RESEARCH   TRIANGLE  INSTITUTE

                                                                July 1988
                                          Phase I — Final Report
                                      Catalytic Dehydration
                                                    of Methanol
                                                              Prepared by
                                                         Don R. vanderVaart
                                                      Research Triangle Institute
                                                Research Triangle Park, NC 27709
                                                              Prepared for
                                              Robert M. Heavenrich, Project Officer
                                              U.S. Environmental Protection Agency
                                                        Ann Arbor, Ml 48105
                                                   EPA Contract No. 68-03-3527
                                                         RTI Project No. 4002
 POST OFFICE BOX 12194  RESEARCH TRIANGLE PARK, NORTH CAROLINA 27 709-2194

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                                                                             CONTENTS
CONTENTS
Section
Page
            Figures	     iii
            Tables	     iv
            Abstract	      v


   1        Introduction	    1-1

   2        Candidate Catalysts....	    2-1
            Alumina	    2-1
            Zeolite	    2-6
            Metal Oxides	    2-6
            Ion Exchange Resins	    2-6

   3        Experimental	    3-1
            Experimental Considerations	    3-2
            Experimental Procedure	    3-5

   4        Results	    4-1

   5        Discussion	    5-1

   6        Phase II Plan of Work	    6-1
            Dissociation Reaction	.-	    6-7
            Process Energetics	   6-10

   7        References	    7-1

   8        Summary and Future Work	    8-1


Appendix

   A       Solicitation for Commercial Methanol Dehydration Catalysts	   A-l
   B        Calculation of Adiabatic Temperature Rise in a Tubular Reactor	   B-l
   C        Calculation of Methanol Required to Start an Engine	   C-l
   D       Estimation of Global Kinetics of Methanol Dehydration	   D-l
   E        Calculation of the Vapor-Liquid Equilibrium (VLE) Data for a
            Two Component Mixture of DME and Methanol	   E-l
                                                                                  RTI

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                                                                               FIGURES
FIGURES

Number                                                                          Page

   1       The effect of spare time on product distribution (T = 371 °C, P = 1 atm)	    1-2
   2       Microreactor catalyst testing facility	    3-6
   3       10-Port sampling valve arrangement	    3-7
   4       MeOH conversion, AL-5207	    4-2
   5       MeOH conversion, AL-5307 E 1/16	    4-2
   6       MeOH conversion, AL-5407	    4-3
   7       MeOH conversion, AL-3945	    4-3
   8       MeOH conversion, AL-3996 R	    4-4
   9       MeOH conversion, CS 331-1	    4-4
   10      MeOH conversion, CS331-4	    4-5
   11      MeOH conversion, LZ-20	    4-5
   12      MeOH conversion, LZ-Y-72	    4-6
   13      MeOH conversion, LZ-M 8	    4-6
   14      MeOH conversion, Z6-06-02	    4-7
   15      MeOH conversion. Z6-06-02,B6980	    4-7
   16      MeOH conversion, MCG-7	    4.8
   17      MeOH conversion, MCG-8	    4-8
   18      MeOH conversion, ZR-0304T	    4-9
   19      MeOH conversion, TI-0720	    4-9
   20      MeOH conversion, T-312	   4-10
   21      MeOH conversion, T-314	   4-10
   22      MeOH conversion, T-317	   4-11
   23      MeOH conversion, T-1502A	   4-11
   24      MeOH conversion, T-1502B	   4-12
   25      MeOH conversion. 7913-S K-306	   4-12
   26      MeOH & DME outputs, AL-5207	   4-13
   27      MeOH & DME outputs, AL-5407 E 1/16	   4-1-3
   28      MeOH & DME outputs, LZ-20	   4-14
   29      MeOH & DME outputs, M-8	   4-14
   30      MeOH & DME outputs, Z6-06-02  1/16	   4-15
   31      Effect of Tc on the temperature profile of a PFTR	    6-4
   32      Relationship between two dimensionless parameters	    6-5
   33      MeOH conversion, dissociation catalyst	    6-8
   34      MeOH conversion, dissociation and AL 39996R	    6-8
   35      MeOH conversion, dissociation in DME	    6-9
                                                                                 RTI  iii

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                                                                                  TABLES
TABLES

Number                                                                            Page

   1        Advantages and Disadvantages of Candidate Catalyst Families	    2-2
   2        Catalyst Samples Received and Tested	    2-4
   3        Harshaw/Fitrol Alumina Catalysts	    2-5
   4        United Catalyst Alumina Catalysts	    2-5
   5        Union Carbide Zeolite Catalysts	    2-7
   6        United Catalyst/Zeochem Zeolite Catalysts	    2-7
   7        Harshaw/Filtrol Metal Oxide Catalysts	    2-8
   8        United Catalysts Metal Oxide Catalysts	    2-8
   9        Ranking of All Candidate Catalysts Tested According to T30	   4-16
                                                                                   RTI  iv

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                                                                                  ABSTRACT
ABSTRACT
                    The results of Phase I of EPA Contract No. 68-03-3527 are presented. It is
                    apparent that several commercially available catalysts are suitable for the
                    methanol dehydration reaction forming dimethyl ether. Problems in
                    developing a prototype dehydration reactor suitable for mounting under the
                    hood of an automobile are presented. In particular, the exothermicity of the
                    methanol dehydration reaction can result in a runaway temperature excursion
                    within the reactor. This can lead to the loss of product selectivity by the
                    formation of higher hydrocarbons with the concomitant formation of coke,
                    which can lead to catalyst deactivation.  Although more sophisticated reactor
                    designs can be used to minimize the likelihood of these excursions, the reaction
                    system is quite sensitive to slight changes in operating conditions.

