Hydrofluoric Alkylation:

Corrosion and Prevention

Supervised by
Dr. Wichitra Wongpromrat

Members
Mr. Jarukit Janjiewchai 57010169
Mr. Techut Promta 57010495
Mr. Thithawat Techan 57010498
Mr. Wanchai Niamtang 57011156
Chemical Engineering Department, Faculty of Engineering
King Mongkut's Institute of Technology Ladkrabang
1
 Overview
• Introduction
Alkylation Reaction Section
Fractionation Section
Treating Section
• Corrosion and Prevention
Hydrogen Induced Cracking
Erosion
Localized Corrosion Cracking
Galvanic Corrosion
Hydrofluoric Corrosion
• Recommendations

2
 Introduction

• The purpose of the HFA unit is to react an olefin feed with isobutane
in the present of the hydrofluoric (HF) catalyst to produce alkylate.

HF
Olefin + iso-butane Alkylate
e.g. iso-octane
(higher octane number)

• Hydrofluoric Alkylation unit (HFA) can be divided into 3 sections:

Reaction, Fractionation, and Defluorinating/Alumina Treating.

3
 Process Flow Diagram
Propane
HFA Reactor Fractionator Treater

HFA KOH
Reactor Treaters
Propane
Stripper

HF Fractionator
Separator

Feed
(Olefin + iC4)

Alkylate

Propane
HF (Recycle HF) Defluorinators 4
 HFA Reactor
Propane

HFA KOH
Reactor Treaters
Propane
Stripper

HF Fractionator
Separator

Feed
(Olefin + iC4)

Alkylate

Propane
HF (Recycle HF) Defluorinators
5
 HFA Reactor (cont.)
Corrosion: Hydrogen Induced Cracking (HIC)
Mechanism: Hydrogen atoms diffuse into a metallic structure and combine
to form hydrogen gas, they produce pressure within the cavity.
Preventions:
• Design: using very high strength steel (most susceptible HIC)
• Alloying: Ni or Mo reduces susceptibility
• Proper welding: use low H welding rods

Hydrogen induced cracking

Ref: Hydrogen induced cracking, www.oakleysteel.co.uk
Hydrogen embrittlement, www2.mtec.or.th/th/research/famd/corro/hic.htm
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 HF Bottom-line
Propane

HFA KOH
Reactor Treaters
Propane
Stripper

HF Fractionator
Separator

Feed
(Olefin + iC4)

Alkylate

Propane
HF (Recycle HF) Defluorinators
7
 HF Bottom-line (cont.)
Corrosion: Erosion

Mechanism: HF acid flows through

metallic pipe leading to damage the
protective film.

Preventions:
• Design: bigger pipe diameter (reduce
fluid speed) and increase thickness
• Operate: reduced operating
temperature and fluid velocity

Pipe thickness in corrosive environment

Ref: NDT Inspections of HF Acid Lines in Alkylation Units, https://inspectioneering.com/

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 HF Separator
Propane

HFA KOH
Reactor Treaters
Propane
Stripper

HF Fractionator
Separator

Feed
(Olefin + iC4)

Alkylate

Propane
HF (Recycle HF) Defluorinators
9
 HF Separator (cont.)
Corrosion: Pitting Corrosion

Mechanism: Pitting is caused by the presence of an “aggressive”

anion in the electrolyte, usually F− ions.

Pitting corrosion
Ref: www.corrosionpedia.com

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 HF Separator (cont.)

