Oilfield Solutions

Glyoxal for use in Production Oilfield Applications

Jennifer Jackson, Q4 2012

1
 H2S Basics: Characteristics of Hydrogen Sulfide

Deadly Extremely Toxic Gas! Molecular formula (H2S)

Colorless gas
More deadly than carbon monoxide (CO) and almost Weak acid
as toxic as hydrogen cyanide (HCN) Strong odor (rotten eggs)
Odor of rotten eggs only in low concentrations, rapidly Mole mass (34.08 g/mol)
deadens the sense of smell (0.2-0.13 ppm) Melting point (-82.9C)
Boiling point (-61.8C)
Do not depend on the smell of H2S to detect!
Colorless, heavier than air, tends to settle in low lying
areas
Flammability ranges with air or oxygen are 4% (LEL)
45% (UEL) in air
Burns with a blue flame producing sulfur dioxide (SO2)
Highly corrosive to certain metals

2
 H2S Basics: Concerns in oil and gas production

Safety Issues
Bad odor similar to rotten eggs 3 Main Reasons
Threshold odor limit = 0.13 ppm Safety for workers
Crude/gas sale price
Maximum exposure limits Corrosion
8 hour = 10 ppm
15 Minute = 15 ppm
Ceiling = 20 ppm
Hazardous Limits
Immediately dangerous to life 300 ppm (pulmonary edema with the possibility of death)
800 ppm is the lethal concentration for 50% of humans for 5 minutes exposure (LC50).

3
 H2S Basics: Concerns in oil and gas production

4 ppmv sales gas pipeline specification (not standard but

widely accepted)
3 Main Reasons
15 ppmv maximum headspace limit for crude imported Safety for workers
into the USA Crude/gas sale price
1 ppm of dissolved H2S in the liquid phase can Corrosion
produce 5 - 500 ppm in the vapor phase
A relationship between headspace H2S
concentrations and the dissolved H2S in the liquid
phase can be determined in the lab
Sulfur containing compounds reduce the value of
production streams
Some gas plants/refineries can not handle even low
amount of H2S

4
 H2S Basics: Concerns in oil and gas production
H2S attacks steel by 3 mechanisms
3 Main Reasons
Acid attack Safety for workers
Galvanic attack Crude/gas sale price
Hydrogen attack Corrosion
Pipelines are specified for corrosion to be either in the presence of H2S or in the
absence H2S
Hydrogen attack
Sulfide ions reduce reaction rate for nascent hydrogen or atomic hydrogen forming
H2 (reaction below)

Small nascent hydrogen atoms diffuse into metal

Hydrogen Blistering (HIC) - H atoms combine to form H2 gas, increasing pressure
in metal > rupture
Hydrogen Embrittlement (SSC) - High strength steels, H incorporated into
metal and weakens the structure then susceptible to cracking
5
 H2S Liquid Scavengers, Triazine
Triazines can be applied in bubble tower and flowline applications
Flowline applications use ~ 7-12 ppm/ppm H2S based on liquid volume
Reaction product of formaldehyde with a primary amine, most common: methyl amine and
triethanolamine
Triazines react selectively with H2S in the presence of CO2
In theory 1 moles of triazine reacts with 3 moles of H2S, however in application this is not
likely. The ratio is closer to 1:1.
Disposal with produced water reinjection or deep well injection
Major disadvantage is the high pH of the product, can cause scaling in high calcium
conditions
Secondary disadvantage is the downstream byproduct of triazine

6
 H2S Liquid Scavengers, Glyoxal
Basolon GL40 (Glyoxal 40%) Glyoxal reaction and by products
Glyoxal is more efficient than Triazine
No precipitation of calcium scale Glyoxal brine
solutions
Glyoxal has very good high temperature stability;
there is no decomposition up to temperatures of
150C
Glyoxal + H2S reaction products are 100% water
soluble and do not precipitate by oversaturation H2S
Glyoxal is non-amine based
Glyoxal has two perceived minor disadvantages
(addressed in next slides)
Slightly slower reaction than triazine
Corrosive in concentrated forms (40%) and
diluted forms
7
 Basolon GL 40: H2S Scavenger