                    It is proposed, in Phase II, to study the kinetic  rate of both the methanol
                    dehyrdation reaction for a limited group of dehydration catalysts as well as the
                    methanol dissociation reaction over available dissociation catalysts. With this
                    information, a relatively simple theoretical analysis is feasible by which a
                    dehydration/dissociation catalyst mixture reactor could be designed. The
                    dissociation reaction  pathway would be  provided only as a heat sink to prevent
                    reactor runaway.

                    Finally, it is shown that the process energetics for such a reactor would require
                    the condensation of the product stream in order to allow operation without a
                    significant amount of external power requirements.  A simple phase
                    equilibrium analysis is presented which shows that the condensed product
                    stream is suitable  for cold-starting an internal combustion in a mechanism
                    completely analogous to winterized gasoline.
                                                                                       RTI v

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                                                                           1. INTRODUCTION
SECTION  1
INTRODUCTION
                    Methanol can be used as a motor fuel with considerable environmental
                    advantages over gasoline. Its use in various mixtures with gasoline is currently
                    being tested by both the Ford Motor Company and ARCO. Using 100% meth-
                    anol rather than blending it with a winterized gasoline, while representing a tru-
                    ly alternative fuel with excellent emission characteristics, does present certain
                    problems. In particular, the high heat of vaporization of methanol (more than
                    seven times that of gasoline on a per Btu heating value basis) combined with
                    the higher fuel to air ratio required for combustion (approximately twice that of
                    gasoline) causes severe cold starting problems. To this end the U.S. Environ-
                    mental Protection Agency (EPA) has suggested that under cold starting
                    conditions an amount of methanol fuel could be catalytically dehydrated to
                    form dimethyl ether (DME) via the following reaction:
                              2CH3OH «- CH3OCH3 + H20   .                               (1)
                    DME exhibits favorable combustion characteristics and is satisfactorily
                    volatile.

                    The catalytic dehydration of methanol is a well-studied reaction.  It forms the
                    first step in Mobil's patented Methanol to Gasoline (MTG) process as well as
                    being an integral part of other chemical production processes.  From the litera-
                    ture relative to reaction (1) two conclusions can be drawn:

                    •   Catalytic dehydration of methanol vapor to dimethyl ether, is an acid
                        catalyzed reaction. Lewis acid sites and almost certainly fairly weak Lewis
                        base sites are necessary on the surface of any successful catalyst. Strong
                        Bronsted acidity promotes the further reaction of DME to olefins and
                        paraffins.   _

                    •   While most research on this reaction has focused on various conventional
                        zeolites, other catalysts have been shown to be successful. These include
                        metal salts, alumina, silica alumina, alumino phosphate molecular sieves,
                        ion exchange resins, and mixed metal oxides.

                    As an example of the work published in the development of Mobil's MTG
                    process, Figure 1 shows the effect of the space time (liquid hourly space velocity
                    (LHSV)'1) (defined as the volumetric flowrate of liquid methanol divided by
                                                                                    RTI  1-1

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                                                                             Paraffins

                                                                             (and Cg Olefins)
                                                                                                                     3)
                                                                                                                     O
                                                                                                                     o
                                                                                                                     c
                                                                                                                     o
Figure 1. The effect of space time on product distribution (T = 371 °C, P = 1 atm) [1].

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                                                        1. INTRODUCTION
the volume of catalyst) on product distribution over a zeolite catalyst. [1]
Figure 1 also illustrates the series reactions that can occur in this system. That
is

            A*B + C                                                 (2)

where A is methanol, B is dimethyl ether, and C constitutes a variety of hydro-
carbon products which make up the gasoline fraction produced by the MTG
process. Obviously, it is this latter product fraction which Mobil attempts to
maximize. The formation of these hydrocarbons (aromatics, olefins, and some
paraffins) has associated with it, however, the formation of carbonaceous
deposits on the catalysts (i.e., coke).  This byproduct has the effect of
deactivating the catalyst over time, necessitating its regeneration. The goal of
the present work is not to produce gasoline in situ but rather to provide a
volatile product suitable for starting the vehicle in cold weather. Dimethyl ether
formed as an intermediate in reaction (2) meets this objective without the
associated deactivation of the catalyst.  In fact, Mobil has remarked [2] that
their first stage unit, which produces DME at equilibrium conversion, has yet to
experience catalyst deactivation at their plant in New Zealand, while their
second stage DME-to-gasoline reactor requires continuous regeneration. The
work presented herein attempts to produce a methanol/DME mixture suitable
for starting an engine.     .

Previous work [3] indicates that this mixture should be  roughly 10 to 15 percent
(by volume) DME in methanol. In terms of Figure  1, then, a reactor should
operate with a space time (1/LHSV) of roughly 10~3 hr  under the conditions
studied in that work, (i.e., 371° C 1 atm).
                                                                  RTI 1-3

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                                                                  2. CANDIDATE CATALYSTS
SECTION 2
CANDIDATE CATALYSTS
Alumina
                    A discussion of the catalytic chemistry involved in the dehydration of methanol
                    to dimethyl ether is beyond the scope of this report. Several investigations of
                    this reaction by various researchers [1,4,5] have been reported.  In the particular
                    application of methanol dehydration to facilitating the cold starting of an
                    automobile engine, three criteria that the optimal catalyst should meet are:

                    •   the catalyst must be sufficiently active to produce a product stream capable
                        of satisfying the cold starting requirements of an engine (roughly 15%
                        DME in methanol).

                    •   the catalyst must be stable under temperature excursions.

                    •   the catalyst must be economical when normalized by its expected lifetime.
                        Deactivation will likely occur due either to coking reactions caused by
                        further dehydration of DME to unsaturated hydrocarbons (reaction (2)) or
                        to high temperature sintering.

                    A list of various catalyst families suitable for the dehydration reaction along
                    with some of their advantages and disadvantages is presented in Table 1.

