Remaining Challenges in the Processing of Hydrocarbons for Fuels and Petrochemicals ?

CPAC-SI 2010

July 2010 Seattle, WA

Overview
Why still worry about crude oil conversion ?
been achieved.

- Evolving energy scene, oil has peaked. - Mature technologies; far up on the learning curve; intrinsic potential has

Intrinsic potential of catalytic technologies Challenges and Enablers

- Feed characterization

- Understanding catalyst functionality

In situ characterization Mechanistic screening

Advances in analytical techniques for heavy oil fractions Finger-printing technology

- Kinetic modeling of complex systems

Data collection and work-up. Reducing dimensionality of hydrocarbon conversion kinetic modeling. Addressing multivariate complexity

- Process performance measurement in the field.

Conclusions.
2

File Number

IEA World Energy Outlook Reference Scenario

18,000 16,000 14,000 12,000
~2% fall in global energy demand 2007 - 10

10,000 8,000 6,000 4,000 2,000 0 1980 1990 2000 2010 2020 2030

Growth Rate Other Renewables 7.3% Biomass 1.4% Hydro 1.8% Nuclear 1.3% Gas 1.5% Oil 0.9% Coal 1.9% WEO- 2008 Total

Mtoe

(Source: IEA WEO, Oct 2009)

IEA Reference scenario assumes no changes from current global energy policies

- Could happen if world stays on current path

Oil would remain largest energy source by 2030 Continued strong growth of gas and coal

~ 2% fall in energy demand between 2007 10 Renewables fastest growth sector, 10% of supply by 2030
3

File Number UOP 5332AH_China-05

Product Demand and Specifications are Changing

50 45
MBPD

Oil Demand Growth

Developed Emerging

40 35 30

Global demand forecast to rise 1.7% in 2010 following two years of decline - Developed economies forecast to be flat in 2010 following 4.4% drop in 2009 Emerging economies will continue to grow
2009 = 2%; 2010 = 3.7%

Source: IEA

2008

2009

2010

2011

2012

2013

2014

Incremental Fuel Demand 2010-20

7

Diesel
Million BPD 5

OECD refining margins and utilization remain low (<80%) 1% of refining capacity in OECD idled in 2009, more to come Growth in transportation fuels, primarily diesel

Gasoline

Kerosene /Jet

Residual Fuel Oil

-1
Source: Purvin & Gertz, 2009 GPMO

UOP 5332AH_China-09 File Number

Fuel Specifications
10000 1000
Sulfur, Wt%

Diesel Sulfur (Indicative Trends)

5 4.5 4 3.5 3 2.5 2 1.5 1 0.5 0

Proposed MARPOL Annex VI Sulfur Specifications

Open Seas Emission Control Areas

100 10 1 2007

2010

2015
North America Asia Pacific

2020

2025

Europe Russia Africa Source: IFQC 2009

South America Middle East

Current

2012

2015

2020

Current Diesel Sulfur Specs

India and China

- Nationwide 350wppm - Metro 50 wppm

Higher quality fuels

More hydrotreating More hydrocracking More bottoms upgrading More hydrogen

Mexico UBA : 15 wppm (Northern frontier and metropolitan areas) Nationwide 500 wppm
5

UOP 5332AH_China-10 File Number

Progress in Mature Technologies

6,200 Octane Barrels / 100 Barrels Feed 6,000 5,800 5,600

Extended Riser New Reactor Concepts Improved Reaction Systems Octane Catalysts

5,400
Zeolite Catalysts

5,200 5,000 4,800

Amorphous Catalysts

Octane Barrel Capacity of FCC

1950 1960 1970 1980 1990 1996

So have we done everything possible in crude oil conversion ?

