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The Hydrogen Sulfide Scavengers (H2S Scavengers) from Direct N-Pakt are primarily those of
methylene reacted systems.
These hydrogen sulfides can be removed from the gaseous, hydrocarbon liquid, or water phases by
direct treatment into the flow stream.
Also, the flow stream may purge through column known as a scrubber with fluid volume and percolate
The chemical molecules can be called Schiff bases, imines, methylene bridged adducts, methylolated
amines, triazines, bis-oxazolidines.
Typical treatment rates are 0.16 to 0.45 liters per MMSCF for line injection.
Gals/ day = 0.04 to 0.06 x MMSCFPD gas x ppm H2S typical for towers.
Typical reaction ratio is 4:1 chemical to H 2S, up to 25 ppm. In some cases % solutions might
be required.
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Hydrogen sulfide is a commonly occurring nasty, toxic, and lethal gas. Hydrogen sulfide is colorless.
Hydrogen sulfide must be reduced to permissible levels for safety and corrosion standpoints, typically 1 to
4 ppm (mole % basis). Severe concern is considered when H2S is above 100 ppm.
Hydrogen sulfide is very corrosive when dry forming FexSX complexes, very adherent, and interferes with
flow passage of gas, especially in dry gas pipelines.
Hydrogen sulfide gas occurs in wet forms in sewage drains, holding pits, and plants at toxic levels,
generated from decomposition of fecal matter.
Hydrogen sulfide occurs form generation by growth of anaerobic (grow in area where oxygen is absent)
Hydrogen sulfide can be produced from the decomposition of waste, garbage, and compost domes.
Hydrogen is produced from handling of sulfur from some natural gas wells, from leakage from storage
domes.
Hydrogen sulfide is produced in high quantities from natural gas and associated gas from oil wells
throughout the world, especially in Canada, Southern US, Mexico, Russia, Iran and others.
Due to producing or disposal or storage of associated brine production in oil and gas production, waters
accumulate H2S from handling and bacterial contamination.
Corrosion Problems:
Locations:
Gas/oil/water separators.
H2S Scavengers:
Direct N-Pakt manufactures liquid chemical reagents to remove or lower the hydrogen sulfide content,
occurring at low % or low ppms.
Direct N-Pakt supplies both chemicals and technical expertise in handling of chemicals and their
applications. Direct N-Pakt can supply specialty blends for particular use.
Direct N-Pakt chemical scavengers will reduce the level of hydrogen sulfide to where corrosion can be
controlled , the IRON (Fe) sulfides can be minimized.
CHEMICALS:
Direct N-Pakt supplies liquid scavengers that are useful in treatment of natural gas, carbon dioxide with
associated gas, liquid condensates or crude oil, and waters of various types, including refinery process,
produced oilfield waters, sewage, drilling fluids and fracturing fluids.
gas soluble
oil soluble
water soluble
Gases associated with oil and gas production usually contain CO 2 (carbon dioxide), which causes an
acidic pH. The addition of H2S scavengers to CO2 containing fluid can cause pH to rise sharply. The
formation of calcium or magnesium carbonates and amine carbonates can occur. Direct N-Pakt H 2S
scavengers usually hold this to a minimum, but it does occur.
In these cases, the DNP-02-00 2022, contains a chelant. Other products and 2022 can use the addition of
Direct N-Pakts high calcium tolerant phosphonates, which are both sequestrants and chelants, @ 1-2%.
The common added is DNP-06-00-68441 or 68481, or 68521. These phosphonates also help to dissolve
Fe xSx.
Formaldehyde can be added to the Direct N-Pakt line of H 2S scavengers except the oils soluble; 2100,
2601, or 2835, to synergize or accelerate reaction ratios.
The use of Direct N-Pakts H2S scavengers can be coordinated with using proper Corrosion Inhibitors to
mitigate even low level of H2S or in process areas not previously removed of H 2S.
Technical information is supplied for the Direct N-Pakts H 2S scavengers and their handling.
