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This Bulletin describes the potentiometric determination of hydrogen sulfide, carbonyl sulfide, and mercaptans in gaseous and liquid products of the oil industry (natural gas, liquefied petroleum gas, used absorption solutions, distillate fuels, aviation gasoline, gasoline, kerosene, etc.). The samples are titrated with alcoholic silver nitrate solution using the Ag Titrode.

This Application Bulletin describes the determination of water in non-explosive and non-flammable gaseous samples using the coulometric Karl Fischer method. This method is ideal for very low water contents.

In natural gas production, the removal of contaminants, and in particular acidic gases such as H2S and CO2, is exceptionally important. These acidic gases are removed in the amine wash through chemical treatment with amines or alkanol amines. This application shows a convenient and precise analysis with the separation of various amines and standard cations on a column of the Metrosep C 6 - 250/4.0 type with subsequent direct conductivity detection.

N-methyldiethanolamine and piperazine are used in scrubber solutions, e.g., in the natural gas process. Testing this type of samples by ion chromatography requires a good resolution and the separation of amines from standard cations. The separation is achieved on a Metrosep C 4 - 150/4.0 column applying direct conductivity detection.

Before the liquefaction process of the natural gas, carbonate and hydrogen sulfide need to be removed through a scrubber solution containing piperazine and N-methyl diethanolamine (MDEA). The concentration ratio of the two components is determined by ion chromatography on a Metrosep C 4 - 150/4.0 column applying direct conductivity detection.

Natural liquefied petroleum gas (LPG) is a mixture of hydrocarbon gases (e.g. propane and butane), but it also contains acidic contaminants (e.g. carbon dioxide or hydrogen sulfide). These gases need to be scrubbed from the petroleum gas as they are highly corrosive. This purification step, referred to as «sweetening», is often performed by using alkaline amine solutions. Thereby the amine solution absorbs the acidic gases, while the raw LPG is neutralized. To guarantee that amine residues in the sweetened gas do not influence the gas quality, the amines in the final LPG are determined by scrubbing the gas with acetic acid as described in UOP 936-96. The recent method enables the quantification of the amines dimethylamine (DMA), diethylamine (DEA), dipropylamine (DPA), and dibutylamine (DBA) by separation from standard cations.

Harmful industrial flue gases like H2S and CO2 cause corrosion of pipes and damage the environment. Adding the correct amount of amines in scrubber solutions, e.g. ethanolamines and methylamines, will neutralize these gases («gas sweetening»). Non-suppressed cation analysis with direct conductivity detection is a straightforward and robust technique for the quantification of monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA) via ion chromatography. Thanks to the high capacity of the Metrosep C 6 column, large volumes can be injected without compromising the peak shapes. The analytical technique can be used at laboratory scale but also for process analysis.

This Application Note looks at the determination of fluorine and sulfur in certified liquefied gas using Metrohm Combustion IC. Sequential determinations proceed in parallel to a certain extent: While the absorption solution of a sample that has already been combusted is being analyzed with IC, the combustion of the next sample is already underway.Keyword: pyrohydrolysis

This Note addresses the determination of the fluorine and chlorine content of a liquefied gas sample (LPG, Liquid Petroleum Gas), i.e. halogens in a mixture of propane and butane. Fluorine originates from perfluorobutane and chlorine from methyl chloride. LPG/GSS modules are used to introduce 50 µL of sample into the combustion system. The halogens released during combustion are determined using ion chromatography with intelligent partial loop injection technique following Inline Matrix Elimination.Keyword: pyrohydrolysis

ASTM D7994 - 17 describes the determination of fluorine, chlorine, and sulfur in liquefied petroleum gas (LPG) by oxidative pyrohydrolytic combustion followed by ion chromatography. A synthetic butane sample is analyzed. 50 µL of the sample is injected into the combustion system using the LPG Module. The combustion products are analyzed by IC applying intelligent Partial Loop Injection Technique after Inline Matrix Elimination.

Sulfur species are critical contaminants in ammonia gas. They can cause high-temperature sulfidation of metals, form aggressive complexes with other elements, or react subsequently in processes where the ammonia gas is used. The concentration of such impurities tends to be very low, but they may not exceed critical levels of 0.5 mg/L. Although this level is very close to the system blank of the Combustion IC system, the setup can be used to prove that such critical limits are not exceeded.

Determination of the water content of liquid ammonia according to Karl Fischer after absorption of the water in ethylene glycol.

Determination of glycolic acid, formic acid, acetic acid and carbonic acid in a scrubber solution using ion-exclusion chromatography with conductivity detection after chemical suppression.

Determination of acetate and formate in an amine solution using anion chromatography with conductivity detection after suppression.

