ITP Materials: Branched vs. Linear Hydrocarbon … · • Economic Analysis: Economic calculations...

Tina M. Nenoff; [email protected]

Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under contract DE-AC04-94AL85000.

BranchedBranched vs.vs. Linear HydrocarbonLinear Hydrocarbon Separations with Novel Modified ZeolitesSeparations with Novel Modified Zeolites

Tina M. Nenoff, Mutlu Ulutagay-Kartın, Kaylynn Johnston, Gary R. Gray, Manuel Arruebo, Richard D. Noble,

Thomas M. Anderson

Sandia National Laboratories, Albuquerque, NM 87185Goodyear Chemical, Akron, OH 44316

Univers ity of Colorado, Boulder, CO 80309Burns & McDonnell, Kansas City, MO 64114

June 1, 2005DOE/Industrial Technologies Program (ITP)

Annual Review Meeting

Research Team

Sandia National Laboratories Ti na M. Nenoff Mutlu Ulut agay-Kartin Marcus G. Martin

University of Colorado Richard D. Noble Manuel Arruebo

Goodyear Chemical Gary Gray Kayl ynn Johnston

Burns & McDonnell Tom Anderson

Viable Process

Economic Analysis

Synthesis Characterization Molecular Modeling

Pilot-Plant Testing


BranchedBranched vs.vs. Linear Hydrocarbon SeparationsLinear Hydrocarbon SeparationsWith Novel Modified Zeolites CPS# 1779With Novel Modified Zeolites CPS# 1779

Schematic: Nonselective porous membrane support w/

Goal: develop modified zeolite adsorbents and membranes for energy efficient

selective molecular purification of isoprene sieve top layer in green.

Challenge: modified membranes show promise for isoprene purification, but need enhanced

Actual Membrane selectivity and lifetime for industrial streams Supports

• CeramicBenefits: replacement of energy intensive • Stainless steel distillation columns with energy-efficient, • Hybrid materials durable ambient separations materials

Potential End-User Applications: Isoprene purification; C2-C5,C7 separations (Energy savings)

FY06 Activities (continuation funds): Evaluate membranes and powders using multicomponent streams; lifetime studies; enrichment goals of 7% for binaries & 3% for quaternary streams

Participants: Sandia National Labs, Goodyear Chemicals Co., Univ. CO, Burns & McDonnell


BranchedBranched vs.vs. Linear Hydrocarbon SeparationsLinear Hydrocarbon SeparationsWith Novel Modified Zeolites CPS# 1779With Novel Modified Zeolites CPS# 1779

Barrier-Pathway Approach Barriers Pathways • low energy-efficiency • development of distillation separations of modified zeolite isoprene feedstock from adsorbents & membranes refinery mixture

• lack of high selectivity, • pilot bench-scale testing

long life, robust separations of bulk and membranes

materials at Goodyear facilities

• simultaneous economic analysis for implementation of technology

Critical Metrics • Isoprene: 7% enrichment translates to 12% Energy savings; baseline for implementation

• translation of technology to C2-C5, C7 stream purifications

GPRA FY2007 (est.) Isoprene Benefits 2020/year

Energy Savings 5 trillion Btu

Cost Savings $67 MM

Carbon Reduction 0.07 MM TCETina M. Nenoff; [email protected]

DOE/ITP Project Funding

“Novel Modified Zeolites for Energy-Efficient Hydrocarbon Separations”

Collaborative Research238K/yr OIT/IMF “Direct to SNL” 188K/yr Goodyear “In-Kind” 120K/16 mo. Univ, of Colorado via SNL 10K/yr Burns & McDonnell “In-Kind”

$1.3M / 3yr program (FY02-04) 50% “in-kind” industry funding, commenced 4/23/2002.


