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IMPURITIES IN CATALYSTS BY ICP-AES

UOP Method 303-87 SCOPE
This method is for determining trace metal elements in fresh, regenerated and spent alumina-, silica- or silica/alumina-based catalysts by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES). Fe, Ni, V, Ca, Mg, Mn, Cr, Sn, Cu, Zn, Ti, Pb, Na, Mo, Co and Si are determined quantitatively on catalysts. Si is not determined when it is a component of the catalyst base. Other elements can be added if required, however, Ba and Hg cannot be determined. In addition, As and P are determined on regenerated or spent alumina-based catalyst. The majority of the specified elements can be determined within the concentration range of 0.005 to 2.0 mass-%. Specific concentration ranges for the elements determined are listed in Table 1. This method is not applicable to noble metals and modifiers on catalysts. Those elements can be determined by UOP Method 873. This method cannot be used for determining impurities in alpha-alumina catalyst.

OUTLINE OF METHOD
The samples are dissolved in sulfuric and hydrochloric acids and then scandium is added to the solution as an internal standard. Hydrofluoric acid is used to remove the silica from silica- or silica/alumina-based catalyst and an appropriate amount of aluminum solution is also added to match the standard composition. The sample solutions are then aspirated into a computer-controlled ICP-AES along with appropriate, matrix-matched standards. Concentrations are determined by comparison of the sample emission ratios to the computer generated standard calibration curves.

APPARATUS
Balance, readability 0.1-mg Beaker, Teflon, 250-mL Catalyst grinding equipment Balls, grinding, 11.1-mm (7/16-inch), tungsten carbide, SPEX Industries, Inc., Cat. No. 8004A, or equivalent
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Container, grinding, 57 64 mm (2-1/4 2-1/2 inches), tungsten carbide, SPEX Industries, Inc., Cat. No. 8004, or equivalent Mixing mill, shaker type, SPEX Industries, Inc., Cat. No. 8000, or equivalent Cylinders, graduated, polypropylene, 10- and 100-mL Flasks, volumetric, polypropylene, 200- and 1000-mL capacity Hot plate, stirring, variable heat to at least 400 C Microliter pipet, 2500-L capacity, RAININ Instrument Co., Cat. No. EDP-2500, or equivalent Pipets, volumetric, transfer, Class A, 5-, 10-, 15-, 20-, 25- and 50-mL Regulator, argon, two-stage, high purity, Matheson, Model 3104-580, or equivalent Regulator, nitrogen, two-stage, high purity, Matheson, Model 3104-580, or equivalent Spectrometer, Inductively Coupled Plasma-Atomic Emission Spectrometer, computer controlled, having sufficient resolving power and dispersion to separate the analytical lines in the 160- to 800-nm region. The computer should be capable of performing background corrections, blank corrections, and weight/volume and dilution corrections. A commercial grating spectrometer with a band pass of 0.018 nm or less in the first order is satisfactory. Tips, disposable, for EDP-2500 microliter pipet, RAININ Instrument Co., Cat. No. RC-2500, or equivalent Watch glass, Teflon, 75-mm diameter

REAGENTS AND MATERIALS

All reagents shall conform to the specifications established by the Committee on Analytical Reagents of the American Chemical Society, when such specifications are available, unless otherwise specified. References to water mean ASTM Type I reagent grade water. Aluminum metal, pellets, 99.9999% purity, Morton Thiokol, Inc., Alfa Products, Cat. No. 00877, or equivalent Aluminum solution, 20,000 g/mL. Weigh 20.00 0.01 g of pure aluminum pellets into a 250-mL Teflon beaker. Add one drop of mercury metal and 100 mL of concentrated, high purity, hydrochloric acid. Cover with a Teflon watch glass and heat on a hot plate to start the reaction. Remove the beaker from the hot plate as the reaction increases, and add water if the reaction becomes too violent. As hydrochloric acid is reacted, add more acid until the aluminum is dissolved. Allow to cool and quantitatively transfer the solution, along with the mercury, to a one-liter volumetric flask, dilute to the mark with water, and mix thoroughly. Argon, 99.995% minimum purity, ICP feed gas Hydrochloric acid, concentrated Hydrochloric acid, concentrated, ultrapure, Sargent-Welch Scientific, Cat. No. SC-12704, or equivalent Hydrofluoric acid, concentrated Hydrogen peroxide, 30% Mercury metal, electronic/instrument grade, 99.9998% purity, Morton Thiokol, Inc., Alfa Products, Cat. No. 00520, or equivalent 303-87

