# XCs-120

- CESIUM CATALYST

SULFURICACID CATALYST UPPERANDLOWER BEDAPPLICATIONS Monsanto Enviro-Chem Systems, Inc. offers a ribbed ring shaped, cesium-promoted sulfuric acid catalyst specifically designed for pressure drop reduction in all beds ofthe converter. This productis designated: 

## "XCs-120". This product is designated XCs-120 (for use in all beds where appropriate); the "X" representing the eXtended surface area of these rings. Installation of the "XCs-120" catalyst will result in a pressure drop decrease in excess of 20 % 

### to Cs-ll0 rings and approximately a 10 % 

### reduction in pressure drop relative to Cs-120 rings. 

## IIMonsanto's Cesium catalysthas allowed us

# to keep ouremission levels wellbelow 100ppm."JI SCX-2000

## I XCs-120 Specifications: Nominal Ring Diameter "Pointto Point"

# =0.48 in (11.9 mm) Average Length

# =0.38

- 0.55 in. (9.5

- 14.0 mm) Avg. Density

# =1.1

- 1.3 lb/liter (0.50

- 0.60kg/liter) Contact yourMonsanto Enviro-Chem sales representative orthe local Monsanto EnviroChern offices for more technical details and for ordering information. 

# M€CS A Monsanto Company ASIA EUROPE SOUTH AMERICA 14522 South OuterForty Road Hong Kong. China Brussels. Belgium Sao Paulo. Brazil St. Louis. Missouri 63017 Phone: 852-2832-8829 Phone: 32-2-658-2620 Phone: 55-11-5503-2600 Phone: 314275-5700 Fax: 852-2907-0033 Fax: 32-2-658-2621 Fax: 55-11-5508-6799 Fax: 314 275-5701 hk.enviroch@monsanto.com enviroeur@monsanlo.com brazil.enviroch@monsanto
.com enviroch @monsanto.com

## . .**': ~~**  

### ..

## :**~** ,

. 

## .,**~** 

# Catal stfor Sulfuric Acid".::..:?oo, 

# Cesium-Promoted Ribbed Rings "MECS's Cesium Catalyst has allowed us 

# to keep our emissions

well below 100

## partspermillion':

Our Catalyst and Process specialists will help you value engineer the best MECS Catalyst products to optimize throughput, energy efficiency and reliability for all your converter passes. Both SCX-2000 and XCs-120 provide benefits from the unique ribbed hollow rings. This design feature results in lower pressure drop characteristics for your converter. The extremely active Cesium component generates the highest conversion rates possible. 

# scx- XCs Applications
SCX-2000: Passes 4. or 5 immediately after IPA
XCs-120: All Converter Passes 

# M€CS www.mecsglobal.com North America 14522 South Outer Forty Road Chesterfield. Missouri 63017 USA Tel: 314-275-5700 Fax: 314-275-5701 E-mail: northamerica@goldwing.mecsglobal.com Hong Kong. China MECS Far East Umited Unit 2802 281F, 88 Hing Fat St. Causeway Bay Hong Kong, CHINA Tel: 852-2832-8829 Fax: 852-2907-0033 E-mail: hongkong@goldwing.mecsglobal.com Brussels. Belgium MECS Europe/Africa BVSA Rozendal, gebouw B Terhulpsesteenweg 6 B-1560 Hoeilaart BELGIUM Tel: 32-2-658-2620**Fax:32-2~2621** E-mail: europe-africa@goldwlng.mecsglobal.com Sao Paulo. Brazil MECS Quimica Ind. Com. Ltda Rua Schilling, 413 - Sala 405 Sao Paulo 05302-001 BRAZIL Tel: 55-11-3644-7788 Fax: 55-11-36449065 brazil@goldwing.mecsglobal.com to MECS

. Inc

. 2( i7

# M€CS www.mecsglobal.com 

# Cesium-Promoted Ribbed Rings MECS offers Cesium-Promoted andSUPER Cesium Catalyst in a ribbed ring design for very high conversion rates and lowpressure drop.

XLP-ll0 Ribbed Rings XLP-220 Ribbed Rings SCX-2000 Ribbed Rings XCs-120 Ribbed Rings 

# • LP-110 Rings T-210 Pellen T-ll Pellets



### Super Cesium 

### byMEC5 has the industry's highest conversion rate. The SCX-2000 Super Cesium Catalyst by MECS is designed for lower pass converter applications
- with or without Interpass Absorption and is ideal for reducing 802 emissions in volume-limited beds. In addition, you can benefit from a 20% increase in activity relative to standard Cesium-Promoted Catalysts under IPA conditions.

The XCs-120 Cesium-Promoted MECS Catalyst is specially designed for lower pressure drop in all beds of the converter. Installation of the XCs-120 MECS Catalyst will result in apressure drop decrease of up to 20% compared to ring type catalysts and offers faster plant start ups due to lower ignition temperatures. Contact your MEC8 sales engineer for recommendations and to tailor the best MECS catalyst combination 

# Cesium ProductHighlights Super Cesium SCX-20aO • Higherplantproduction ratesfrom

Cesium-enhancedsupportformulation. •Lower ignition temperatures resultin

faster start ups andhigherconversion. • Loweracidplantstack emissions
. 

### Cesium-PromotedXCs-720 •Designedfor lowerpressure drop in all

beds of

### the converter. • Extendedsurface area andimproved

dustmanagement. •Ignition temperature atapproximately

360degrees C/680degrees F 

### SCX-2000/XCs-720 Nominal Dimensions Point to PointDiameter

## = Approx. 72 mm 

### Inside Diameter =

### Approx. 4.0mm Average length 

### = Approx. 73.0mm 

### Applications SCX-2000: Passes 4, 

### or5, 

### immediately afterIPA. XCs-720:All ConverterPasses 

# CATALYST
for your particular converter design and acid plant operating requirements.

# M€CS.JNC.

14522 South Outer Forty Rd. Chesterfield, MO 63017 314-275-5700 314-275-5701 FAX www.mecsglobal.com


### SULFURIC ACID CATALYST TECHNOLOGY



### - Presented by: Atis Vavere
- Catalyst Technology Manager, MECS, Inc.
INTRODUCTION Vanadium-based sulfuric acid catalyst has been utilized to oxidize S02 to S03 since the early 1900's. This versatile product displaced the expensive and easily-poisoned platinum-based

.catalyst in nearly all applications by the 1930's. Monsanto Company has been manufacturing the vanadium-based catalyst since 1925 and is currently one of the leading suppliers of this product in a variety of forms. Currently, Monsanto Enviro-Chem has world-wide customer/technical support for the catalyst as well as a dedicated catalyst manufacturing plant in Martinez, California. Enviro-Chem also has a strong technical and research and development program which supports the existing catalyst and creates new and improved products and services. This paper will describe some of the technical details of vanadium-based sulfuric acid catalysts and provide e;{amples ofsome ofthe applications ofthis technology in both products and services. CATALYST COMPOSITION Sulfuric acid catalyst is composed of potassium (K) and vanadium (V) salts supported on a silica (Si02 ) carrier. The silica support is diatomaceous earth (DE) which consists of the skeletons of diatoms (microscopic sea creatures); the DE provides the ideal properties for the sulfuric acid catalyst at an acceptable cost. The potassium/vanadium salt mixture actually liquefies under reaction conditions (> 660°F (350°C)) and forms a molten salt catalyst. The salt formation reaction can be shown as follows: 1) + 

## ---------> KwVxSyOz (molten salt compound(s)) The actual composition of the critical molten salt is still under investigation in a number of laboratories around the world; hence, the generic labeling ofthe salt compound with w, x, y, and z values.
REACTION MECHANISM The S02 and 02 udissolve" into this molten salt, react to form the S03 which eventually escapes from the melt. The mechanism for the oxidation reaction is not well understood. A simplified version ofa possible mechanism is shown below:

# M€CS, INC. 14522 South OuterForty Rd. Chesterfield, MO 63017 314-275-5700 314-275-5701 FAX www.mecsglobal.com 

### 2) S02 

### + 2 V

## s+ 

### + 0 2

- ------> 

### S03 

### + 2 

### V4+ <-----­ 

### 1/202 + 2 V4+ 

# --------> 0 2

- 

### + 2 V

### s+ 

### This mechanism requires the reduction/oxidation cycle between V

### s+ 

### and V4+; 

### some recent mechanisms predict that the vanadium does not reduce below the + 

### 5 state. The crucial "chemicals" which are required to generate the oxidation reaction are S02, O2, 

### and VS+. 

### The lack of any ofthese materials will reduce the reaction rate and lower the conversion efficiency ofthe catalyst. FACTORS AFFECTING CATALYST LIFE AND QUALITY 

### There are a number offactors which can impact the life of the sulfuric acid catalyst and also the initial quality of the material. The catalyst life can be shortened through the following mechanisms: 

### Vanadium Loss: dust accumulation in the bed; iron oxide corrosion products; chlorides in the gas stream; and acid/moisture contact with catalyst. 