Goodyear/Sandia/UC/B&M Project Milestones

Milestones (current project) Yr1: Zeolite Modification and testing; Go/No Go

Initial Economic Analysis

Yr2: Selection of “best” modified zeo lite through characterization and testing; modification optimization

Yr3: Pilot Plant testing, material modification; In-depth economic calculations; Engineering Analysis

Commercialization Plans, pathways, risks (ie., FY06-09): target enrichments, figures of merit identified lifetime studies of modified zeolites (bulk vs. membranes)

with binary and quaternary gas mixes Go-No/Go decisions of membrane vs. adsorbents Module design, building & testing Partnerships: end users, module builders, economic analysis


Potential Energy Benefits to U.S.

• ) •

( )

;

• 2-C5 ’ ( ):

Chemical Industry Goodyear is the domestic leader in isoprene production (60%Economic Modeling from Burns & McDonnell shows 22% reduction in Energy of

Isoprene Process Using modified Zeolites membranes• Reduced environmental emissions:

steam generation; feedstock/raffinate transportation VOC's, COx's, NOx's

Extrapolation to C industries predicts 64 Trillion BTU s savings Burns & McDonnell

Btu/yr 2002 Trillion Billion lbs Btu lb./

Ethylene C2 214 53 4,058 Propylene C3 53 39 1,359 Butadiene C4 21 4 5,366

5 l 293

illi

i


Isoprene C5 0.4 8,000+ Tota

64 Tr on Btu’s

Source: CMAI - 2003 DOE/OIT Energy & Environ. Profile 2002

22 % Reduct on


Currently extractive and cryogenic distillations are the dominant separation technologies

Current vs. Proposed Technology


11 PresentationPresentationPresentation Back upBack upBack up

Objective: Reduced Energy Consumption Using Membranes

Current Isoprene Monomer Technology Proposed Isoprene Monomer Technology

PI

Specialty

TX

Isoprene

Isop

rene

Uni

t

Polymers n-pentane (99+%)isopentane

M

External Sales

Feed for Hydrocarbon Resins: Feedstock Pentadiene (55%) 2-MB-2 (15%) Wingtack

6-19 % Isopentane 15-60 % Isoprene

Product 7-20 % n-Pentane Raffinate10-20 % 1-Pentene, etc. External sales to “gas pools”

M = Membrane Location

Goals

Overall goal: develop novel modified zeolites for energy efficient hydrocarbon (HC) separations

Focus: surface control + framework modification =

selectivity (adsorption + molecular sieving)

Develop new separation-based adsorbents or membrane materials via "modification of commercially-available zeo lites"

Establish zeolite structure-property models for this technology & others (C2-C5)

Decrease energy consumption in the chemical & petroleum industries by employing these new & improved materials


Experimental

• Preparation of Zeolites: Bulk zeolites variations of framework and cations. Membranes hydrothermally synthesized, seeded growth methods.

• Bulk Carbonization*: The regenerated zeolites are carbonized by exposure to an inert carrier gas stream containing binary mixture of hydrocarbon at elevated temperatures.

• Characterization: The effect of bulk carbonization on pore size and acid sites studied with BET and NH3-TPD. Structures studied by XRD, ICP-MS & TGA.

• Separation Experiments: Pure and mixed gases at varying temperatures; bulk and membranes. RGA and GC used for permeation analyses.

• Economic Analysis: Economic calculations of energy and transportation savings for isoprene separation from a hydrocarbon stream are being evaluated by Burns and McDonnell.

• Modeling: Determination of Adsorption Isotherms underway.

Tina M. Nenoff; [email protected] * US Patent Pending: Nenoff, Thoma, Kartin; submitted 4/03

Results- Bulk Zeolites

5.1 x 5.5; 5.3 x 5.6highZSM-5 (MFI)

7.1lowZeolite-L (LTL)

7.4medium-highZeolite-Y (FAU)

6.6 x 7.7, 5.6highZeolite-β (BEA)

Pore diameter (Pore diameter (ÅÅ))Relative acidityRelative acidityZeolite typeZeolite type

5.5isoprene 5.1n-pentane

Kinetic diameter (Kinetic diameter (ÅÅ))HC typeHC type

BEA FAU LTL MFI 12 MR (3-D) 12 MR (3-D, cages) 12 MR (1-D) 10 MR (3-D), Intersecting

straight pores intersecting straight straight pores straight / sinusoidal pores pores


