Disulfide Additives for Cracking Reactor Coke Inhibition

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Solution Overview

Problem

The rapid formation of coke deposits on the internal walls of hydrocarbon cracking reactors and heat exchangers leads to frequent shutdowns, increased maintenance costs, and reduced operating time due to the limitations of existing coke inhibition methods, particularly the thermal decomposition of sulfur-based additives which reduce olefin yields.

Innovation Solution

The use of diethyl disulphide (DEDS), dipropyl disulphide (DPDS), or dibutyl disulphide (DBDS) as coke and carbon monoxide inhibitors, which are added to the steam or feedstock, pretreat the metal surfaces at specific temperatures to reduce coke formation and increase olefin yields by minimizing thermal decomposition into methane.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Object-affected harmful factors

If sulfur-based additives (DMS, DMDS) are used to reduce coke formation, then coke deposition is reduced, but thermal decomposition reduces olefin yields

Engineering Contradiction:
Improvecoke depositionVSAvoidolefin yield
Core Design Contradiction:
Object-affected harmful factorsVSProductivity

Solution Approach 1:

The patent changes the chemical structure parameter of the sulfur-based additive by using dibutyl disulfide (DBDS) instead of conventional DMS or DMDS. This structural modification alters the thermal decomposition pathway to reduce methane formation and increase olefin yield while maintaining coke inhibition effectiveness.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates an alternative copy of the sulfur-based additive mechanism by using dibutyl disulfide, which replicates the coke-inhibiting function through sulfur release but produces a different decomposition profile that favors olefin production over methane formation.

Inventive Principle:
Principle #26Copying

2Object-generated harmful factors

If high-temperature gasification is used to remove coke deposits, then coke is converted to carbon oxides, but structural limitations prevent in-line decoking in heat exchangers

Engineering Contradiction:
Improvecoke deposit removalVSAvoidin-line decoking capability
Core Design Contradiction:
Object-generated harmful factorsVSEase of operation

Solution Approach 1:

The patent applies preliminary protective action by introducing dibutyl disulfide additive into the hydrocarbon feed before it enters the cracking reactor and heat exchangers. This preventive approach forms a protective layer on metal surfaces that inhibits coke formation in the first place, eliminating the need for subsequent high-temperature decoking operations.

Inventive Principle:
Principle #10Preliminary action

3Object-generated harmful factors

If oxidizing decoking treatment is performed, then coke is removed, but catalytic activity of metal surface increases leading to faster coke formation

Engineering Contradiction:
Improvecoke removalVSAvoidoperating time between decokings
Core Design Contradiction:
Object-generated harmful factorsVSDuration of action of stationary object

Solution Approach 1:

The patent converts the potentially harmful effect of sulfur (which can poison catalysts) into a beneficial effect by using controlled amounts of dibutyl disulfide that passivate the metal surface to prevent coke formation. The sulfur acts as a protective agent rather than a contaminant, extending operating time between decokings.

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

4Object-affected harmful factors

If conventional sulfur additives are used, then coke formation is reduced, but frequent shutdowns are still required for maintenance

Engineering Contradiction:
Improvecoke formation reductionVSAvoidshutdown frequency
Core Design Contradiction:
Object-affected harmful factorsVSLoss of time

Solution Approach 1:

The patent changes the physical and chemical parameters of the sulfur additive by using dibutyl disulfide with higher molecular weight and different thermal stability characteristics. This results in more stable and durable coke inhibition that lasts through longer operating periods, reducing the frequency of maintenance shutdowns.

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

These additives effectively reduce coke and carbon monoxide formation, increasing the yield of olefins like ethylene, propylene, and butene by stabilizing the metal surfaces and preventing methane production, thus enhancing the operational efficiency and reducing maintenance needs.

Implementation Method 1

the sulphur passivates the active metal sites of the surface of the steam cracking tubes which are known to catalyze the formation of coke

Methodology Applied
Scientific EffectPassivation: Adsorption

Implementation Method 2

compounds which generate hydrogen sulphide (H2S) in order to reduce the formation of coke

Methodology Applied
Scientific EffectThermal decomposition: Pyrolysis

Implementation Method 3

the metal surfaces coming into contact with the organic substance to be cracked are pretreated with a stream of steam comprising in particular the additive according to the invention

Methodology Applied
Scientific EffectSteam flow transport: Convection

Data Source

PatentUS8791314B2Additive for reducing coking and/or carbon monoxide in cracking reactors and heat exhangers and use of same
Publication Date: 2014.07.29 ARKEMA FRANCE SA

AI summary

The present invention concerns an additive for reducing the formation of coke and/or carbon monoxide in thermal hydrocarbon cracking units and/or of other organic compounds in heat exchangers. The additive according to the invention is essentially composed of diethyl disulphide (DEDS) or dipropyl disulphide(s) (DPDS) or dibutyl disulphide(s) (DBDS) and can be used on the metal walls of a cracking reactor and on the metal walls of a heat exchanger placed downstream from the cracking reactor, and during the process of cracking hydrocarbons and/or other organic compounds.