Crosslinked PDMS Defoamer Reduces Silicon Contamination in Coker Feedstocks

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Solution Overview

Problem

The delayed coking process in petroleum refineries faces issues with foaming, which leads to undesirable silicon contamination in products, poisoning catalysts and requiring premature replacement, as existing silicone-based defoamers are not viable alternatives due to high silicon content and thermal instability.

Innovation Solution

The use of crosslinked polydimethylsiloxane (PDMS) with a siloxane or alkyl polysilicate crosslinker, which reduces the amount of silicon in coker products while effectively controlling foam, allowing for less crosslinked material to achieve the same foam reduction as traditional linear PDMS, thereby minimizing catalyst poisoning and contamination.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of operation

If silicone-based defoamers (polydimethylsiloxanes) are added to control foaming in delayed coking, then foam control is improved, but silicon contamination of products increases causing catalyst poisoning

Engineering Contradiction:
Improvefoam controlVSAvoidsilicon contamination
Core Design Contradiction:
Ease of operationVSObject-affected harmful factors

Solution Approach 1:

The patent changes the molecular weight parameter of the polydimethylsiloxane from conventional high molecular weight to a specific range (500-50,000 cst viscosity) that provides effective foam control while reducing thermal degradation and silicon carryover in products. This parameter optimization resolves the contradiction by finding a viscosity range that balances defoaming effectiveness with reduced catalyst poisoning.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses composite defoamer formulations combining polydimethylsiloxane with specific hydrocarbon carriers and optional additives to achieve effective foam control with reduced silicon contamination. The composite nature allows the active silicone component to be delivered efficiently while minimizing the amount that reaches downstream catalysts.

Inventive Principle:
Principle #40Composite materials

2Stability of the object's composition

If high molecular weight silicone oil is used as defoamer, then thermal stability is improved, but silicon distills over with liquid products at coker temperatures

Engineering Contradiction:
Improvethermal stabilityVSAvoidsilicon distillate
Core Design Contradiction:
Stability of the object's compositionVSQuantity of substance

Solution Approach 1:

The patent optimizes the molecular weight and viscosity parameters of the polydimethylsiloxane to a specific range that provides sufficient thermal stability for coking conditions while preventing excessive distillation. The viscosity range of 500-50,000 cst represents an optimal balance where the silicone is stable enough to withstand coker temperatures but not so high molecular weight that it breaks down into distillable fragments.

Inventive Principle:
Principle #35Parameter changes

3Ease of operation

If conventional linear PDMS is used for foam control, then defoaming effectiveness is achieved, but large quantities are required leading to increased silicon carryover

Engineering Contradiction:
Improvefoam control effectivenessVSAvoidsilicon carryover
Core Design Contradiction:
Ease of operationVSQuantity of substance

Solution Approach 1:

The patent changes the viscosity parameter of the polydimethylsiloxane to an optimized range that enhances defoaming effectiveness per unit quantity. By selecting specific viscosity grades within the 500-50,000 cst range, the patent achieves better foam control with smaller dosages, thereby reducing total silicon carryover to downstream units.

Inventive Principle:
Principle #35Parameter changes

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 significantly reduces silicon carryover and foam levels, enabling more efficient coking operations, longer catalyst life, and increased product output by minimizing the need for frequent catalyst replacement and reducing downtime due to foaming.

Implementation Method 1

Due to silicone oil's unique surface properties and thermal stability

Methodology Applied
Scientific EffectSurface tension: Surface Tension

Implementation Method 2

crosslinked polydimethylsiloxane (PDMS) with a siloxane or alkyl polysilicate crosslinker

Methodology Applied
Scientific EffectChemical bonding: Chemical Bonding

Implementation Method 3

Breakdown products are primarily cyclic trimers and tetramers of polydimethylsiloxane, and have boiling points of 134° C. (273° F.) and 175° C. (347° F.)

Methodology Applied
Scientific EffectThermal decomposition: Thermolysis

Implementation Method 4

the original silicone molecule can break down into small enough pieces to distill over with the liquid products

Methodology Applied
Scientific EffectDistillation: Distillation

Data Source

PatentUS7427350B2Silicone defoamer to better control hydrocarbon foam and reduce silicon content of liquid hydrocarbon products
Publication Date: 2008.09.23 BAKER HUGHES CO

AI summary

It has been discovered that crosslinked polydimethylsiloxane (PDMS) resins are useful defoamers and antifoamers for hydrocarbon-containing liquids, such as delayed coker feedstocks and feedstocks to preflash and atmospheric towers. These PDMS resins are crosslinked with either alkyl polysilicate or siloxane. The crosslinked PDMS resins may be used alone or together with linear PDMS, and are typically blended with a carrier such as kerosene for easier handling. Importantly, the use of crosslinked branched PDMS resins permit less total amount of polysiloxanes to be used, which reduces the silicon carryover in coker products and reduces poisoning of downstream catalysts.