolution Tanks

  • Confirm with the board operator that the tank is ready for additions
  • Add each raw material in the correct order: water, acrylamide, urea, acrylic acid, caustic, and salt (if applicable)
  • Keep manual valves open only when adding raw materials

Dissolution Tank Ingredients

  • Water (solvent)
  • Acrylamide (monomer)
  • Acrylic Acid or Sodium AMPS (monomer)
  • ATN (ATBS 50) (monomer)
  • Sodium Hydroxide (caustic) (pH Adj.)
  • Other Additives: Urea, Ammonium Sulfate, Salt

Polymer/Polyacrylamide

  • Mono = one, Poly = many
  • Polymer = many -mers
  • Polyacrylamide = Many acrylamide monomers (charged using Acrylic Acid)

Monomers

  • Acrylamide - Neutral Backbone
  • Acrylic Acid - Anionic Backbone
  • Sodium AMPS (JMS50) - Anionic Backbone
  • All are dissolved in water and charged with Caustic (NaOH)

Flocculation

  • Colloid - A substance (e.g., dirt in pond water or fat in milk) microscopically dispersed within another substance.
  • Floc - The grouping of the dispersed substance (via polymer) to overcome molecular interactions and settle out of the solution

PolyACM Types & Differences

  • Anionic (-) Charge - Acrylic Acid, Sodium AMPS, Acrylamide
  • Cationic (+) Charge - Cationic Monomer, Acrylamide
  • Nonionic () Neutral Charge - Acrylamide

Raw Material and Hazards

  • This section contains details on the hazards associated with various raw materials used in the production process
  • Includes details about acute hazards and symptoms for each material

Raw Materials and Hazards - Acrylamide

  • Most hazardous in solid form (carcinogen)
  • Inhalation: Cough, sore throat, weakness
  • Skin: May be absorbed(redness, pain)
  • Eyes: Redness, pain
  • Ingestion: Abdominal pain, weakness

Raw Materials and Hazards - Urea

  • Inhalation: Irritation to the respiratory tract
  • Skin: Irritation, redness, itching, pain
  • Eyes: Irritation, redness, pain
  • Ingestion: Irritation to the gastrointestinal tract, nausea, vomiting, diarrhea

Raw Materials and Hazards - Acrylic Acid

  • Inhalation: Cough, sore throat, shortness of breath
  • Skin: May be absorbed, redness, blisters, pain
  • Eyes: Redness, pain, severe deep burns, loss of vision
  • Ingestion is not specifically mentioned

Raw Materials and Hazards - Caustic

  • Inhalation: Severe irritation of nose and throat (only if mist or dust)
  • Skin: Pain, redness, burns, blistering, severe exposure can cause death
  • Eyes: Burns, redness, swelling, pain, blurred vision, permanent damage/blindness
  • Ingestion: Burns to lips, tongue, throat, stomach; symptoms include nausea, vomiting, stomach cramps, diarrhea, and can cause death

Raw Materials and Hazards - Salt

  • No known hazards

ATN Grades Used in Powders Process

  • Plaquemine ATN is in two grades
  • XG - highest quality, used for Post-Hydro products
  • HQ - lower quality, used for standard products, AN 125SH/VHM, AN 113SH/VHM, AN 118SH/VHM

Inhibitors

  • Acrylamide is inhibited by copper and oxygen, which is added during manufacturing.
  • Oxygen reacts with free radicals to form stable radicals, preventing the initiation of polymerization reactions.
  • MEHQ (hydroquinone monomethyl ether) is another inhibitor used.

Inhibitors (Cationic monomer and acrylic acid)

  • Cationic monomer and acrylic acid are inhibited by MEHQ (mono methyl ether of hydroquinone) and oxygen.
  • Cationic monomer is also inhibited by Versenex 80.
  • MEHQ transfers a hydrogen atom to a free radical which prevents initiation of a polymerization reaction.

Dissolution Tanks

  • Images of different components of dissolution tanks (pipes, pumps, valves etc.)

Why Should We Keep Raw Material Valves Closed?

