PhD student

Henrik Tkker Madsen

Aalborg University, Esbjerg

 Hydrogen sulphide scavenging in general
The problem A case study in practical issues with using a triazine
based scavenger
Reaction system
Mass balance where does the problem come from
Production of models for explanation

Empirical analysis
Electrospray ionization analysis
Structural analysis

An expanded model for the reaction system

Experience from use of a different scavenger
 Component Formula Volume %
Methane CH4 >85
Ethane C2H6 3-8
Propane C3H8 1-5
Butane C4H10 1-2
Pentane C5H12 1-5
Nitrogen N2 1-5
Carbon dioxide CO2 1-2
Hydrogen sulphide H2S 1-2

Natural gas with:

- CO2 and no H2S = sweet gas
- H2S and/or CO2 = sour gas
 Where does it come from?
Thermal cracking of sulphur containing compounds
Thermochemical sulphate reduction through
oxidation of hydrocarbons (above 140C)
Indigenous sulphate reducing bacteria

+
CH 2O+ 2H + SO CO2 + H 2 S+ 2H 2O
2-
4

Where does sulphate come from?

Seawater injection to maintain pressure (2800 ppm)
 Why at all remove H2S???
Toxic (and obnoxious)
Concentration (ppm) Effects
0.003-0.02 Clearly detectable by smell
3-10 Very unpleasant smell
20-100 Distinct smell of rotten eggs
50-100 Stinging pain in eyes and irritantion of respiratory organs
100-200 Sedation of the olfactory sense
250-500 Fluids in lungs, cyanosis, bloodstained cough, pneumonia
500 Headache, vertigo, paralysis of respiratory muscles,
unconsciousness
500-1000 Stop for respiration, immediately collaps, death
 Why at all remove H2S???
Corrosion and sulphide stress cracking

Fe Fe2+ + 2e- Anode

2H + + 2e- H 2 Cathode

H 2 S HS- + H + S2- + H +
Fe2+ + S2- FeS(s)

Hydrogen atoms may recombine in metal

structure leading to intense pressure and stress
that may lead to fracturing
 In general one of two approaches may be
chosen
Regenerative
Non regenerative
 Typical example is
Regenerative solutions monoethanolamine (MEA)

Based on the use of amine solutions in which the amine

absorbs the hydrogen sulphide, which may then be released
again later.
Amine creates alkaline environment
-
2 HS
H 2 S +H
+ + +

Increase in temperature lowers

solubility of H2S and leads to release
from solution

Problem with CO2??

 H
H
H N + O C O
H N + O C O
H
H

Amine based solution: CO2 problem

Bicarbonate/carbonate formation
RNH 2 + CO2 + H 2O RNH3+ + HCO3-

Carbamate formation
Ammonium carbamate example
H
H +
H N H
H N + O C O
-
Will only happen if
C
H
O O
the amine is primary
H H
or secondary
+ NH2
H N H
H N + H Why???
C
H C - +
- O O H N H
O O
H
 Non regenerative solutions
Metal oxide absorbtion
Oxidising chemicals
Aldehyde and aldehyde related products

Triazines
 Non regenerative solutions
Metal oxide absorbtion

Fe2O3(s) + 3H 2 S(g) Fe2 S3(s) + 3H 2O(g)

2Fe2 S3(s) + 3O2(g) 2Fe2O3(s) + 6S(s) Possible regeneration,

but not practical
possible (lowering of
bed porosity)
 Non regenerative solutions
Oxidising chemicals
Typical 5-10 % solutions of KMnO4 or K2Cr2O7
- +
8MnO4(aq) + 5H 2 S(g) +14H(aq) 8Mn(aq)
2-
+ 5SO4(aq)
2-
+12H 2O(l )

Very efficient, but

expensive (plus some
reactants and reaction
products may be
carcinogenic)
 Non regenerative solutions
Aldehydes

3HCHO(l ) + H 2 S(g) C3 H 6 S3(s) + 3H 2O(l )

s-trithiane

Aldehydes react with hydrogen

Very efficient, but sulfides forming a whole range of
toxic reactants and products.
problematic reaction One example is s-trithiane seen in
products the above equation. We will
return to that one later.
 Non regenerative solutions
Triazines
One of the most used solutions

Benefits:
- Modifiable water/oil solubility
- H2S selective (why ??)
- Reaction products are water
soluble, corrosion inhibitors and
low toxicity
- Rapid reaction
 Production of fouling during refining of
oil at Shell refinery at Fredericia
Process technological problems
Large costs

Analysis of fouling showed it to

consist largely of carbon and
sulphur, which lead the suspicion
to the H2S scavenging process as
performed by Mrsk
 Reaction system
Thiadiazine

Triazine

Dithiazine

Trithiane
 Could the scavening process explain the
observed amounts of fouling?

