Analysis by Gas Chromatography Engineered Solutions, Guaranteed Results. WASSON - ECE INSTRUMENTATION
The Challenge Carbon dioxide, used in the production of carbonated soft drinks and other beverages, can be produced from a variety of sources including ammonia plants, fermentation plants, chemical plants, and oil refineries. This variety of production sources results in an array of possible chemical contaants which can be found in carbon dioxide. In addition, companies are now limited by industry stipulations on maximum levels of these impurities. The impurities that must be assessed and controlled include hydrogen, oxygen, nitrogen, oxides of nitrogen, oxygenated hydrocarbons, sulfur compounds, phosphine, cyanide, chlorinated compounds, ammonia, light paraffins, olefins, non-volatile hydrocarbons, benzene, and other aromatic hydrocarbons. Because of the wide variety of compounds that must be analyzed, a gas chromatograph (GC) is an excellent tool for the analysis, with its ability to separate and quantify a large range of compounds. GC 1: FID/FID Analysis ANALYTE Methane Non-methane hydrocarbons C -C paraffins and olefins 1 6 Methanol Oxygenates BTEX GC 1: MSD Analysis ANALYTE Acetaldehyde CONCENTRATION 1 ppm 1 ppm 1 ppm 0.25 ppm mol 0.25 ppm mol 0.25 ppm mol CONCENTRATION 0.2 ppm Chemical Analysis (FID/FID/MSD) Wasson-ECE Instrumentation has a customized solution for the analysis of beverage grade carbon dioxide using two GCs. The first system is configured with dual flame ionization detectors and a mass selective detector (FID/FID/MSD). The power of the MSD is two-fold. First, in the Selected Ion Monitoring (SIM) mode, this detector can measure in the parts-per-billion (ppb) concentration range. Second, because the MSD is programmed to respond only to a known molecular fragmentation pattern, or spectrum, at any given time, it can confirm the presence of each analyte in question rather than relying only on chromatogram retention time. This is very important as different trace impurities have different product impact thresholds. Thus, without the confirmation power of the MSD, it is easy to accidentally confuse the presence of a low impact analyte with that of a higher priority analyte, which would generate a false-positive report. Phosphine 0.3 ppm Benzene 0.02 ppm Toluene 0.02 ppm Ethylbenzene 0.02 ppm m, p, o-xylenes 0.02 ppm WASSON - ECE INSTRUMENTATION Carbon Dioxide Analysis
Chromatograms for the Analysis of Trace Impurities in Beverage Grade Carbon Dioxide by Dual FIDs and MSD 2400000 2200000 2000000 1800000 1600000 1400000 Methanol m-xylene p-xylene o-xylene 0.25 ml gas sample injection of oxygenates and BTEX in carbon dioxide (% levels) by FID1. 1200000 000 800000 600000 Acetaldehyde Toluene 400000 200000 Benzene 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 4200000 4000000 3800000 3600000 Propane 3400000 3200000 3000000 0.2 ml gas sample valve injection of ppm level hydrocarbons in carbon dioxide by FID2. 2800000 2600000 2400000 2200000 2000000 1800000 1600000 1400000 1200000 000 800000 600000 Ethylene Ethane Methane Isobutane Propylene Acetylene n-butane Propadiene t-2-butene 1-Butene Isobutylene c-2-butene 1,3-Butadiene n-pentane Isopentane n-hexane 400000 200000 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 Abundance 40000 38000 36000 34000 32000 30000 28000 26000 24000 Toluene p-xylene m-xylene 1.0 ml gas sample valve inject of a 1.0 ppm standard blended in carbon dioxide by MSD. 22000 20000 18000 16000 14000 Benzene 12000 0 8000 6000 4000 2000 Acetaldehyde Ethylbenzene o-xylene 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00 9.50 10.00 10.50 11.00 11.50 12.00 12.50 13.00 13.50 14.00 14.50 15.00 15.50 Ph. 970.221.9179 www.wasson-ece.com