  • Excess raw material can accumlate up to 25-30kg.
  • The pH of the product is sensitive to propagating polymerization.
  • Delays in the process can result in poor reaction and a low yield
  • Closing the valves helps maintain a good reaction and quality in the product.

BVE

  • BVE is used in the production of A 3338, and more foam is generated.
  • A special anti-foam (Sag 30) is used in conjunction with BVE to help reduce foam.

Anti-Foam

  • Anti-foam is used to eliminate foam from the dissolution tank before transfer
  • Excess anti-foam can slow down heat-ups in the reactor
  • Insufficient anti-foam may lead to foam regeneration, and interfere with catalyst mixing

Measurement of Additives in Dissolution Tanks

  • Mass flow meters calculate the amount of liquid moving through a pipe
  • Pressure transmitters measure the force of solution against a membrane; higher levels mean higher bottom pressure.
  • The in-line pH meters on recirculation lines are useful when adding acids or bases to the dissolution tank.

Adjusting pH

  • The pH of the dissolution tank should be adjusted carefully for each product type.
  • Caustic/Sulfuric acid is used to adjust the pH.
  • The amount/concentration of acid is measured precisely to avoid overshooting the target pH
  • Supervisor must be notified in case of errors

pH Probe

  • pH probes are calibrated using buffer solutions with known pH values.
  • Bench top calibration instructions are provided (PAM-COM-005)

Acrylic Acid

  • Acrylic acid gives the polymer a negative charge
  • Too much acrylic acid leads to high anionicity and too little leads to low anionicity.

Acetic Acid

  • Used for pH control in the post-hydro process, this protects anionicity from being adversely affected

Salt Tank

  • Oversaturation from too much salt is a particular concern, and accurate records are necessary
  • Ensure the agitators in the tank are working to avoid clogging of the pump.

Sampling a Dissolution Tank

  • All dissolution tanks must have a retaining sample
  • Samples are needed to troubleshoot problems with product quality (polymerization and drying upsets) if samples are not received
  • The samples are matched to the corresponding reactor samples to detect off-spec issues

D-Tank Transfer Pump

  • Centrifugal pumps transfer aqueous solutions to reactors to prevent damage during high pressure conditions
  • Glycol heat exchange is fragile
  • Short periods of time without damaging the pump can be used for short periods.
  • A motor monitor protects the motor during pump cavitation.
  • A low level probe is on the discharge side of the pump to shut off if no level.

Dissolution Tank Temperature

  • The dissolution tank is cooled to prevent unwanted auto-polymerization
  • The target temperature of the tank is 0 degrees C.
  • A temperature difference of -2 degrees C in the tank is equivalent to 0 degrees C in the reactor.
  • If the temperature exceeds 15 degrees C an alarm will go off, preventing caustic addition.
  • If the temperature exceeds 25 degrees C, the caustic addition will shut off automatically.

Environmental

  • Aqueous solutions must be stored in diked areas to control accidental spills and prevent environmental damage
  • The finished product is detrimental to aquatic organisms
  • Water or condensate (pH 6.0-9.0) in the sump or dike must be neutralized with acid/base, if outside of this range

Rotation Checks

  • Mechanics and electricians need training on the proper direction of equipment, which must not be reversed to operations.
  • Operations personnel are ultimately responsible for proper direction.

Leak Checks Following Line or Equipment Openings/Breaks

  • Equipment should be pressure tested in the shop before installation
  • Hazardous material systems (AN, AA, NaOH, Oleum) must be pressurized and leak checked before use
  • Develop a contingency plan if this isn't possible, involving PPE and safe monitoring distances
  • Non-Haz systems can be pressure checked or monitored, at the discretion of the Supervisor.

Emulsion Management – Empty Drum/Tote

  • The Emulsions department manages the empty drum roll-off bins for plastic or metal drums
  • The Powders Shift Supervisor coordinates with the Emulsions team on drum usage.
  • Drums are checked and the condition is noted for each drum.