                    Upon award of this contract, a number of commercial catalyst vendors were
                    contacted to obtain catalysts suitable for the methanol dehydration reaction.
                    An  example of the request is given in Appendix A. -Of the catalyst families
                    listed in Table 1, only four were represented by samples received in response to
                    this solicitation. These are presented in Table 2 categorized by family.  A brief
                    description of these catalysts, including the limited information provided by
                    each vendor, is presented below.
                    Aluminum oxide (A12O3) exhibits significant acid properties suitable for metha-
                    nol dehydration reaction. These acid properties can be varied somewhat by the
                    calcining procedure used in their manufacturing so that a large variety of
                    aluminas exist. Harshaw/Filtrol provided a number of alumina catalysts as
                    listed in Table 2. A summary of the composition of each of these catalysts is
                    presented in Table 3. The properties of the United Catalyst alumina catalysts
                    are presented in Table 4. Note that the surface areas do vary somewhat.
                                                                                    RTI

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                                                 2.  CANDIDATE CATALYSTS
  Table 1.  Advantages and Disadvantages of Candidate Catalyst Families
      Catalyst
Advantages
Disadvantages
  Zeolites
      aluminosilicates
      aluminophosphates
  Silica-aluminas
  Aluminas
_ Metal salts

     phosphates
     sulfates
Much research has been done Possible selectivity
on this catalyst; methanol     problems since DME
dehydration is fairly well     readily react further
understood                 on these catalysts
Probably has the right mix
of acid-base site strengths
Well-studied catalysts for
this reaction
Bronsted/Lewis acid site
ratio is controllable by
calcining conditions

Low cost catalyst

Acid strength distribution
is controllable by calcin-
ing temperature
                          Bronsted/Lewis acid/base
                          character is controllable
                          by dehydroxylation
May have surface acidity
comparable to alumina
Bronsted/Lewis acid-base
sites are controllable by
calcination
Relatively new
materials; methanol
dehydration has not
been well studied

High density of very
strong acid sites may
lead to low
selectivity and/or
coking
Selectivity may be
poor; alumina is very
active for olefin
formation from
alcohol dehydra-
tion

Small amounts of
impurities can affect
the acid site strength
and thus the activity/
selectivity
Selectivity may be
poor due to strength
of acid sites

Inherently strong acid
sites may lead to
coking
                                                               (continued)
                                                                   RTI  2-2

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                                             2.  CANDIDATE CATALYSTS
Table 1  (continued)
   Catalyst            Advantages                 Disadvantages

Ion exchange resins      High activity at low tempera-  Poor mass transfer
                       tures                        in some resins due
                                                   to small pore sizes

                       Acidity is controllable by      Deactivation may
                       synthesis conditions          occur if temperature
                                                   excursions above
                                                   ~150° C occur

Mixed metal oxides      Acid site strength con-        Selectivity may be
                       trollable by synthesis          poor since some
                       conditions                   mixed oxides also
                                                   promote dehydroge-
                                                   nation and olefin
                                                   formation.
                                                               RTI  2-3

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                                          2. CANDIDATE CATALYSTS
Table 2. Catalyst Samples Received and Tested
Aluminas


Zeolites



Metal oxides




Harshaw AL-5207
AL-5307
AL-5407
AL-3945
AL-3996R
United CS 331-1
CS 331-4

Union Carbide LZ-20
LZ-Y-72
LZ-M8
United Z6-06-02
Mobil MCG-7
MCG-8

Zeochem Z6-06-02, B6980
Harshaw ZR-0304T
TI-0720
United T-312
T-314
T-317
T-1502A
T-1502B
7913-S, K-306
Ion Exchange Resins
                  Rohm & Haas
XE-386
6-928  Not tested
6-9852
                                                          RTI 2-4

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                                           2.  CANDIDATE CATALYSTS
Table 3. Harshaw/Filtrol Alumina Catalysts
Catalysts
AL-5207
AL-5307
AL-5407
AL-3945
AL-3996R
Surface Area
(m2/g)
200
200
190
250
200
Fe203
0.1
0.1
0.1
< 0.01
0.07
Composition (wt%)
w/Balance AI203
SiO2 Na2O
0.2
0.2
0.2
<0.01
0.01
0.08
0.08
0.08
<0.01
0.06
Table 4. United Catalyst Alumina Catalysts
Catalysts
CS 331-1
CS 331-4
Surface Area
(m2/g)
200-300
200-300
Fe203
<0.20
<0.20
Composition (wt%)
w/Balance AI2O3
Na Cl S
<0.05 <0.02 <0.05
<0.05 <0.02 <0.05
                                                            RTI  2-5

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                                                                   2.  CANDIDATE CATALYSTS
Zeolite
Metal oxides
                    The term zeolite refers to crystalline aluminosilicate compounds which have
                    well-defined pore structures and geometries. They also contain an exchange-
                    able metal cation and considerable water of hydration as synthesized.  By
                    varying the cation and the amount of water present in the structure during
                    manufacturing, the acid/base properties can be somewhat controlled.