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Nitric acid, concentrated Nitrogen, 99.99% minimum purity, ICP optics purge gas Scandium solution, aqueous, 1000 g/mL, SPEX Industries, Inc., Cat. No. PLSC-2, or equivalent Standard solutions of metals, Fe, Ni, V, Ca, Mg, Mn, Cr, Sn, Cu, Zn, Ti, Pb, Na, Mo, Co, Si, As and P solutions of 1000 g/mL concentrations, SPEX Industries, Inc., Cat. Nos. PLFE-2, PLNI-2, PLV-2, PLCA-2, PLMG-2, PLMN-2, PLCR-2, PLSN-2, PLCU-2, PLZN-2, PLTI-2, PLPB-2, PLNA-2, PLMO-2, PLCO-2, PLSI-2, PLAS-2 and PLP-2, respectively, or equivalent Sulfuric acid, concentrated

PREPARATION AND STANDARDIZATION OF APPARATUS

Preparation of Standards
Prepare standards at approximately the concentrations shown in Table 1 by appropriate dilution of the standard metal solutions, using the high purity hydrochloric acid. Prepare the standards in the same matrix as the samples, see Sample Preparation. Also prepare a blank having the same matrix. Due to the linear response of the ICP, single point standards can be used.

Table 1 Elements Sought, Concentration Ranges Covered and Recommended Standard Concentrations Element Fe Ni V Ca Mg Mn Cr Sn Cu Zn Ti Pb Na Mo Co Si* As P Sc Al _______________ *See Note 1 , nm 238.204 231.604 292.402 393.366 422.673 285.213 257.610 205.552 189.989 324.754 213.856 323.452 220.353 589.592 202.030 238.892 251.611 193.795 213.618 424.683 Concentration Range, mass-% 0.005-2.0 0.005-1.0 0.003-1.0 0.001-0.10 0.100-2.0 0.001-0.50 0.001-0.50 0.005-1.0 0.010-1.0 0.001-0.50 0.005-0.50 0.005-2.0 0.010-1.0 0.005-2.0 0.005-1.0 0.005-2.0 0.005-0.20 0.020-1.0 0.010-1.0 Internal Standard Sample Matrix g/mL Std. 1 100.0 50.0 50.0 5.0 100.0 25.0 25.0 50.0 50.0 25.0 25.0 100.0 50.0 100.0 50.0 100.0 10.0 50.0 2500 50.0 50.0 50.0 2500 Std. 2

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Spectrometric Procedure
Start up the ICP-AES and ignite the plasma according to the manufacturers recommendations. Allow a minimum of 30 minutes warm up after the plasma is ignited before starting the analysis. When recommended by the manufacturer, perform a wavelength calibration prior to the start of the analysis. Aspirate the standards and blank to establish the calibration curves prior to aspiration of the sample.

PROCEDURE
Sample Preparation
The number of steps required to prepare samples for analysis depends on whether silica is a constituent, whether organic compounds or carbon are present and if the catalyst contains platinum group metals. Analyze samples according to the following procedure: 1. Grind the sample in a mixing mill to a consistency of approximately 80 mesh or finer. Weigh, to the nearest 0.1 mg, approximately 1.0 g of sample into a tared 250-mL Teflon beaker. Add 10 mL of water and 10 mL of concentrated sulfuric acid to the beaker. If the sample does not contain silica, proceed to Step 3. 2. If the sample contains silica, slowly add 10 mL of concentrated hydrofluoric acid from a polypropylene graduated cylinder. 3. Swirl to mix the contents of the beaker, and place the uncovered beaker on a 150 C hot plate. Heat until white fumes of sulfuric acid begin to evolve. Remove the beaker from the hot plate and allow it to cool. If the solution is clear and uncolored, proceed to Step 6. 4. A dark-colored solution indicates the presence of organics, carbon or platinum group metals (see Note 2). Add a few drops of concentrated nitric acid and place the beaker on a hot plate until white fumes begin to evolve. Remove the beaker from the hot plate and allow it to cool. If the solution is clear and uncolored, proceed to Step 6. 5. If the solution remains dark-colored after the nitric acid treatment, it can be assumed that reduced platinum group metals are present. Add 10 mL of concentrated hydrochloric acid and 2-3 drops of hydrogen peroxide to the beaker. Cover with a Teflon watch glass and return the beaker to the hot plate. Boil gently until the solution is clear. Remove the beaker from the hot plate and allow to cool. 6. Add approximately 40 mL of water to the beaker, cover with a Teflon watch glass and return it to the hot plate. Boil gently to dissolve any aluminum sulfate crystals. If a white precipitate remains, see Note 3. Quantitatively transfer the contents of the beaker to a 200-mL polypropylene volumetric flask, rinsing the beaker and watch glass several times with water. 7. If the aluminum content of the sample is unknown, determine it by UOP Method 879. When the aluminum content is known, convert it to alumina by multiplying the aluminum concentration by 1.89. Add the appropriate amount of 20,000 g/mL aluminum solution to the volumetric flask (see Table 2). Add 20 mL of concentrated hydrochloric acid and 10 mL of 1000 g/mL scandium solution to the flask and bring to volume with water. Mix the contents of the flask thoroughly.