6
File Number

US Patenting Activity related to Fuels

Petroleum Processing/Refinery Engineering

Fuel Products Not of Petroleum Origin

3000 2500 No. Publications 2000 1500 1000 500 0 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 Publication Year
No. Publications

3000 2500 2000 1500 1000 500 0 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 Publication Year

Patenting Activity in Petroleum Processing Remains High

File Number

Intrinsic Potential of Technologies Heat and Mass Transfer

60

Relative Intensity

LESS

IDEAL PT CLUSTERS

36
CRUSHED

ATTENUATION

22 18 3
CURRENT NO HYDRAULIC LIMITATION ISOTHERMAL

CATALYST

Process Geometry
8
File Number

Intrinsic Technology Potential : Extreme control of Reaction Conditions

Selective hydrogenation of CDT to CDE would open up alternative route to Nylon 12

Try to achieve selective hydrogenation by extreme control of reaction conditions

Weissmeier and Hoenicke, Proceedings IMRET 2, 1998

9

File Number

Intrinsic Technology Potential :

Control of Reaction Conditions by Micro-Engineering

a a

b b

c c

Extremely regular short pores (a) are obtained by anodizing aluminum. These nanostructures are built into regular microchannels (b) and stacked (c).
10

Weissmeier and Hoenicke, Proceedings IMRET 2, 1998

File Number

Intrinsic Technology Potential :

Control of Reaction Conditions by Micro-Engineering

a a

b b

c c

Extremely regular short pores (a) are obtained by anodizing aluminum. These nanostructures are built into regular microchannels (b) and stacked (c).
11

Weissmeier and Hoenicke, Proceedings IMRET 2, 1998

File Number

Intrinsic Technology Potential :

Control of Reaction Conditions by Micro-Engineering

a a

b b

c c

Extremely regular short pores (a) are obtained by anodizing aluminum. These nanostructures are built into regular microchannels (b) and stacked (c).
12

Weissmeier and Hoenicke, Proceedings IMRET 2, 1998

File Number

Intrinsic Technology Potential : Results of Micro-engineered structures

Removing dead Removing dead volumes volumes

Effect of regular Effect of regular small pores small pores

Base case Base case

Evolution in Micro Engineering of catalysts leads to more precise control of reaction conditions, opening up new pathways in chemistry

Weissmeier and Hoenicke, Proceedings IMRET 2, 1998

13

File Number

The Challenge of Heavy Oil Analysis

1.E+14 Number of Isomers 1.E+12 1.E+10 1.E+08 1.E+06 1.E+04 1.E+02 1.E+00 0 10 20 30 40 50 C Number
Source: ASTM Manual of Hydrocarbon Analysis

GCxGC Analysis of Light Cycle Oil

14

File Number

Heavy Oil GCxGC analysis

s 4+ ring aromatic

3 ring aromatics
2 ring aromatics
tics a m o nes r a e g h n t i 1r ph a n and s n lefi o , fins f a r pa int o p g boilin
File Number

polarity
15

Verifying Compositional Info against Bulk Data

G C xG C /F ID
U nits = m as s % S am ple ID: 127-3606 naphthenic s ubs t 1-ring arom atic s naphthenic s ubs t 2-ring arom atic s Da ta ca te g o riz e d b y b o ilin g p o in t b a se d o n n -a lka n e s 1 ring naphthenes 2+ ring 1-ring naphthenes arom atic s 2-ring arom atic s 3-ring 4-ring arom atic s arom atic s

GCxGC vs Simulated Distillation (D7213)