### Moisture Contact: leaching ofthe active salts; decreased catalyst hardness. 

### Poison: arsenic (oxide coating ofthe catalyst). 

### Carrier Degradation: fluorine attack (forms volatile SiF4); 

### thermal cycling. The initial quality ofthe sulfuric acid catalyst can be affected by the following: 

### Salt Chemistry: vanadium content (6-8 % 

### V20S 

### =optimum); 

### KJV ratio (- 

### 3/1). Carrier Support: optimal surface area (1-2 

### m2 

### /gm); pore size distribution; purity 

### Pellet Characteristics: external surface area; porosity; hardness. 

### Manufacturing Process: mixing, extrusion, drying, calcining

# = all critical quality control is crucial to optimizing catalyst reactivity.
All ofthese factors can impact the catalyst performance in the sulfuric acid converter. The following features will insure that the highest quality sulfuric acid catalyst is provided to the customer:

2

# M€CS, INC. 14522 South OuterForty Rd. Chesterfield, MO 63017 314-275-5700 314-275-5701 FAX www.mecsglobal.com 

### Total Quality Manufacturing: Statistical process control is critical to properly produce the sulfuric acid catalyst. Data on the raw materials, manufacturing process variable, intermediate and final product quality parameters must all be monitored to insure a consistent and prerTlium quality final catalyst product. Specially Designed Carrier: The composition ofthe silica support (carrier) is critical to the production of a thermally stable catalyst. The presence of crystalline silica (cristobalite) in the carrier produces a stable, non-changing support of the molten salt. Ifthe DE does not initially contain cristobalite, the crystalline silica will slowly form under reactor conditions and destabilize the catalyst structure. This destabilization will lead to breakdown ofthe rings/pellets and high screening losses and/or pressure drop buildup. Enviro-Chem's sulfuric acid catalysts contain the stabilizing cristobalite as they are shipped from the plant and hence are stable to the thermal changes occurring in the sulfuric reactor. Fully Sulfated Catalyst: Sulfuric acid catalyst can be supplied in a partially or fully sulfated (approx. 15 % 

### free S03). In the former state, the catalyst must pick up the additional S03 from the converter which generates a temperature rise. Partially sulfated catalyst is also very moisture sensitive relative to fully sulfated material. Enviro-Chem fully sulfates their catalyst products in the manufacturing plant, insuring optimum conversion immediately upon startup and less moisture sensitivity. Partially sulfated catalysts generally have a green appearance, indicating the presence of V4+. 

### The fully sulfated "gold" catalyst contains a very high level ofthe desired V5+

### species.
TECHNICAL SERVICE Most catalyst suppliers offer various technical services to support their customers. These services include sample analysis and some computer simulation studies. Enviro-Chem offers these services as well as complete sulfuric acid process support. Also, over the last 6 years, Enviro-Chem has offered the Portable Gas Analysis System (PeGASyS) service for an extensive evaluation of the customer's plant operations. This gas chromatography-based system allows for evaluating the S02 and O2levels in any accessible gas stream. Uniquely designed gas sampling techniques provide the analytical sample free of S03 which would damage the equipment. Utilizing this analytical data along with the computer simulation program (S020PT), the operation of the plant can be fully characterized with the results appearing in a detailed report supplied to the customer. There are many examples where the PeGASyS service has solved conversion problems, identified heat exchanger leaks, and increased the productivity of sulfuric acid plants.

3

# M€CS, INC. 14522 South Outer Forty Rd. Chesterfield, MO 63017 314-275-5700 314-275-5701 FAX www.mecsglobal.com 

### CESIUM-PROMOTED CATALYST 

### The cesium-promoted sulfuric acid catalyst has become an important product in the ever changing acid industry. This catalyst was created to allow for low temperature operation in the first and lower beds of the converter, resulting in greater conversion and lower bed outlet temperatures. The cesium catalyst consists of the standard vc:madium-based formulation in which some of the potassium (K) has been replaced with an equi-molar amount of cesium (Cs). The cesium helps to stabilize the vanadium in the molten salt and prevents the precipitation of the vanadium below 770°F (410°C) as is observed for the conventional sulfuric catalysts. This precipitation results in catalyst deactivation and very low activity at low inlet temperatures. The conversion generated by the stabilized Cs catalyst is high for reasonable catalyst loadings down to inlet temperatures near 735°F (390°C). Use of the Cs catalyst in the first bed (as a 30 0/

0

### cap) will reduce the bed outlet temperature at high conversion levels. A full final bed ofthe Cs catalyst will allow for low temperature (735
- 800°F (390
- 427°C», resulting in much higher conversion levels due to a higher equilibrium conversion limit. The advantages ofthe Cs catalyst in both double and single absorption plants are shown in Figures 1 and 2. Note that the minimum possible 

### 502 emissions with conventional 4th pass catalyst (in these cases MEC LP-110 rings) are much higher than those observed using the cesium-promoted Cs-110 rings. The equilibrium conversion limit is raised as the fourth bed inlet temperature decreases, allowing for the high conversions observed in the cesium catalyst beds. There are numerous examples of conversion improvements in both single and double absorption plants utilizing the cesium-promoted Cs-120 (first pass) and Cs-11 0 (lower passes) catalysts. Furthermore, the Cs catalyst Cs-110 has been used in third beds of spent acid and metallurgical plants where heat exchanger limitations allow for only low bed inlet temperatures. The Cs-110 rings will generate much higher conversion than the standard catalyst and permit higher production rates with acceptable emissions. Also note that the cesium-promoted catalysts will operate with the same conversion levels as standard catalyst above the 800°F (427°C) bed temperature.

4

# · , "

# ... Sulfuric Acid Catalyst (Types: II. 210, [5-0ct-2009 516, Cs-I !O. Cs-120, Cs-210, LP-IIO, LP-110. LP-220, LP-1150, TD-750, XCs120, XLP-[ 10, XLP·220, WXC-[20. WXP-I10, WXP-220) 

# MATERIAL SAFETYDATA SHEET

I 

### 1 PRODUCTAND COJ\'IPANY IDENTIFICATION Product Name: Sulfuric Acid Catalyst (Types: 11,210,516, Cs-I10, Cs-120, Cs-210, LP-IIO, LP-120, LP-220, LP-1150, TD-750, XCs-120, XLP-IIO, XLP-220, WXC-120, WXP-IIO, WXP-220) Synonyms: None
ManufacturerName: MECS, INC 14522 South OuterForty Road Chesterfield, MO 63107 Telephone: 314-275-5700 Intended Use: Catalyst for use in Sulfuric Acid Manufacturing
HAZARDS IDENTIFICATION Emergency Telephone: Toll free from North America: 800-514-1746. When calling from outside North America: 

### +I 760­ 602-8897. Access Code: 10280
Contact Person: MECS E-mail: CatalystMSDS@mecsglobal.com

EmergencyOverview Physical State: Pellets, rings or ribbed rings Color: Yellow-green Odor: Odorless WARNING! Causes skin, eye and respiratory tract irritation. May be harmful ifswallowed. Cancerhazard

- can cause cancer. Potential Health Effects Inhalation: Causes respiratory tract irritation. Frequent inhalation offume/dust overa long period of time increases the risk ofdeveloping lung diseases. Eye Contact: Causes eye irritation. Exposed individuals may experience eye tearing, redness, and discomfort. Sldn Contact: Causes skin irritation. Skin irritation occurs on contact with moist orIvet skin. Ingestion: May be harmful ifswaJlowed. Chronic Health Effects: Cristobalite and quartz: Crystalline silica (inhaled in the form ofcristobaliteor quartz) has been classifiedby IARC, NTP and ACGIH as a known human carcinogen and suspected human carcinogen respectively_

9 

### NORTH AMER[CAN 

### MSDS 1ISulfuric Acid Catalyst (Types: 11, 210. 516, Cs-llO. C5-120, Cs-210, LP-IIO. LP-120, LP-220, LP-1150. TD-750. XCs120, XLP-IIO, XLP-220, WXC-120, WXP-IIO, WXP-220) \S-Oct-l009



### The substance (silica) may have an effect on the lungs, resulting in fibrosis (silicosis). 

### Target Organ(s): 

## I Eye 

## I Skin 

## I Respiratory system 

## I Lung 

## ! Potential Physical/Chemical Effects: This product is not flanunable. 

### OSHA Regulatory Status: When used for its intended purpose, this material is classified as hazardous in accordance with OSHA 29CFR 1910.1200. 