Reactor Type

  • SNF has two types of reactors for polyacrylamide production.
  • The Plaquemine plant uses "Tube Reactors" with electro-polished internal walls.

Oil Reactor Before Drawdown

  • Oil prevents gel from sticking to internal reactor parts, preventing contamination
  • Oil improves gel draining speed, and reduces equipment strain caused by friction

Dissolution Tank To Reactor Draw Down Diagram

  • A flow diagram outlining how substances are moved from a dissolution tank to a reactor
  • Fluid flows from the Dissolution Tank to the Reactor. The process uses a flow meter to regulate transfer rate and to maintain a specific temperature

Polymerization Table Color Code

  • This is a table outlining the types of polymers and their attributes, which are color-coded by the type of polymer.

Catalyst Handling

  • Mixing oxidizing and reducing catalysts results in a violent reaction, which can lead to burns, trauma, and even death
  • High standards of care and housekeeping should be maintained when handling catalysts
  • Specific safety precautions for each catalyst (e.g., TBHP, Persulfate, MBS, Mohr's Salt, VA-044) should be followed.

What is Hypo Doing?

  • Sodium Hypophosphite is a chain transfer agent, creating free radicals that terminate or initiate the polymer chain growth.
  • This control of free radicals allows for fine-tuning of the final product's molecular weight
  • Faster reaction rates equate to lower hypo weight, and slower rates to higher hypo weight

Hypo (DEA List 1 Chemical)

  • Sodium Hypophosphite is used as an emulsifier and stabilizer, meeting Food Chemical Codex guidelines for use in food, beverages, and nutritional supplements.
  • This chemical must be kept in a locked cage

Catalyst Storage

  • Daily plant operations should only hold a 24-hour supply of catalysts

MBA in A3338

  • Too much MBA causes crosslinking, which can lead to a low UL (Ultimate Level) value
  • Insufficient MBA leads to problems such as low UL and poor solubility

MBA and MBS Confusion

  • MBA, used in A3338, is less common and does not have the strong odor of MBS

Thermo-Catalyst

  • Thermal catalysts decompose at temperatures between 30 and 40 degrees C
  • These catalysts produce free radicals, initiating further polyacrylamide solution reaction
  • Common catalysts include Vazo 67, 64/AIBN, 52, AZDN and ABNR, VA-044

What is Vazo Doing?

  • VAZO 64, a thermal catalyst, decomposes above 30° Celcius into free radicals.
  • These radicals stimulate polymerisation of the product, generating heat that keeps the reaction proceeding
  • The process continues until all monomer has polymerised or runs out and the thermal catalyst is then used up.

What is VA-044 doing?

  • VA-044 is another thermal catalyst used for polymization; it performs slightly below 30 degrees C compared to VAZO
  • This catalyst functions as a "bridge" between the redox catalysts and VAZO
  • It produces free radicals for the reaction process, and is most commonly used to help mitigate stalling/dying before VAZO is used up in higher molecular weight products

Catalyst Mix times

  • Mixing times should be followed for various catalysts (AZDN, Versenex 80, Hypo, VA-044, Sodium Persulfate)
  • Time limits vary depending on the specific catalyst
  • A brownish gel color indicates unreacted catalyst in the reaction.

Catalyst Add Time

  • Ensure catalyst is precisely measured and mixed into the solution to ensure uniform mixing

Why do we need to be precise with Hypo weights?

  • Different polymers have different molecular weights, and the amount of hypo needed to adjust this is very specific.
  • Hypo adjusts the molecular weight needed for a suitable product, and to remove insolubles

I'm done polymerizing my Reactor, Can I discard my catalyst bags?

  • Catalyst bags must be emptied and placed into separate waste bags.
  • Tied off and properly disposed of in plant trash.