c arbon # n-paraffins BP is oparaffins 5 0.0000 N C4to5 6 0.0000 N C5to6 7 0.0037 N C6to7 8 0.0000 N C7to8 9 0.0000 N C8to9 0.0000 10 0.0138 NC 9to10 0.0000 11 0.0695 NC 10to11 0.0253 12 0.2379 NC 11to12 0.1337 13 0.2132 NC 12to13 0.1728 14 0.1048 NC 13to14 0.1244 15 0.0784 NC 14to15 0.0509 16 0.0989 NC 15to16 0.0250 17 0.1779 NC 16to17 0.0599 18 0.2345 NC 17to18 0.0654 19 0.2401 NC 18to19 0.0889 20 0.3276 NC 19to20 0.1048 21 0.4029 NC 20to21 0.2054 22 0.5382 NC 21to22 0.2895 23 0.7439 NC 22to23 0.3576 24 1.0435 NC 23to24 0.5220 25 1.2980 NC 24to25 0.7038 26 1.5800 NC 25to26 1.0406 27 2.0178 NC 26to27 1.1057 28 2.1506 NC 27to28 1.4096 29 1.7958 NC 28to29 1.4000 30 2.1534 NC 29to30 1.2583 31 2.1274 NC 30to31 0.3877 32 1.4528 NC 31to32 0.6016 33 1.4158 NC 32to33 0.4819 34 1.4829 NC 33to34 0.7331 35 1.0510 NC 34to35 0.0000 36 0.8090 NC 35to36 0.2623 37 0.7761 NC 36to37 0.2468 38 0.2002 NC 37to38 0.1781 39 0.4446 NC 38to39 0.0000 40 0.3127 NC 39to40 0.1039 41 0.2814 NC 40to41 0.0844 42 0.1920 NC 41to42 0.0000 43 0.0947 NC 42to43 0.0707 44 0.1493 NC 43to44 0.0321 45 0.0557 NC 44to45 0.0000 46 0.0551 NC 45to46 0.0000 47 0.0307 NC 46to47 0.0082 48 0.0288 NC 47to48 0.0000 total 26.4845 12.3345

0.0000 0.0000 0.0361 0.0486 0.0729 0.0216 0.0103 0.0373 0.0404 0.0656 0.0890 0.1164 0.0983 0.1413 0.1840 0.2283 0.2603 0.2291 0.0000 0.0000 0.0000 0.4351 0.5832 0.4163 0.3501 0.3301 0.4544 0.2853 0.2207 0.5958 0.1020 0.0858 0.0000 0.0000 0.0000 0.0205 0.0000 0.0000

0.0000 0.0027 0.0298 0.0046 0.0080 0.0152 0.0145 0.0000 0.0000 0.0000 0.0000 0.0000 0.0054 0.0000 0.0000 0.0000 0.0445 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

0.0061 0.0000 0.0000 0.0027 0.0314 0.1492 0.1229 0.0879 0.0242 0.0200 0.0322 0.0356 0.0929 0.1209 0.1479 0.2226 0.2791 0.5101 0.3687 0.5076 0.6995 0.7238 0.9944 1.1411 0.6577 1.1627 0.3184 1.5501 0.0628 0.8804 2.7261 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

0.0265 0.0829 0.0203 0.0076 0.0000 0.0033 0.0155 0.0351 0.0456 0.0441 0.1008 0.1165 0.1360 0.3098 0.3690 0.2721 1.1734 0.4474 0.9070 0.6116 0.4266 0.0000 0.2608 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

0.0132 0.0307 0.0393 0.0151 0.0487 0.0575 0.0404 0.0492 0.0651 0.1170 0.1767 0.1527 0.2724 0.7128 0.5654 0.5595 0.7924 1.3992 1.3876 1.3810 1.1196 1.1224 1.6154 0.3151 2.4801 0.9831 0.2476 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

0.0000 0.0140 0.0085 0.0231 0.0013 0.0144 0.0314 0.0563 0.1057 0.1393 0.1072 0.1151 0.0682 0.0395 0.0574 0.0000 0.2989 0.0753 0.0827 0.0906 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

0.0066 0.0238 0.0635 0.2127 0.3164 0.2837 0.4375 0.5200 0.4675 0.3913 0.3207 0.5572 0.5727 0.7693 0.8746 0.4893 0.5352 1.0661 0.1761 0.1068 0.0605 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

0.0023 0.0379 0.1119 0.1791 0.5134 0.7101 0.9780 0.9434 1.2566 0.5246 0.8354 0.7015 0.5826 0.5731 0.7459 0.8545 0.6046 0.6218 0.0000 0.2232 0.0316 0.0357 0.0000 0.0000 0.0000 0.0000

5.5589

0.1247

13.6789

5.4119

15.7589

1.3289

8.2515

11.0672

total 0.0000 0.0000 0.0099 0.0000 0.0000 0.0165 0.1650 0.6389 0.7141 0.4149 0.2247 0.2458 0.3922 0.5122 0.7149 1.0988 1.4736 1.9033 2.4983 3.4796 4.6737 5.4949 5.9533 8.0492 7.9415 8.6590 7.5492 6.3705 4.8065 7.6116 2.8052 5.6786 5.6179 1.8436 0.5465 0.7256 0.3973 0.2277 0.1654 0.2019 0.0557 0.0551 0.0389 0.0288 100.0000

