Catalytic Upgrading of Glycerol to Propylene Glycol - Download as DOC

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Catalytic Upgrading of Glycerol to Propylene Glycol - Download as DOC Powered By Docstoc
					         Catalytic Upgrading of Glycerol to Propylene Glycol
The purpose of this project is to develop enabling                                                  ADM-Lead Commercialization
                                                                                                    ADM-Lead Commercialization
technology leading to an integrated process for
the production of propylene glycol (PG) from
inexpensive glycerol.    This is a joint project
                                                               ADM (Paul Bloom)
                                                               ADM (Paul Bloom)                        UOP (Syed Taqvi)
                                                                                                        UOP (Syed Taqvi)            PNNL (John Holladay)
                                                                                                                                     PNNL (John Holladay)
                                                             -Reaction Engineering
                                                              -Reaction Engineering                  -Catalyst Characterization
                                                                                                      -Catalyst Characterization    -Process Definition
                                                                                                                                     -Process Definition
between Pacific Northwest National Laboratory                -Economic Modeling
                                                              -Economic Modeling
                                                                                                     -Catalyst Commercialization
                                                                                                      -Catalyst Commercialization   -Process Optimization
                                                                                                                                     -Process Optimization
                                                                                                                                    -Catalyst discovery
                                                                                                                                     -Catalyst discovery
(PNNL), Archer Daniels Midland Company (ADM),                                                                                       -Catalyst life-tests
                                                                                                                                     -Catalyst life-tests
                                                                                                                                    -Fundamental studies
                                                                                                                                     -Fundamental studies
and UOP.

Organization of Approach

ADM is the overall commercialization lead on the project. They are contributing in kind
research supporting reaction engineering, economic modeling and process commercialization.
UOP is leading catalyst commercialization efforts. Like ADM they are contributing in kind
research in the area of catalyst characterization. PNNL is leading the catalyst discovery and
process development efforts. Michigan State University is working with PNNL on fundamental
aspects of the research.

The program is broken down into four tasks over a roughly three year period.                                                             Over the
course of the project research moves from 30 cc flow
reactors to continuously larger systems (200-300 cc            U 300 cc Reactor
                                                                 300 cc Reactor                                                        1 L Pilot
                                                                                                                                       1 L Pilot
                                                     30 cc Flow
in Task 2 and 1 L pilot in Task 3).                                                   Product Out

                                                          Year 1                                       Year 2                             Year 3
Task 1
 Catalyst optimization/validation and process economics
Decision 1
   1. Catalyst to meet technical targets
    2. Verification of overall economics
Task 2
 Validation including larger scale reactor systems
Decision 2
   1. Verify economic analysis & catalyst cost
   2. Final product meets application requirements
Task 3
 Pilot scale testing
Decision 3
   1. Verify scaled-up reactor performance
   2. Final product meets application requirements
Task 4
 Conceptual design for a commercial unit
Decision 4
 ADM internal funds for plant construction

Each Task is broken down into numerous activities.        Exemplary Task 1 activities are
summarized below.
    Reaction Modeling (ADM). The purpose of this activity is to define preliminary
      economics and set technical targets (conversion, selectivity, WHSV, life).
    Optimization in fixed bed mode (PNNL). Verification of top catalysts identified in
      combinatorial work, catalyst scale-up (to bench scale) and reduction/activation
      studies, as well as other fundamental studies.
    Catalyst life studies—500 h continuous flow reactor—(PNNL). Top catalyst candidates
      are validated under continuous operation.
    Catalyst characterization (UOP). Candidate catalysts are fully characterized by SEM,
      x-ray diffraction, x-ray photoelectron spectroscopy, in situ x-ray absorption
      spectroscopy (XANES and EXAFS), and STEM. This data provides invaluable insights
      pertaining to catalyst performance over time.

Milestones and Go / No Go Metrics

Milestones are clearly delineated for each Task. Technical targets are set based on ADM’s
economic models. For Task 1 the milestones include catalyst must meet technical targets
and verification of economics. A similar milestone is set in Task 2 for the scaled up process,
Task 2 also includes a milestone that product meets application requirements. Task 3
milestones mirror Task 2 but pertain to pilot scale operation. Go / No Go decision point is
based on the outcome of the economic verification of the process at each step.


The major risks in the project can be divided into technical risks and market risks.
Technical risks include…
   – catalyst being insufficiently stable for commercial use
   – final product does not meet spec within economic constraints
   – feedstock impurities impact economics
These types of risks are managed as part of the research effort. And we have preliminary
data on each of these risks that provide confidence that the risks will be met.

Market risks include…
   – price of propylene stabilizes at a cost that offsets economic advantage
   – PG market saturates and market penetration is difficult
   – Partner’s business strategies change
These risks are offset by the flexibility of feedstocks (glycerol, C6 sugar or mixed C5/C6
sugar streams), the size of the PG market and flexibility in potential market partners.