Polymerization Reaction

  • Initiator (thermal catalysts, redox),
  • Propagation,
  • Termination

Redox Reactions

  • Primarily used to kick off the polymerization reaction.
  • Oxidizers: Sodium Persulfate, Tert-Butyl Peroxide and Potassium Bromate
  • Reducers: Sodium Metabisulfite, Sodium Sulfite and Mohr's Salt

Thermal Degradation Reactions

  • Vazo67, Vazo64/AIBN, Vazo52, AZDN, ABNR, VA-044 are the main catalysts
  • These catalysts are kept in cold storage to maintain chemical stability and extend shelf life up to 3 months

Chain Transfer Agents

  • React with the growing polymer chain to create free radicals.
  • This termination of the polymer chain initiates the growth of a new chain.

Steps of Polymerization

  • Initiation: Free radicals attack C=C bonds in the monomer, creating a free radical
  • Propagation: The growing chain continues to add monomers until a stopping agent is introduced
  • Termination: The reaction ends when the chain transfer agent is used up or the reactants are used up

Polymerisation-Initiation

  • Free radicals attack C=C bonds in the monomer, creating a free radical on the end.
  • Initiation occurs when the reducer from the redox package is added to the monomer solution

Polymerization-Propagation

  • The newly formed free radical at the end of a monomer attacks the C=C bond of another monomer to extend the chain
  • Polymerisation continues until chain transfer agents are used up or the reactants are used up
  • Thermal catalysts and chain transfer agents are involved in initiating this step

Polymerisation-Termination

  • Reaction ceases when a free radical attacks the end of the polymer chain
  • The chain reaction terminates when two free radicals combine

Reaction Curve Polymerization Steps

  • A graph demonstrating the temperature variation during various stages of the polymerization process, including initiation, propagation, and termination.

Auto-Initiation

  • Auto-initiation may occur if hot gel is left over from a previous reaction.
  • Or if the solution is not at the set point in the dissolution tank during transfer to the reactor
  • It could also occur if there is leftover catalyst in the reactor during drawdown

Sparging

  • Nitrogen is injected into the reactor to remove oxygen and initiate the polymerization process.
  • Sparging helps produce a good, even reaction rate.
  • Improper sparge pressure or flow rate could lead to poor catalyst mixing, slow starting reactions, and product quality issues

Why Nitrogen is Required?

  • Sparging is vital for removing oxygen, an inhibitor, from the solution to start the polymerization process efficiently.
  • Too low flow of nitrogen means not enough oxygen removal and the production may be affected
  • Too high of a nitrogen flow rate or leaks in the line can cause the production to be slower or a dead batch, due to air entering the system

Nitrogen Hazards

  • Asphyxiation is the main hazard associated with an uncontrolled release of Nitrogen
  • Prolonged exposure to low levels of oxygen can cause symptoms, such as headaches, ringing in ears, dizziness, etc.
  • Symptoms can escalate to: Unconsciousness, nausea, vomiting, depression of senses, and eventually death..

Chelating Agents

  • Copper must be removed from acrylamide to control initiation
  • Versenex 80 is a chelating agent with high affinity for copper
  • Preventing premature initiation and maintaining optimal polymerization reaction

Branching and Cross-linking

  • Branching increases the molecular weight without noticeably changing the viscosity
  • Certain applications benefit from this characteristic (increased viscosity), but excessive branching or crosslinking in our polymerisation would cause issues
  • Crosslinking is a form of extensive branching that will decrease solubility.

Product Solubility

  • Excessive temperatures during drying and polymerization can cause crosslinking, reducing solubility
  • Primary culprits include extremely high UL values, very high branching concentrations, and significant residual acrylamide buildup

Hydrolysis

  • Hydrolysis occurs when water reacts with the neutral amine group in acrylamide, converting it to anionic acrylic acid
  • Hydrolysis occurs more in lower anionic products, where over-drying could lead to a blue or green tint
  • Controlling the temperature of the aqueous monomer during caustic addition is essential for preventing hydrolysis.

