Product Brief. - Hydrocarbons alkanes, alkenes, alkynes, dienes including natural gas, refinery gas, liquified petroleum gas

Transcription

1 Agilent Porous Polymer PLOT Columns: New Products, Expanded Uses, Prices Cut in Half! Product Brief Need improved resolution of small volatile compounds? Didn't try a PLOT column due to high price, short lifetime, particle spikes? Here's your answer.. Until recently, porous polymer PLOT columns were typically used for samples containing small polar volatiles and hydrocarbons. Problems with chemical and physical stability, reproducibility, and high bleed/long conditioning times, restricted their use. However, Agilent Technologies developed BONDED porous polymer columns several years ago, overcoming these limitations. Consequently, these columns can be used for many applications not regularly done with PLOT columns. To continue to expand the application base for these columns, they are now available at a 0-0% decreased price. In early 000, the bonded HP-PLOT U was added to the Agilent line of porous polymer PLOT columns, joining the very popular, bonded, HP- PLOT Q. Both HP-PLOT U and HP-PLOT Q columns can be used for a variety of optimized applications including the analysis of: - A broad range of polar compounds: solvents, alcohols, ketones, aldehydes, ethers, acids, amines, halogenated hydrocarbons - CO, methane, air/co - Hydrocarbons alkanes, alkenes, alkynes, dienes including natural gas, refinery gas, liquified petroleum gas Both PLOT U and PLOT Q columns use the same proprietary bonding process. The bonding process used for Agilent porous polymer PLOT columns virtually eliminates particle emission, allowing these columns to be used for valved, on-line and MS applications. Both also provide: ) outstanding reproducibility, chemical inertness and lifetime, even in the presence of samples containing large amounts of water and alcohol, ) ability to quantitate water and alcohols, ) very low bleed/short conditioning times, and ) rinsability with solvents. Table. Properties of HP-PLOT Q and PLOT U Columns HP-PLOT Q HP-PLOT U Stationary Bonded, polystyrene divinylbenzene Bonded, divinylbenzene/ethylene glycol phase dimethacrylate Temperature limit To 00 C To 90 C Table compares properties of HP-PLOT Q and HP-PLOT U. Stability for Valved, On-Line or MS Analysis The proprietary process used by Agilent to bind polymeric particles to the Agilent PLOT Q and U column wall results in excellent mechanical stability making use of a particle trap unnecessary. A customer reported that "even without a particle trap, we observed absence of spiking. This demonstrated that the HP- PLOT Q immobilization process is superior to commercially available DVB technologies. The lack of spiking was observed even Relative polarity Lower (RI ethyl acetate ) Higher (RI ethyl acetate 0) Hydrocarbon Can elute up to C. Resolution of all Can elute up to C. Resolution of separation C-C isomers. In general, better resolution of all C-C isomers except propylene hydrocarbon isomers than PLOT U. and propane. C elution order: C elution order: ethylene/acetylene/ethane ethylene/ethane/acetylene Natural Gas Baseline resolution of air/co /methane Baseline resolution of air/co /methane even at 0 C at 0 C. Better resolution of CO / methane than Q (CO not effected by methane overload). Water gives excellent, symmetric peak. Polar compounds More retention/different and More retention/different and often improved selectivity often improved selectivity for small for small polars versus polars versus WAXES and siloxanes. WAXES and siloxanes More retention for polars versus Q. Better peak shape for very polar compounds like water and methanol versus Q.