Glyoxal has been reported to be utilized as a H2S scavenger since early 1990s
Several literature reference to usage
Colin T. Bedford et al, The first characterization of a glyoxalhydrogen sulfide adduct J.
Chem. Soc., Chem. Commun., 1992, 1035-1036
A Bos and J Van Dijk "An experimental study of the Reactivity and Selectivity of Novel
Polymeric "Triazine-Type" H2S scavengers" Proceedings of the Chemicals in the Oil
Industry VI 14-17 April 1997 page 170
Mabire F; Trouve C; Hoffman, H H2S Scavengers Based on Glyoxal in Oil and Gas
Treatment Chem. Prod. in Petrol. Prod. Mtg. Petroleum Abstracts V31 N.21 September
12, 1990, Language: German
Along with several application patents (patent # available upon request)
First patent dates around 1987

8
 Reaction of H2S and Glyoxal
Reaction of H2S and Glyoxal
Glyoxal is stabilized in water and forms Glyoxal-water adducts
These adducts are in a dynamic equilibrium and undergo rapid interconversion
The H2S can nucleophilically attack a (free carbonyl/aldehyde group) dissociated
Glyoxal molecule
The products are thioacetal and hemithioacetal like structures

H O O H H O O H H O S H

+nH2S +
-nH2O
H O O H H O S H H O S H

H O S H

+
......etc
H S S H

9
 Reaction Rate Glyoxal versus Triazine
Scavenger Reaction Rates
Typically dependent on the rate at which H2S
dissolves in the scavenger media
The reaction of scavenger + H2S is fast thus the
process is mass transfer limited
Scavenger + H2S is a fast reaction especially with
triazine
Glyoxal does not react as fast as triazine
Most likely due Glyoxal-water adducts and the
water must disassociate from the Glyoxal before
the glyoxal molecule can react the H2S
Bos et al studied the reaction time and based on
their work at pH=3.0
Glyoxal (11% solution) at 50 min affords a 50%
reduction in H2S content
Triazine (10%) at 10 minutes affords a 43%
reduction in H2S content
1A Bos and J Van Dijk "An experimental study of the Reactivity and Selectivity of Novel Polymeric "Triazine-Type" H2S scavengers" Proceedings
of the Chemicals in the Oil Industry VI 14-17 April 1997 page 170
10
 Reaction Rate Improvements

pH adjustments
Shifting the pH to higher values allows for a
faster and more efficient reaction1
Other H2S scavengers also exhibit increasing
reaction rates with increasing pH
Actual species is the HS- which reacts with
Glyoxal
The HS- ion is dissolved in water at higher pH
values
Surfactants
It has been noted in the literature that the
addition of surfactant to scavenger matrixes
improves mixing of H2S and the scavenger
allowing for shorter reaction times1

1Mabire F; Trouve C; Hoffman, H H2S Scavengers Based on Glyoxal in Oil and Gas Treatment Chem. Prod. in Petrol. Prod. Mtg. Petroleum
Abstracts V31 N.21 September 12, 1990, Language: German
11
 Efficiency of Glyoxal versus Triazine

Independent lab completed a study on the efficiency of Glyoxal versus Triazine

Conclusions
3 Report available upon request

Increasing the temperature improves the effectiveness of both Glyoxal and Triazine
Glyoxal tends to show a strong concentration dependence with low doses being
ineffectual whereas higher doses were very effective
Throughout the tests one observation has been apparent, weight for weight,
Glyoxal appears a more efficient scavenger. In many cases it was more efficient
than four times the concentration of triazine3

12
 Acidity of Glyoxal

Commercial Glyoxal sold as a 40-wt% solution is essentially a mixture of monomers, dimers

and trimers4
The acidity of glyoxal (~pH 2.5) is most likely attributed to the formation of hydrates or
byproduct in the production of glyoxal
For example, Glyoxal dimer, dihydrate [(CHO)2]2[H2O]2, 1,4-Dioxane-trans 2,3-diol has a pKa
11.72 (most acidic) has 2 available H+ Donors.
Glyoxal trimer, dihydrate [(CHO)2]3[H2O]4, [1,4]dixoino[2,3-b]1,4-dioxin-2,3,6,7-tetrol,
hexahydro has a pKa 10.54 (most acidic) has 4 H+ donors.