Kinetics

  • Kinetics refers to the rate of polymerization, measured by temperature variations over time
  • Polymerization needs to reach a high enough temperature without exceeding a safe limit (100°C) to avoid steaming.
  • If the temperature is not high enough, the monomer may remain in liquid form exceeding the permitted 1000ppm limit

Kinetics (Time)

  • The time it takes for reactions to occur and reach a specific product rate
  • Reaction times can range greatly depending on product weight (faster for lower, slower for higher)
  • Reactions running too quickly can result in a low UL viscosity (off-spec).
  • Reactions running too long may not reach the necessary temperature, resulting in a high monomer content

Free Monomer

  • Free monomer is the amount of acrylamide in a product that isn't properly converted into polyacrylamide
  • These problems are often due to leaking drain valves.

Molecular Weight

  • Molecular mass (m) is the mass of a given molecule measured in unified atomic mass units (u or Da).
  • Different isotopes of an element can give different molecular masses for the same compound

Reactor

  • Reactors are vessels used to prepare liquid monomers and change them into polymer gel.
  • Removal of oxygen and addition of catalyst are key in the polymerization process

Reactor–How does it work?

  • Polymerizers mix monomers with water, additives, and pH adjusters to prepare the reaction mixture.
  • The reaction starts at freezing point (0°C) and can rise significantly once the reaction begins
  • The temperature is monitored and the time for dumping the gel is recorded (peak time)
  • The product hold time is pre-determined in the lab and used to determine optimal dumping times
  • A 60/30/10 spray on the reactor liner makes gel dumping easier

Reactor – How does the Reactor work? (Continued…)

  • To assure good operation, there is a "double-checking" process for operators, checking temperatures and correct reactor selection
  • Use of a 60/30/10 spray on the reactor liner helps with making the emptying procedure easier

Reactor Trouble Shooting

  • Issues like not properly lubricating the reactor to cause poor discharge, or not having the right temperature could make the product difficult to fully dry.
  • Problems such as overheating can cause the gel to be violently forced out, resulting in equipment damage or injury to operators
  • An operator checking for leaks in the piping before drawdown can help prevent these types of problems and improve production outcomes

What to Do When Bad/Slow Reaction Detected?

  • Notify supervision and Poly Tech immediately for analysis and testing.
  • Use the troubleshooting guide for the specific issue
  • Follow the facility's bad reaction protocol/management plan, which might include: sucking out the reaction, letting the reactor peak, and separating the gel.

Reactor Safety Concerns

  • The extremely hot gel can cause burns or skin irritation.
  • Precautions should be taken around the gel since it's dangerous to have it fall on someone
  • To avoid oxygen leaks that could cause issues in closed environments, separate and lock-out the nitrogen lines when working inside

Solenoid Control Panel

  • Electricians and authorized employees may operate the solenoid control panel
  • Ensure the actuators are not in operation before working on the apparatus.

Gel Hoppers

  • Maintain consistent flow of product
  • Gel is fed to the granulator using gravity
  • Load cells measure gel weight to trigger automatic filling and refill sequences

Pre-grinders (Why do we need them?)

  • Some plants use pre-grinders to break down the gel into consistent-size pieces.
  • This ensures the feed to the granulator is consistent to allow for more efficient processes and prevent future issues.

Pre-grinders (How does it work?)

  • Pre-grinders use rotating screws to grind the gel
  • The appropriate pre-grinder settings to ensure production quality depend on the type of product
  • The lower the gel density, the harder it is to pre-grind
  • Issues that lead to abnormal operation may involve the product quality, or a change of temperature.

Pre-grinders - How does it work? (Continued…)

  • Lubrhophos PK455 is a grinding aid to help with certain products. The aid must be evenly placed, mixed and spread.
  • The first half of the post-treatment additive is applied before the gel is dumped, while the second half is added once the gel is reversed.
  • Different products have different treatment levels, as detailed on the conditions sheet.

Pre-Grinder - How does it work? (Continued...)

  • Monosodium Phosphate is added in some cases to reduce corrosion and unwanted effects on product.
  • The amount is 0.1% relative to the gel weight.
  • Dust rework in the pre-grinder usually involves placing dust on top of the gel followed by mixing in water to create a usable gel product.

Pre-Grinder Safety Concerns

  • Safety for the personnel working inside the confined space during maintenance and operations.
  • Risks of being injured by moving equipment parts.

