Cyclopentadiene Production via C1-C4 Co-feedstock Pressurization

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Solution Overview

Problem

Current processes for producing cyclopentadiene (CPD) and dicyclopentadiene (DCPD) face challenges such as low yield, high impurity levels, and equipment damage due to air and oxygen ingress, along with thermodynamic equilibrium constraints that suppress conversion of acyclic C5 hydrocarbons to CPD, especially when operating at sub-atmospheric pressures.

Innovation Solution

A process involving the catalytic conversion of acyclic C5 hydrocarbons with a C1-C4 hydrocarbon co-feedstock to increase reactor outlet pressure above atmospheric levels, minimizing air and oxygen ingress, while maintaining low partial pressures of CPD and hydrogen, and an effective separation process to minimize Diels-Alder reactions, allowing for high-yield production of CPD and high-purity DCPD.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If acyclic C5 hydrocarbons are converted to CPD under thermodynamic equilibrium conditions, then CPD production is suppressed, but if conversion conditions are intensified (high temperature), then cracking of C5 hydrocarbons occurs

Engineering Contradiction:
ImproveCPD conversion yieldVSAvoidcracking of C5 hydrocarbons
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The process is divided into two distinct stages: (1) catalytic conversion stage where acyclic C5 hydrocarbons are converted to CPD at controlled conditions, and (2) separation stage where CPD is rapidly separated from the reaction mixture. This segmentation allows the conversion to proceed without reaching thermodynamic equilibrium that would suppress CPD formation, while avoiding prolonged exposure to high temperatures that cause cracking.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent applies preliminary action by rapidly cooling and separating CPD immediately after formation from the catalytic conversion. This preliminary separation prevents the system from reaching thermodynamic equilibrium and avoids subsequent cracking reactions, effectively locking in the CPD yield achieved during the brief conversion period.

Inventive Principle:
Principle #10Preliminary action

2Productivity

If reactor operates at sub-atmospheric pressure to favor CPD formation, then conversion is improved, but air and oxygen ingress causes equipment damage

Engineering Contradiction:
ImproveCPD conversionVSAvoidair and oxygen ingress
Core Design Contradiction:
ProductivityVSObject-affected harmful factors

Solution Approach 1:

The patent introduces an intermediary inert gas (nitrogen or carbon dioxide) that serves as a buffer between the atmospheric environment and the reaction zone. This intermediary gas allows the reactor to operate at sub-atmospheric pressure favorable for CPD formation while preventing direct contact between air/oxygen and the sensitive catalyst and CPD product, thus avoiding equipment damage and unwanted oxidation reactions.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Manufacturing precision

If conventional distillation is used to separate CPD from C5 hydrocarbons, then separation is attempted, but CPD loss occurs due to azeotropes and reactivity

Engineering Contradiction:
ImproveCPD separation purityVSAvoidCPD loss
Core Design Contradiction:
Manufacturing precisionVSLoss of substance

Solution Approach 1:

The patent changes the separation parameter from conventional distillation (which relies on boiling point differences) to extraction or adsorption methods. By using an selective solvent or adsorbent material, CPD is separated based on its specific chemical interactions rather than volatility, avoiding the problems of azeotrope formation and thermal degradation that occur in distillation.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent replaces the mechanical separation system (distillation columns relying on vapor-liquid equilibrium) with a chemical separation system using selective solvents or adsorbents. This substitution eliminates the need for high-temperature vaporization that causes CPD loss through azeotropes and unwanted reactions, achieving high-purity separation at lower temperatures.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

4Manufacturing precision

If dimerization process is used to recover CPD, then CPD can be separated from C5 hydrocarbons, but co-dimers form contaminating DCPD

Engineering Contradiction:
ImproveCPD recoveryVSAvoidco-dimer contamination
Core Design Contradiction:
Manufacturing precisionVSLoss of substance

Solution Approach 1:

The patent extracts CPD from the reaction mixture using a selective solvent or adsorbent that specifically binds CPD while leaving C5 hydrocarbons and other components in the raffinate. This extraction method isolates CPD before it can undergo dimerization reactions, obtaining pure CPD without co-dimer contamination and avoiding the need for subsequent cracking steps.

Inventive Principle:
Principle #2Taking out (Extraction)

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This approach enables high-yield production of CPD with high-purity DCPD, reducing downstream processing costs and preventing equipment damage by maintaining acceptable pressure conditions and minimizing unwanted reactions.

Implementation Method 1

contacting the at least one acyclic C5 hydrocarbon with a catalyst under conversion conditions to obtain a first reactor hydrocarbon effluent

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

sufficient light hydrocarbon co-feedstock is provided in step (I) such that: (i) the total absolute pressure of the first reactor hydrocarbon effluent at the outlet is P(fre); (iv) P(fre) is greater than 100 kilopascal absolute

Methodology Applied
Scientific EffectPressure increase: Pressurisation

Implementation Method 3

an effective separation process to minimize Diels-Alder reactions, allowing for high-yield production of CPD and high-purity DCPD

Methodology Applied
Scientific EffectDistillation: Distillation

Implementation Method 4

DCPD can be thermally depolymerized (aka cracked) via retro-Diels-Alder reaction to CPD at the point of use

Methodology Applied
Scientific EffectDiels-Alder reaction: Chemical Bonding

Data Source

PatentEP3371133B1Process and system for making cyclopentadiene and/or dicyclopentadiene
Publication Date: 2020.07.01 EXXONMOBIL CHEMICAL PATENTS INC
  • EP3371133B1 patent drawingFigure 1
  • EP3371133B1 patent drawingFigure 2
  • EP3371133B1 patent drawingFigure 3~4

AI summary

Processes and systems for making cyclopentadiene and/or dicyclopentadiene include converting acyclic C5 hydrocarbon(s) into CPD in a first reactor in the presence of a C1-C4 co-feedstock to obtain a product mixture, separating the product mixture in a separation sub-system such as compression train to obtain a C5-rich fraction comprising CPD and essentially depleted of hydrogen and C1-C4 hydrocarbons, dimerizing the C5-rich fraction in a dimerization reactor to obtain a product effluent comprising DCPD, followed by separating the product effluent to obtain a DCPD-rich fraction. Multiple-stage of dimerization and separation steps can be optionally used to obtain multiple DCPD-rich fractions of various degrees of purity and quantity. C5-rich fractions from various stages of the process may be recycled to the first reactor, or converted into mogas components after selective hydrogenation. C5-rich fractions and mogas components may be optionally separated to produce value-adding chemicals.