Air Products Pressure Swing Adsorption at the National Carbon Capture Center

Project Objectives

Gasification is a promising alternative to traditional coal-fired combustion that can be adapted to CO2

capture while supplying synthesis gas (syngas) for hydrogen, power, or chemical products. A key

challenge for coal gasification is to reduce its cost. Downstream processing of syngas for CO2 capture

requires separation of the crude stream into the desired products (H2/CO), a sulfur stream (primarily H2S),

and sequestration-ready CO2. The process most commonly employed for this separation is acid gas

removal (AGR) based on absorption in a physical solvent. Air Products has developed a proprietary

alternative that consists of two process blocks: Sour Pressure Swing Adsorption (PSA) that separates CO2

and H2S from the desired products, and a tailgas disposition block which separates the sulfur-containing

compounds and purifies the CO2 to a sequestration-grade product (see Figure 1). Sour PSA is the key

enabler of the technology, but only limited testing of the adsorbent technology has been performed on

high-hydrogen syngas streams.

Methanol
H2 + CO
FT Diesel
H2
GTCC
Sour Power
PSA Generation
~ ~
Air N2
HRSG

1 Claus / Sulfur

H2S 2 CPU / Sulfuric Acid

CO2
Tailgas
Disposition CO2
Technology
Vent

Figure 1. Sour PSA System

 Air Products successfully demonstrated under DOE project DE-FE0007759i a 4% reduction in cost of

electricity (COE) from a low-rank coal-based, integrated gasification and combined cycle (IGCC) plant

with CO2 capture. This represents a 14% decrease in the cost of carbon capture compared to the NETL

S3B reference caseii. However, testing to date was only conducted for one week periods of time and did

not allow for prolonged stability testing on authentic syngas. This is a critical limitation for

commercialization that will be addressed in our proposal.

In this project, Air Products proposes to operate a two-bed mobile system at the National Carbon

Capture Center (NCCC) facility. A slipstream of authentic, high-hydrogen syngas based on low-rank coal

will be evaluated as the feedstock. Testing will be conducted for approximately eight weeks, thereby

providing far longer adsorbent exposure data than demonstrated to date. By utilizing real-world, high-

hydrogen syngas, information necessary to understand the utility of the system for methanol production

will be made available.

In addition, Air Products will also operate a multi-bed PSA process development unit (PDU), located

at its Trexlertown, PA headquarters, to evaluate the impact of incorporating pressure equalization steps in

the process cycle. This testing will be conducted utilizing a sulfur-free, synthetic syngas, and will improve

the reliability of the prediction of the system’s operating performance at commercial scale.

Finally, information obtained from both the two-bed PSA system operated with authentic high-

hydrogen syngas and the multi-bed system operated with synthetic syngas will be combined to build a

techno-economic analysis (TEA) of Sour PSA utilization for methanol production. It will also be used to

update the TEA already completed for IGCC in the above-referenced DOE project.

i
. Advanced Acid Gas Separation Technology for the Utilization of Low Rank Coals, DE-
FE0007759, Dec. 2012
ii
. Black, J.B. “The Cost and Performance Baseline for Fossil Energy Plants - Volume 3A: Low
Rank Coal to Electricity: IGCC Cases,” DOE/NETL, 2010/1399
Background

The major benefit of Sour PSA discovered in the techno-economic studies conducted to date is the

reduction in capital cost of the acid gas removal system. Estimates from studies on H2 production for

refinery applications and clean power indicate a projected savings of >14% in capital cost for purifying

the syngas and producing CO2 and sulfur products. This leads to a significant reduction in the cost of CO2

capture. Based on CO2 capture case studies conducted to date, Sour PSA technology and Rectisol® and

Selexol™ technologies are about the same on an operating cost basis. When producing power from a

high-sulfur fuel, up to an estimated 4.5% of additional net power is produced from the plant.ii,ii The results

are sensitive to the feedstocks and gasification technology employed. Recent experimental validation of

the models used to predict the benefits of a large-scale, commercial plant was key to increasing

confidence in the results of the studies. A long-term study of Sour PSA performance on gasified low-

rank coal is essential to provide a more robust assessment of the system’s long-term performance and

economic benefits when applied to syngas plants. A comparison of state-of-the-art acid gas removal

technologies and the Sour PSA system is presented in Table 1.