Granulation (Why do we need the Granulator?)

  • Granulation is used to reduce gel size and improve particle uniformity, to ensure even drying of the product.
  • Smaller particles have a larger surface area for improved contact with the air, thus better drying.

Granulation (Why do we need the Granulator? – Continued…)

  • The Granulator system has two types of blades: fly knives and bed knives, which grind the gel to produce uniformly sized granules
  • The granulator has standardized screens that are used to control the size of the finished product, as specified by customer specifications.

Granulation (How can you tell if the blades need to be changed?)

  • Performance issues such as product difficulty being pushed through the dryer or chipping can indicate wear
  • Excessive gap widths between the fly knives and bed knives may reduce effectiveness for granulation
  • Adjusting the gap size is done by moving the bed knives

Granulation – Granulator Screens

  • If the granulator screen has a hole or tear then metal will pass through and cause damage to blades.
  • The right screen (size) needs to be on the Kason, as different screens are used for different products (e.g., 8mm for some, 10mm for others)
  • The screen should be checked monthly for damage.

Granulation – Granulator Screens - How does it work? (Continued…)

  • The appropriate grinding aid (Lubrhophos PK455) assists in separating the gel and ensures smooth pre-grinding of products like 934SH or 923SH
  • The second half of the post-treatment additive should be added when the gel is reversed. The optimal monomer content is around 1000 ppm.
  • The conditions sheet specifies the type and concentration of post-treatment added to each product.

Granulation – Granulator Screens - How does it work? (Continued…)

  • Monosodium Phosphate is occasionally used as a grinding aid to reduce corrosion or unwanted specks in the gel.
  • The appropriate quantity is typically 0.1% of the gel's weight.

Granulation (Oil Spray Nozzle)

  • The oil spray nozzle in the granulator is used to help the cutting process of the gel
  • The oil mixture is composed of oil (i.e. LPA210) and surfactant (i.e.S-275) to help maintain consistency for drying
  • Proper air pressure is essential for effectively atomizing the oil

Granulation (Oil Spray Nozzle – Continued…)

  • The installation of the Nozzle needs to be done correctly, see the PAM-03-205 manual for complete instructions.
  • The OPR personnel are responsible for the correct identification and labeling of the lines before, and after, disconnecting the lines.
  • The ports for air and oil should be clearly identified and marked before installation.

Oil Tank

  • The oil tank is used to mix oil and surfactant to aid in the smooth operation of the granulator.
  • The oil and surfactant mixture coats the gel to help prevent stickiness to the equipment.
  • The mixture is pumped through the granulator using a spray nozzle.

Oil Mixing

  • The oil (and surfactant) needed for each product is found on the dryer condition sheet
  • The S-275 is measured volumetrically in totes.
  • Air passing through flowmeters may be registered as liquid, leading to inaccuracies in volume measurement. A minimum liquid height in the tote should be the equivalent of about 15".
  • Density testing is used to determine the correct amount of S-275 to add to the oil.

Past R-9 Screw Problems

  • Gearboxes for the R-9 screws should be the same distance from the tank wall, to prevent gel transfer inefficiency, or damage to supports.
  • Alignment of screws is vital to consistent process operation and reported discrepancies during maintenance/operations tasks should be compared.

Oil Tank Safety Concerns

  • The oil/surfactant mixture is an irritant and should be handled with care
  • The mixture is also flammable.

Span/Tween 80 Additive

  • This additive coats Vazo 64 to keep it in a slurry form for efficient reactor transfer.

Surfactant

  • Surfactants reduce the surface tension between liquids
  • They act as detergents, wetting agents, emulsifiers, or foaming agents

When do we need to pull Granulator Samples?

  • Samples are required when products don't meet specific quality control standards (e.g., non-conformance, off-grade product)
  • Samples from the granulator, dryer, and other relevant processes are required for analysis and quality control.

How Do We Know a Product is Good for Sale?