Prevention:
• Maintain the electrode potential
• Add inhibitors
• Avoid the stagnation of solution
• Control fluoride concentration
and temperature

Corrosion rate as a function of temperature for carbon steel in

anhydrous acid under stagnant conditions in 100-hr laboratory test
Ref: Jonathan D. Dobis, The Effect of Operating Conditions on Corrosion in HF
Alkylation Units

The resistance to pitting corrosion increases in the order:

Fe-12% Cr < 304 stainless steel < 316 stainless steel < alloy C-276 < titanium

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 HF Separator (cont.)
Corrosion: Crevice corrosion
Mechanism: Difference in concentration of some chemical constituents,
usually oxygen leading to concentration cell and crevice corrosion.
Prevention:
• Use of corrosion inhibitors
• Materials selection
• Removal of organic fluorides by the alumina treaters

HF  H+ + F-
Crevice

e- M+

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 Fractionator
Propane

HFA KOH
Reactor Treaters
Propane
Stripper

HF Fractionator
Separator

Feed
(Olefin + iC4)

Alkylate

Propane
HF (Recycle HF) Defluorinators
13
 Fractionator (cont.)
Corrosion: Galvanic Corrosion
Mechanism:
• Two dissimilar materials are coupled in a corrosive electrolyte.
• The driving force for corrosion is a potential difference between
the different materials.

Ref: Kopeliovich, Galvanic corrosion

14
 Fractionator (cont.)
Prevention:
• Avoid unfavorable area effect
• Feed lines operates under 66 0C (avoid critical condition)
• Use Alloy 400 (Monel) if corrosion rates are excessively high
• Avoid threaded joints for materials

Compositions of Alloy 400 (Monel)

Ref: http://www.nickelpiping.com/alloy-400

15
 Fractionator (cont.)
Prevention (cont.)
• Avoid threaded joints for materials

Welding

Cross-section of a carbon steel pipe showing preferential corrosion of the pipe with a high residual
element content on the left as compared to the low residual pipe section at the right of the weld
Ref: Jonathan D. Dobis, The Effect of Operating Conditions on Corrosion in HF Alkylation Units
16
 Defluorinators/KOH Treaters
Propane

HFA KOH
Reactor Treaters
Propane
Stripper

HF Fractionator
Separator

Feed
(Olefin + iC4)

Alkylate

Propane
HF (Recycle HF) Defluorinators
17
Defluorinators/KOH Treaters (cont.)
Corrosion: Uniform corrosion
Mechanism: General attack corrosion proceeds more or less uniformly
over an exposed surface without appreciable localization.
Prevention:
• Proper materials
• Addition wall thickness
• Adding inhibitors

The corrosion rate of carbon steel at 21 to 38oCbased on

laboratory testing and field experience
Ref: Jonathan D. Dobis, The Effect of Operating Conditions on Corrosion in HF Alkylation Units
18
Defluorinators/KOH Treaters (cont.)
Corrosion: Stress corrosion cracking(SCC)
Mechanism: SCC results from the conjoint action of three components
1) a susceptible material
2) a specific chemical species (HF acid environment)
3) tensile stress

Stress corrosion cracking

Ref: www.faculty.kfupm.edu.sa/ME 19
Defluorinators/KOH Treaters (cont.)
Prevention:
• Eliminating the critical environment
• Changing the alloy

Ref: Baker, CORROSION CONTROL MATERIAL SELECTION ALTERATION OF ENVIRONMENT, 2015

20
 Recommendations

Vaporized HF !!!

Rate of corrosion of alloy 400 in hydrofluoric acid

Ref: Rebak, Corrosion of Non-Ferrous Alloys, 2013
21
 Recommendations
Propane

Vaporized HF !!!

HFA KOH
Reactor Treaters
Propane
Stripper

HF Fractionator
Separator

Feed
(Olefin + iC4)

Alkylate

Propane
HF (Recycle HF) Defluorinators
22
 Recommendations (cont.)
Guide for Selecting Materials

Ref: www.waverleybrownall.co.uk/special-metals/
23
Recommendations (cont.)

24
Recommendations (cont.)

Ref: www.pwrmfg.com/power-manufacturing/technical-info/designing-with-metals/ 25
 Q&A

Corrosion, Immunity and Passivation

Ref: E. McCafferty, Introduction to Corrosion Science
26