                    Table 2 lists the zeolites received. Their properties are given in Tables 5 and 6.
                    It is possible that the Mobil samples (MCG-7 and 8) are variations of their
                    ZSM-5 zeolite which is used in their second stage MTG reactor. No infor-
                    mation was provided by Mobil in this regard, however, so that positive
                    identification is impossible.
                    Metal oxides are of particular interest for this application because the acidity
                    and basicity of the catalyst can be easily altered through changes in catalyst
                    formulation. A number of metal oxide catalysts on different supports were
                    received as shown in Table 2. Their properties are shown in Tables 7 and 8.
Ion Exchange Resins
                    Ion exchange resins have shown low temperature (30° -150° C) activity for
                    alcohol dehydration [4]. These catalysts are extremely sensitive to both high
                    temperature (> 150° C) and hydration effects, so no testing was undertaken at
                    this time. In addition, the ion exchange resins cannot be formed into monoliths
                    thereby disqualifying them from consideration in this automotive application.
                                                                                     RTI 2-6

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                                          2. CANDIDATE CATALYSTS
Table 5. Union Carbide Zeolite Catalysts
Catalysts
LZ-20
LZ-M8
LZ-Y-72
Composition (wt%)
AI2O3 Si02
<40 <80
-
<40 <80
Na20
<5
-
<5
NHL Remarks

< 20 Ammonium
Exchanged
-
Table 6. United Catalyst/Zeochem Zeolite Catalysts
   Catalysts
Surface Area
   (m2/g)
AI203
Composition (wt%)
  Na2OAI2O3x
    Si02 x H20
MO
United Z6-06-02
Zeochem Z6-06-02
     B6980
    375
 25-35
 25-35
      65-75
      65-75
 2.4
                                                           RTI 2-7

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                                           2.  CANDIDATE CATALYSTS
Table 7. Harshaw/Filtrol Metal Oxide Catalysts
Catalysts
ZR-0304T
0720
Surface Area
m*/g
52
205
Composition (wt%)
ZrO2 Ti02 AI2O3 Si02
980 __,.. 2.0 0.1
100
Table 8. United Catalysts Metal Oxide Catalysts
Catalysts
T-312
T-314
T-317
T-1502A
T-1502B

K-306
Surface Area
m2/g
183
. 190
187
124
152

250
Ni
8-10
8-10

15
27
Si02
71.7
Composition (wt%)
Cu Cr Ti
10

10-12


AI203
12.5

1.6
0.1-0.2


Fe2O3 CaO
5.2 2.7
Balance
A1203
A1203
A1203
SiO2
SiO2
MgO
3.6
                                                            RTI 2-8

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                                                                         3.  EXPERIMENTAL
SECTION 3
EXPERIMENTAL
                    The primary objective of Phase I was to screen and rank a variety of commer-
                    cially available catalysts with the potential of effecting the dehydration of meth-
                    anol to dimethyl ether (DME). The minimum requirement of a catalytic dehy-
                    dration system is to deliver a gas stream of roughly 15 percent DME in metha-
                    nol to the automobile fuel system under cold start conditions. This
                    corresponds to 30% conversion of methanol by reaction (1). Given that
                    objective and the constraints of available space onboard an automobile, the
                    catalyst must exhibit sufficient activity to produce the required stream in a reac-
                    tor of feasible size.  In addition, to reduce high temperature deactivation, the
                    catalyst must convert approximately 30 percent of the methanol feed at as low a
                    temperature as possible. The rate at which methanol will dehydrate is a
                    function of the reactor temperature and catalyst.  Once these are  fixed, the ex-
                    tent of conversion of methanol to DME depends on the product of this rate
                    times  the time which the methanol spends in contact with the catalyst. This
                    contact time is conveniently given by the liquid hourly space velocity (LHSV).
                    The LHSV is defined as:

                       T ncv - the volume of liquid methanol/time                   /«->
                       LHb  ~      the volume of  catalyst^ }

                    The overall conversion is then given by :

                        (conversion of methanol  in moles)  = r^nov                    (4)

                    where:

                       r  = overall reaction rate of methanol dehydration in moles converted per
                            unit time

                    The reaction rate (r) is normally given in the form of:
                                  r =  Ae E/RT  (C)n                                   (5)
                    where:
                    A   =  pre-exponential factor which is approximately constant
                    E   =  activation energy of the reaction
                    R   =  gas constant
                    T   =  reaction temperature
                    C   =  concentration of the reactants
                    n   =  order of reaction
                                                                                   RTI 3-1

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                                                                           3.  EXPERIMENTAL
                    For a given methanol feedstream and catalyst at constant temperature, r can be
                    considered constant. Thus, the conversion of methanol can be increased by
                    decreasing LHSV by Equation (4). Physically, this means that for a given
                    reaction rate, a lower flow rate will permit a higher conversion of methanol.
                    Alternatively, the reaction rate for a given catalyst can be increased dramatical-
                    ly by increasing the reactor temperature, T. The activity of a catalyst is
                    manifested by the activation energy, E. By Equation (5), a lower E has the
                    effect of increasing the reaction rate at a given temperature. Hence, a catalyst
                    that is more "active" exhibits a lower activation and therefore a higher reaction
                    rate for a given temperature, T. Consequently, a more active catalyst will in-
                    crease conversion of methanol for a given reactor size and capacity (LHSV).
                    Finally, the reaction order (n) can be considered to be equal to one for the het-
                    erogeneously catalyzed methanol dehydration reaction as a first approximation.

                    In the application of onboard methanol dehydration, the total volume of the
                    proposed catalytic reactor must be small. In addition, the reaction is intended
                    to operate  under cold start conditions so that a minimum reaction temperature
                    is sought. It should be noted that for a given catalyst this presents a tradeoff in
                    that the lower the reaction temperature, the higher the reactor volume must be
                    to maintain a given level of methanol conversion. The objective of Phase I,
                    then, is simply to identify those catalysts that exhibit the lowest activation ener-
                    gy for the methanol dehydration reaction. These will, in turn, provide the best
                    level of conversion for the minimum reaction temperature and reaction
                    volume.
Experimental Considerations

                    The rate of a heterogeneously catalyzed reaction of gas phase reactants on the
                    surface of the solid catalyst is determined by the slowest of the following steps:

                    •   External mass transfer - the rate at which either the gas phase reactants reach
                        or the products leave the surface of the catalyst.  This is a function of both
                        the bulk motion of the gas around the catalyst particle as well as the
                        diffusion properties of the reactants and products under the experimental
                        conditions.

