CHEM F337: Green Chemistry Lecture 08
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Questions and Answers

What is the starting material used in the green route to styrene production?

  • Benzene
  • Xylene (correct)
  • Toluene
  • Ethylene

What is the primary concern associated with polyacrylates?

  • Degradability (correct)
  • Chemical stability
  • Toxicity of materials
  • Cost of production

Which catalyst is used in the traditional route for styrene production?

  • Alumina catalyst
  • Fe-oxide catalyst (correct)
  • Nickel catalyst
  • Zeolite based catalyst

Which of the following is a key characteristic of polyaspartates compared to polyacrylates?

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

What is one of the by-products generated in the traditional route for allyl alcohol production?

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

What is the source material for synthesizing polyaspartates?

<p>L-aspartic acid (D)</p> Signup and view all the answers

What is the overall selectivity to styrene in the green route using toluene and methanol?

<p>60% (A)</p> Signup and view all the answers

Which application is NOT mentioned for polyacrylates?

<p>Electrical insulators (B)</p> Signup and view all the answers

In the green route to allyl alcohol, which reactants are used in the first step?

<p>Propylene, acetic acid, and oxygen (B)</p> Signup and view all the answers

Which property of polyaspartates makes them a suitable alternative to polyacrylates?

<p>Similar performance characteristics (D)</p> Signup and view all the answers

What is a notable property of polyaspartate?

<p>It is biodegradable. (A)</p> Signup and view all the answers

What are the components used to synthesize polyaspartate?

<p>Aspartic acid and NaOH. (B)</p> Signup and view all the answers

Which organization awarded the Donlar Corporation for its green chemistry innovations?

<p>Presidential Green Chemistry Challenge. (B)</p> Signup and view all the answers

What type of award did the Donlar Corporation receive in 1996?

<p>Presidential Green Chemistry Challenge Award. (B)</p> Signup and view all the answers

What chemical reaction occurs during the synthesis of polyaspartate?

<p>Condensation of aspartic acid. (D)</p> Signup and view all the answers

In which category did the Donlar Corporation win the Presidential Green Chemistry Challenge Award?

<p>Small business category. (B)</p> Signup and view all the answers

What role does NaOH play in the synthesis of polyaspartate?

<p>It serves as a catalyst. (C)</p> Signup and view all the answers

What is the relationship between polyaspartate and aspartic acid?

<p>Polyaspartate is a polymer derived from aspartic acid. (B)</p> Signup and view all the answers

What was the main disadvantage of the Boots process for ibuprofen in the 1960s?

<p>It generated unwanted chemical waste. (B)</p> Signup and view all the answers

How many steps did the Hoechst-Celanese process use for ibuprofen synthesis?

<p>3 steps (B)</p> Signup and view all the answers

What type of linkage was primarily utilized in Donlar's polyaspartates manufacturing facility?

<p>70% α-linkage (C)</p> Signup and view all the answers

In what year did Boots win the Queens Award for Technical Achievement?

<p>1987 (B)</p> Signup and view all the answers

Which award did the Hoechst-Celanese process win in 1991?

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

What temperature range is optimal for microwave processing in high-temperature water reactions?

<p>100–200 °C (C)</p> Signup and view all the answers

What is a limitation of pure water in microwave heating as temperatures increase?

<p>It is difficult to heat above 130 °C. (D)</p> Signup and view all the answers

What percentage of atom efficiency does the Hoechst-Celanese process claim for its steps?

<p>100% Atom efficient (B)</p> Signup and view all the answers

What was a major characteristic of the Boots process compared to the Hoechst-Celanese process?

<p>More eco-friendly (D)</p> Signup and view all the answers

What is a common feature of the processes for synthesizing ibuprofen mentioned in the content?

<p>Both reduced chemical waste. (D)</p> Signup and view all the answers

Flashcards

Styrene Production

Involves traditional and green methods for producing styrene from benzene and ethylene or xylene.

Traditional Styrene Method

Two-step process using benzene and ethylene to produce ethylbenzene and then styrene.

Green Styrene Route

Uses xylene converted to styrene via toluene and methanol at high temperatures.

Conversion Rate in Green Process

Achieves approximately 60% selectivity to styrene at 1 atm pressure.

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Allyl Alcohol Production

Traditional production method generates hydrochloric acid by-product from allyl chloride.

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Shell Process

Uses NaOH for allyl alcohol production, causing NaCl waste generation.

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Green Allyl Alcohol Synthesis

Processes propylene, acetic acid, and oxygen to produce allyl alcohol without chlorine.