16

File Number

Advanced Analytical Techniques For Feed and Product Characterization

Applications of Ionization Sources
EI Aromatics, aromatic polars, IP<11 eV Aromatics, aromatic polars some non-polar aromatics, IP<10.6 eV Polars, both aromatic and non-aromatic, trace polars Distillates to HVGOs

APPI

Distillates to Resids, Biomass Polars in Distillates to Resids and Biomass

ESI

MALDI

Solids, heavy liquid polars

Biomass, Resids

Typical Performance
Mass Resolution Mass Accuracy Max Mass Range Sensitivity 1,000,000 .0001 amu >3,000 amu <1 PPM
200

Examples of Mass Spectra VGO

Resid
300 400 500 700 900 1000 1100

600

800

High Resolution Mass Spectrometer: FT-ICR-MS

17

(Fourier Transform Ion Cyclotron Resonance Mass Spectrometry)

File Number

Continuing Challenges in Feed Analysis

Distillate

Vacuum Gas Oil

Pyrolysis Oil

18

File Number

Characterizing Industrial Catalysts

Often complex: support, active element(s), modifier(s), zeolite, binder. Often contain low concentrations (<<1wt%) of the active element/modifier. Several phases of the active element may be present e.g. PtSn/-Al2O3 reforming catalyst may contain PtxSny clusters (with varying x,y), unreduced Sn, and chloride present on the -Al2O3 Often range of cluster sizes of supported metal(s). Model catalysts may or may not be relevant.
19
File Number

Catalyst Characterization Techniques

Structural
XRD Microscopy - SEM - HRSEM - TEM - STEM - AFM - Optical NMR

Active Sites
XPS XAFS Gas Adsorption - Temp. Prog. Desorption - Temp. Prog. Reduction FTIR Raman Moessbauer ESR X-Ray Fluorescence

Reactivity/Adsorption
Calorimetery - High Temperature - Liquids Diffusion - ZLC Reactivity Testing - Microreactors - TAP - TSR - SSITKA - Pulse Microreactor - TEOM - Isotopic Labeling

20

"The information lost by not using in situ methods would be similar to studying life having access to only pre-natal and post-mortem information"

File Number

High Resolution Microscopy

Diesel Molecule Size
32593-56-NH-2

Details of mesopores clearly visible Able to correlate performance with meso-porosity and diffusion path
21
UOP 5222I-11 File Number

Elucidation of Single Pt Atoms : Aberration corrected STEM

Oxidized Pt/Alumina
Individual Pt atoms Single Pt atoms

Reduction
10 Pt cluster 8-10 Pt cluster Pt dimer

Pt-atom dimers

2 nm

2 nm

Fully Dispersed Pt Atoms Control of Metal Impregnation

Morphology of Metal Clusters on the Atomic Scale Degree of Metal Support Interaction

22

File Number

Sulfated Zirconia Paraffin Isomerization Catalyst

Addition of Tm to Pt/sulfated zirconia paraffin isomerization catalyst leads to activity enhancement. Are there structural differences in the zirconia as a result of the Tm promoter? Literature teaches that for Fe/Mn promoted SZ that promoters are incorporated into Zr lattice leading to stabilization of the tetragonal (or cubic phase) but evidence is circumstantial.