2 with pressure swings as high as -0 psig/min making the column suitable for valved applications, in an on-line environment, and for MS applications". In fact, every Agilent porous polymer PLOT column undergoes multiple pressure tests during manufacturing. Outstanding Chemical Inertness and Reproducibility Until now, the analysis of samples containing water and alcohol has been problematic when using PLOT columns. This was due to the loss of reproducibility and column lifetimes associated with moisture and alcohol induced hydrolysis, active site formation, and peak tailing. Agilent's bonded porous PLOT columns exhibit excellent stability over hundreds of injections of samples containing large amounts of alcohol or water, for unmatched reproducibility and column lifetime. This is demonstrated in the analysis of alcohols (over 00 injections shown, Figure ). These samples were injected using headspace (0 C) onto an HP-PLOT Q column with an initial temperature of 0 C to recondense the sample then ramped to 0 C. These conditions were selected to thoroughly test PLOT Q s inertness to alcohols. The HP-PLOT Table. 0 Sequential runs of alcohols on HP-PLOT Q Q column did not show any sign of peak shape deterioration after 00 injections. Other commercially available DVB (divinylbenzene-based) columns are reported to show degradation after 0-0 injections. Table provides additional proof of Agilent's porous polymer PLOT columns stability and reproducibility with samples containing alcohol and water. Retention time and area ratios are shown for a ul injection of an aqueous sample with 00 ppm of alcohols injected on-column for 0 sequential runs. The ability to quantitate water and alcohols is also shown in Figures and. Figure demonstrates the analysis of HPLC-grade acetone on HP-PLOT U. Analysis of acetic acid on HP-PLOT U is shown in Figure. Note the sharp peaks generated by various polar impurities, particularly the symmetric peaks of low-level water and methanol. The synthesis and binding technology used to manufacture Agilent's Figure. Consecutive runs for up to 00 injections of alcohol on HP-PLOT Q Column Retention Time (min) Average RSD% Area Ratio Average RSD% Methanol.9 0. MeOH/EtOH 0.. Ethanol IPA/EtOH..0 IPA Peak Width (IPA) Figure : Analysis of Acetone on HP-PLOT U Column Air Water Methanol Acetone 0 min Column: HP-PLOT U column 0. mm x 0 m Oven: 0ºC ( min) 0ºC/min to 90ºC ( min) Inlet: 0ºC Split ratio 0: Detector: TCD Sample: 0 µl Acetone, HPLC grade (typically 99.9%) Figure : Analysis of Acetic Acid on HP-PLOT U Column Water Air Methanol Formic Acid Acetic Acid 0 9 min Column: 0. mm x 0 m Oven: ºC ( min) 0ºC/min to0ºc ( min) Inlet: 0ºC Split ratio 0: Detector: TCD Sample: µl Acetic Acid, 99.9% (Part no. 909P-Q0) Oven: 0 C ( min), to 0 C at C/min Carrier: Helium, psig Concentration: 00 ppm (v/v) 0 0 min. Methanol. Ethanol. Propanol. -Butanol. -Methyl--Propanol. -Pentanol. -Methyl--Pentanol. -Ethyl--Butanol porous polymer PLOT columns results in very low bleed and reduced conditioning times. Figure shows four consecutive thermal conditioning cycles. A customer reported that "after one hour of conditioning, this column could be used for analytical work. This was three times better than commercially available DVB technology". Applications Volatile polar compounds analysis: Because of the enhanced mechanical stability and resistance to

3 Figure : Bleed profile of HP-PLOT Q Column, 0. mm x 0 m x 0 µm Oven: 0 C ( min), to 0 C at C/min Carrier: Helium, psig 0 pa First Cycle Second Cycle Third Cycle Fourth Cycle 0 pa 0 0 min Figure : Volatile Solvents on HP-PLOT Q Column. Ethanol. Pentane. Acetonitrile. Ethyl Acetate.00. Acetone. Hexane.0. Dichloromethane 9. Benzene. Diethylether.0 Methanol Time (min) Column: 0. mm x 0 m HP-PLOT Q Oven: 0ºC Carrier: Hydrogen 9 ml/min Injection: 0ºC Split mode (:) 0ºC Sample: µl 0.-0.% solvents in Methanol water and alcohols that may be present, bonded porous PLOT columns are being used for a variety of new applications, like analysis of small volatile compounds. Porous polymer PLOT columns have been demonstrated to provide more retention and different and often greater selectivity (i.e. greater retention time differences) versus Figure : Industrial Solvents on HP-WAX Column, 9 0 WAX-based and siloxane-based (i.e. "-type") columns for analysis of relatively small, low-boiling compounds (i.e. C-C derivatives). Figures and compare selectivity on an HP-PLOT Q and HP-WAX column. Note the close separation of methylene chloride (dichloromethane), benzene and ethanol on the HP-WAX column versus the wide separation of. Pentane. Methyl Formate. Acetone. Ethyl Acetate. Methyl Ethyl Ketone. Methanol. -Methyl--Propanol. Methylene Chloride 9. Benzene 0 Time (min) Column: HP-WAX, 0 m x 0. mm x 0. µm (Part no. 909X-) Oven: C (. min) 0 C/min to C Carrier: Hydrogen, 0 cm/sec Injection: Split (00:), 0. µl 00 C 0. Ethanol. -Butanol. Toluene. n-propanol. Ethyl Benzene. p-xylene. m-xylene. -Butanol. o-xylene these compounds on HP-PLOT Q. Also note that the HP-PLOT Q separation occurs at 0 C versus C for the HP-WAX, permitting analysis at starting temperatures that don't require long cool down times or cryogenics. HP-PLOT U is more polar than HP- PLOT Q, providing even greater retention and selectivity for certain polar solvents. Figures and compare selectivity for HP-PLOT Q and HP- PLOT U. Compare the retention times for acetone and ethyl acetate. Consequently, BONDED porous polymer PLOT columns should be tried when: ) resolution of small polar compounds is not satisfactory, ) higher starting temperatures are desired. Hydrocarbons: In general, HP-PLOT Q will provide better resolution of hydrocarbon isomers than HP-PLOT U. Figure shows the resolution of C-C isomers, including all C-C isomers on HP-PLOT Q. Since HP- PLOT U is a more polar phase than HP-PLOT Q, some unsaturated hydrocarbons will elute after saturated hydrocarbons. Note that acetylene elutes after ethane on HP-PLOT U. (Figure 9).