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Reclaiming Acetic Acid

Acetic acid produced in hydrolysis can be reused, enhancing sustainability.

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Alternative Allyl Alcohol Method

Utilizes glycerol reacting with formic or oxalic acids for production.

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Thermal Polyaspartate

Biodegradable polymer derived from L-aspartic acid, alternative to polyacrylates.

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Polyacrylate Concerns

Widely used but raises issues regarding environmental degradability.

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Green Polyaspartate Applications

Used as dispersants and superabsorbers, exhibiting similar properties to polyacrylates.

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Donlar Corporation

Won the 1st Presidential Green Chemistry Challenge Award for polyaspartate development.

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Ibuprofen Production

Boots process originally required 6 steps, generating waste and high costs.

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Queens Award for Technical Achievement

Boots recognized in 1987 for advancements in ibuprofen production.

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Hoechst-Celanese Ibuprofen Method

More efficient process achieved with only 3 catalytic steps, with 100% atom efficiency.

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Kirkpatrick Award

Recognized Hoechst-Celanese in 1991 for innovative green chemistry methods.

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Green Reaction Conditions

Optimal reactions for green chemistry often involve high-temperature water in sealed vessels.

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Challenges of High-Temperature Water

Pure water's microwave energy absorbance decreases above 130 °C.

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Zeolite Catalyst

Used in green styrene production for effective conversion at high temperatures.

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Biopolymer

A naturally occurring polymer derived from renewable biological sources.

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Sustainable Cycle

A closed-loop system where waste is minimized and resources are reused.

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Acetoxylation

First step in green allyl alcohol synthesis involving acetic acid.

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Hydrolysis in Production

Second step in green synthesis, where acetoxylation transforms products.

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Superabsorber

Material that can absorb and retain large amounts of liquid.

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Dangers of Chemical Waste

Chemical processes can generate harmful by-products impacting the environment.

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Green Chemistry

Design of chemical processes that reduce or eliminate hazardous substances.

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Catalytic Steps

Steps in chemical processes that use catalysts to proceed efficiently.

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Study Notes

Case Studies - Green Chemical Products

  • Styrene Production

    • Traditional two-step method starts with benzene and ethylene for ethylbenzene, followed by dehydrogenation.
    • Step II uses Fe-oxide catalyst and K2CO3 promoter, achieving 65% conversion and 95-97% selectivity to styrene.
    • Green route utilizes xylene as a less toxic starting material, converting to styrene via toluene and methanol at >400 °C using a proprietary zeolite catalyst.
    • Overall selectivity to styrene in the green process is approximately 60% at 1 atm pressure, making it the cheapest route.
  • Allyl Alcohol Production

    • Traditional method involves alkaline hydrolysis of allyl chloride, producing hydrochloric acid as a by-product.
    • The Shell process uses NaOH, resulting in significant NaCl generation.
    • Green synthesis avoids chlorine by processing propylene, acetic acid, and oxygen in two steps: acetoxylation followed by hydrolysis.
    • Acetic acid from hydrolysis can be reclaimed for reuse, providing a sustainable cycle.
    • An alternative method uses glycerol reacting with formic or oxalic acids.
  • Thermal Polyaspartate as an Alternative to Polyacrylates

    • Polyacrylates are widely used in products like paints, fibers, resins, and cosmetics but raise concerns about degradability.
    • Polyaspartates, developed by Donlar Inc., are biodegradable biopolymers derived from L-aspartic acid with no waste by-products.
    • Exhibit similar properties to polyacrylates, making them suitable for applications as dispersants and superabsorbers.
    • Donlar Corporation won the 1st Presidential Green Chemistry Challenge Award in 1996 and opened the largest polyaspartates facility in 1997.

Green Reaction Conditions

  • Ibuprofen Production
    • The Boots process from the 1960s involved 6 steps with stoichiometric reactions, leading to chemical waste and high costs.
    • Boots was recognized with the Queens Award for Technical Achievement in 1987 for their contributions.
    • Hoechst-Celanese developed a more efficient green chemistry method with only 3 catalytic steps, achieving 100% atom efficiency.
    • The HC process received the Kirkpatrick Award in 1991 for its innovative use of catalytic processes over traditional stoichiometric methods.

Green Modes of Activation

  • High-temperature water reactions (100–200 °C) are optimal for microwave processing in sealed vessels.
  • Challenges arise as pure water's absorbance of microwave energy decreases above 130 °C, complicating heating efforts.

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Description

Dive into the case studies of green chemical products, focusing on styrene production. This lecture explores traditional and innovative methods, including the use of Fe-oxide catalysts. Learn about the efficiency and environmental impact of these processes.

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