Bench Scale Reactor-Surface Modification

MFC Chille r & bubble r

Furnace RGA

Sandia bulk modification unit


Pilot-Scale Industrial Reactor

On-line GC

Retentate

Pe rme ate

Zeolite Membrane

He lium

MFC

Syringe Pump to Fee d HCs

He lium s wee p

MFC

Goodyear separation unit Tina M. Nenoff; [email protected]

Characterization of BulkModified and Unmodified Zeolites

Unmodified Modified

Micropore area measurements of modified vs. unmodified Na-Y samples. Pore size and pore volume reduction are monitored

by the adsorption of N2 at 77 K Tina M. Nenoff; [email protected]

Characterization of ModifiedZeolite Membranes (NMR*)

27

13C{1

Al MAS

H} MAS

• 27Al MAS NMR – Tetrahedral AlO4/2

• 1H MAS 1H MAS

– H2O, Si-OH sites – Minor, unknown

organics

• 13C{1H} MAS – Broad resonance

consistent with char

Tina M. Nenoff; [email protected] *Robert Maxwell, LLNL

50

50:

400:

400:

Pilot Scale Testing of Unmodified ZSM-5with Different Si/Al Ratios

Unmodified Bulk ZSM-5 Separation Experiments

0

50

100

150

200

250

300

350

0 100 120

#2

#2

#1

#1

Si/AlSi/Al

20 40 60 80

min

gc a

rea

:1 Permeate P

1 Permeate Is opr ene

1 Permeate Pentane

1 Permeate Isoprene

Pentane

50:1 400:1


Pilot Scale Testing of Various BulkModified Zeolites

GC

are

a

Permeate Isoprene vs. Modified Zeolite Types 300

250

200

150

100

50

0

#2 ZSM-5

K-L

Na-Y

#1 ZSM-5

Cs-Y

0 10 20 30 40 50 60

min Tina M. Nenoff; [email protected] Longer time to desorb isoprene : 50:1 (#2 ZSM-5)

Pilot Scale Adsorption Selectivity Testing of Modified ZSM-5

50

1

0

100

150

200

250

300

2

3

4

5

6

7

8

y

Are

a

Adso

rptiv

e Se

lect

ivitRetentate

Pentane

Retentate Isoprene

Permeate Pentane

Permeate Isoprene

Adsorptive Selectivity

0

0 40 80 1 20 16 0 200 240 280

Time (


Demonstrated isoprene/pentane separation using modified zeolite in dilute concentrations

Initial experiments show selectivity towards isoprene separation

min)


H-Y 30:1 Zeolite Powder

0

50

100

150

200

250

300

0 200 400 600 800 1000 1200Time (min)

0

1

2

3

4

5

6

7

8

9

10

11

12

Adso

rptiv

e Se

lect

ivity

Retentate Pentane

Retentate Isoprene

Permeate Pentane

Permeate Isoprene

Selectivity

Protected CRADA Information

H-Y 30:1 Powder @100C, 50/50 n-pentane/isoprene

Pilot Scale Testing of ModifiedProtonated ZSM-5

200 250

Pilot Scale Testing of Bulk ModifiedZSM-5 vs. Temperature

n-

0

50

100

150

200

250

300

0 100 150 ( )

0

50

100

150

200

250

300

0 40 60 80 100 120 (min)

imi ii i

Modified zeolite

Isoprene/pentane mixture

ZS M-5 Modifie d

50 Time min

GC

area

RT C P 100 C P RT C I 100C I

ZS M-5 Modifie d

20 Time

GC

area

RT C P 100 C P RT C I 100 C I Temperature opt zat on

stud es cont nue


M 59 Silicalite-1 SEPARATION ISOPRENE/n-PENTANE WITH TBC

Pilot-Scale Tubular Membrane Testing on Various Temperatures

6.00E-08

Separation selectivity

isoprene permeance

n-penta ne permeance 40.0

35.0 5.00E-08

30.0

4.00E-08 25.0

Perm

eanc

e [m

ol/P

a.s.