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Table 2 Aluminum Addition Alumina in Sample, mass-% 0 10 20 30 40 50 60 70 80 90 100 Sample Analysis

Follow the spectromeric procedure as described under PREPARATION AND STANDARDIZATION OF APPARATUS. Following aspiration of the standards and blank, aspirate the samples after entering the appropriate weight per volume in the computer. The computer will calculate the mass-% metal in the original sample and print the result.

20,000 g/mL Aluminum Solution to be added, mL 25 22.5 20 17.5 15 12.5 10 7.5 5 2.5 0

CALCULATIONS
Calculate the mass-% concentration of each element in the original sample, from the uncorrected concentration of each element, using the following equation:

C=
where:

R 104 W

C = concentration of element in original sample, mass-% R = uncorrected concentration of element in diluted sample, g/mL, from instrument readout W = mass of sample used per diluted volume, g/200-mL 104 = conversion factor, mass-ppm to mass-%
The calculations are normally performed by the computer software after the analyst enters the appropriate value for W.

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NOTES
1. The maximum solubility for silicon in the acid matrix used in this method is 60 mass-ppm in solution, or 1.2 mass-% on the catalyst. The upper concentration limit for silicon by this method has been placed at 10 mass-ppm in solution, or 0.2 mass-% on the catalyst. If silicon determination above this level is required, use UOP Method 894. 2. Samples containing more than 10% carbon should be carbon burned before attempting analysis by this method. Analysis of samples with higher carbon levels will lead to erroneous results due to mismatched aluminum levels between the samples and standards. Samples that are carbon burned may lose volatile elements such as arsenic and phosphorus. 3. Barium cannot be determined by this method since barium sulfate is insoluble in the acids used. If barium is present, an insoluble precipitate will form which must be removed by filtering. Mercury cannot be determined because it is used in the preparation of the aluminum addition solution that is added to both samples and standards.

PRECISION
Based on 6 replicate determinations, the estimated standard deviation (esd) was calculated for the metals listed in the following table. Duplicate results by the same operator should not differ by more than the allowable difference shown (95% probability).

Metal Iron Vanadium* Calcium Manganese Tin Copper Zinc Titanium Sodium Silicon Phosphorus* ________________ *Near the detection limit

Level, mass-% 0.48 0.003 0.005 0.0037 0.12 0.006 0.026 0.066 0.03 0.03 0.02

esd, mass-% 0.011 0.0012 0.0012 0.0002 0.0046 0.0002 0.0021 0.0008 0.0049 0.0064 0.0049

Allowable Difference, mass-% 0.04 0.004 0.004 0.001 0.02 0.001 0.008 0.003 0.018 0.023 0.018

It is expected that all elements will have similar precision above 0.03 mass-%. Precision for levels below 0.03 mass-% can vary depending on the detection limit for the specific element.

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TIME FOR ANALYSIS

The elapsed time for one analysis is 4 hours. The labor requirement for one analysis is 2 hours, or in groups of 5 or more samples, 1.75 hours.

REFERENCES
UOP Method 873 UOP Method 879 UOP Method 894

SUGGESTED SUPPLIERS
Matheson, P.O. Box 96, Joliet, IL 60434 Morton Thiokol, Inc., Alfa Products, 152 Andover St., Danvers, MA 01923 RAININ Instrument Co., Mack Road, Woburn, MA 01801 Sargent-Welch Scientific Co., 7300 N. Linder Ave., Skokie, IL 60077 SPEX Industries, Inc., P.O. Box 798, Metuchen, NJ 08840

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