  • Each product undergoes a specific testing criteria to determine if it meets the required standards
  • Key parameters measured are: total solid content, residual acrylamide, insolubles, Brookfield viscosity, filtration quality, %solids, pH, anionicity, etc.

Rx to S1

  • A process flow diagram illustrating how materials are transferred from the reactor to the dryer, showing the involved equipment and their respective functions

Now lets reduce the particle size of the polymer

  • Product viscosity is improved if the particle size is reduced using the granulator

Drying – Fluidization

  • This process of fluffing the product is done to assure even drying
  • Air flows through the product in a controlled manner
  • Using a vibrator to maintain the product moving is necessary in some fluidized bed dryers

Drying - Tips

  • Dryer 2 (Part Two) is controlled by product temperature, while dryer 1 (Part One) can be controlled by either burner or product temperature
  • Maintaining a consistent temperature and feed rate is crucial to avoid issues (e.g. over/under-drying)
  • Operator should run moisture tests every 2 hours and adjust to maintain consistent operation of the dryers

Gas Train

  • Prevents natural gas explosions/asphyxiation hazards at the dryer burners.
  • Includes pressure switches to control gas flow, so that the dryer will not run when the gas train is not operational

Gas Train How Does it Work?

  • The gas train is a series of valves and safety switches with double block and bleed valves within the system
  • In case of a problem, these valves isolate the gas
  • The system uses special pilot systems (e.g. an electronic brain box) that also controls the burner system

Gas Train Trouble Shooting

  • Troubleshooting steps to identify and correct problems in the gas train system
  • Common problems include situations where the burner won't light because of safety mechanisms or issues with gas pressure detection or air flow.
  • The importance of working closely with electrical maintenance to diagnose and fix any gas line leaks.

Burners (Why do we need them?)

  • Burners use natural gas to create heat for drying
  • Efficiently burning the gas ensures maximum heat output with minimal pollutants

Burners (How does it work?)

  • Natural gas and airflow mix via openings within the burner pipe, which are often designed for optimal combustion
  • Airflow is managed by a large dryer fan and a burner fan, to get the correct ratio of gas-to-air.
  • The burner temperature can be tested and adjusted via probes

Burner Trouble Shooting

  • Common issues with the burner are often related to the gas train system (e.g. problems with safety systems or flame detection), issues related to faulty gas or air flow can affect the proper operation of the burner system
  • Inspect the burners for damaged air shields periodically

Burner Safety Concerns

  • The gas train is designed to prevent explosions of gas but the burners can still be hot.

Cyclones (Why do we need them?)

  • Cyclones separate particles (product and dust) from the air streams by leveraging centrifugal force
  • Products are routed back into the dryers via cyclones, or to the next process stage using the cyclone blower

Cyclones (How do they work?)

  • Particles enter the cyclone at a high speed through the inlet, impacting the wall.
  • Separation of product stream and air proceeds, with larger and heavier particles directed towards the bottom
  • These particles are collected, and the air exits through the outlet

Cyclone Trouble Shooting

  • Wet product buildup in the discharge area of the cyclone can lead to plugging
  • Cyclones becoming plugged if there isn't enough airflow and may cause a blockage if the fan is not pulling sufficiently.
  • It takes more than 10 minutes to clear a plugged cyclone; the system needs to be shut down.

Cyclone Safety Concerns

  • Hazards of dusty or wet products hitting the eyes or causing injury to hands/fingers from moving parts/actuated valves/rotary valves

Stacks (Why do we need them?)

  • Stacks disperse combustion gases and unreacted monomers from dryers, preventing ground-level pollution.

Stack Process Description

  • The stacks exhaust gases from dryers into atmosphere. This is regulated by pre-set permits for particular stack materials

Stack Trouble Shooting

  • Discharges of powder, coarse dust, or flakes can cause plugging in the cyclone
  • High pressure when loading or unloading the dryers may cause such discharges
  • Excessive fluctuations in relative humidity can cause these clogs

Stack Safety Concerns

  • Stack water drain totes need to be checked and replaced as they become near full to prevent accidents and spills

Particulate Monitoring Overview

  • This system tracks emitted particulate matter, to maintain compliance with permits.