6 C5+ RONC Improvement over Zeolite 4 2 0 -2 -4 -6 -8 -10 100 150 200 DABT. C 250 300

Vapor equilibrium

Tm/Pt/SZ

Pt/SZ

Liquid equilibrium

Zeolite

23

File Number

Bulk Zirconia Structures

At RT only the monoclinic structure of ZrO2 is stable. Tetragonal phase can be stabilized at RT by addition of cationic dopants.
24
File Number

Zr EXAFS Spectra of Tm/SZ Modeled with Tetragonal ZrO2

Real part of Fourier transform Magnitude of Fourier transform
14

Comparison of Tm and Zr
Real part of Fourier transform Magnitude of Fourier transform
Tm-SZ Tetragonal Model
21 18 15 12 0 2 4 6 8

12 10 8 6

Tm Zr

R ()

18 15 12 9 6 0 2 4 R () 6 8

R ()

24

18

12

Tetragonal ZrO2 Neighbor Zr-O Zr-O Zr-Zr Zr-Zr Zr-O Zr-O Zr-O Number 4 4 4 8 4 8 8 R () 2.1 2.4 3.6 3.6 4.1 4.2 4.3

Selected Paths from Model R () 2.10 0.01 2.31 0.01 3.63 0.01 3.67 0.01 3.93 0.08 4.06 0.08 4.27 0.06 2 (2) 0.005 0.001 0.013 0.001 0.005 0.002 0.013 0.002 0.030 0.004 0.009 0.002 0.015 0.003

6 0 2 4 R () 6 8

Zr structure is consistent with tetragonal ZrO2 Tm and Zr Spectra are similar but also different, particularly in the first shell signal

25

File Number

Determine Tetragonal Unit Cell for Tm in SZ

Real part of Fourier transform Magnitude of Fourier transform Tm in SZ Distorted Tet Model

Tetragonal Unit Cell a=b=3.6 ; c=5.2

Distorted Unit Cell a=b=c=4.0 to 4.3

R ()

16 14 12 10 8 0 2 4 R () 6 8

Real part of Fourier transform Magnitude of Fourier transform

Extreme distortion forcing unit cell to be cubic-like It is not possible for the tetragonal phase to be so distorted, as the Zr EXAFS spectra is consistent with a normal tetragonal unit cell Try cubic ZrO2 structure instead!

Cubic Model for Tm in SZ

12

Tm in SZ Cubic Unit Cell

R ()

18

12

4 R ()

26

File Number

Tm addition Results in Cubic Super-lattice

EXAFS Results
Cubic Tm
Intensity 10000 8000 6000

Modeling of XRD
Tetragonal Only
Observed Calculated
10000

Tetragonal & Cubic

Observed Calculated

8000

4000

Intensity
' 15a_tet_obs' ' 15a_tet_calc'

6000

4000

2000

2000
'15a_cubtet_obs' '15a_cubtet_calc'

Number of Zr neighbors

24 20 16 12 8 4 0 24 20 16 12 8 4 0

cubic ZrO2

Zr Distribution

0 35 36 37 38 Degrees 2 theta 39

0 35 36 37 38 Degrees 2 theta

40

39

40

tetragonal ZrO2

XRD confirms the presence of small amount of cubic phase

6 7 8

R (Angstroms)

Tm has cubic structure within the tetragonal ZrO2.- related to similarity in cation distribution between the cubic and tetragonal ZrO2. This leads to unique structure of the zirconia - resulting in enhanced activity by modifying acidity of surface sulfate group.
27
File Number

Mechanism Tools for Process Development 1-10 mg

LAMIMS

100 mg Reactivity Testing

Atm. Reactivity Testing

1 - 10 g TSR

TEOM

104 105 kg Process Monitoring

Process Model
Diffusion Adsorption Heat of Ads. Capacity
IR Thermography

Rxn Mechanism
Isotopic Labeling

ZLC

Characterization
28
File Number

Representative screening at the microscale ?

Feed Effluent Upper section Lower section O-ring seal Cylindrical section Catalyst position Conic section

Sinter Syringe (side port)

29

File Number

Data Analysis Suggests Problems

25 C
50 45 40 35 % conversions 30 25 20 15 10 5 0 0 5 10 15 20 25 comparable flows (ml/30 mg) Em pty m icroreactor Micro reactor (4 m m i.d) Conventional reactor Perfectly Mixed Flow

62 C

1. Temperature ?

Micro reactor (3 m m I.d.)

250 C 215 C

250C

2. Mass Transfer?
Internal : unlikely at 50-200 microns External : unlikely in Fluidised Beds
File Number

30

Alternative Bed Design Jetting into the bed ?