Accomplishments to Date

Our last quarterly report contained 70 pages of experimental documentation. The project is
on strong footing. Current catalysts developed at PNNL are highly selective (<90% based on
carbon-mole %). The catalysts
have been scaled-up on the           100
bench scale level (10 – 100 g)
and we have completed initial
activation      studies     using     90
temperature          programmed
                                    Catalyst activity measure

reduction (TPR) techniques.
The main focus now is on
validating       the      catalyst
performance over time in
continuous flow reactors. Two
catalyst life studies have been       70
completed; each ran in excess                 F25 Catalyst Activity
of 500 h. In the initial test,                F24 Catalyst Activity
using ADM derived glycerol,           60
activity eroded by 25% over
500 h. Using characterization
techniques we identified site-
blocking mechanisms to be             50
primarily responsible for the            0      100       200        300     400      500    600
erosion. This hypothesis was                                Time on stream (h)
validated in a second test, in
which we used ―pristine‖ feed and ―PNNL-treated‖ feed.              Catalyst stability was vastly
improved (see Figure). Catalyst characterization uncovered important information pertaining


to catalyst morphology changes that occur over time. We are using this information to direct
our current research efforts.

                                                                                                                                                        Characterization activities



                      Concetration ml/min   2.0



                                                  50   100   150   200   250   300   350       400     450    500   550   600   650   700   750   800
                                                                                           Temperature (°C)

Future Plans

We are continuing our efforts as listed in the SOW with an emphasis on catalyst stability,
feedstock impurities and economic evaluation. In out years the research focus will include a
series of scale-up operations leading to conceptual commercial design (as outlined in the
Gantt chart).

Markets and Customers

The PG market is 3.5 billion lbs worldwide and divided into various segments as shown.
                      liquid detergents paints and
                                                                    Customers can be divided into three families: (1)
       food, drug and
                            (17%)        coatings
                                                                    Glycerol producers—biodiesel producers, ag
          cosmetics                                miscellaneous
                                                                    processors,   chemical    industry;    (2)    PG
                                                                    consumers—Industrial application developers,
                                                                    consumer    products    developers,     chemical
                                                                    industry; and (3) technology delivery—catalyst
 Functional fluids
(Antifreeze, deicing,
                                                   polyester resins manufacturers, technology licensers.
   heat transfer)

Competitive Advantage
                                                                                                                                                                       Existing Natural
With the new energy bill there is an increased interest in domesticLethicin,
                                             Oil Processing Mill      Oil Seed
                                                                                           Protein          biodiesel production. Soaps
                                                                                                        Sterols,    Edible Oils

Glycerol co-product is formed 10% by weight in biodiesel production. InE Europe, the price of
                                               Improvements            Meal              Coproduct,                                Oils
                                                                                           Isolates      Vit.
crude glycerol is $0.10-0.12 /lb. Similar prices can be expected in the US. The renewable
route provides competitive technology for petroleum-based Isolation (from propylene oxidation).
                                                                                 Extraction/                            O                       Saponification

Current petroleum-based processes are based on chlorine chemisty (e.g. DOW) or form New Products from Oils
                                                Oil Seed Production
                                                (Including Soybean,
                                                                                                                                        M 3.3 co-

products such as MTBE (e.g. Lyondell). We Sunflower, Safflower, theCrushing &
                                                                         renewable route is cost competitiveOil Conversion to
                                                                                                    Oil Deodorizing
                                                                                                       & Refining
                                                                                                                        O                    O       Chemical
with glycerol feeds less than $0.40 /lb.

                                                                                                                                                                                                                                                                           Oil or Intermediate
                                                                                                                                                                                                                                                                             Conversion to

Strategic fit                                                                                                                                                            M 3.1 New Oil Seed                                                                                     Products
                                                                                                                                                                         Production           Crushing,
                                                                                                                                                                                              Separation                   O
                                                                                                                                                                            New Oil Seed      & Refining                                                                        Recover New
                                                                                                                                                                               Crop                                                                                              Coproducts

The three partners in the program have a synergistic                                                                                                                                                                   Oil Processing Mill
                                                                                                                                                                                                                       Oil Processing Mill

relationship each bringing complimentary skills. Conceptually                                                                                                                                                            Transesterification
                                                                                                                                                                                                                                                           M 3.2 New Products
                                                                                                                                                                                                                                                           from Glycerol

the research fits strongly within ADM’s biodiesel and sugar
                                                  Crop                                                                                                                                                     Methanol                                O
                                                                                                                                                                                                                          and Separation
                                                                                                                                                                                                                                                               Conversion to
portfolios;   it    fits strongly   within   UOP’s        catalyst
                                                                                                                                                                                                                                                               New Products

commercialization and biodiesel technology portfolios; and it                                                                                                                                                                                                   Recover New

fits strongly within PNNL’s condensed phase catalyst expertise

and process development skills.                                                                                                                                                                                                                  Crude
                                                                                                                                                                                              Oil Seed                                                         New Products
                                                                                                                                                                                                                               Biodiesel                                              Products
                                                                                                                                                                                               Meal                                             Glycerol       from Glycerol
                                                                                                                                                                                                                                                                                      from Oils

Within DOE’s biorefinery construct, this research supports each
conceptual refinery and is applicable to glycerol feeds, C6 sugar
feeds or mixed sugar feeds.
                                                                                                                                                                                                                       ethanol                  C5 or C6 or mixed
                                                                                                                                                                                                                                                  C5 or C6 or mixed
                                                                                                                                                                                                                                           Sugars conversion to Chemical
                                                                                                                                                                                                                                            Sugars conversion to Chemical
                                                                                                                                                                                                                                               and Material Products
                                                                                                                                                                                                                                                and Material Products

Within DOE’s Stage gate construct the work is best described in      Sugar streams
                                                                      Sugar streams
―Research Track, exporatory research‖ with strong commercial
partners. We anticipate the technology to be ready for commercial prototype by FY08.


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