### Environment: Harmful to aquatic organisms, may cause**long~tenn** 

### adverse effects in the aquatic environment. 

## I**~3---------C-O-M--PO--SI-T-IO--N-/-IN-FO-RM---A-T-IO-N--O-N-I-N-G-RE--D-I-E-N-T-S--------------~** 

### General Information: This product is a mixture that consists ofa Vanadium salt complex (oxosulfatovanadates) containingpotassium and vanadium on a diatomaceous earth support (Group I) or Vanadium saltcomplex (oxosulfatovanadates) containing cesium, potassium and vanadium on a diatomaceous earth support (Group 2).



### Chemical Name CAS-No. Concentration* tVanadium salt complex (oxosulfatovanadates) group 1 or 2 

# - >= 

### 40

- <=49% tCristobalite 14464-46-1 >= 

### 23

- <= 31% tAmorphous silica (diatomaceous earth) 68855-54-9 >= 

### 25

- <= 27% tQuartz 14808-60-7 >=

### 0.1

- <= 

### 10/0 

### *All concentrations are In percent by weight unless mgredlent IS agas. Gas concentrations are Inpercent by volume. 

### t This chemical is hazardous according to OSHNWHMIS criteria.


### FIRST AID MEASURES Inhalation: Move to fresh air. Ifbreathing is difficult, give oxygen. Ifnot breathing, give artificial respiration. Get medical attention immediately. 

### Eye Contact: Immediately flush with plentyofwater for at least 15 minutes. Remove any contact lenses and open eyes wide apart. Do not rub eye. Ifirritation occurs, get medical assistance. 

### Skin Contact: Rinse the skin immediately with lots ofwater. Take offimmediatelyall contaminated clothing. Ifirritation occurs, get medical assistance. 

### Ingestion: Rinse mouth thoroughly. Remove**partiL~cs** 

### from mouth. Never give liquid to an unconscious person. Onlyinduce vomiting at the instruction ofmedical personnel. Get medical attention. 

### FIRE-FIGHTING MEASURES

NORTH AMERICAN MSDS 21 9 

# 15

# . 

# .

.. Sulfuric Acid Catalyst (Types: II, 2!0, IS-Oct-2009 516, Cs-IIO, Cs-120, Cs-210, LP-IIO, LP-120, LP-22D, LP-1150, TD-7S0, XCs120, XLP-IID, XLP-220. WXC-120. WXP-) 10, WXP-210) 

### Extinguishing l\Iedia: The product is non-combustible. Use appropriate extinguishing media for any nearby fire. Unsuitable Extinguishing lVledia: Not applicable. SpeciaJ Fire Fighting Procedures: No specific fire fighting procedure given. Use appropriate extinguishingmedia for any nearby fire. Unusual Fire & Explosion Hazards: Product will release sulfuroxides upon heating. Hazardous Combustion Products: Metal oxides, SulfurOxides ProtectiveMeasures: Self-containedbreathing apparatus and full protective clothing must be worn in caseoffire. Selection ofrespiratory protection for fire fighting: follow the general fire precautions indicated in the workplace. Flammability Class: N.FPA Rating Fire = 

### O. Materials that will not bum. ACCIDENTAL RELEASE lVlEASURES Personal Precautions: Avoid inhalation ofdust and contact with skin and eyes. See Section 8 ofthe MSDS for Personal Protective Equipment. SpillCleanup Methods: Use a vacuumcleaner. Ifnotpossible, moisten dust before it is collected with shovel, broom or the like. Avoid dust formation. Collect and reclaim or dispose in sealed containers at licensed waste disposal site. For waste disposal, see section 13 ofthe MSDS. Environmental Precautions: Avoid spreading dust or contaminated materials. Avoid discharge into drains, water courses or onto the ground. 

# 17 HANDLINGAND STORAGE Handling: Avoid any exposure. Should be handled in closed systems, ifpossible. Ifenclosed handling cannot be guaranteed, ventilation and protective clothing must be used. Only trained personnel should use this product. The product, ifwetted to the point ofcreating free liquid, will drip sulfuric acid. Corrosive when wet. Do not eat, drink or smoke when using the product. Wash hands after handling. Washcontaminated clothing before reuse. Thoroughly clean equipmentafter use. Storage: Keep container dry. Keep container tightly closed in a cool, well·ventilated place. Keep away from food, drink and animal foodstuffs. Store awayfrom incompatible materials. EXPOSURE CONTROLS 

### I PERSONAL PROTECTION 

# /8

Notes

NORTH AMERICAN MSDS 3/ 9I 

## · 

# .
Sulfuric Acid Catalyst (Types: II. 210. 15-0ct-2009 516, (s-IIO, Cs-120, Cs-210, LP-IIO, LP-120, LP-220, LP-1150, TO-750,

### xes120, XLP-IIO, XLP-220. WXC-120, WXP-IIO, WXP-220) earth) (Respirable dust.) Amorphous silica (diatomaceous 3000 mg/mJ earth) Amorphour.ril1clt(diatomaceous US. NIOSH Guide IOLH 0.8 mg/ml earth) Amorphous silica (diatomaceous US. OSHA Z-3 PEL TWAC US. OSHA Z-3 PEL TWA 20 Mppcf earth) Cristobalite (Respirable 0.05 mg/mJ particles.) Cristobalite (Respirable CA. Alberta OELs TWA 0.025 mg/mJ fraction.) TWA CA. British Columbia OELs Cristobalite (Respirable 0.05 mg/ml fraction.) Cristobalite TWA CA. Ontario OELs TWA 0.05 mgtmJ Cristobalite (Respirable MEX.OELs 0.025 mg/ml fraction.) Cristobalite**(Res~rableJ** TWA US. ACGIH TLV 0.05 mg/m) 1.2 Mppcf Cristobalite (Total dust.) US. OSHA Z-3 PEL TWAC 0.15 mg/m) ICTWA) Qua11z (Respirable particles.) US. OSHA Z-3 PEL OSHA Z3 0.1 mg/ml Quartz (Respirable fraction.) CA. Alberta OELs TWA 0.025 mg/ml OELs Quartz (Respirable fraction.) CA. British Columbia TWA 0.1 mg/ml Quartz (Respirable dust.) CA. Ontario OELs TWA CA. Quebec OELs TWA 0.1 mg/m3 I Quartz MEX.OELs 0.1 mg/m3 !Quartz(Respirable fraction.) TWA 0.025 mg/ml Quartz US. ACGIH TLV TWA 25 mg/m3 Quartz US. NIOSH Guide IDLH 50 mg/m) ion I Quartz (Respirable.) US. NIOSH Guide Concentrat 0.1 mg/m3 2.4 Mppcf Quartz (Totaldust.) US. OSHA Z-3 PEL TWAC 0.3 mg/ml I(TWA) Vanadium salt complex US. OSHA Z-3 PEL OSHA Z3 35 mg/m) (oxosulfatovanadates) group 1 or 2 US. NJOSH Guide IDLH


### Engineering Controls: Ifenclosed handling cannotbe guaranteed, ventilation and protective clothing must be used. Observe occupational exposure limits and minimize the risk ofinhalation ofdust. 

### RespiratoryProtection: Ifengineeringcontrols do not maintain airborne concentrations below recommended exposure limits (where applicable) orto an acceptable level (in countries where exposure limits have not been established), an approved respirator must be worn. In the United States ofAmerica, ifrespirators are used, a program should be instituted to assure compliance with OSHA Standard 63 FR 1152,January 8, 1998. Respirator type: High-efficiency particulate respirator. 