4 Colin T. Bedford et al, The first characterization of a glyoxalhydrogen sulfide adduct J. Chem. Soc., Chem. Commun., 1992, 1035-1036
13
 Corrosion Studies of Glyoxal in Produced Water

Requirement for products used in the production of crude oil or natural gas: It must
not increase the corrosion of the rate of fluids
Corrosion of Glyoxal against carbon steel has been known from the beginning of its usage in
production environments
Corrosion in fluid streams containing 1-10 % (i.e. 1000 -10,000 pm) of Glyoxal can easily be
mitigated by standard production corrosion inhibitors
For example Hoffman et al. (US 5225103, 1993, patent) used standard corrosion
inhibitors in produced water to mitigate corrosion the products listed below were
formulated at 1 to 5% in 40% glyoxal
quaternary ammonium compounds
ester of oxalkyated alkylalkylenediamine
fatty acid salts and derivatives
BASF can offer an excellent product to mitigate the corrosion issues of Glyoxal

14
 Corrosion Studies of Glyoxal (40%)
Materials compatibility testing with Glyoxal (40%) for 14 days at 60C (NACE standard TM-
01-69)
Stainless Steel 304 and 316: no corrosion observed
Mild Steel C1018: very heavy corrosion
Aluminum 7075-T6: very heavy corrosion
BASF has completed a corrosion study to identify a way to reduce the corrosion of Glyoxal
(40%) against low grade carbon steel

Carbon Steel Coupon BASF Corrosion Study Parameter

Coupon 1.0037 (1018)
Temp 60C
Glyoxal 40%
Inhibitor concentrations 1%
pH 5.5 and 2.5
Duration 14 d
Glyoxal 40%, no inhibitor
7- 12 mmpy Target 0.1 mmpy

15
 Corrosion Results, not buffered, pH = ~2.5

Test Inhibitor (1% total in CR % Pitting

Glyoxal (40%)) (mmpy) inhibited observed
1 Blank 7.07 --- yes
2 Inhibitor A 12.57 -77.7 yes Blank Inhibitor A Inhibitor B

3 Inhibitor B 4.82 31.7 yes

4 Inhibitor C 0.67 90.5 yes
5 Inhibitor D + Inhibitor E 0.26 96.3 yes
6 Inhibitor D + Inhibitor F 0.095 98.7 no
7 Inhibitor F 0.115 98.4 no Inhibitor C Inhibitor D Inhibitor D +
+ Inhibitor E Inhibitor F
8 Inhibitor E 16.485 -133.1 yes
9 Inhibitor G 4.81 31.8 yes

Inhibitor F Inhibitor E Inhibitor G

16
 Corrosion Results, buffered, pH = 5.5

Test Inhibitor (1% total in CR % Pitting

Glyoxal (40%)) (mmpy) inhibited observed
10 Blank 0.652 90.8 no
11 Inhibitor F 0.255 96.4 no
Blank Inhibitor F Inhibitor D +
12 Inhibitor D + Inhibitor E 0.187 97.4 yes Inhibitor E

13 Inhibitor D + Inhibitor F 0.211 97.0 no

14 Inhibitor C 0.854 87.9 yes
15 Inhibitor G 16.76 -17.1 yes

Inhibitor D +
Inhibitor C Inhibitor G
Inhibitor F

17
 Repeat Corrosion Results, pH = 2.5

Test Inhibitor CR % Pitting

(mmpy) inhibited observed
10 Blank 8.845 0.0 yes
11 Inhibitor F (0.4% ) 0.12 98.6 no
12 Inhibitor F (0.8%) 0.15 98.3 no
Blank

Tests repeated with Inhibitor F at lower concentration ~0.4% and 0.8%

Inhibitor F is able to almost reach target of 0.1 mmpy with ~0.4%
inhibitor dosage with no pitting
30 day stability testing was completed with Inhibitor F and Glyoxal
Inhibitor F (0.4%)
No issues were observed

Glyoxal Stability Testing with Inhibitor F

Temp 4C 25C 50C
Duration 1d 7d 15d 30d 1d 7d 15d 30d 1d 7d 15d 30d
Inhibitor F (0.4%) clear clear clear clear clear clear clear clear clear clear clear clear
Inhibitor F (0.8%) clear clear clear clear clear clear clear clear clear clear clear clear