m2 ]

Sepa

ratio

n Se

lect

ivity

3.00E-08 20.0

15.0 2.00E-08

10.0

1.00E-08 5.0

0.00E+00 0.0 0 50 100 150 2 00 250

Temperature [oC]

(≈ )/n


Initial separation experiments 3% enrichment on tubular membranes demonstrate the possibility of isoprene -pentane separation

Pilot-Scale Modified Zeolites on Tubular Membrane

Permeance (mol/Pa-s-m2) Permeance Results for Tubular Membra

Temperature MK-7-37 MK-7-39 25 #N/A 3.00E-08

23.5 3.50E-08 #N/A 60 5.30E-08 #N/A

1.0E-07

8.0E-08

6.0E-08 Process Info

Retentate & Sweep Rates = 50 ml/min Organic Rate = 0.25 ml/hr

Total Organic Composition in Feed ~ 2.1 mole % Isoprene/Pentane (by volume): 50/50

4.0E-08

2.0E-08

0.0E+00 0 20 40 60 80

MK-7-37 MK-7-39

Membranes MK-7-37 Modified B-ZSM-5 Tube MK-7-39 Modified Al-ZSM-5 Tube

Temperature (oC)

(from 10/15/2004 batch from Mutlu)

⇒


Similar pentane permeance values as previously reported but with zero isoprene permeance! Results: 4.1% enrichment

Economic Analysis Based on MembraneSeparation Results


Separation % isoprene % Energy Performance enrichment Savings

Base 0 0 Demonstrated 3.0 6 Best case to date 4.1 7.8 Goal 6.7 12

Realistic and possible!Realistic and possible!

Pentane

Possible Module Design

Enhanced Selectivity: Molecular Sieving + Adsorption

Feed Isoprene Isoprene Enriched Pentane

• •

Pentane Isoprene


Conclusions

• Adsorption/desorption on bulk unmodified zeolites showed isoprene adsorbed by zeolite-L and n-pentane adsorbed by zeolite-Y and ZSM-5.

• Bulk carbonization is used to passivate zeo lite activity toward organic adsorption/decomposition.

• Based on the bulk modified zeolite separation results, we have determined that the MFI type has the most potential for isoprene enrichment.

• Modified MFI type membranes are are jointly made by Sandia and the Univ. of Colorado. Separation experiments are performed by Goodyear Chemical.

• Isoprene/n-pentane separations have been demonstrated by using both zeo lite membranes and modified bulk zeolites at various temperatures on the Goodyear Pilot-scale unit.

• Target zeolite membrane separatio ns values of 6.7% isoprene enrichment have been established by economic analysis calculations by Burns & McDonnell.


Project Timeline - Proposed

igatiigati2001

l2006

l

2009

Detailed Invest on 2002-2005

Preliminary Invest on Deve opment Validation

2007-2008

CommerciaLaunch

Identification of most promising Zeolite type and

Modification process for Isoprene separation

From butane

Modif ication of zeolites By carbonization

Synthesis and testing of Modified zeolite

Membrane testing On complex simulants

Module design, building, & testing Pilot plant start-up

Separations testing in Module with

Simulant mixtures Comparison studies & downselect btwn

Membranes & bulk (PSA)

l ical decision

ienri

i

i

i

li

il

ii i


Exploratory Research

Deve opmental Research

Validation Research

TechnSupport

Milestone stage-gate

points

6.7% soprene chment 4.1% Isoprene

Enrchment

Sy nthes zed Defect-f ree

Zeolte membranes

Deveopment of cost-effectve

separat on techno ogy

Lifet me studies

Membranes at Goodyear On b nary m xture

Acknowledgements

• Funding from the DOE/Industrial Technology Program.

• Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under contract DE-AC04-94AL85000.

• Modeling of Adsorption Isotherms: Dr. Marcus Martin, SNL • MAS NMR : Dr. Robert Maxwell, LLNL

• For more info: www.sandia.gov/nenoff


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