AIChE Paper 13F Use of Molecular Sieves and other Adsorbents for Contaminant Removal in Ethylene and Propylene

Production
Jay Gorawara Senior Development Associate Catalysts, Adsorbents and Specialties
UOP LLC A Honeywell Company

UOP LLC All Rights Reserved

Prepared for Presentation at the 2009 Spring National Meeting Tampa, FL, April, 26 30, 2009

AIChE and EPC shall not be responsible for statements or opinions contained in papers or printed in its publications

Use of Molecular Sieves and other Adsorbents for Contaminant Removal in Ethylene and Propylene Production
Jay Gorawara Senior Development Associate Catalysts, Adsorbents and Specialties UOP LLC

Abstract: Ethylene and propylene producers have faced the challenge of contaminants for decades. Adsorbents, both molecular sieve and alumina based, have been successfully used to help olefin producers manage their operations as contaminated feeds and increasingly sensitive polymerization catalysts continue to offer them increasing challenges. The most widely used adsorbents are the 3A based molecular sieve products utilized to remove water from the cracked gas, liquids, ethylene-ethane and hydrogen. Elsewhere in the production of ethylene, adsorbents are used to remove not only water but also other contaminants from product ethylene and propylene. As we move downstream to the polymer plant, contaminants are a problem for sensitive polymerization catalysts and polymer quality. Catalyst life can be greatly diminished by the presence of oxygen compounds, sulfur compounds, nitrogen compounds and even arsine and phosphine. In this part of the plant, adsorbent beds of various combinations can be utilized to remove a variety of compounds. Key to trace contaminant removal from olefinic streams is the use of adsorbents with low reactivity towards the process stream. Although adsorbents are a cost effective option for olefin stream dehydration and purification, it is critical to select the right product. Selection criteria for matching adsorbent products with specific streams and contaminants as well as tips for optimal operation will be covered.

Use of Molecular Sieves and other Adsorbents for Contaminant Removal in Ethylene and Propylene Production

Introduction

Adsorbents such as molecular sieves and activated aluminas are widely used in the processing industries to remove water and other contaminants. The use of adsorbents in ethylene and propylene production and downstream processing, however, is typically more demanding because of the reactive nature of the streams processed. Type 3A based molecular sieves, promoted activated aluminas, and combinations of larger pore molecular sieve and promoted aluminas have the advantage of being able to operate in reactive environments without special processing steps. They are capable of removing detrimental impurities to extremely low levels to avoid endangering plant equipment, achieving design throughput, or poisoning sensitive downstream catalysts. The process typically involves passing the contaminated stream through one or more beds at ambient temperature to remove (adsorb) the contaminants, while simultaneously, heating a previously contaminant loaded bed with hot gas at a high temperature (>400 F) to desorb the contaminant. The hot bed is then cooled and is ready for another adsorption step. Although dehydration of reactive process streams is still one of the largest applications for adsorbents in ethylene and propylene production, in recent years there has been a growing need for the removal of other contaminants in ethylene and propylene production. This paper will discuss the capability of these adsorbents to remove many contaminants in reactive streams using both regenerative and non-regenerative adsorbents, show where current applications exist, and help processors identify potential applications to improve their operation or upgrade the quality of their products.

Zeolite Molecular Sieves

Zeolite adsorbents are synthetically produced molecular sieves that are microporous, crystalline, metal aluminosilicates. Metal cations contained in the crystalline structure of molecular sieve adsorbents balance the negative charge of the framework. These metal cations create an electrical field resulting in a strong attraction for polar molecules. Higher polarity generally results in a higher attraction for a molecular sieve. Table 1 shows the relative polarity of common impurities and carrier streams found in ethylene and propylene production and processing. Because of its high polarity, water can be removed by molecular sieves from most process streams. Table 1
Order of Selectivity Water Ammonia Methanol Hydrogen Sulfide Carbon Dioxide Carbonyl Sulfide Propylene Ethylene

The size of the pore opening on each face into the internal structure where the contaminants pass through is determined during manufacturing by the type of crystal and occupying cation (Figure 1). Thus some molecules can be readily adsorbed or completely excluded (even highly polar molecules) according to their relative molecular size.