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Theoretical relation of standard triazine as 2151, is 1.71 # (0.14 kg/liter) removed by 1 gallon,
1 Liter of scavenger will remove 3.2 ppm of H2S from one MMscf gas.
0.5 Liter of scavenger + 0.5 liter of 37% formalin will remove 5.6 ppm H2S from one MMscf gas.
I gallon of scavenger will remove 12.1 ppm of H2S from one MMscf gas.
16 ppm H2S will be removed from one MMscf gas per gallon of scavenger.
The question comes from which are the most effective and which are the fastest and which are best
suited for what system.
Schiff Base
Imine
Methylene Bridge
The steric hindrance can interfere or control rate. Rate controls efficiency.
Rohm & Haas Primene 81-R C12-14 tertiary carbon, primary amine or similar
The reactant is methylene [CH2] to form a stable reaction product. Therefore the molecule must use its
amine for capture and the methylene must be easily released in the system. The system can be gas,
hydrocarbon liquids, aqueous liquids, or mixtures. The methylene of formalin is the most reactive.
For towers, the product density has a physical effect, as well as it should not easily carry with the gas if
radial velocity is exceeded. Considered the most for money is MEA triazine or this MEA/CH 2O reaction
product mixed with formaldehyde, if local restrictions or companies allow.. Some have discussed DEA
as some improvement. EDA can be used as well.
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DNP Soluble In
CH2O Rxn Product CH2, % Gas/Air Hydrocarbons Water
#
Methylamine 2033 13.84 yes yes yes
MEA 2022 14.28 nil nil yes
It must be noted that the reaction products continue to react, saying reaction products react further.
The form sought is S-S-S or maybe S-S-S-S-S. This is achieved from the (CH2-S) n, where n= most
commonly 3 and 4.
MEA is typically the lowest cost. MMA is expected to perform but may be too volatile for most producers
to handle.
Gatlin has patent on DMAPA assigned to WFT, Dimethylaminopropyl triazine, also made by Taminco.
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The reaction of formaldehyde, including formalin (37% inhibited with 3 to 25% methanol), 49-51% tackifier
grade, or methyl formcel (normally 55% formaldehyde in 35% methanol and 10% water) with primary or
secondary amines is an exothermic condensation to form methylol groups, Schiff Bases, methylene linkages as
Triazines or Oxazolidines, methylene bridge condensates, and other impurities.
Impurities:
The primary constituents are present as shown or as mixtures in equilibrium with the methylol or Schiff forms,
as these reactions are run as solution combination and not as dehydrating (water removal).
The reaction can be run with tertiary amines but forms quaternary type bases, which are very alkaline and
unstable.
HANDLING:
Formaldehyde is easily handled and monitored due to its odor and low level of detection. Suitable method
should be set to specifically identify any low level presence.
Adequate cleaning of any possible spills should be available separate from all other containment systems.
Ethanolamine/water mixture rapidly destroys small quantities of formaldehyde. Sodium or Ammonium
Bicarbonate assist in handing large spills. Formaldehyde is acidic about 3.5 to 6.5 pH, depending on free
acid present.
Trace contaminants can cause excessive changes in final product distribution, and especially insoluble
residue polymers, not easy to remove, causing suspended particles and turbidity.
The use of the higher 12-15% methanol inhibited grade can be helpful, but the 7% grade is preferred.
Warming of formalin prior to use is not required.
The most common linkage is methylene bridge to produce the Triazines, oxazolidines, Schiff bases, methylol
adducts all commonly called amine aldehyde adducts. Most common adjunct additives are formaldehyde,
acetaldehyde. Acetadol.
STORAGE:
Preferably store liquid H2S scavengers by controlling the temperature at 105 +/- 10 F. Storage above these
temperatures need to be stabilized blends.
Keep the storage from direct light if a drum or tank. If Totes are used and are transparent keep from any
Ultraviolet Light. Maintain a positive pressure against tank vapor outlets to inhibit breakdown and release of
any aldehydes, especially odors.