                    •   Intraparticle mass transfer - once the gas phase reactants have reached the
                        catalyst pellet, they must find their way to an active site on the surface.
                        Similarly, after reaction, the products must diffuse away from the active site.

                    •   Surface reaction rate - Once the gas phase reactant has reached an active site
                        on the catalyst, it must react to form the reaction products. The inherent
                        activation energy describes the rate of this reaction and varies from catalyst
                        to catalyst.

                    The relative contribution of each of these steps is most easily visualized by con-
                    sidering a varying reactor temperature. Obviously, at very low temperatures.

                                                                                      _____

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                                                       3. EXPERIMENTAL
the reaction rate on the surface is extremely slow and therefore rate controlling.
The conversion of the gas phase reactants is limited by the reaction rate on the
surface of the catalyst. As the temperature is increased, however, this reaction
rate increases (Equation [5]) to the point at which it exceeds the rate at which
the reactants reach the surface. Mass transfer is said to be limiting the reaction
rate. This resistance could be the rate of reactant transfer from the bulk gas
stream to the catalyst pellet (external mass transfer). Most catalysts are porous
so that the mass transfer into the pellet pores to the actual surface could also be
limiting the overall reaction rate (internal mass transfer). Usually, however, the
surface area of the catalyst is large and the particles are small, in which case
external mass transfer from the bulk gas stream to the catalyst particle is rate
limiting.

In any event, practical systems utilize high reactor temperatures to ensure that
the surface chemical kinetics do not limit the production rate. The overall mass
transfer of the reactants to the catalyst particle is, therefore, oftentimes the rate
limiting step in these heterogeneous systems.

For the purposes of the Phase I screening tests, it was determined to fix as
many of the  experimental factors as possible so that the evaluation of each cata-
lyst would be under uniform conditions.  This need for constancy was effected
by a number of experimental considerations each of which will be treated sepa-
rately.

The LHSV as defined by Equation (3) was kept constant for each catalyst test-
ed. This was done by using the same volume of each catalyst for each test while
maintaining a constant methanol volumetric flow rate.  In particular, a 0.4 cm
I.D. glass tube was packed with catalyst to a length of 4 cm. The volumetric
flow rate was constant at 200 cm3/min of 1,000 ppm methanol in nitrogen. By
Equation (3), this equals a LHSV of 6.08 x 10"2 hr"1 (see Section 6).

Within the catalyst bed, the amount of time that the methanol feed spends in
contact with the candidate catalyst should be uniform over the cross-section of
the packed reactor.  In this study, the candidate catalysts were crushed and
sieved to produce a  60-80 mesh size sample (0.18 to 0.25 mm).  This was done
to minimize  non-uniformities in the velocity-profile (and, hence, the contact
time) of a gas flowing through the packed bed which can arise due to two
mechanisms. The first is simply the diffusion of the species in the axial direc-
tion of the flow.  For most gases, the ratio of diffusional to convective (or bulk
flow) transport increases as the Reynolds number of the fluid in the packed
bed decreases. For  a given gas flowing above a Reynolds number of 1 [6] this
ratio is less than 1. The present system, 1,000 ppm methanol in nitrogen flowing
at 200 cm3/min through a packed bed mean particle diameter of 0.21 mm, has a
Reynolds number greater than 2 and is, therefore, in the convective transport
                                                                 RTI 3-3

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                                                                           3.  EXPERIMENTAL
                    dominated regime, thereby limiting non-uniformity in contact time due to dif-
                    fusion.

                    The second mechanism of dispersion in a packed bed reactor is due to a non-
                    uniform bulk velocity profile. In particular, it has been shown that in tubular
                    reactors of small diameter, Dt, with respect to the particle size diameter, D , the
                    voidage, or fraction of cross sectional area which is devoid of solid particles,
                    increases dramatically near the wall of the reactor.  This effect is due to the in-
                    terference of the wall with the packing of the solid material. A general criterion
                    states that the ratio of tube diameter to particle diameter should be above 20.
                    In the present case, we have a tube diameter of 4 mm with an average particle
                    size of roughly 0.2 mm resulting a Dt/D   = 20.

                    Hence, the physical conditions of the experimental microreactor were chosen
                    to minimize the dispersion effects of both axial diffusion and non-uniformities
                    in the bulk velocity profile.

                    An additional concern of exothermic reactions studies is whether the heat
                    produced by the reaction is sufficient to raise the reactor temperature
                    significantly. In such cases the furnace temperature can read one value while
                    the local catalyst temperature (which is the temperature of the gas at the
                    reaction site) can be somewhat higher. This would lead to inaccurate
                    conclusions concerning the required temperature for a given extent of conver-
                    sion of the  methanol. Since the microreactor was operated in an electrical
                    furnace, it could be assumed that the reactor operated under nearly adiabatic
                    conditions.  An estimate of the adiabatic temperature rise across a packed bed
                    reactor is given in Appendix  B.  Using the values for our system, the tempera-
                    ture rise across the reactor can be calculated to be  roughly 53° C for 30 percent
                    methanol conversion when a pure methanol feedstock is used.  This would be
                    unacceptably high since that  temperature rise could induce further reactions of
                    the DME to subsequent hydrocarbons as described in reaction (2). The same
                    calculation with even complete conversion of a 1,000 ppm methanol feedstream
                    in nitrogen shows an adiabatic temperature rise of only 0.18° C. Hence, it was
                    determined to use a dilute (1,000 ppm) mixture of methanol and nitrogen for
                    the screening test.