Figure 1. Zeolite Type Sodium A

Table 2 lists the two types of molecular sieve adsorbents most commonly used for olefin processing and the molecules that they will adsorb and exclude. Table 2 *General Molecules Adsorbed Type 3A <3 angstroms effective pore diameter H2O , NH3, 13X <8 angstroms effective diameter H2O,NH3, CH3OH, H2S, CO2, C2H4, C3H6 **Larger Oxygenate and Sulfur compounds Molecules Excluded >3 angstroms effective diameter acetylene, ethylene, propylene and larger hydrocarbons >8 angstroms effective diameter All common contaminants and hydrocarbons in ethylene and propylene processing are smaller than 8 angstroms

* Chart depicts basic molecular sieve types only. In all applications, these basic forms are customized for specific use. ** Typically found in C4+ olefins present in refinery streams

Type 3A molecular sieve is highly effective for removal of water and ammonia to extremely low levels from reactive streams in ethylene plants because of the polarity of these contaminants and the fact that the reactive carrier stream components are excluded. As long as a non-reactive binder with high breakup resistance is used to form the finished molecular sieve product, long life is expected. Because Type 13X zeolite molecular sieve has one of the highest capacities of any molecular sieve for most polar compounds and will adsorb larger contaminants such as branched chain oxygenates and sulfur compounds, it is frequently used for contaminant removal from olefinic streams. Type 13X and other large pore molecular sieves require special operating procedures when used in an olefin stream where they readily adsorb the carrier stream. When a molecular sieve adsorbs a compound, heat is released. Most contaminants are at low enough levels that the heat release is minimal. But when the adsorbed compound is at high level such as in a stream containing significant olefins, a large amount of heat can be released triggering possible exothermic reactions that endanger equipment and personnel. To prevent this situation, a preload step is used before the initial exposure of a fresh or regenerated adsorbent to the olefin containing stream. This procedure involves using a low (<5 wt%) concentration of the olefin in a non-adsorbed carrier stream to slowly saturate the adsorbent with the carrier stream olefin and safely remove the heat of adsorption. The operating sequence is illustrated in Figure 2.

24

32

38

48 Hours

PRELOADING

COOLING

HEATING

Bed 1

ADSORPTION

PRELOADING

COOLING

HEATING

Bed 2

ADSORPTION

14

24

48 Hours

Figure 2. Typical Adsorber Operating Sequence It is also possible to use type 4A and 5A molecular sieves to dry and purify olefin streams. However, there is typically no advantage over 13X since they adsorb the reactive components such as ethylene and propylene, have lower overall capacity, and cannot adsorb larger oxygenate and sulfur compounds.

Promoted Aluminas

Modified activated alumina adsorbents are synthetically produced, transitional phase aluminas. Unlike zeolites, activated aluminas have a pore system that is accessible to practically all compounds present in ethylene, propylene and polymer plants. Hence, the size exclusion phenomenon cannot be used in alumina based adsorption processes. Instead, the complex surface chemistry of aluminas offers tremendous opportunities for designing adsorbents for particular applications. The modification of surface functionality by inorganic additives, or promoters, during manufacturing is an especially useful method for enhancing adsorbent performance. The promoted alumimas have excellent performance for removal of specific contaminants to very low levels. In olefinic streams, light acid gases such as CO2, H2S and COS are common contaminants that can be most effectively removed with this type of modified activated alumina. As these aluminas rely on chemisorption to remove CO2, H2S and COS, they exhibit high capacities for these contaminants even at very low concentrations.