4 Figure : Volatile Solvents on HP-PLOT U Column Figure : Hydrocarbons C-C using an HP-PLOT Q Column Methanol Ethanol Pentane Column: HP-PLOT U 0. mm x 0 m x 0 µm Oven: 0ºC Inlet: 0ºC, Split ratio 0: 00ºC Sample: µl, 0.% range solvents C, 0. mm x 0 m Oven: 0 C ( min),. C/min to 0 C Carrier: H, 0 C Inlet: 0 C Split ratio :, 0 C Sample: HC, µl (C-0%, C to C-% to %) Ether Acetone Hexane Ethyl Acetate Cs Cs Cyclopropane Cs Isobutene n-butane Cs 0 9 min min Natural Gas: Both HP-PLOT Q and U provide baseline resolution of air/co, CO and methane, H O and H S, and various hydrocarbon isomers. For shortest analysis time, choose HP-PLOT Q, which can provide this resolution starting at 0 C. (Figure 0). Competitive "Q" columns typically require starting at 0 C to achieve this resolution. (See Table ). Starting at 0 C versus starting at 0 C results in 0% savings in GC cycle time. For maximum resolution of CO and methane, choose HP-PLOT U. (See Figure ). Figure 9: Hydrocarbon C to Cs on HP-PLOT U Column 0 Ethylene Ethane Acetylene Cyclopropane Propadiene nc + cis-c= Propylene 0 min Cs I-C Column: HP-PLOT U 0. mm x 0 m x 0 µm Oven: 0ºC ( min), 0ºC/min to 0ºC Inlet: 0ºC, Split ratio 0: 00ºC Sample: µl, (% level hydrocarbons) I-C= t-c= Cs Figure 0: Baseline Resolution of Air/CO, CO, and Methane in a Natural Gas Sample on HP-PLOT Q Column Table. Comparative Analyses: Resolution of PLOT Q, Brand X, and Brand Y columns Methane CO Resolution HP-PLOT Q Brand X Brand Y Air/CO R (Air/CO, Methane, 0 C)... Ethane H O R (Air/CO, Methane, 0 C)..0. R (CO, Methane, 0 C).. 0. R (CO, Methane, 0 C)... i-c/n-c Column size: 0. mm x 0 m x 0 µm. Sample size: 0. cc. H S C neo-c i-c/n-c C C 0 min, 0. mm x 0 m (Agilent Part no. 909P-Q0) Oven: 0ºC ( min), 0ºC/min to 0ºC ( min) Carrier: Helium,. 0ºC Detector: TCD 0ºC Injection: 0º C Split mode (:) Sample: 0. cc Natural Gas sample, Methane, 0% +

5 Figure : Natural Gas Sample on HP-PLOT U Column Figure : Separation of Refinery Gas Sample on HP-PLOT Q Column Air 0 C CO C Column: 0. mm x 0 m x 0 µm Oven: 0ºC () 0ºC/min to 90ºC min Sample: 0. cc Natural Gas; Methane 0+% 00 sec Refinery Gas: In GC/TCD analysis of refinery gas (Figure ), HP-PLOT Q columns show good separation of analytes even with a 0. ml sample size, and COS is well separated from propylene. (00 ppb COS has been reported to be resolved from 99% propylene using ml gas phase injection, SCD). An example of Olefin separation on HP-PLOT Q is shown in Figure. Chlorinated Hydrocarbons are used as catalyst moderators in industrial reactors, and these hydrocarbons can be degraded by commercial PLOT columns. In contrast, HP-PLOT Q columns exhibit excellent peak shape for chlorinated hydrocarbons, with no evidence of degradation. (Figure ) min. Air/CO. C. CO. Ethylene. C. H S. COS. H O 9. Propylene 0. C. MeOH. i-c. t-c. n-c,. cis-c. i-c. n-c Figure : Chlorinated Hydrocarbons on HP-PLOT Q Column min, 0. mm x 0 m Oven: 0 C (min), 0 C/min to 00 C (min) Carrier: Helium p=9.0 0 C Inlet: 0 C Split mode 0. cc valve Split flow: 00 ml/min Detector: TCD 0 C Sample: Refinery Gas and others. Chloromethane. Vinyl chloride. Chloroethane.,-Oxybis -propene C H 0 O Oven: 0 C ( min), to 0 C at C/min Carrier: Helium, psig concentration: 00 ppm Figure : Olefins to C on HP-PLOT Q Column. Ethylene. Propylene. -Butene. -Pentene. -Hexene Amines: The proprietary bonding and deactivation process for HP-PLOT U allows the column to be used for analyzing small amines, including ammonia (Figure ) min Oven: 0 C ( min), to 0 C at C/min Carrier: Helium, psig concentration: 00 ppm v/v