Comments:
Triazines are an unstable form. Normally it has been assumed that Oxazolidine or Triazines are the color
constituents. The color constituents are deemed results of oxidation and heat. If the triazine exists then
assume it is a formyl [2, 4 6- formyl-1, 3, 5-hydroxyethyl-1, 3, 5-S-triazine (with the 1:1 molar reaction ratio.)]
Diimines are very possible. These are the Schiff bases or the similar to even though we are talking of
tautomer forms.
The imines or enamines of tautomers (C=N or C=C), acetals, hemi-Acetals, and amine/acetals, or dimers or
polymers (i.e. multimer).
Patent by Pounds and Cherry claim the product composition of glyoxal and amines are unknown, no triazines
or imines are present (WO1996005907).
REACTION:
The reaction of the imines, Schiff bases, enamines, Aldehydes, Triazines, oxazolidines, Acetals,
hemi-acetals, and the new coined term of methylene bridged reaction products are through the
CH2--, methylene group.
It is known that the excess amine is not required for effective reaction. Currently Ethanolamine Triazines are
mixed 50% with formalin and increase reaction by 2 times.
Early products of industry used formalin with about 2 to 9% volume of diethnaolamine, triethanolamine,
hydroquinone and others.
So the methylene reacts with the H2S , mercaptan, or other sulfur compounds and the amine is liberated.
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COMPOSITIONS:
Simply:
1. Methylamine=CH3NH2 MW = 31.
2. 1, 3, 5 S-triazine= (CH2)3[CH3N] 3 MW = 129, trimer, EQ= 29
3. 1, 3, 5-hydroxyethyl-1, 3, 5-S-triazine MW = 219, trimer, EQ= 73
Aldehyde % Reaction
Product Activity % Active EQ Ratio
MeAm/CH2O 37 27 31 115
MeAm/CH2O 50 31 31 100
NH3/CH2O 50 36 29 81 *
MEA/CH2O 37 49 73 149
MEA/CH2O 50 57 73 128
MEA/CH2O 93 72 73 101
CH3CH2/NH3 100 69 43 62
MEA/GLY (1:1) 40 34 50.5 148.5
MEA/GLY (2:1) 40 71.5 72 101
EDA/CH2O (2:1) 37 48 42 87.5
EDA/CH2O (2:1) 50 57 42 74
#4 and #8 compare, meaning, versus a standard MEA triazine that is 1:1 MEA to formalin.
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Samples of solids extracted from oils can be subjected to magnet to see if associated Fe will separate. Apply
the magnet direct to the crude oil.
A desalting process offers the advantage of using NaOH or KOH with the washing action.
Also the proper surfactant can be used.
Possibly an oil dispersible aldehyde can react with the caustics, lithium, sodium, or potassium to form the
sugars or carbohydrates insitu.
An oxidizer may be included in a wash step and convert mercaptans to dialkyl disulfides. Drawback is dialkyl
sulfides will not remove by this method. US patent 3,449,239.
A relatively standard method is to dissolve sulfur with strongly alkaline Na2S to form Na2S2. The sulfur exists
in chains terminating with negative charges. Acidification of such a solution yields a mixture of hydrogen
polysulfides (sulfuranes) and chain compounds that will decompose to sulfur and hydrogen sulfide.
Dialkyl disulfides (C4 to 22 carbons) [Merox are normal] with amine (4 to 12 carbons) additive as
Diethylamine or N-alkyl-1, 3-propane diamine. US patent 4,239,630.
Sulfur reacted disulfide. 15.5 lbs. sulfur per barrel solvent @ 75F. US patent 3,531,160.
NMP and M-Pyrol will reduce films and disrupt crystal liquid interface.
Sulfur is soluble in M-Pyrol. H2S is soluble in M-Pyrol @ 32 volumes.
Maltose is a stabilizer for polysulfides.
Sodium Borohydride reacts with disulfides; will hydrogenate double bonds or nitriles.