These promoted alumina adsorbents also have the additional advantage in that unlike molecular sieves, they do not have a strong affinity for reactive, polar compounds such as olefins. With little or no selective capacity for olefins, there is a very low heat of adsorption when olefins are exposed to promoted aluminas, hence a preload step is not required. In addition, these adsorbents exhibit very low reactivity towards the main carrier stream. The formation of additional contaminants, such as olefin oligomers, is practically non-existent at typical process conditions. By combining high selectivity and capacity for light acid gases with low reactivity and heat of adsorption of hydrocarbons, a properly modified activated alumina is very suitable for the purification of olefinic streams. Correspondingly, molecular sieves have a high capacity for polar molecules. Ideally, one adsorbent could exhibit the properties of both zeolitic and promoted alumina adsorbents. A hybrid adsorbent, a homogenous combination of a promoted alumina and a large pore molecular sieve adsorbent can take advantage of the complementary performance characteristics of both materials. A properly designed high quality hybrid adsorbent can simultaneously have good capacity for light acid gases as well as a broad range of polar molecules. Though a hybrid adsorbent contains zeolite, when properly produced it typically may not require a preload step when processing olefinic hydrocarbons. The elimination of the preload step, while retaining the effective removal of polar compounds and light acid gases, provides the olefins producer and polymer manufacturer with significant process advantages. The unique properties of a hybrid adsorbent may enable the processor to use a single product for the adsorptive removal of the broadest range of contaminants without a preload step. The result is an adsorbent that provides additional protection against unanticipated contaminants with a simplified and safer process. There are various hybrid adsorbents available in the market today and the characteristics discussed above may vary. Consult your adsorbent supplier to clarify operating procedures for your operations. This class of adsorbents is a must have for propylene purification, where the removal of contaminants such as AsH3, PH3, COS to low part per billion (ppb) levels is critical for the economic production of polypropylene. These trace contaminants adversely effect performance of the very sensitive modern polymerization catalysts. The metal oxide component in these adsorbents irreversibly binds the hydride contaminants via an oxidationreduction mechanism; hence water is a by-product of the reaction. It is critical for these advanced metal oxide adsorbents to have high contaminant capacity combined with low reactivity towards the carrier stream. An optimized pore structure is also essential for this liquid phase application. A high binder surface area can help to retain the water produced in the arsine and phosphine scavenging reactions.

Hybrid Adsorbent

Metal Oxide Containing Adsorbents

Note: There is a potential for the metal oxide products to form hazardous (potentially explosive compounds) in the presence of acetylene under certain conditions. Consult your adsorbent supplier for recommendation of the proper adsorbent, as well as operating procedures for your operations. Table 3 shows the comparative performance and typical processing recommendations of various adsorbents for specific contaminants found in ethylene plants, propylene production, downstream storage systems and polymer plants. Depending on the contaminant type, either a molecular sieve, a promoted alumina or a metal oxide containing adsorbent has the highest capacity. Type 13X requires a preload step; however, hybrid adsorbents offer the broadest range of contaminant removal typically without requiring a preload step, although it may be at the expense of somewhat lower capacity. Ideally, adsorbents should not exhibit any appreciable catalytic activity towards the stream to be purified. Most adsorbents fulfill this requirement when used in non-reactive streams, but potential problems arise in the case of reactive feeds. This topic was discussed in a previous AICHE paper written by Vlado Kanazirev and Dave Smith, Adsorbent Reactivity: An Important Factor in Contaminant Removal presented in 2004. One of the important potential reactions is the oligomerization of olefins which can occur over strongly acidic sites on the adsorbent. These oligomerization reactions are exothermic, can cause uncontrolled temperature excursions, and are hence a safety concern. In less severe cases, green oil can be produced which results in deposition of heavy hydrocarbons and coke precursors on adsorbents, thereby reducing their efficiency and operational life. In addition, it is possible to form different contaminants than those present in the carrier stream by reactions catalyzed between the carrier stream and the contaminants, or between the contaminants themselves. The challenge in such cases is that some of the newly created contaminants may be more difficult to remove than the original ones. Some metal oxide containing adsorbents, can create by-products while removing the targeted contaminant. Figure 3 is a plot measuring the temperature of initiation of polymerization of isobutylene over various adsorbents. This type of testing is useful to rank the relative reactivity of various types of adsorbents. The temperature at which the pressure of isobutylene decreases is an indication of the onset of polymerization activity. Hence, more reactive adsorbents will polymerize isobutylene at lower temperatures. For example, both of the 13X materials tested are more reactive than the AZ-300 adsorbent, and the 3A shows no measurable reactivity. Note from the plot that the reactivity of similar materials can also vary between adsorbent manufacturers.