Scrubber solutions for scrubbing flue gas often contain amines for absorbing acid gases, e.g., sulfur dioxide (SO2). 1-(2-hydroxyethyl)piperazine and 1,4- Bis(2-hydroxyethyl)piperazine from gas scrubber solutions are separated in the Metrosep Carb 2 - 150/4.0 column and then determined using pulsed amperometric detection.

Carbon capture systems strip carbon dioxide from flue gases. Online analysis of amines and carbon dioxide enhances amine usage efficiency and reduces operational costs.

This Process Application Note deals with the online monitoring of calcium and sulfate in flue gas scrubbing solutions using titration. Other contaminants that can be measured are sulfite, chloride, and chlorine. Low concentrations of heavy metals such as cadmium, zinc, copper, and lead can be measured in the ppb/ppm range with the ADI 2045VA Process Analyzer using voltammetry.

Determination of chloride, bromide, nitrate, sulfite, sulfate, phosphate, oxalate, thiosulfate, and thiocyanate (heat stable salts) in scrubber solutions using anion chromatography with conductivity detection after chemical suppression.

Hydrogen sulfide (H2S) and carbon dioxide (CO2) are disruptive byproducts of natural gas that must be eliminated during conveyance. This is accomplished with the aid of gas scrubbing, during which the gas flow is cleaned with absorbers such as alkanolamines or akylalkanolamines (e.g., methyldiethanolamine, MDEA). Reliable analysis is imperative, given that heat-stable salts often accumulate in the absorber and thus inhibit the absorption capacity for acid gases.The determination of heat-stable salts (SCN–, S2O32–, SO32–, SO42–, etc.) in MDEA solutions takes place on the Metrosep A Supp 5 - 250/4.0 column with conductivity detection following sequential suppression.Key words: amine gas treating, scrubber

Monoethylene glycol is used for dehydration of the natural gas before liquefaction and has to be checked for its purity on routine basis. Inorganic anions and their corresponding acids are corrosive. Therefore, they have to be kept at minimum level. The separation is performed on a microbore Metrosep A Supp 16 - 250/2.0 column and quantified by conductivity detection after sequential suppression.

Determination of arsenic in dust from a waste incineration plant is performed. This is required as the environmental risk depends on the degree of oxidation of the arsenic species. Due to the different pKa of the respective anions, selenite requires non-suppressed conductivity detection, while arsenate is best determined with suppression. The determination of both species is achieved by switching the suppressor in and out, respectively.

In the petrochemical industry, natural gas is processed to remove contaminants and meet product specifications. Process contaminants include acidic gases such as hydrogen sulfide and carbon dioxide, which can corrode costly refinery equipment downstream. Typically, the acidic gases are removed via alkanolamine treatment using monoethanolamine (MEA) or methyldiethanolamine (MDEA). The amine solutions absorb the acidic gases, and then the amine compounds are removed from the natural gas. In addition to the acidic gases, heat stable salts (HSS) that remain in the natural gas are also corrosive to the treatment plants. These are also removed via gas sweetening and need to be determined in the used gas sweetening amine solution. Some typical heat stable salts of interest include acetate (1), formate (2), chloride (3), phosphate (4), sulfate (5), oxalate (6), thiosulfate (7), and thiocyanate (8).

Determination of the alkalinity of gas washing solutions containing alkanolamines by potentiometric titration with sulfuric acid using the combined glass electrode.

Determination of vanadium(IV) and vanadium(V) in Benfield solution using anion chromatography with UV detection.

The Benfield Process is a well known procedure to remove H2S and CO2 from petroleum and industrial gases. Vanadium pentoxide is added as a corrosion inhibitor and is most effective in a certain V(IV)/V(V) ratio. Therefore, speciation and determination of V(IV) and V(V) is important. This speciation is easily achieved on A Metrosep A Supp 5 - 50/4.0 column with EDTA as an eluent and UV/VIS detection at 282 nm.

Polarographic determination of cyanide in gases resulting from the incineration of plastic insulation materials after sample preparation.

Near-Infrared spectroscopy (NIRS) is a widely used analytical technique for quantitative analysis of various products in research and industrial applications. This white paper summarizes the workflow of the development of quantitative methods according to ASTM E1655.

This White Paper explores the critical role of advanced online and inline process analysis in brine chlorine operations, emphasizing their advantages over traditional methods.

Propylene oxide (PO) is a major industrial product used in assorted industrial applications, mainly for the production of polyols (the building blocks for polyurethane plastics). Several production methods exist, with and without co-products. This white paper lays out opportunities to optimize PO production for safer and more efficient processes, higher quality products, and substantial time savings by using online process analysis instead of laboratory measurements.