6 Ethylene Oxide: HP-PLOT U (Figure ) and HP-PLOT Q (Figure ) have been used for analyzing ethylene oxide., Butadiene and Vinyl chloride are well separated on HP-PLOT U (Figure ). Figure : Volatile Primary Amines on HP-PLOT U Column Counts 0, Ammonia Column: HP-PLOT U 0. mm x 0 m x 0 µm Oven: 0ºC ( min), 0ºC/min to 90ºC ( min) Carrier: Hydrogen, ml/min Inlet: 0ºC, Split ratio 0: Detector: TCD 00ºC Sample: µl, Amines in Methanol, -0% 000 Iso Propyl Amine Triethyl Amine Water 000 Air Propylamine 000 Butylamine min Figure : Ethylene Oxide in Water on HP-PLOT U Column Figure : Vinyl Chloride and,-butadiene on HP-PLOT U Column pa Ethylene Oxide Column: HP-PLOT U 0. mm x 0 m x 0 µm Oven: ºC Carrier: Hydrogen,. ml/min Inlet: 0ºC, Split ratio 0: 00ºC Sample: µl, Aqueous solution; % level Ethylene Oxide Vinyl Chloride,-Butadiene Cs 0 min min Figure : Ethylene Oxide Synthetic Standard on HP-PLOT Q Column. Ethylene Oxide. -Chloropropene Oven: 0 C ( min), to 0 C at C/min Carrier: Helium, psig Injection: µl liquid injection, :0 split concentration: 000 ppm Column: HP-PLOT U 0. mm x 0 m x 0 µm Oven: 00ºC ( min) 0ºC/min to 0ºC ( min) Carrier: Hydrogen, ml/min Inlet: 0ºC, Split ratio 0: Detector: TCD 00ºC Sample: 00 µl, 000 ppm VC and blend,-bdn Figure 9: Butadiene and Aromatics on HP-PLOT Q Column., Butadiene. Cyclopentene. Benzene. Toluene min min Oven: 0 C ( min), to 0 C at C/min Carrier: Helium, psig Butadiene concentration: 00 ppm

7 In the analysis if, butadiene and aromatics,, Butadiene exhibits no polymerization (Figure 9). Polymerization is sometimes seen during identical separations with other commercially available DVBbased phases. BETX has also been resolved on PLOT Q (Figure 0). Sulfur Compounds can be well separated from hydrocarbons using HP-PLOT Q and U, including mercaptans, H S, COS and disulfides (Figure and ). COS shows excellent peak symmetry. Note however that DVB columns are not typically used for low-level analysis of sulfur-containing compounds due to adsorption. This is true also of HP-PLOT Q and U. However, detection of COS at 00 ppb has been reported with HP-PLOT Q using ml gas phase direct injection, SCD. Conversly, PLOT U demonstrates improved inertness and lower detection limits (low ppm) for H S. PLOT U and Q will show similar selectivity for H S, COS and mercaptans. Figure 0: BTEX on HP-PLOT Q Column min. Methanol. Benzene. Toluene. Ethyl Benzene. Xylenes Oven: 0 C ( min), to 0 C at C/min Carrier: Helium, psig Figure : Sulphur Compounds in Hexane on HP-PLOT Q Column min. Propyl Mercaptan. Dimethyl Disulfide. Diethyl Disulfide GC System: Agilent 90/FID Oven: 0 C ( min), C/min to 0 C Carrier: 0 psi He head pressure Concentration: 0 ppm Figure : Odor Additives Separation of Mercaptans and Other Sulphur Compound s on HP-PLOT Q Column 0 0 min. Hydrogen Sulfide. Carbonyl Sulfide. Ethanelthiol. Iso-Propyl Mercaptan. n-propyl Mercaptan. n-butyl Mercaptan Column: HP-PLOT Q, 0. mm x 0 m Oven: 0 C ( min), C/min to 0 C (min) Carrier: Hydrogen p=. 0 C Inlet: 0 C Split mode 0. cc injection Split flow: 00 ml/min 0 C Concentrations: H S, COS: < % mercaptans: < 0%

8 HP-PLOT Q and PLOT U Ordering Information Diameter Length Film thickness Part Number Part Number (mm) (M) (um) (0 cm) cage ( cm) cage HP-PLOT U P-UO 909P-UOE P-UO 909P-UOE P-UO 909P-UOE HP-PLOT Q P-UO 909P-UOE P-QO 909P-QOE P-QO 909P-QOE P-QO 909P-QOE P-QO 909P-QOE Ordering information: Copyright 000 Agilent Technologies Printed in USA 0/00 Printed on recycled paper Publication Number 9-9E