### Eye Protection: Wt!ar approved safety goggles. 

### HandProtection: Wear protective gloves. 

### Skin Protection: Wear appropriate clothing to prevent any possibility ofskin contact.

NORTH AMERICAN MSDS 41 9

# · 

# .
Suifuric Acid Catalyst (Types: II, 210, I5-0ct-2009 516, Cs-I [0, Cs-[20, Cs-21O, LP-IIO. LP-120. LP-220, LP-1150. TD-750. XCs120, XLP·ll0, XLP-210. WXC-120. WXP-IIO. WXP-220) 

### Hygiene lVleasures: Always observe good personal hygiene measures, such as washing afterhandling the material and before eating, drinking, and/or smoking. Routinelywash work clothing and protective equipment to remove contaminants. Personal protection equipment should be kept separate from other clothing. Personal protection equipment should not be worn during lunch breaks. 

### Environmental Exposure Controls: Environmental manager must be informed ofall major spillages. 

# /9 PHYSICAL AND CHE]\tIICAL PROPERTIES Color: Yellow-green 

### Odor: Odorless 

### OdorThreshold: No data available. 

### Physical State: Pellets, rings or ribbed rings 

### pH: Not applicable 

### l\'lelting Point: No data available. 

### Freezing Point: No data available. 

### Boiling Point: No data available. 

### Flash Point: Not applicable. 

### Evaporation Rate: No data available. 

### Flammability (Solid): No dataavailable. 

### FlammabilityLimit

- Upper (0/0): 

### Notapplicable. 

### Flammability Limit

- Lower (%): 

### Notapplicable. 

### Vapor Pressure: No data available. 

### VaporDensity (Air=l): No data available. 

### Specific Gravity: 0.5

- 0.61 Solubility in Water: Slightly soluble in water. 

### Solubility (Other): No data available. 

### Partition Coefficient (n-Octanol/water): No data available. 

### Autoignition Temperature: Not applicable. 

### Decomposition Temperature: No data available. 

### Viscosity: Not applicable. 

### PercentVolatile: OO/ovol 

### /10 STABILITY AND REACTIVITY Stability: Stable under normal temperature conditions and recommended use. However when wetted the product is corrosive. 

### Conditions to Avoid: Water, moisture. 

### Incompatible Materials: Water. 

### Hazardous Decomposition Products: When wetted: Sulfuric acid. When heated: sulfur oxides. 

### Possibility ofHazardous Reactions: None. 

### TOXICOLOGICAL INFORl\1ATION III

NORTH AMERICAN MSDS 51 9

### /12 Slllfuric Acid Catalyst (Typt!s: I I, 210, 516. ('s-IIO, Cs-120. ('s-210, LP-IIO, LP-120. LP-220, LP-1150, TD-750. XCs120, XLP-IIO, XLP-220, WX(,·120, WXp·IIO. WXP-220) 15-0ct-2009



### Specified Substance(s) Acute Toxicity: Other Acute: Vanadium salt complex: Causes skin, eye andrespiratory tract irritation. 

### Chronic Toxicity: Vanadium salt complex: May cause damage to the liver and kidneys. May cause lung damage. Crystalline silica: Overexposure to the respirable dust ofcrystalline silica (quartz or cristobalite, less than orequal to 5 microns in size) may lead to silicosis in humans, which is a progressive and irreversible lung disease. 

### L'

IstedCarcmogeils: ChemicalName IARC NTP OSHA ACGIH Amorphous silica (diatomaceous earth) 

### 3 Not Listed Not Listed NotListed Cristobalite 

### 1 Listed Not Listed A2 Quartz

I 

### 1 Listed Not Listed A2 [ARC: 1 = Carcinogenic to Humans; 2A 

### =ProbablyCarclllogemc to**Humans~** •.2B

### := Possibly**C~mogenlc** to Humans; 3 = Not classifiable as to carcinogenicity to humans; 4

### =Probably not carcinogenic to humans; Not listed

### =Not evaluatedby fARe. ACGIH: AI Confirmed Human Carcinogen; A2 Suspected Human Carcinogen; A3 =Confirmed Animal Carcinogen; A4 =Not classifiable as a human carcinogen; A5 Not suspected to be a human carcinogen; Not listed = Not evaluated by ACGTH. 

### Product Information Acute Toxicity: TestResults: Oral LD50 (Rat): 1460 mg/kg Dermal LD50 (Rabbit): > 5000 mg/kg 

### Other Acute: Causes skin, eye and respiratory tract irritation. Maybe hannful ifswallowed. 

### Chronic Toxicity: Cancerhazard. Can cause cancer. May cause lung damage. 

### ECOLOGICAL INFOMIATION Ecotoxicity: Harmful to aquatic organisms, may cause long-term adverse effects in the aquatic environment. 

### l\'lohility: No data available. 

### Persistenceand Degradability: None known. 

### BioaccumulationPotential: Nodata available on bioaccumulation. 

### DISPOSAL CONSIDERATIONS General Information: Do not discharge into drains, watercourses or onto the ground. It may be necessary to dispose this material orits container as a hazardous waste. Please consultyour local regulations for guidance. FOLLOW LABEL WARNINGS EVEN AFTER CONTAINER HAS BEEN EMPTIED. Empty containers maycontain productresidues. 

### DisposaJ Methods: Recover and reclaim orrecycle, ifpractical. Disposal recommendations are based on material as supplied. Disposal must be in accordance with current applicable laws andregulations, and

NORTH AMER[CAN MSDS 61 9 

### 113". Sulfuric Acid Catalyst.(Types: II, 210. IS-0ct-2009 516, Cs-110, Cs-120, Cs-210. lP-IIO, lP-120, LP-220, LP-1150, TO-750, XCs120, XLP-IIO. XLP-220. WXC-120, WXP-IIO, WXP-220)
material characteristics at time ofdisposal.


### TRANSPORT INFOAAlATION 

### 114 DOT Not regulated. 

### TDG Not regulated. 

### lATA Notregulated. 

### IMDG Not regulated. 

## I 15 REGULATORYINFORl\'1 A

### TION Canadian Controlled Products Regulations: This producthas beenclassified according to the hazard criteria ofthe Canadian Controlled Products Regulations, Section 33, andthe MSDS contains all required infonnation. 

### WHlVIIS Classification: D2A, D2B 

### Mexican Dangerous Statement: This product is dangerous according to Mexican regulations. 

### Inventory Status Thisproduct or all components are listed orexemptfrom listing on the following inventory: TSCA


### Thisproductor one or more component(s) arenot listed on the following inventory: AlCS, DSL 

### US Regulations CERCLA Hazardous Substance List (40 CFR302.4): Not regulated. 

### SARATitleIII Section 302 Extremely Hazardous Substances (40 CFR 355, Appendix A): Not regulated. 

### Section 311/312 (40 CFR370): 

# 00Acute (Immediate)**~Chronic** (Delayed) DFire DReactive D Pressure Generating 

### Section 313 Toxic Release Inventory (40 CFR372): ChemicalName CAS-No. Reporting threshold forother users Reporting threshold for manufacturing and processing Vanadium salt complex I(oxosulfatovanadates) group I or 2 

## - 10000Ibs 250001bs

... Forreporting purposes: the De MinimiS ConcentratIOn for a tOXIC chemIcal In a mixture IS 0.1 % for carcinogens as defined m29 CFR 191O.1200(d)(4) or 1% for others.

NORTH AMERICAN MSDS 71 9, " ". Sulfuric Acid Calalyst (Types: I L 210, IS-Od-2009 516, [s-IIO, Cs-120, Cs-:!IO, LP-lIO, LP-I:!O. LP·220, LP-1150, TO·7S0. 