Chemical Analysis (SCD/PDHID) The second GC is configured with a sulfur chemiluescence detector (SCD) and cryogenic cooling to quantify trace level sulfur compounds in the low part-per-million (ppm) range. A pulsed discharge helium ionization detector (PDHID) is also included on the second system to detect low level permanent gases. GC 2: SCD Analysis ANALYTE Hydrogen sulfide Carbonyl sulfide Sulfur dioxide Ethyl mercaptan Dimethyl mercaptan Carbon disulfide Isopropyl mercaptan Ethyl methyl mercaptan Butyl mercaptan Isobutyl mercaptan Diethyl mercaptan Dimethyl disulfide 2-Methylthiophene 3-methylthiophene Diethyl disulfide Phenyl mercaptan Total sulfur GC 2: PDHID Analysis ANALYTE Oxygen Argon Nitrogen Carbon monoxide Methane CONCENTRATION 0.1 ppm 0.06 ppm CONCENTRATION Sample Phase The carbon dioxide samples can be introduced as a pressurized liquid or in the gas phase. A selection valve is provided to address the appropriate sample input. In the case of pressurized liquid, an internal vaporizer converts the sample to gas phase with fused silica-lined internal components so that the loss of trace sulfur or oxygenated components is avoided. In the case of heavy hydrocarbons/oils analysis, the sample is syringe-injected through a hot inlet and gas injection valve. Non-Volatile Organics Concentrator (NVOC) for Liquid Carbon Dioxide Liquid carbon dioxide may have heavy organic contaants such as ethylene glycol, or pump oil. The NVOC concentrates these analytes into a vial which contains a measured amount of solvent. The heavy organics dissolve in the solvent for syringe injection. The NVOC extracts the heavies from the captured, known volume of carbon dioxide. The matrix is flashed off with heat in a controlled fashion while the heavies remain in liquid phase. WASSON - ECE INSTRUMENTATION Carbon Dioxide Analysis
Chromatograms for the Analysis of Trace Sulfurs in Beverage Grade Carbon Dioxide by SCD 15 μv 25000 Diethyl Disulfide 20000 15000 0 5000 Hydrogen Sulfide Carbonyl Sulfide Sulfur Dioxide Methyl Mercaptan Ethyl Mercaptan Dimethyl Sulfide 2-Propanethiol/Isopropyl Mercaptan 2-Methyl-2-Propanethiol 1-Propanethiol Composite Thiophene/2-Butanethiol Composite Diethyl Sulfide 1-Butanethiol Dimethyl Disulfide Phenyl Mercaptan 3.0 ml gas sampe injection of 20 ppm sulfur standard blend in air, spiked with sulfur dioxide, by SCD. 0 5 10 15 20 15 μv 1800 Hydrogen Sulfide 15 μv 1600 Carbonyl Sulfide 15 μv Methyl Mercaptan 1600 1400 1600 1400 1200 1400 1200 1200 800 800 800 600 600 600 400 400 2.4 2.5 2.6 2.7 2.8 2.9 3 3.1 3.6 3.8 4 4.2 4.4 4.6 9.4 9.6 9.8 10 10.2 Ph. 970.221.9179 www.wasson-ece.com
Chromatograms for the Analysis of Permanent Gases in Beverage Grade Carbon Dioxide by PDHID pa 5000 4000 3000 2000 Hydrogen Argon Oxygen Nitrogen Methane Carbon Monoxide 0.1 ml gas sample injection of permanent gases in carbon dioxide by PDHID. 5.0 ppm Ar 28.0 ppm O 2 5 10 15 20 25 pa Oxygen 5000 Enlargement showing argon and oxygen separation on a PDHID. 4000 LDL* (Ar peak): 11.6 ppb LDL* (O peak): 6.9 ppb 2 * LDL denotes the concentration at which the signal is 2.5 times greater than the background noise signal. 3000 Argon 2000 4.2 4.4 4.6 4.8 5 5.2 5.4 5.6 WASSON - ECE INSTRUMENTATION Carbon Dioxide Analysis
Wasson-ECE Instrumentation Engineered Solutions, Guaranteed Results. Wason-ECE Instrumentation specializes in configuring and modifying new or existing gas chromatographs exclusively from Agilent Technologies to become guaranteed, turn-key analytical systems. Our customers describe their objectives and their samples: analytes, concentration ranges, phases, temperature, throughput, and any special needs. From this dialog we configure a task specific instrument. We add extra ovens, valves, plumbing, flow control, columns, electronics, software, etc., to yield a complete solution. This saves our clients valuable time and delivers instruments that are state-of-the-art and ready for use upon installation. The complete analytical method is developed, tested, and documented utilizing our experience working with numerous companies with similar needs and goals. The resulting chromatograms and reports are inspected by our application chemists and you, to ensure system performance and design quality. Our field engineers then install each system and provide training. After installation, and throughout the life of the chromatograph, our support chemists are ready to help. We can assist with application details, questions, training, calibration, maintenance, and on-site service. Wasson-ECE brings experience and efficiency to your project, giving you confidence in the quality of your results. Ph. 970.221.9179 www.wasson-ece.com
Please contact us for more information. Engineered Solutions, Guaranteed Results. Ph. 970.221.9179 Fx. 970.221.9364 www.wasson-ece.com sales@wasson-ece.com