Comparative Performance of Various Adsorbents in Olefin Service

800 Onset of Polymerization 600 Pressure, psig

13X MOLSIV Adsorbent Empty Cylinder 3A Adsorbent AZ-300 Adsorbent

400

200

13X-Source A

0
0 100

Selective Adsorbent 2

200 Temperature, oC

300

400

Figure 3: Isobutylene Conversion at Process Relevant Conditions Adsorbent Reactivity Testing Table 3 Comparative Product Capabilities for Contaminant Removal from Olefins* Contaminant Contaminant Family Oxygenates Water CO2 Methanol **other Alcohols, Ketones, Aldehydes, Ethers and Peroxides Product Type Type 3A Hybrid Adsorbent Promoted Alumina Hybrid Adsorbent Modified 3A Hybrid Adsorbent Type 13X Hybrid Adsorbent Adsorbent Capacity High Moderate High Moderate High Moderate High Moderate Olefin Preload? No No No No No No Yes No

Sulfur compounds

H2S COS **Mercaptans, Sulfides and Disulfides **Amines and Nitriles Ammonia

Promoted Alumina Hybrid Adsorbent Promoted Alumina Hybrid Adsorbent Type 13X Hybrid Adsorbent Type 13X Hybrid Adsorbent Modified 3A Hybrid Adsorbent HgSIV-3 ***Metal Oxide Product ***Metal Oxide Product

High Moderate High Moderate High Moderate High Moderate High Moderate High High Low

No No No No Yes No Yes No No No No No No

Nitrogen compounds

Other

Mercury Arsine Phosphine

* Based on UOP products and experience ** These compounds are typically found in C4 olefins sourced from crude oil refineries *** Non-regenerative

The many locations where adsorbents are currently removing contaminants from ethylene and propylene production streams and downstream processing are shown in Figures 4A, 4B and 4C. Table 4 shows the contaminants being removed, the products employed, and the typical reactive components in the carrier stream for those locations.
Ethylene

Steam Injection

Acetylene Converter

Feed Recycle Cracking Furnaces

4
H2

Primary Drier/Treater Quench Towers Compressors

C2 C3

Recycle

1
II III IV
Cold Box

C1/H2

Propylene

C2 Splitters

Secondary Drier/Treater

5
C3 Splitters

Drier/ Treater

Refinery Gas Drier/Treater Addl Contaminates

Acid Gas Caustic Wash

2
Cracked Liquid Drier
C2+ C3 + C4+ to Export

De-Methanizer

De-Ethanizer

De-Propanizer

Recycle

Figure 4A: Treating Reactive Feeds with Adsorbents in Ethylene Plants

Ethylene H2O Removal Drier

Ammonia & CO2 Removal

Treater

Polymerization Catalyst

Salt Dome

Polyethylene

Propylene H2O Removal

Oxygenates & Sulfur Removal

Drier

Treater

Polymerization Catalyst

Propylene Salt Dome

Figure 4B: Olefin Plant Adsorbent Applications

Propylene from Refineries

C4 and Lighter Crude Column Straight Run Gasoline Kerosene AGO Crude Oil VGO Gasoline

PRU

Propylene Fuel Gas LPG

FCC

Downstream Processing

Depropanizer

Deethanizer
C2-

C3 Splitter

Vacuum Column Vacuum Residue

Diesel Heavy Fuel Oil

Water Removal

COS Removal

Arsine Removal

10

Drier

11

Treater

12

Treater

Propylene Propane

C4+

Figure 4C: Propylene Recovery Unit

Table 4 Current Adsorbent Contaminant Removal Locations in Reactive Streams for Ethylene and Propylene Processing

Location 1

Adsorber Designation Cracked Gas Drier/Treater Cracked Liquids Drier/Treater Refinery Gas Drier/Treater

Reactive Components Diolefins, Olefins Diolefins, Olefins Diolefins, Olefins

Contaminants H2O Ammonia Mercury H2O Mercury H2O Ammonia H2O CO2 H2O Methanol COS, H2S

Type Adsorbents Used Type 3A Modified 3A HgSIV 3 Type 3A HgSIV 3 Type 3A Modified 3A Type 3A Modified Activated Alumina Type 3A Hybrid Adsorbent Modified 3A Modified Activated Alumina Metal Oxide Product Metal Oxide Product Type 3A Type 3A Hybrid Adsorbent

2 3 4

Secondary Drier Ethylene /Treater Propylene Drier/Treater Propylene

6 7 8

9 Not Shown

Dome Storage Ethylene Drier Dome Storage Polyethylene Plant Feed Drier/Treater Polypropylene Plant Feed Drier/Treater Polybutylene Plant Feed Drier/Treater