## xes120, XLP·lI0, XLP-220, WXC-120, \VXP·IIO, WXP-220)



### Clean Air Act (CAA) Section 112(r) Accidental Release Prevention (40 CFR 68.130): Not regulated. 

### Clean WaterAct Section 311 Hazardous Substances (40 CFR 117.3): Not regulated. 

### DrugEnforcementAct: Not regulated.



### TSCA Section4(a) FinalTest**Rule~** & 

### TestingConsent Orders: Not regulated. 

### TSCA Section 5(a)(2) Final Significant New Use Rules (SNURs) (40CFR721, Subpt. E): Not regulated. 

### TSCA Section 5(e) PMN-Substance ConsentOrders: Not regulated. 

### TSCA Section 12(b) Export Notification (40 CFR 707, Subpt. 0): Not**regulat~d.** 

### StateRegulations California Safe DrinkingWater and Toxic EnforcementAct of 1986 (Proposition 65): Cristobalite; Quartz 

### i\tlassachusetts Right-To-Know List: Amorphous silica (diatomaceous earth); Cristobalite; Quartz 

### i\tIichigan Critical Materials List (Michigan Natural Resources and Environmental Protection Act (Act. 451 of 1994»): Notregulated.**~Iinnesota** 

### Hazardous Substances List: Amorphous silica (diatomaceous earth) 

### New Jersey Right-To-Know List: Amorphous silica (diatomaceolls earth); Cristobalite; Quartz 

### Pennsylvania Right-To-Know List: Amorphous silica (diatomaceous earth); Cristobalite; Quartz 

### Rhode Island Right-To-Know List: Not regulated. 

### 116 OTHER INFORlVlATION HAZARD RATINGS Health Hazard Fire Hazard ecial Hazard NFPA 

### 2 

## o Hazard rating:

# °- Minimal; I - Slight; 2 - Moderate; 3 - Serious; 4 - Severe NFPA Label colored diamond code: Blue

- Health; Red

- Flammability; Yellow

- Instability: White

- Special Hazards 

### Health Hazard Flammabilit Personal Protection 

## x HMIS 2* 0 Hazard rating: 0 - Minimal; I - Slight; 2 - Moderate; 3 . Serious; 4 - Severe *- Chronic Health Effect
NORTH AMER[CAN MSDS 81 9,

# .' 

## '. Sulfuric Acid Catalyst (Types: 11, 210, 15-0ct-2009 516. (s-IIO,C5-120,(s-210, lP-IIO, lP-120, lP-220, lP-IISO, TD-750, XCs120, XLP-llO, XlP-220, WXC-120, WXP-IIO, WXP-220)
HMIS labd coloredbar code: Blue

- Health; Red

- Flanunability; Orange Physical Hazards; White

- Special 

### Issue Date: 

### 15-0ct-2009 Supercedes Date: 

### 07-Sep-2007 SDS 

### No.: 1005383 Disclaimer: 

### This information is provided without warranty. The information is believed to be correct. This information should be used to make an independent determination ofthe methods to safeguard workers and the environment.

9 NORTH AMERICAN MSDS 9/January 2003 

### HALDCR TCPSCE. 

### INC. Page I of6 

### Houston,Texas, USA


# MATERIALSAFETYDATA SHEET VK-38

1.1 IDENTIFICATION OFPRODUCT. Designation: VK38. Sulphuric acid catalyst.
1.2 COMPANY INFORMATION. HaldorTopsoe, Inc. Phone: 281-228-5000 17629 EI CaminoReal Fax: 281-228-5209 Houston, Texas 77058 Chemtrec

- TransportationEmergencies: 800-424-9300
2 INFORMATION ON INGREDIENTS. %w/w Compound CAS No EECNo Classification (67/548IEEC)*

5-9 Vanadiwn 1314-62-1 215-239-8 Mut3**~** R68 Rep3**~** R63 pentoxide T R48/23 Xn R20/22 Xi; R37 N; R51/53 10-30 Potassiwn sulphate K2 S04 7778-80-5 231 9155 1-7 Sodium sulphate Na2S04 7757-82-6 231 8209 55-70 Silica, Si02 61790-53- Xn; R20 diatomaceous earth 2 1-5 Silica, crystalline Si02 Carc 3 R40 Xn; R20 Forthe text ofhazard classes and R phrases see section 16.
3 HAZARDS IDENTIFICATION. Fire, explosionandreactivity hazards: Notapplicable. Routesofentry: Inhalation,eyeand skincontact, ingestion. Healthhazards: Acute: Harmful. Inhalation of excessive amoWlts of dust may cause irritation of the respiratory system; symptoms may include coughing and difficulty in breathing. May cause physical irritation of eyes. May initate skin. For further information on healthhazards, see section 11. Chronic: Crystalline silica is listed as a possible carcinogenic substance. Inhalation ofsilica may result in silicosis, a non-cancerous lWlg disease. Vanadiwn pentoxide is in EU classified as a mutagenic substance in category 3 i.e. may cause possible risk of irreversible effects. Vanadiwn pentoxide is also inEUclassified as toxic for reproduction incategory 3, i.e. possible risk ofharm to the unbornchild. Synergistic effects: Noneknown. Environmental hazards: The product contains vanadiwn pentoxide, which is toxic to aquatic organisms and may cause longterm adverse effects inthe

VK-38/USJanuary 2003 

### HALDClR TClPSClE. INC. Page 2of6 

## Houston, Texas, USA

aquatic environment.
4 FIRST-AID MEASURES. Inhalation: Ifdust is inhaled, move to fresh air. In case ofsignificant inhalationofdust: seekmedicalattention if uncomfortable. Eye contact: Immediately flush eyes withwater. Ifirritationpersists, seek medical attention. Skincontact: Wash with soap and water. Remove contaminated clothing. Ingestion: In case ofsubstantial ingestion,drink plenty ofwaterand induce vomiting. Seek medical attention.
5 FIRE-FIGHTING MEASURES. Product is compatible with standard fire-fighting agents. Check runofffor metals. May release toxic S02 whenheated above 400°C n50°F.
6 ACCIDENTAL RELEASE MEASURES. Personal precautions: Avoid inhalation ofdust. Environmental precautions: Do not wash spills into water ways orpublic treatment systems. Methods for cleaning up: Collect by vacuwning or sweeping (minimizing dust) and place in labelled container for proper reclamation or disposal.
7 HANDLING AND STORAGE. Handling: Avoid excessive dust formation. Use mechanical ventilation when appropriate. Use goodhousekeeping and personal hygiene practices. Do not eat,drink or smokewhenhandling materials. Storage: In dry warehouse, preferably with floor of concrete, tiles or wood. The catalyst must be protected against moisture and water.
8 EXPOSURE CONTROLS I PERSONAL PROTECTION. Exposure limits: Exposure limits may vary. It is recommended that information about locally applicable exposure limits are obtained. Compound CAS no OELmg/mJ TLV mg/m 3 PELmg/m3 (ACGIH) (OSHA) Vanadium V2

### O, 1314-62-1 0.05 0.05 (A*, 0.5 «dust),C*) pentoxide (dust & fume» 0,1 «fume), C*) Potassium sulphate K2S04 7778-80-5 Sodium sulphate Na2S04 7757-82-6 Silica, Si02 61790-53-2 1,2 (A*, 10 6

VK·38IUS.) January 2003 

### HALCCR TCPSCE. 

### INC. Page 3of6 

### Houston, Texas, USA

diatomaceous earth natural resp. dust)

- calcinated 68855-54-9 0,08 (A*) Silica. crystalline Si02 14464-46-1 0.3 (A*) 0.05 (A*) 0.05 (A*) Cristobalite *A = respirable *C=ceiling limit 

### Personal protection: Respiratory protection: Use approved respirator with particle filter type P3(EUstandard)/PlOO(US-standard), when exposure may exceed recommended limits. Handprotection: Gloves recommended. Eye protection: Goggles recommended. Contact lenses should not be worn when working with this product. Otherprotection: Change work clothing daily. Safety shoes recommended when handling heavy containers. Wash hands thoroughly afterhandling.
9 

### PHYSICAL AND CHEMICAL PROPERTIES. State: Solid Appearance and odour: Greenishyellow. Extruded pellets. Odourless. pH: Not applicable. Boiling point or range: Not applicable. Melting point or range: Silica above 1600 °C I 2910 

### OF**~** alkali sulphates above approx 400 °C1750 of. Flammability and limits: Non-flammable. Auto-flammability: Not applicable. Explosive properties: Non-explosive. Oxidizing properties: Non-oxidizing. Vapour pressure: Not applicable. Vapour density: Not applicable. Density relative to water: Above 1 Solubility in water: Alkali-sulphates soluble. Vanadium compOlmds partly soluble. Partition coefficient (n- Not applicable. octanollwater): Other data:


### 10 STABILITY AND REACTIVITY. The product is stable under nonna! handling and storage conditions. Conditions to avoid: Not relevant. Materials to avoid: Waterand moisture for catalystintegrity. Hazardous decomposition products: Heating above 400°C I750°Fmay resultinemission ofS02