Inhibitor F (0.8%)
18
 Secondary Properties of Glyoxal

No foaming is observed with Glyoxal, inhibited

glyoxal can formulated with defoaming agent upon
request
No emulsion is observed with glyoxal
Water miscible solvent such as MEG/ MeOH are
compatible
Flash point > 200F (93C)
Materials compatibility testing with Glyoxal 40% for
14 days at 60C (NACE standard TM-01-69)
Plastics and elastomers
HD PE and PP, Hytrel 6356, PTFE, Viton,
EPDM: no significant changes
Nylon 11, Nitrile Buma N, HNBr: satisfactory

19
 Field Examples 1 of Glyoxal: Onshore

Challenge:
H2S scavenger that could be applied to produced fluids prior to depressurization and
separation either at wellhead or downhole
The primary goal of this was to reduce levels of H2S for primarily for HSE and cost
efficiency
Storage Tank H2S levels 3,600ppm, Acceptable level <1,000ppm
Fuel Gas H2S levels 2,800ppm, Acceptable level <500ppm
Results:
86% reduction of H2S levels in storage tank was achieved,
64% reduction in fuel gas whilst injecting Glyoxal (40%) at 4,500ppm
During the field trials Glyoxal (40%) had no adverse effects on
Produced water pH and bicarbonate levels therefore did not affect the carbonate
scaling potential
No issues in oil-in-water quality or fluid separation were observed
Actually, increase in production of approx. 4% crude was observed

*Please note: BASF did not service this account and was given the information from an oilfield service provider 20
 Field Examples 2 of Glyoxal: Offshore
Challenges:
In the North Sea sector, H2S levels in gas are typically maintained at the required
specification by injecting triazine based H2S scavengers topside into the gas stream.
Triazine scavenger residuals and reaction by-products that are returned from the gas
system into produced water can cause severe scaling problems
Offshore Example 2:
Calcium carbonate scale was found to build up within equipment to an unworkable level
within 2 weeks and production had to be halted for the application of a dissolver
The service provider formulated Glyoxal and recommended it for field trial
Glyoxal was found to reduce topside H2S levels by 83% from 32 ppm to 4 ppm with
injection at 850 ppm based on total fluids
Due to the nature of Glyoxal, the scaling tendency of the produced waters was reduced
and no build up/restriction was observed
Glyoxal treatment eliminated the requirement of the regular process shut-downs to carry
out scale dissolver treatments
*Please note: BASF did not service this account and was given the information from an oilfield service provider
21
 Field Examples 3 of Glyoxal: Offshore
Offshore Example 3:
Glyoxal has been used since 2006 to control the H2S from a field which is tied back to a
highly sensitive separation process 14km away
The product is supplied subsea directly into the wellheads, providing excellent reaction
temperature for the Glyoxal
The long tie back provides excellent reaction environment for the Glyoxal with long
contact time and high turbulence during the transit time to the installation
It efficiently reduces H2S at an average of 88% to 4ppm, which is well below the 9ppm
gas lift riser specification for this field.
Glyoxal has been found to have no detrimental effect on the OIW or separation of the
process
Conclusions:
In all cases scavenger efficacy results for Glyoxal were found to be consistently around
13 liters of scavenger per kilogram of H2S. It is therefore more effective than the
previous triazine treatment (typical efficacy of 15-17 litres of scavenger per kg of H2S)
*Please note: BASF did not service this account and was given the information from an oilfield service provider
22
 Conclusions
Suggested applications: 3-phase production streams, 2-phase gas streams, downhole, subsea, wellhead
bulk storage tanks and produced water streams
Non-suggested application: Extremely dry crudes, bubble towers and dry gas systems
Glyoxal is non-amine based
Glyoxal is more efficient than triazine
No precipitation of calcium scale Glyoxal brine solutions
Glyoxal has very good high temperature stability up to 150 C
Reaction rate of Glyoxal with H2S can be increase by adjusting the pH between 5.5 and 7 and by adding a
surfactant
Corrosion in fluid streams containing 1-10 % (i.e. 1000 -10,000 ppm) of Glyoxal can easily be reduced by
standard production corrosion inhibitors
Corrosion by Glyoxal (40%) can be reduces by 0.4 % Inhibitor F to ~0.1 mmpy at 60C and 14 days
No detrimental secondary effects such as foaming or increased emulsion stability from the application of
Glyoxal has been observed
Several case histories have been documented illustrating the successful application of Glyoxal in oilfield
applications
23