Experimental Procedure

                    Each catalyst was crushed and sieved. The 60-80 mesh cut was-calcined.in a
                    muffle furnace at 300° C for  1-1/2 hr. A 0.40 cm I.D. pyrex glass tube approxi-
                    mately 62 cm long was used for the reactor vessel.  A small amount of glass
                    wool was compressed and forced into the reactor to form the support for the
                    catalyst bed. Sufficient catalyst was then added to  form a 4 cm long catalyst
                    bed after gently tapping the sides to induce particle settling.  The final mass
                    varied from catalyst to catalyst due to differences in particle densities.  Another
                                                                                     RTI  3-4

-------
                                                      3.  EXPERIMENTAL
compressed plug of glass wool was added to contain the catalyst particles. The
glass tube containing the 4 cm catalytic bed was then placed in the reactor fur-
nace and connected to the incoming and outgoing lines. A complete schematic
of the experimental apparatus is given in Figure 2.

For the reasons described above, a 1,000 ppm methanol in nitrogen stream was
used as the feedstream for this phase of the work. Sufficient back pressure was
made available for the system by setting the bottle regulator at 80 psi during
each run. The methanol was metered from the bottle through a Tylan FC-260
mass flow valve. The valve was controlled by a Sierra "Flow Box" mass flow
controller.  The methanol then passed directly to a 10 port gas chromatographic
sampling valve (see Figure 3). The sampling valve provided an in situ
calibrating procedure for the methanol feed stream as follows, (with reference
to Figure 3):

First, the methanol coming from the vaporizer (which was not needed in Phase
1 since a gaseous feed stream was used) entered the 10-port-sampling valve.
There it was routed through a bypass loop, leaving the valve to be fed to the re-
actor inlet (see Figure 2). After passing through the catalyst bed, the stream re-
entered the 10-port-sampling valve as labeled in Figure 3 from  the reactor.
When the sampling valve was positioned as in the configuration to the left in
Figure 3, the stream passed directly to the vent and was routed to the laborato-
ry flue.  The sampling valve then switched to the configuration shown on the
right in Figure 3. At this time, the helium carrier gas for the gas chromatograph
swept the sample out of the bypass loop to the gas chromatograph for analysis.
At the same time, the reacted gas stream from the reactor entered the 10-port-
sampling valve to be routed through a reactor loop of the same size as the
bypass loop and then to vent. While still in this configuration, the unreacted
methanol stream from the vaporizer was routed directly to the reactor inlet
without  passing through the bypass loop.  After the bypass gas sample analysis
by the gas chromatograph was completed, the valve was switched back to the
configuration on the left in Figure 3.  Now the helium carrier gas swept the
sample out of the reactor loop passing it on to the gas chromatograph for analy-
sis. In this manner, both inlet and outlet streams could be alternately
monitored, thereby correcting for daily fluctuations in GC performance.

A Varian Model 3700 Gas Chromatograph equipped with a flame ionization
detector (FID) was used for hydrocarbon analysis. Separation  was effected by
a 1% SP -1,000 60/80 carbon packed column. The injector temperature,
column  temperature and detector temperature were maintained at 80°, 60°,
and 200° C, respectively. Peak  area integration was calculated  by a Hewlett-
Packard 3392A Integrator. Since each injection of the gas sample to the gas
chromatograph required 5 minutes for the complete elution of'all the reaction
components, the valve was switched every 5 minutes. This was effected by a
Hewlett-Packard 19405A Sampler-Event Control Module. Using a prepro-
                                                                RTI  3-5

-------
      o
      o
      o
       o
       c
       re
       -C
                             Mass Flow     VA A
                             Control Valve /Y^*
                   Thermocouple
                     Readout
                     I      I
                     Selector
                            O
                    Furnace
                    Temperature Controller
                                 Liquid Pump
                                   (Phased)
         Mass Flow
        Control Box
                    Vaporizer
                    Temperature Controller
                                             y
                                             y
                                                                      Vaporizer
                                                                      (Phase II)
                                                                                                                       Vent
                                                                                                                         1i
                                                                                                          10-Port
                                                                                                          Sampling Valve
                                                                                    Reactor Furnace
                                                                                rooooooooooooooi
                                                                                                                  Gas
                                                                                                             Chromatograph
                                                                                                                                  u

                                                                                                                                  m
                                                                                                                                  X
                                                                                                                                  •o
                                                                                                                                  m
CO
en
Figure 2. Microreactor catalyst testing facility.
m
I

-------
        To
        Reactor Inlet
                              To Gas
                          Chromatography
Vent
JO
H
       Figure 3. 10-Port sampling valve arrangement.
                                                                                             He
                                                                       From
                                                                       Vaporizer
                To Reactor
                Reactor Inlet
    To Gas
Chromatography
Vent
m
x
•o
m
3J
                                                                         m
                                                                         •z.

-------
                                                      3.  EXPERIMENTAL
grammed method, the 3392A integrator controlled the 19405A sampler-event
module. The ten-port sampling valve was housed in a Carle Model 4301 Valve
Oven configured with a Carle Model 4200 Valve Actuator.

Since the experimental testing required analysis at a variety of reactor
temperatures for a given LHSV, a temperature control unit was needed to
drive the Thermcraft reactor furnace. To this end, an Omega microprocessor
based controller (Model No. CN2011)  unit was interfaced with a Tandy 1200
HD personal computer.  Software developed by RTI enabled various setpoints
to be stored and fed to the Omega temperature controller at timed intervals.
For a given set point, the Omega temperature controller brought the reactor
furnace to the set point within a ±5° C  tolerance. A typical run involved storing
a series of nine set points in the computer and beginning the run.  Typically the
set points were 50°, 85°, 100°,115°, 130°, 150°, 175°, 200° and 225° C.  The
50° C run provided a pure methanol output to the gas chromatograph which
could be used later for calibration purposes since no reaction occurred.at this
low temperature.  Each set point was maintained for 1 hour  during which
approximately five samples were taken. Of these, the last three were used for
methanol conversion calculations.