VK-38/USJanuary 2003 

### HALCCR TCPSCE. INC. Page 4 of6 

### Houston, Texas, USA

11 TOXICOLOGICAL INFORMATION. CompoWld RTECS No Toxicity data Vanadiwn pentoxide YW2460000 No data Potassiwn sulphate TT5900000 Oral Woman LDLo 750 mg/kg Oral Rat LD50 6600 mglkg Subcutaneous GuineaPig LDLo 3gm/kg Sodium sulphate WE1650000 Oral Mouse LD50 5989 mglkg Intravenous Mouse TDLo 1220mg/kg Silica, diatomaceous earth HL8600000 No data Silica, crystalline Cristobalite VV7325000 Intratracheal Rat LDLo 200 mg/kg Intravenous Mouse LDLo 40 mglkg Intravenous Dog LDLo 20 mglkg Dangerousto health effects: Inhalation: Dust and fumes from vanadiwn compoWlds can irritate the respiratory**system~** symptoms may include nose bleeding, sore throat, cough, bronchitis, expectoration, chest pain; serious exposure may cause pneumonia and pulmonary oedema. The symptoms of pulmonary oedema often do not become manifest Wltil several hours have passed and they are aggravated by physical effort. Rest and medical observation is therefore essential. Vanadium compoWlds may cause green discoloration of the tongue. Eye contact: May cause physicalirritationofeyes. Skin contact: May irritate skin. Ingestion: Ingestion may cause irritation ofthe mouth and throat and may cause discomfort. Ingestion of large quantities may give risk to gastrointestinal disorders. Chronic effects as listed 

### by OSHA, IARC, NTP, MAK: Carcinogenic: Cristobalite (lARC CancerReview: Group**2A~** NTP) Teratogenic: Not listed. Mutagenic: Not listed.
12 ECOLOGICAL INFORMATION. Constituents classified by EU for environmental hazards: The product contains vanadium pentoxide which is toxic to aquatic organisms and may cause long tern adverse effects in the aquatic environment. Otherecological determinations: Notavailable
13 DISPOSAL CONSIDERATIONS. May be reclaimed. Dispose ofwaste in accordance with applicable federal, state and local regulations. HaldorTopsoe, Inc makes no claim for the classificationofusedorcontaminatedmaterial.

VK.-38/USJanuary 2003 

### HALDCR TCPBCE. INC. Page 5 of6 

### Houston, Texas, USA

14 TRANSPORT INFORMATION. Not classified 

### as hazardous under: IMO/IMDG ADR-RID lATA DOT TOO


### 15 REGULATORY INFORMATION. EEC label for product following directive 1 999/451EC: Warning: Xn Hannful. Contains: Vanadiwn pentoxide, Silicacrystalline. R40: Possible risks ofirreversibleeffects. R48120: Hannfu1: dangerofseriousdamage to healthby prolonged exposure through inhalation. R63: Possible risk ofhann to the unbornchild. R68: Possible risk ofirreversible effects. R52153: Hannful to aquatic organisms, may cause long-tenn adverse effects inthe aquatic environment. S22: Donotbreathe dust. S24: Avoidcontactwith skin. S36/37: Wearsuitableprotective clothing and gloves. US LabelforProduct: Warning: Suspectcancerhazard. Containsmaterial which may cause cancer. May cause respiratory tract irritation. May cause allergic skinreaction.


### 16 OTHERINFORMATION. Textofhazard classes and R phrases: T Toxic Xn Hannful Xi Irritant N Dangerous for the environment R20: Harmful by inhalation. R20/22: Harmful by inhalation and ifswallowed. R37: Irritatingtorespiratory system. R40: Limited evidence ofa carcinogenic effect. R48123: Toxic: danger of serious damage to health by prolonged exposure through inhalation. R51153: Toxic to aquatic organisms, may cause long-tenn adverse effects in the aquatic environment. R63: Possible risk ofhann to the unbornchild. R68: Possiblerisk ofirreversible effects. Mut3 Mutagenic, category 3. Substancesofconcernowing topossible mutagenic effect. Rep3 Toxic to reproduction, category 3. Substancesofconcernto manbecause ofpossible risk ofhann to the unbornchild. Carc 3: Carcinogeniccategory 3. Possiblehwnancarcinogens. All components are included in TSCA (USA), DSL (Canada) and EINECS (EEC) inventories. Chemicalreleasereporting (SARA section 313, as codifiedin40 CFRpart 372): Reportingrequired for vanadium compounds.

VK-38/USJanuary 2003 

### HALDCR TCPSCE. INC. Page 6 of6 

# LiJ Houston, Texas, USA

CanadianWHMIS classification: Class D, Division 2A, Division 2B. References and additional information: RTECS (Registry of Toxic Effects ofChemical Substances, National Institute for Occupational Safety and Health, 4676 Colwnbia Pkwy., Cincinnati, Ohio 45226, USA).

The above information is believed to be accurate and is based on our present state ofknowledge and eltperience. However, no warranty or representation withrespectto such information is intended or given. This information is intended to be used for safety and environmental purposes only and shouldnot be relied upon for any other purposes.

VK-38/US

# .. Page I of4 

### " VK48/usIMay 1997 

# l]j' HALDDR TDPSDE. INC. 

# MATERIAL SAFETYDATA SHEET VK48

1.1 IDENTIFICATION OFPRODUCT. Designation: VK48. Sulphuric acid catalyst.
1.2 COMPANY. HaldorTopsoe, Inc. 17629 EI Camino Real Houston, TX 77058, USA

2 HAZARDOUS AND OTHERINGREDIENTS. Phone: (281) 228-5000 Fax: (281) 228-5209 Emergency Phone: (281) 228-5000

Exposure limits may vary. It is recommended that information about locally applicable exposure limitsbe obtained. %w/w Compound

5-10 Vanadiumpentoxide 10-30 Potassium sulphate 3-7 Sodium sulphate 55-70 Silica,diatomaceousearth

- calcined Silica, crystalline

Cristobalite Quartz Tridymite
3 PHYSICAL DATA. State: Appearance and odour: pH: Boiling point orrange: Melting point orrange: Vapourpressure: Vapour density: Density relative to water: Solubility in water: Partition coefficient (n-octanol/water): Other data: CAS No MAKmglm3 TLVmglm3 PEL mglm3 (Germany) (ACGIH) (OSHA) V20 S 1314-62-1 0.05 (resp) 0.05 resp 0.05 (resp) K2SO. 7778-80-5**N~S04** 7757-82-6 Si02 61790-53-2 4 10 6 68855-54-9 0.3 (resp) Si02 14464-46-1 0.15 (resp) 0.05 (resp) 0.05 (resp) 14808-60-7 0.15 (resp) 0.1 (resp) 0.1 (resp) 15468-32-3 0.15 (resp) 0.05 (resp) 0.05 (resp)