Compound Std. During Factor

production maintenance
(kg/day) (kg/day)

Triazine
Triazin 6,41 129,7 20,2

Thiadiazine 0,78 33,52 43,0

Dithiazine 0,64 27,40 42,8

- Batch problem?
 Hypothesis A: Trithiane S S

Only reaction product with sufficiently high S

amount of carbon and sulphur
Hypothesis B: Dithiazine-polymer
Could explain the small amount of N and O that is
detected
 No fouling previously
reported for this
Study of reaction system experimental setup

Reaction between HS- and triazine Lab controlled

chemicals and
conditions
Reaction between H2S and triazine

Reaction between H2S and spent

Approaching
scavenger refinery conditions

Polymer like fouling

reported for this
experimental setup
 Identification of peaks
Nominel mass
Spent scavenger + NaCl
Triazine 219

Thiadiazin 192

Dithiazine 165

Trithiane 138

MEA 61

Triazine + Na 242

Thiadiazine + Na 215

Dithiazine + Na 188

Trithiane + Na 161

MEA + Na 84
 Reaction between HS- and triazine
 Reaction between H2S og triazine
 Reaction between H2S og spent scavenger
Effect of heating
 IR analysis

S-C

CH2
 s-trithiane
XRD analysis

Shell fouling

Mrsk fouling
 Comparision of precipitate and fouling
Fouling Precipitate

3400 3388

2956 2959
Precipitate

2923 2911

2867-2855

1584 1675

1449 1367

1366 1282
Fouling
1175 1175

1051 1058

880 881

745, 734, 707 745, 734, 708

 Precipitate from experiments and fouling
from Shell are identical
Fouling originates from scavenging process

No trithiane is formed during scavenging

Fouling must be the proposed dithiazine polymer

How can this be explained? No fit with existing reaction system model.
What about unexplained peaks seen in MS analysis
Overall system

Mechanism
Proposed reaction scheme from: H.T. Madsen and E.G. Sgaard, 2012. Use of ESI-MS to determine reaction pathway for
hydrogen sulphide scavenging with 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine. Eur. J. Mass Spectrom. 18, 377-383
 Use of alternative triazine S
CH3 CH3

N N
HO OH

H3C OH

CH3
N N

CH3 OH
SH

CH3
H3C CH2
N
+
H2C N OH
OH
87 Da SH

134 Da
Empirical formula: (C7H15S4.5NO)n

Equal to what is found in experiments

 Conversion of -OH to =O may be key
The disintegration of dithiazine step in reconfiguration

Strategies:
Replace -OH group with =O group
May however lead to lower solubility of dithiazine and hereby promote precipitation of
crystalline dithiazine

Use tertiary -OH group instead of primary or secondary

1) How do we improve the scavenging process? (Design of new
scavengers)
Criterias:
Fast
Efficient
Low fouling potential

2) How do we reduce the environmental impact?

Triazine based compounds and reaction products are classified as
biocides (pesticides).
Dumping of untreated spent scavenger may affect the local maritim
environment.
High alkalinity may complicate reinjection into the well bore.
Applied Computational
Gaussian
Chemistry
Example of a program for computational chemistry
Properties to be calculated
Geometry (length, width
of molecules)
UV-Vis/IR/Raman spectra
Chemical properties (dipole
moment, pKa values)
Enthalpies and free energy of
reactions
Rate constants
Transition states, reaction
pathways
. Software to draw the The program doing the
desired molecular calculations
structure and choose
calculation scheme
Applied Computational Chemistry

Example of thermochemistry calculations based on the

use of the CBS-QB3 algorithm
Reaction enthalpy (kJ/mol)
Experimental Gaussian Diff
Water gas shift -41.2 -49.6 -8.4
Steam reforming 206.2 191.2 -15.0
Methane combustion -802.2 -806.4 -4.2
MeOH combustion -676.1 -678.2 -2.0
Methane to MeOH 115.7 108.8 -7.0
 Applied Computational Chemistry
Design steps

1) Choose
candidates

Determine G values for overall thermodynamic driving

2) Thermochemistry
force and stability of reaction products

Transition state Find TS structure and use this to calculate

3) calculation the activation energy

DGA0
kBT RT

4) Reaction rate k(T) = e
hC0
From Physical Chemistry, A Molecular
Approach by D. A. McQuarrie and J. D.
 Process diagram Mass balance

Possible solution Membranes?

Stay tuned for next lecture