Alkanolamines are unable to absorb dialkyl sulfides, since the lack of an acidic proton. Alkanolamines
are very inefficient in absorbing thiols (mercaptans)
Diethylene glycol and triethylene glycol-to remove sulfur compounds, oxygenates, and C4-C6 olefins.
US patent 5,689,033.
Amine Ethoxylates. EO-fatty amine. Improves contact with H 2S, COS, RSH, RS-SR, reactive sulfur,
and other organic sulfides.
Scavenges H2S and sulfur. Operates by insertion into the double bond (olefinic).
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Stabilized CLO2.
1. Make a solution of 80% sodium chlorite of 31.25% to equal 25% solution.
Surfactants to assist these: alkyl, Hydroxyalkyl, quaternary ammonium, polyether, phenol, alkyl phenol,
ethoxylated phenol, amino compounds, carboxylic acids and their salts, and sulfonic acid salts. See US
patent 6,531,103.
Possibly Erythorbic acid in ammonium bisulfite to inhibit oxidation and to chelate the Fe.
Iron sulfide clusters in polar solvents are [4Fe-4S], [3Fe-4S], and [4Fe-2S], in nonpolar are [8Fe-7S].
Glyoxal: dimer aldehyde, typical 40% solution in water. Used by Clariant and Servo.
See US patent 4,680,127.
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Reactive groups:
Alpha olefin epoxides (glycidols), varying chain lengths, including epichlorohydrin. Ethylene imines.
Buffered Sodium Nitrite: Sodium Nitrite has been used in Exxon/NL Sulfa check. Normally used in towers.
Now finds use as for continuous injection. See US patent 4,515,759.
Carbon Disulfide:
Best is Cocodimethyl like DNP-08-00-8080. Also is Soya dimethyl like DNP-09-00- PS9.
In this procedure, surface active substances are used as emulsion breakers and to facilitate the transfer of
sulfur from the organic phase into the aqueous phase. German patent 2,707,057.
Do not use benzene, toluene, xylene, kerosene, or diesel oil.
Dimethyl sulfoxide. DMSO.
Thiourea.
Borated Thiourea, amine salt.
Due to strange nature or density of solids and variable composition, the use of ether amine tetraphosphonic
acid is recommended to polarize the iron and break the bonded sulfur. The acid for is DNP-06-00- 68461,
sodium salt, pH of 4 is 68441, and ammonium salt, pH of 7 is 68561.
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LOWEST MOLECULES
REACTION MECHANISM
Ideal structure:
or RCHO
R N = CH2 - H2O
SCHIFF BASE / IMINE
C (S C) x (C S) x
CSCSC
linear polysulfides
DNP-02-00-2033 CH3NHCH2OH/[CH3NCH2]3
DNP-02-00-2110 [ R N CH2 ] 3
Dew point
Gas composition
Production, gas rate
Condensate
Triazine:
The conversion from the semi-stable methylene forms or Schiff base or imine to a Triazine can
occur or does when admixed with water..
Does methanol addition slow this?
It slows any transition.
FORMADELHYDE
Very reactive
Reacts with alkali controlled to alkali formates (salts) generate methanol by-product.
SIMPLY
COLORLESS IS EXCELLENT
ORANGE IS GOOD
RED IS FAIR
PURPLE IS POOR
As color increases, the consumption and the reaction time increase. Product is
DNP
Product# Nominal Activity Molecular
REACTIVE COMPARISON
#/Product per
Product # Ratio #/H2S
2022 1:01 4.13
2:01 8.26
2411 1:01 5.00
2:01 10.00
2033 1:01 3.00
2:01 6.00
3:01 9.00
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Below the ratio of chemical used in ppm ratio of volume to mole ppm H 2S is listed. The factor is
the number required to fit the equation for direct calculation.
Ratio
Chemical (0.01)
Per ppm
gals/dayH2S scavenger =
factor x 0.01 x MMscfgas x ppmH2S