Solid Greenish yellow.Extrudedpellets.Odourless. Not applicable. Not applicable. Silica above 1600 °C I 2910OF ;alkalisulphates above approx 400°C/ 750OF. Not applicable. Not applicable. Above I. Alkalisulphates soluble. Vanadium compoundspartly soluble. Not applicable.Page 20f4 VK48/usIMay 1997
4 FIREAND EXPLOSION HAZARD DATA. Fire, explosion and reactivity hazards: Not applicable. Flammability and flammability limits: Non flammable. Autoflammability: Not applicable. Explosive properties: Non explosive. Oxidizing properties: Non oxidizing. Firefighting measures: Product is compatible with standard firefighting agents. May release toxic S02 when heated above 400°C 1750°F. Check runofffor metals.
5 STABILITY AND REACTIVITY DATA. Theproduct is stable undernormal handling and storage conditions. Conditions to avoid: notrelevant. Materials to avoid: not relevant. Hazardous decomposition products: Heating above 400°C I750 OF may result in emission ofS02'
6 HEALTH HAZARDS. Routes ofentry: Inhalation, eye and skin contact, ingestion. Health hazards: Acute: Inhalation ofexcessive amounts ofdust may cause irritation ofthe respiratory system; symptoms may include coughing and difficulty in breathing. Vanadiumcompounds can irritate the mucous memM branes oftherespiratory system; symptoms may include nose bleeding, sore throat, cough, bronchitis, expectoration, chestpain; serious exposure may causepneumonia &pulmonary edema. Exposure to fumes and dust ofsome metal oxides have been associated with, within4-12 hours resulting in fluelike symptoms known as metal fume fever. Vanadiumcompounds may cause green discoloration of tongue. May cause physical irritation ofeyes. May irritate skin. Chronic: Crystalline silicais listed as apossible carcinogen. Inhalation ofsilicamay result in silicosis, a noncancerous lung disease. Synergistic effects: Noneknown. Toxicological data: Compound RTECS No Toxicitydata Vanadium pentoxide YW2460000 no data Potassium sulphate TT5900000 Oral Woman LOLo 800 mglkg Oral Rat L050 6600 mglkg Subcutaneous Guineapig LOLo 3 gmlkg Sodium sulphate WE1650000 Oral mouse L050 5989 mglkg Intraveneus MouseTOLo 1220 mglkg Silica,diatomaceous earth HL8600000 no data Silica,crystalline Cristobalite W7325000 Intratracheal Rat LOLo 200 mglkg Quartz W7330000 Intravenous Rat LOLo 90 mglkg Intravenous Mouse LOLo 40 mglkg Intravenous Dog LOLo 20 mglkg Tridymite VV7335000 Inhalation Man TCLo 16mppcf/8H117.9Y-I Intratracheal Rat LOLo 200 mglkgPage 3of4 VK48/usIMay 1997
Chroniceffects aslisted by OSHA, IARC, NTP, MAK: Carcinogenic: Quartz (lARC group 2A; NTP) Cristobalite (IARC group 2A; NTP) Tridymite (IARC group 2A; NTP) Teratogenic: not listed. Mutagenic: not listed.
7 PREVENTIVE MEASURES. Avoid handling methods creating excessive dust. Use mechanical ventilation when appropriate. Use good housekeeping and personal hygiene practices. Do not eat, drinkorsmokewhen handling materials. Wash hands thoroughly afterhandling. Personal protection: Respiratory protection: Use approvedrespiratorwhen exposure may exceedrecommended limits. Hand protection: Gloves recommended. Eyeprotection: Goggles recommended. Otherprotection: Change workclothingdaily. Safety shoes recommended when handling heavy containers.
Accidental release measures. Personal precautions: Avoid inhalation ofdust. Environmental precautions: Do notwash spills into waterways orpublic treatment systems. Methods for cleaning up: Collectby vacuuming or sweeping (minimizing dust) and place in labelled container. Disposal considerations May be reclaimed. Dispose ofin accordance with applicable federal, state and local regulations. Unused product is not an EPA hazardous waste. HaldorTopsoe, Inc. makes no claim for the classification ofused orcontaminated material. Handling and storage. Handling: A void excessivedust formation. Storage: Product maybe damaged bywater. TransportInformation Notclassified as hazardous under: IMOIIMDG ADR-RID lATA DOT TDG
8 FIRST-AID MEASURES. Inhalation: Ifdust is inhaled, move to fresh air. For significant inhalation: Ifbreathing is difficult, give oxygen ifavailable. Ifnot breathing, give artificial respiration. Seek medical attention. Eye contact: Immediately flush eyes with water. Ifirritation persists, seekmedical attention. Skin contact: Wash with soap and water. Remove contaminated clothing. Ingestion: In case ofsubstantial ingestion, drink plenty ofwaterand induce vomiting. Seekme­ dical attention.
9 OTHERINFORMATION. Regulatory Information: All components are included in TSCA (USA), DSL (Canada) and EINECS (EEC) inventories. Chemical release reporting (SARA section 313, as codified in 40 CFR part 372): Reporting notrequired. Canadian WHMIS classification: Class D, Division 2.A.

## • Page4of4 VK48/uslMay 1997
EEC label for productfollowing directive 88/J79/EEC: Warning: Contains crystalline silicaand vanadium pentoxide. Possible risks ofirreversible effects. Harmful by inhalation. Do notbreathe dust. A void contactwith skin. Xn Harmful. R40 R20 S22 S24 References and additional information: RTECS (Registry ofToxic Effects ofChemical Substances, National Institute for Occupational Safety and Health, 4676 ColumbiaPkwy., Cincinnati, Ohio 45226, USA). The above infonnation is believed to be accurate and is basedonourpresent state ofknowledge and experience. However, no warranty orrepresentation withrespect to such infonnation is intendedorgiven.

# MECS, Inc. SALES PROPOSAL P.o. Box 

### 14547•st. MO 63178' Phone: 

### RC199556·00 6/11/2012 TO: Asarco LLC 5285 EWilliams Circle Suite 2000 Tuscon, fj2 85711 SULFURIC ACID CATALYST XCS

..120/200 XCS-120 IN 200 L TR DRUMS XLP-220/1200 XLP-220 IN 1200 LTR BAGS XLP

..110/1200 XLP-110 IN 1200 LTR BAGS 20,000 Liters 60,000 Liters 30,000 Liters 11.35 5.26 5.26 USD/LT USD/LT USD/LT 227,000.00 315,600.00 157,800.00 USD USD USD Total Price FOB DESTINATION 700,400.00 USD Price does not include any applicable state use or sales tax. Ifyour company is tax exempt, send a copy ofyour tax exempt certificate with your purchase order. Terms are ADVANCE WIRE TRANSFER.
PACKING: 200 LITER STEEL DRUMS

.. XCS-120 1200 LITER BAGS

.. XLP-220 AND XLP-11 0 PAYMENTTERMS: 100% ADVANCE WIRE TRANSFERTO: MECS, INC. C/O PNC BANK NA 120 S. CENTRAL CLAYTON, MO 63105 ABA# 041000124 SWIFT CODE: PNCCUS33 PLEASE REFERENCE ACCT#4612918902
ADDITIONAL TERMS AND CONDITIONS:

- PRICE IS FIRM FOR30 DAYS

.

.. PRODUCT WILL SHIP FROM MARTINEZ, CA

- FREIGHT IS PREPAID &ADD

.. VIAAN MECS

DESIGNATED CARRIER.

- FUNDS RECEIVED BY MECS AFTER THE DUE DATE

SPECIFIED IN THE CONTRACTWILL BE CHARGED A LATE PAYMENT FEE OF 0.05% PERDAY. THE LATE PAYMENT FEE WILL CONTINUE UNTILTHE DAYTHE OVERDUE FUNDS ARE RECEIVED.

ACCEPTED AS OF THIS DATE: DATE: June 

### 11, 2012 ("BUYER") MECS, Inc. ("SELLER") BY:

# *~ BY: TITLE:



# ------------------------------­ The terms and conditions attached and/or set forth on face and reverse side hereof are a part ofthis proposal. Please understand that by sending your acknowledgement, purchase order or other document for the equipment which is the subject ofthis proposal or by accepting delivery ofsuch equipmentyou agree to the terms and conditions set forth on the reverse side hereofas well as those set forth on the face hereof. Any different or additional terms in your acceptance of this offer are hereby objected to. PE.PRO.CA (REV. 01197) RC199556-00 Page 1

# ------------------------------- " 

# MECS, Inc. 

# SALES PROPOSAL P.o. Box 

### 14547 •Sl Louis. 

### MO 63178· Phone: RC198649'()0 

### 1117/2011 TO: Asarco LLC 5285 EWilliams Circle Suite 2000 Tuscon, AZ 85711 SULFURIC ACID CATALYST XLP-220/1200 XLP·220 IN 1200 LTR BAGS 37,200 

### Liters XCS-120/1200 XCS-120 IN 1200 LITER BAC 20,400 

### Liters 4.10 7.60 USDILT USDILT 152,520.00 USD 155,040.00 USD Total Price FOB DESTINATION 307,560.00 USD Price does not Include any applicable state use or sales tax. Ifyour company Is tax exempt, send acopy ofyour tax exempt certificate with your purchase order. Terms are 50% ADVANCE /50% RECPT INV. PACKING: 1200 LITER BAGS
- PALLETIZED
PAYMENTTERMS:

50% ADVANCE WIRE TRANSFER TO:

MECS, INC. CIO 

### PNC BANK NA 120 S. CENTRAL, CLAYTON, MO 63105 ABA# 041000124 SWIFTCODE: PNCCUS33 PLEASE REFERENCE ACCOUNT NO: 4612918902 50% PAY RECEIPT OF INVOICE ADDITIONAL TERMS AND CONDITIONS:

- PRICE IS FIRM FOR 30 DAYS FOR SHIPMENT

IN FEBRUARY, 2012.

- PRODUCT IS AVAILABLE FROM MARTINEZ, CA• • FREIGHT IS PREPAID AND ADD, VIA AN MECS

DESIGNATED CARRIER
- OR· COLLECT, VIA AN ASARCO DESIGNATED CARRiER.
- FUNDS RECEIVED BY MECS AFTERTHE DUE DATE SPECIFIED

WILL BE CHARGED A LATE PAYMENT FEE OF 0.05% PER DAY. 