Heat Tracing

  • Heat tracing maintains the desired temperature in the lines to prevent freezing or problems due to low temperature.

Stack Monitor Operation

  • The monitoring system will collect powder or materials and track and report any excessive airborne emissions into the surrounding atmosphere.
  • The system runs in a background active state until a high-pressure controller reaches a high value which then triggers a 5-minute backup timer.
  • If the HH value isn't back to normal after 5 minutes, the plant shuts down

Process Alarm Activation Steps

  • Obtain new screen and gaskets for any issues
  • Have PMO or outside operator remove the locking clasp on the fan's suction side
  • Rotate the butterfly nut to release the clasp and separate the pipe connections
  • Remove the filter and install a new filter
  • Realign the pipe for a tight connection. Re-install the clasp, and tighten the butterfly nut.
  • Check the areas around the plant for particulates that came out of the stack, and report concerns immediately.

Alarm

  • Visual representation of various alarms on a panel display and their associated values, to aid in problem solving.
  • Critical parameters being monitored include the pressures for LP1, LP2 and LP3 and others

Kason

  • The Kason is used to separate the oversized product from the remainder of the intended product when exiting a dryer or blender.
  • It's used to remove clumps of product

Kason (How does it work?)

  • The Kason is a vibration screener with an off-center weight mechanism
  • The vibration causes particles to move according to their size, and the larger, heavier particles get rejected or "scalped" from the product stream

Kason Troubleshooting

  • An 8-10mm screen is needed at the end of the dryer
  • A 2.5-3.5mm screen should be above the bagging/blending machinery
  • The screen needs to be monitored monthly for holes or damages to the gasket
  • The flow rate below normal will indicate problems associated with the screen getting plugged

Granulator Safety Concerns

  • The high-speed turning screws pose the risk of injury to personnel
  • The presence of nitrogen poses asphyxiation risks and should be monitored
  • Proper lockout/tagout procedures should be followed during maintenance and operations

Drying (The Theory)

  • Polymerization with water
  • Drying steps using different temperatures to remove water and avoid drying problems

Drying (Temperature)

  • Temperature control is a critical aspect of the drying process.
  • Burner temperatures need to work synergistically with product temperatures to maintain optimal drying conditions without causing crosslinking.

Drying – Temperature (Continued…)

  • Probes are inside the windbox for immediate reading, and in the dryer bed for point in time feedback
  • Measurements may need to be taken consistently to account for potential issues such as spikes or inconsistencies

Drying – Level

  • Drying rate is maintained by regulating the level of the product in the dryers
  • Maintaining consistency allows for proper and controlled drying using optimized temperature and air flow
  • If level is too high or too low this could impede drying processes or cause products/products to be out of specification (e.g., re-massed or not adequately dried)

Drying – Feed Rate

  • The feed rate is a variable in drying, and needs to be adjusted for different products
  • High feed rates are used if the burner is operating fully and lower feed rates are used if the temperatures need adjustment to stay on-line or avoid plugging
  • If the feed rate is too slow, the temperature may not fully maximize or be within range; if too fast, there is risk of causing issues due to product being too hot or improperly dried
  • Adjusting the feed rate is important in maintaining adequate levels in the dryers.

Drying – Feed Rate (Continued…)

  • Product characteristics like molecular weight (e.g., VHM, SH) influence optimal feed rates for different types of product
  • Maintain adequate feed rates to maintain consistent dryer temperatures

Drying – Fluidization

  • The use of air and mechanical action to maintain consistent product flow
  • Maintaining the appropriate levels of air-flow, humidity, and temperature helps ensure proper drying conditions

Drying – Dryer Types (Original Rotary Dryer)

  • Rotary dryers use a combination of airflow and mechanical forces to fluff the product for even drying
  • Air pressure is created by the dryer fan; air moves through the dryers and air injectors to keep the product moving

Drying – Dryer Types (Fluidized Bed Dryer

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