 Table 1: Comparison of Technologies for CO2 Capture from Gasification Systems
Capability Conventional Technologies - Air Products’ Advanced CO2
(physical solvent absorption process Capture System
such as Selexol™ or Rectisol®)
Applicable end markets Power, syngas or H2 (with some Power, syngas, H2 or Poly-gen
(Clean Power/Syngas/H2) limitations) or combinations thereof
Produce product gas at Yes Yes
pressure
Ability to produce high- No, needs another unit operation Yes
purity H2 (PSA). Needs a sink for low BTU
PSA tail gas.
Ability to produce high- Good; but limitation on purity from Better; non-acid gas impurities like
quality syngas non-acid gas impurities; N2, Ar, CH4, N2, Ar, CH4 removed by PSA
etc., slip to product
Availability of high- Single location-sour syngas cooling Multiple locations - both oxy-
quality heat system combustion system and sour syngas
cooling system
Capital expense Significant portion of power plant Reduced portion of power plant
scope scope
Operating expense Solvent costs and power costs Incremental O2 for combustion. CO2
(especially for refrigeration). CO2 compression power.
compression power.
Economies of scale Economic only at large scale Economic at small and large scale
Carryover of Yes, solvent losses to product gas No, application of solid sorbent in a
contaminants to syngas fixed bed
Claus plant required Yes No, optional
Sulfur export form H2S (for later processing) H2SO4 or H2S (for later processing)
Amenable for CO2 Yes, with design changes Yes
capture
Ability to retrofit for CO2 Yes, but may require major Yes, capture grade available without
capture modifications major modifications
% CO2 capture ~90% max; > 90% requires more >95%
extensive integration, unit operation,
and capital and operating expense
A. OBJECTIVES

In this project, Air Products proposes to operate a two-bed mobile pressure swing adsorption

(PSA) unit at the National Carbon Capture Center (NCCC) facility utilizing a slipstream of authentic,

high-hydrogen syngas generated from low-rank coal. Testing will be conducted for approximately eight

weeks, therefore providing data on a far longer adsorbent exposure period than has been demonstrated to

date. By utilizing high-hydrogen syngas, it will provide information necessary to further understand the

utility of the system for methanol production. Air Products will also operate a multi-bed PSA process

development unit (PDU), located at its Trexlertown, PA headquarters, to evaluate the incorporation of

pressure equalization steps in the PSA cycle, and to improve predictions of system operation at

commercial scale. This testing will be conducted utilizing a sulfur-free, synthetic syngas. Lastly,

information obtained from the PSA system operated with authentic high-hydrogen syngas and the multi-

bed system operated with synthetic syngas will be combined to 1) build a techno-economic assessment

(TEA) of PSA utilization for methanol production; and 2) update the existing TEA for IGCC provided in

DOE project DE-FE0007759. The entire project will be conducted in one budget period. The objective of

Task 1 is to manage the project efficiently and cost-effectively. The objectives of Task 2 are to construct a

weatherproof, mobile system containing a guard bed unit in series with a pre-existing Sour PSA unit, and

to install the mobile system in a suitable location at the NCCC facility in Wilsonville, AL. In Task 3, the

objective is to evaluate PSA performance with authentic syngas containing high levels of CO and H2 in

prolonged testing for approximately eight weeks. The objective of Task 4 is to operate a multi-bed PSA

incorporating pressure equalization steps, utilizing a sulfur-free, synthetic syngas. The objectives of Task

5 are to perform a TEA based on the experimental data to predict the economic benefits of incorporating

Sour PSA for chemicals production from low-rank coal, as well as to update the TEA for the already-

conducted IGCC case.

Task 3.0 – Operate TSA and PSA Unit and Evaluate Performance

Subtask 3.1. Operate the TSA/PSA Module. After connecting them to the NCCC system (Task 2), Air
Products shall pack the guard bed and PSA vessels with fresh adsorbent. Air Products shall conduct a

series of CO and H2S breakthrough tests with the PSA to determine the initial adsorption capacities. The

mobile system will then be operated in cyclic mode with pressurized sour syngas from NCCC’s gasifier

(taken after gas cooling and knockout of condensable species by NCCC). Air Products, or NCCC with

Air Products’ guidance, will run the PSA in cyclic mode with sour feed gas for a total on-stream time of

approximately eight weeks. The PSA operator will modify the feed gas rate to maintain a desired level of

H2S in the PSA product gas. Air Products will then assess PSA stability and performance by evaluating

the CO2 and H2S rejection and the CO and H2 recovery to the product gas. The breakthrough of benzene

from the guard bed unit shall be monitored by gas chromatography (GC) to determine relative

performance during the test period. NCCC or Air Products shall periodically withdraw gas samples to

characterize the levels of H2, CO, CO2, H2S, and N2 in the feed, waste, and product gas streams. After

consultation with NCCC to determine the most effective approach, Air Products or NCCC shall determine

the fate of trace-level contaminants. At the end of the testing period, Air Products shall conduct a second

set of CO and H2S breakthrough experiments to determine if the adsorption characteristics of the PSA

have changed with exposure. Air Products will remove the guard bed and PSA adsorbent beds and ship

them to Trexlertown for sample extraction and post-mortem studies of the adsorbent.