After each run, the peak areas calculated by the 3392A integrator were entered
in a macro-driven LOTUS spreadsheet with the 50° C input and output
methanol peak areas being entered as calibration peaks. The ratio of outlet to
inlet areas (in this case, the 0% conversion case) provides a correction factor
taking into account the pressure drop across the reactor bed. This is required
since the FID is a mass detector rather than a concentration sensitive detector.
Hence,  the sample stored in the bypass and the reactor loops (see Figure 3) are
gases of slightly different densities. Although the reactor and bypass loop
volumes are nominally of the same size, different methanol or product masses
are injected  in each case to the GC. Even when no conversion is occurring
across the catalyst bed, the total amount of methanol passing through the flame
ionization detector will be less in the case of the reactor loop since the gas there
-is of lower density due to the pressure drop through the catalyst bed. By
entering the input and output peak at 0% conversion (50° C) that ratio can be
used to  correct the data for the rest of the run since this density difference
should remain essentially constant.  This was done automatically by the
LOTUS spreadsheet.

Once the data were entered, two plots were produced: one showing the metha-
nol conversion as a function of reactor  temperature, the other showing approxi-
mate concentrations of both methanol  and dimethyl ether in the product
stream.  These plots are discussed in Section 4.
                                                                RTI  3-8

-------
                                                                                4.  RESULTS
SECTION 4
RESULTS
                    The results of each catalyst test are presented in a graph depicting the conver-
                    sion of methanol as a function of reactor temperature. Figures 4 through 10
                    show these conversion plots for the alumina catalysts tested.  Similarly, Figures
                    11 through 17 present the results for the zeolite catalysts while Figures 18
                    through 25 present results for the metal oxide catalysts. The  equilibrium con-
                    version of methanol to dimethyl ether was shown in the RTI  July 1987 proposal
                    to be approximately 90% under these conditions. However, small amounts of
                    DME will react further to higher products, thereby allowing  more methanol to
                    be converted.

                    For selected catalyst tests, a mixture of 290 ppm dimethyl ether in nitrogen was
                    fed to the reactor at room temperature to provide DME calibration areas.
                    Subsequent results could then be represented in terms of actual ppm quantities
                    of methanol and  DME in the product stream.  These data are shown in Figures
                    26 through 30 for selected catalysts. An approximate material balance is
                    possible in that,
                               2CH3OH
(6)
                    produces one part of DME for every two parts of methanol consumed. The
                    data in Figures 26 through 30 are presented in terms of parts per million by
                    volume, so multiplying the DME levels by two and adding them to the metha-
                    nol level should yield roughly the 1,000 ppm level of methanol feed.  At higher
                    levels of conversion, it is likely that some conversion of the DME to higher hy-
                    drocarbon occurs which is not detectable at these levels using present equip-
                    ment. It is significant to note that at a methanol conversion of roughly 30% the
                    material balance is quite accurate, indicating that virtually all the methanol
                    converted at these lower levels forms DME only.

                    This result can be used  to develop a meajure to rank the catalysts since a
                    product stream containing 15% by volume of DME in unreacted methanol is
                    required to start an engine under cold start conditions and a 15 volume %
                    DME stream corresponds to 30% conversion of methanol. As the data in
                    Figures 25-30 would indicate, substantially all of the. methanol converted at
                    these lower levels of conversion forms DME rather than the higher hydrocar-
                    bons with  a concomitant formation of coke. Hence, selectivity at these
                    minimum  conversion levels is not an important criterion for catalyst selection.
                    The data presented in Figures 4-25 were then used to identify the reactor tem-
                    perature required to convert 30% of the feed methanol for each catalyst. That
                    temperature, T30, was then used  to rank the activity of the  candidate catalysts.
                    These results are given in  Table 9.  .

                                                                                    RTI 4-1

-------
                                                                             4.  RESULTS
 I
 o
 HI



 0
 c
 0
 o
i
o
II
5
c
0
o
                 100     120     140     160     180     200
                                                              220
                                                                     240
                                    Temperature


                         Figure 4. MeOH conversion, AL-5207.
         80      100      120     140      160     180     200     220    . 240
                                   Temperature


                     Figure 5.  MeOH conversion, AL-5307 E 1/16.
                                                                                 Rtl  4-2

-------
                                                                                4.  RESULTS
I
o

I

"5
0
o
      0.1 -
         80
                 100
                         120
                                         1	i	r

                                         160     180
                                                  i	1	1	r

                                                 200      220
240
                                     Temperature


                         Figure 6. MeOH conversion, AL-5407.
 x
 o
 a


 'o
  c
  o
 o
0.9 -




0.8 -




0.7




0.6




0.5




0.4




0.3




0.2




0.1
            -O |
           80
                  100
                                                              i    i    i
                          120
                                                  180
                                                         200
                           140     160


                               Temperature



                   Figure 7.  MeOH conversion, AL-3945.
                                                                 220
                                                                         240
                                                                                     RTI  4-3

-------
                                                                                  4.  RESULTS
        1
i
o
01
c
0
o
0.9 -



0.8 -



0.7



0.6



0.5



0.4



0.2



0.2 -



0.1 -
        o I  o—i	9	r~s~T	v	1	1	1	1	1	r	1	1	1	1	1—

          80      100     120      140      160      180   .   200      220      240

                                      Temperature


                         Figure 8. MeOH conversion, AL-3996 R.
        1
 o
 0)
 2

 'o
 c
 o
 O
0.9 -



0.8 -



0.7 -



0.6 -



0.5 -



0.4 -



0.3 -



0.2 -



0.1 -



  0
                                                                    -Q—
               i    t    i    i    i    i    i    i    i    T   i     n  n    i    i    i