*Ethylene *Propylene Ethylene

Arsine / Phosphine H2 O H2O H2O, Ammonia, CO2

Propylene **Butenes

H2O, MEOH, COS, RSH Hybrid Adsorbent H2O, Alcohols, Aldehydes, Carbonyls, Ethers, Ketones, Peroxides Mercaptans, Sulfides and Disulfides Hybrid Adsorbent Type 13X

* Regeneration at high pressure with drier product or feed recycled to drier feed ** Contaminants typically found in crude refinery sourced butenes

Tables 3 and 4 can be useful for processors to help identify potential opportunities to use adsorbents to remove contaminants from olefin streams to help protect plant equipment, throughput, and expensive catalyst downstream.

Commercial Experience Ethylene Plants

In a typical cracked gas drier where dehydration is the only duty required, one would look for adsorbents with good attrition resistance, low reactivity, good mass transfer efficiency and predictable performance. UOP recommended the following configuration to a large ethylene producer in the Middle East, but this is very similar to numerous other installations around the globe.

1-inch Ceramic Balls Floating Screen

EPG-2 1/8-INCH

3A-EPG 1/16-INCH

1/ 1/ 1/

8-inch

Ceramic Balls Ceramic Balls

4-inch

2-inch Ceramic Balls

Bed Support

Figure 5: Typical Cracked Gas Drier for Dehydration

If additional contaminants, such as mercury and ammonia were required to be removed, UOP would recommend adding HgSIV-3 and MOLSIV EPG-N adsorbents as layers in the cracked gas driers such as seen in Figure 6.

1-inch Ceramic Balls 20 Mesh Floating Screen

3A-EPG-2 1/8 inch

3A-EPG 1/16 inch

3A-EPG-N 1/16 inch

HgSIV-3 1/16 inch

1/ -inch 8 1/ -inch 4 1/ -inch 2

Ceramic Support Ceramic Support Ceramic Support

20 Mesh Screen 4 Mesh Screen Bed Support System

Figure 6: Cracked Gas Drier with Hg and NH3 Removal

Propylene Production/Polymer Plants

There are three main sources of propylene; co-product from an ethylene plant, on purpose production by dehydrogenation of propane, and propylene from FCCU and coker units. Each of these sources contains varying contaminants. The propylene from an ethylene plant has fairly low levels of contaminants. A full bed of AZ-300 is an excellent choice as it will capture a wide range of unidentified contaminants. The treatment of propylene from a refinery is much more complex, as there are many more contaminants to be handled. Figure 7 shows the treating system designed for a Propylene Recovery Unit (with the mixed C3 feed supplied from both FCCUs and coker units) to assure very tight product specifications.
Two Beds in Regenerative Duty 1 Bed in Non-regenerative Duty

Product C3= to Polypropylene Plant

H2S, COS RSH, DMS, DMDS, COS, H2S H2O Feed C3= from FCC and Coker Units

SG731 AZ300 ODG442 GB238 COS, H2S, AsH3, PH3

Figure 7: An Asian Propylene Recovery Units Purification System

Removal of trace contaminants using adsorbents is one of the most economical methods of purification of a process stream. However, purification of very reactive hydrocarbon streams such as those present in ethylene and propylene processing is not straight forward. Selection of proper adsorbent products is critical in economically achieving product specifications, and operating the processes reliably and safely.

Conclusion

References Brayden, M. et al., Top 5 Contaminants in Ethylene Production Unit Feedstocks, AIChE 2008 Ethylene Producers Conference. Coleman, S. et al., Mercury Removal from Cracked Gas and Liquid Streams, AIChE 2004 Ethylene Producers Conference. Kanazirev, V., and Smith, D. L., Adsorbent Reactivity: An Important Factor in Contaminant Removal, AIChE 2004 Ethylene Producers Conference. Reid, J. A., and McPaul, D. R., Control Contaminants in Olefin Feedstock and Products, Hydrocarbon Processing, (September, 1996). Reid, J. A., An Overview of Hydrogenation Catalyst Poisons in Olefin Units, AIChE 2001 Ethylene Producers Conference. Sicard, J., and Richman, P., Product and Process Improvements in Cracked Gas Drying, UOP Brochure F-4343.