### THE LATE PAYMENT FEE WILL CONTINUE UNTIL THE DAY THE OVERDUE FUNDS ARE RECEIVED.

ACCEPTED AS OF THIS DATE: DATE: November7,2011 ("BUYERft) MECS, Inc. 

### rSELLER', BY:

# By:als=a~ TITLE: The terms and conditions attached and/or setforth on face and reverse side hereofare a part ofthis proposal. Please understand that by sending your acknowledgement, purchase order or other documentfor the equipmentwhich is the subject ofthis proposal or by acceptIng delivery ofsuch eqUipmentyou agree to the terms and conditions set forth on the reverse side hereofas well as those set forth on the face hereof. 

### Any different or additional terms in your acceptance of this offer are hereby objected to. PE.PRO.CA (REV. 01/97) RC198649-00 Page 1

### Page 2 of2 Oscar, we need a change orderto add the 20k liters ofXCS-120; price is $7.25/Iiter exworks. The balance ofthe orderwill be shipped later in time for your April SID. Ithink I covered all that was discussed; ifnot callIe-mail me. Thanks Carlos Iwaszkowiec MECS, Inc. 14522 South Outer Forty Road Chesterfield, MO 63017 Ph.: 314-275-5742 Fax: 314-275-5918 Cell: 314-308-4916



### This e-mail contains information intended only for the use oftheindividual or entity named as the addressee. This communication may contain information that is the confidential and proprietary property ofMECS, Inc. Ifthe reader ofthe e-mail is not an intended recipient or the employee or agent responsible for delivering it to an intended recipient, any review, dissemination, distribution orcopying is strictly prohibited. Ifyou have received this e-mail in error, please immediately notify us at (314) 275­ 5700 and delete the copy you received. All e-mails and attachments sent and received are subjectto monitoring, reading and archival by MECS, Inc. The recipient ofthis e-mail is solely responsible for checkingfor the presence of"Viruses" orother "Malware". MECS, Inc. accepts no liability for any damage caused by any such codetransmitted by or accompanying this e-mail or any attachment. This e-mail has been scanned using Skeptic(TM) technology powered by MessageLabs. This e-mail contains information intended only for the use ofthe individual or entity named as the addressee. This communication may contain information that is the confidential and proprietary property ofMECS, Inc. Ifthe reader ofthe e-mail is not an intended recipient orthe employee oragent responsible for delivering itto an intended recipient, any review, dissemination, distribution orcopying is strictly prohibited. Ifyou have received this e-mail in error, please immediately notify us at (314) 275­ 5700 and delete the copy you received. All e-mails and attachments sent and received are subjectto monitoring, reading and archival by MECS, Inc. The recipient ofthis e-mail is solely responsible for checkingfor the presence of"Viruses" or other "Malware". MECS, Inc. accepts no liability for any damage caused by any such code transmitted by or accompanying this e-mail or any attachment. This e-mail has been scanned using Skeptic(TM) technology powered by MessageLabs.

11/3/2010

### ..... 

### Page 1of3 Murphy, Jim From: IWASZKOWIEC, CARLOS [STL] [CARLOS.IWASZKOWlEC@MECSGLOBAL.COM] Sent: Monday, November29, 2010 11 :48 AM To: Murphy, Jim Cc: WARREN, LINDA P [STL]; IWASZKOWlEC, CARLOS [STL] Subject: RE: Catalist PO H26667 and Shipments Jim, As a follow up to your phone call/request last Wednesday regarding the subject plus additional catalyst you will need for the March shutdown, here is the status on what is left to ship plus the additional amounts you are requesting MECS to quote: Existing PO

# ~ 

# rtJ JJIi JI4 Ifll"lff)

# r~ 

# (.)
) II.J)

# p,;, tj,..1

- XLP-11 0 (1,200 Itr bags) 22,800 literto ship in February

. 

# .",-7 "J..NIJ P4 

### ,2- XLP-220 " 63600 liters
- Shipped 51,600 - to ship in February 12,000) T,**8~** 

### , :Jf 3 - XCS-120 20,000 liters
- Shipped ,

### ~ 

## '4 #{ 

### 1'1"; 

# ..,**~_~** 

# \., V /' FEf3 /1\( Additional quantities you requested (also to be shipped in February): '" . \ 1- lJ \I" 1 • XLP-220 (1,200 Itr bags) 10,800 liters Price $3.85I1iter FOB shipping point 

# L 2 - XLP-11 0 (1,200 Itr bags) 21,600 liters Price $3.85I1iter FOB shipping point ./' 3 - Cs-11 0 (1,200 Itr bags) 34,')0 liters Price $7.25/liter FOB shipping point V Please note that we kept the price as perthe existing order and, an easy way to transact this additional amount would be to issue another revision to it. Let me know ifyou have any questions and ofyour decision, so we can lock this in to be delivered in February. Thanks, Carlos Iwaszkowiec MECS,lnc. 14522 South Outer Forty Road Chesterfield, MO 63017 Ph.: 314-275-5742 Fax: 314-275-5918 Cell: 314-308-4916



### From: IWASZKOWIEC, CARLOS [STL] [mailto:CARLOS.IWASZKOWIEC@MECSGLOBAL.COM] 

## Sent: Wednesday, November 03, 2010 11:09 AM 

### To: Murphy, Jim; Robles, Gilbert 

## Cc: Stacy, Donna; Hise, Doyle G.; Jimenez, Juan; WARREN, LINDA P[STL]; Fernandez, Alberto; WINKLER, CHRISTOPHER D; FULGHUM, WAYNE L[AVON]; David Huerta Castillo Subject: Catalist Shipments Importance: High Jim/Oscar, 51 k+ liters ofXLP-220 (two trucks) will be leaving ourwarehouse near N. Orleans this afternoon with team drivers; the catalyst is being loaded as we speak; we will get the driver's cell phones and pass it to you so their progress can be monitored; according to Google maps, from N. Orleans to Hayden it is
­



### 12/2/2010

### Page 2of3 1,500 miles; I don't know what the restrictions are even on team drivers, but I expect there might be some down time, so ETA could be Friday or early Saturday. The 20k liters ofXCS-120 will be shipped (tomorrow/Friday) from MECS plant in Avon, CA, also with team drivers and should be there Saturday sometime. Once we get cell phones, weill pass these to you. As I don't have all the e-mails, please pass this on to the other folks that were in the conversations/contacted about this. From our end, Linda Warren is coordinating this order/shipment and will be sending the invoice forthe 30% shortly. Her phones are: office
- 314-275-5748. Oscar, we need a change orderto add the 20k liters ofXCS-120; price is $7.25/liter exworks. The balance ofthe orderwill be shipped later in time for your April SID. Ithink I covered all that was discussed; if not call1e-mail me. Thanks Carlos Iwaszkowiec MECS, Inc. 14522 South Outer Forty Road Chesterfield, MO 63017 Ph.: 314-275-5742 Fax: 314-275-5918 Cell: 314-308-4916



### This e-mail contains information intended only for the use ofthe individual or entity named as the addressee. This communication may contain infonnation that is the confidential and proprietary property ofMECS, Inc. Ifthe reader ofthe e-mail is not an intended recipient or the employee or agent responsible for delivering it to an intended recipient, any review, dissemination, distribution or copying is strictly prohibited. Ifyou have received this e-mail in error, please immediately notify us at (314) 275­ 5700 and delete the copy you received. All e-mails and attachments sent and received are subjectto monitoring, reading and archival by MECS, Inc. The recipient ofthis e-mail is solely responsible for checking for the presence of"Viruses" orother "Malware". MECS, Inc. accepts no liability for any damage caused by any such code transmitted by or accompanying this e-mail or any attachment. This e-mail has been scanned using Skeptic(TM) technology powered by MessageLabs. This e-mail contains information intended only for the use ofthe individual or entity named as the addressee. This communication may contain infonnation that is the confidential and proprietary property ofMECS, Inc. Ifthe reader ofthe e-mail is not an intended recipient orthe employee or agent responsible for delivering it to an intended recipient, any review, dissemination, distribution orcopying is strictly prohibited. Ifyou have received this e-mail in error, please immediately notify us at (314) 275­ 5700 and delete the copy you received. All e-mails and attachments sent and received are subjectto monitoring, reading and archival by MECS, Inc. The recipient ofthis e-mail is solely responsible for checking for the presence of"Viruses" orother

12/2/20]0