Subtask 3.2. Conduct Post-Mortem Analysis. Air Products shall conduct lab tests, including thermo-

gravimetric analysis (TGA), surface area analysis and chemical composition, to evaluate the relative

condition of the exposed adsorbents. Air Products will conduct SIMPAC process simulations at the

experimental conditions of the Sour PSA tests and compare the results with the observed performance.

SIMPAC has been previously developed at private expense, and shall be considered as Restricted

Computer Software for the purposes of this project.

Test Unit Description

The test unit consisted of a pretreatment skid followed by a PSA skid. The pretreatment skid contained
a two-bed guard bed used to remove organic tar species from the raw syngas, an electrically classified

compressor for compression of the clean sour syngas to ~350 psig, and an air cooled cooler/knockout

assembly for rejecting water and other condensables from the sour syngas. This gas was then passed to

the sour PSA skid where it entered one of two PSA vessels containing adsorbent for the removal of

sulfur species and CO2. The cleaned gas exiting the PSA was characterized (flow, composition) and

vented to the NCCC thermal oxidizer. Each bed was cycled through the predetermined PSA cycle steps.

During the regeneration steps the bed was depressurized, purged with product gas at atmospheric

pressure, and then re-pressurized with product gas. Gas exiting the bed during regeneration was also

characterized and vented to the thermal oxidizer. The PSA product gas composition was monitored during

cycling. Once stable, the inlet and outlet gas flows / compositions and column pressure/temperatures were

measured during one cycle to provide data for comparing with process simulations.

Summary of Campaign

A set of CH4 and H2S breakthrough tests were conducted on each of the PSA beds before syngas

was introduced to the unit. The fresh adsorbent capacities were in line with the expected values from

previous isotherm measurements.

Feed of sour syngas to the system was started on 10/8/2014 at 10AM. The sour syngas passed

through the guard beds where organic tars were adsorbed. We monitored progression of the tars through

the bed by measuring the benzene level in the inlet and outlet syngas. The inlet level was typically around

300 ppm (molar basis) and no evidence of benzene was ever detected in the guard bed effluent gas.The

guard bed does a great job of eliminating tar species from the sygnas stream. H2S is also removed from

the gas by this adsorbent. Our previous experience at the Energy and Environmental Research Center

suggested that breakthrough of H2S from the guard beds would take about 2-5 days. Instead, in part due

to the much lower H2S level in the feed gas (~300 ppm compared to 2400 ppm), the breakthrough time

was much longer. After 8 days on sour syngas, we decided to accelerate the breakthrough of H2S by

feeding 0.5% H2S/He cylinder gas to the unit at atmospheric pressure, thereby loading the adsorbent with
H2S more rapidly than via the sour syngas. This approach was successful and sour syngas started to pass

through the guard bed on 10/21. The PSA was then started on the sour syngas feed.

The PSA operated for a total of 12 days, or 1460 PSA cycles, on the sour syngas. The guard beds

accepted sour syngas for a total of roughly 625 hours. In addition to processing sour sygnas, the PSA was

operated for another 560 cycles on syngas that did not contain H2S (before breakthrough in the guard

beds).

Five separate PSA operating points were characterized, two for syngas without H2S and three for

sour syngas. In all cases, the PSA operated at a feed pressure of ~300 psig, then was depressurized and

purged at about 5 psig. Performance results for one of the sour gas runs are listed below. The overall mass

balance was within 1%, while component balances were within about 8%. The PSA rejected nearly all of

the H2S (99.7%) and more than 95% of the CO2 in the feed gas. Product gas purity was maintained at 1.4

ppm H2S even though the feed level was around 250 ppm. The recovery of H2 to the product gas was

72%. Simulations are underway to compare the model predictions with these performance values.

The PSA system appeared to yield the same performance when similar process setpoints were

used at the beginning and end of the sour gas testing, suggesting that the adsorbent characteristics

remained stable through that period.

 After the syngas tests, another set of breakthrough runs were conducted, and the results showed a

very modest 3% reduction in the CH4 capacity and essentially no change in the H2S capacity. These

results are plotted in Figure 2 and support the observation of stable cyclic PSA performance.