31

File Number

Tapered Element Oscillating Mass-Analyzer: TEOM

Measure conversion, selectivity,and mass changes at process conditions
800 psig 600oC

Oscillating Reactor

- Frequency related
to mass

m = K o

1 1 1 2 2 f1 f0

32

File Number

CFD Modeling of the FCC Riser

Problem Statement :

- An existing 200k BPSD FCC unit with a 6.5 ft ID riser has

poorer than expected yields and conversion
Gasoline Selectivity: Conversion: Dry Gas Yield: - 18% - 5 wt% +30 wt%

Systematic approach to trouble-shooting :

Operations reports and data CFD evaluation of existing equipment Tracer and tomography evaluation of existing equipment Update CFD to incorporate learnings from the field and use code for revamps. Tomography for the modified equipment Incorporate final finetuned learnings into CFD design tool.

33

UOP 5201C-04 File Number

Catalyst Density Above Feed Distributors

CFD Prediction Actual Riser Gamma Scan:
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 27-30 24-27 21-24 18-21 15-18 12-15 9-12 6-9 3-6 0-3

24

0 -0.1 -0.2 -0.3 -0.4 -0.5 -0.6 -0.7 -0.8 -0.9 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.9

lb/ft3

Vapor annulus High density core

Confirmed CFD analysis Quantified max distributor penetration: 24 inches

Penetration Problems Likely for any FCC Riser over 48 Inches in Diameter
34
UOP 5201C-05 File Number

Solution - Dual Radius Feed Distributors

6 Inner Injectors
Inner 50% of riser area 18 inches deeper

Tips at identical elevation Positioned to avoid adjacent spray impact that could lead to erosion

35

UOP 5201C-06 File Number

CFD and Commercial Results for Dual Radius Feed Distributors

Dual Radius Feed Distribution Eliminates Dense Core

Commercial startup 2Q 2009

- 1.9 wt% dry gas yield (3.4 wt%

design)

lb/ft3

36

UOP 5201C-07 File Number

Single Stage UOP UnicrackingTM Unit Reactor Section- Process Analyser Map
NH3 0-100 ppm Catalyst activity
H2S 100 ppm-3wt% Catalyst activity H2 (in presence of H2S) 80-97% process control Current TCD drifts

Pretreat Reactor Cracking Reactor

Top bed of cracking Reactor

CO <10 ppm Catalyst activity

Make-up Hydrogen

Wash Water
H2 (in presence of H2S) 80-97% process control Current TCD drifts

Cold Separator

Flash Gas
Organic N/Total N
500-2000ppm Rx1 5-50ppm Rx2 Catalyst activity

Hot Separator

Flash Drum
to Fractionator Sour Water to Treating
Total S <10 ppm - 50ppm Main spec Distallation temp Main spec

Fresh Feed
Viscosity Index Temp 100F 2ndary spec

Recycle Oil From Fractionator

HPNA <<1000ppm speciation Catalyst activity process control

to Fractionator

Refinery Process Management and Models need integrated sensor Measurement and Control for Optimization and Value
37
File Number

Conclusions

Advances in Crude Oil Conversion Technologies Critical to Energy Growth, Now and in the Foreseeable Future. Significant Potential for Technology Improvement; Step Changes still occur. Understanding Feed Composition & Catalyst Functionality, Measuring Field Performance are Key to Continued Technology Improvement. Fundamentals and Analytics strongly impact this Technology Area from the Nano- to the Macro-scale.

38

File Number

Acknowledgements
Stimulating discussions and contributions by the following colleagues are gratefully acknowledged :

M. Stine G. Venimadhavan J. Donner S. Bare D. Galloway A. Ringwelski M. Caracotsios C. Stevens C. Gosling P. Sechrist B. Ellis S. Philoon C. Romatier

G. Towler G. Funk R. Rosin D. VandenHoff M. Cohn D. Adams P. Adams S. Kelly B. Arena W. Rathbun

The opinions and observations expressed in this presentation are those of the authors and do not necessarily represent those of UOP LLC or Honeywell International Inc.
39
File Number