          80      100     120     140     160     180     200     220     240

                                      Temperature


                          Figure 9. MeOH conversion, CS 331-1.
                                                                                       RTI  4-4

-------
                                                                               4.  RESULTS
i
o
a
o
o
o
I
o
c
0 .
o
         .80      100      120'      140     160     180     200      220      240
        1
0.9 -




0.8 -




0.7




0.6




0.5



0.4




0.3




0.2 -




0.1 -
         80
                                    Temperature


                         Figure 10. MeOH conversion, CS331-4.
                 100
                 My i

                   120
                                             i    i    i
                                 140
                                        160
                                                180
                                                        200
                                                                220
                                                                       240
                                    Temperature


                          Figure 11. MeOH conversion, LZ-20.
                                                                                    RTI  4-5

-------
                                                                            4.  RESULTS
 i
 o
 a
  c
  0
  o
X
o
0)
2
c
0
o
          80
                  100
                                                       200
                                                              220
                                                                      240
                                    Temperature


                         Figure 12. MeOH conversion, LZ-Y-72.
                100
                        120
                               140
                                       160
                                              180
                                                     200
                                                             220
                                                                    240
                                   Temperature


                        Figure 13. MeOH conversion, LZ-M 8.
                                                                                 RTI 4-6

-------
                                                                                 4.  RESULTS
I
o
01
2

'o
c
0
o
        1
0.9 -



0.8 -



0.7 -



0.6 -



0.5 -



0.4 -



0.3 -



0.2 -



0.1 -
              i    i    i    i    i    i    i    i    t    i    i    i    i    i

         80      100     120     140     160     180     200     220
                                                                   240
                                     Temperature


                         Figure 14.  MeOH conversion, Z6-06-02.
         1
 r
 o
  c
  0
 o
 0.9 -



 0.8 -



 0.7 -



 0.6 -



 0.5 -



 0.4 -



 0.3 -



 0.2 -



 0.1 -



   0
                  100
                          120
                                                          200
                                                                  220
                                  140     160     180

                                      Temperature


                      Figure 15. MeOH conversion, Z6-06-02,B6980.
                                                                          240
                                                                                      RTI  4-7

-------
                                                                           4.  RESULTS
i
o
2

'o
c
0
o
                                              180
                                                     200
                                                            220
                                                                    240
                                  Temperature


                        Figure 16. MeOH conversion, MCG-7.
i
o
2


'B
 c
 0
o
         80
                100
                        120
                                              180
                                                     200
       140     160

           Temperature


Figure 17. MeOH conversion, MCG-8.
                                                                    240
                                                                               RTI 4-8

-------
                                                                               4.  RESULTS
X
o
2

'o
c
0
u
      0.1 -
         80
           100
                         120
                                                180
~\	1	1	1	r

200     220      240
                                    Temperature


                        Figure 18.  MeOH conversion, ZR-0304T.
I
o
c
o
0
0.9 -



0.8



0.7



0.6



0.5



0.4



0.3



0.2 -



0.1 -



 0
              1	1

         80      100
                  —i	1	1	1	1	1	1	1	1	1	1	1	1—

                   120     140     160     180      200     220     240

                              Temperature


                   Figure 19. MeOH conversion, TI-0720.
                                                                                     RTI  4-9

-------
                                                                               4.  RESULTS
i
o
c
0
o
 I
 o
 o
 C
 0
 o
        1
0.9 -



0.8 -



0.7



0.6



0.5



0.4



0.3



0.2 -



0.1 -
        0 -I-B

         80
           100
                   120
                                 140
                                  160
                                          180
                                                  200
220
                                                                 240
                                    Temperature


                          Figure 20. MeOH conversion, T-312.
                                                         200
                                     Temperature


                          Figure 21. MeOH conversion, T-314.
                                                                 220
                                                                        240
                                                                                   RTI 4-10

-------
                                                                              4.  RESULTS
i
o
9
2
c
0
o
                                140     160     180   .  200     220     240
         80
                               • • •   Temperature


                          Figure 22. MeOH conversion, T-317.
        i
i
o
ai
2
 c
 0
 o
0.9 -



0.8 -



0.7



0.6



0.5



0.4



0.3



0.2 -



0.1 -
                       -B-
          80
                 100
                         120
                                                180
                                                        200
                           HO"    160


                              Temperature


                  Figure 23. MeOH conversion, T-1502A.
                                                                220
                                                                        240
                                                                                 RTI 4-11

-------
                                                                          4.  RESULTS



I
o
5
0
c
0
u



1 -
0.9 -
0.8 -
0.7 -
0.6 -

0.5 -
0.4 -
0.3 -
0.2 -
0.1 -
0 -
8










— o-— 	 * 	 "a-
-_O 	 D 	 '
— n — i n — rr^^
n I 9 \^J I I I I I I I ' • I 	 I 1 "1 1 ' • •
0 100 120 140 160 180 200 220 240










X
o
c
o
o
                                  Temperature
                      Figure 24. MeOH conversion, T-1502B.
      0.1 -
         80
                100
                       120
                              140
                                  Temperature


                    Figure 25. MeOH conversion, 7913-S K-306.
                                                                             RTI 4-12

-------
4.  RESULTS
1.1 -
1 -
0.9 -
0.8 -
a 0.7 -
u"""
3= 0.6-
Q D
(A
o J °-5 ~
? 0.4-
5
0.3 -
0.2 -
0.1 -
0 -
e


~~~^^8^lv
\
\
\
V ^ 	 +_ 	 +_
x^*


0 100 120 140 160 180 200 220 240








Temperature
Q MeOH + DME
1.1 -
.1 -
0.9 -
0.8 -
a 0.7 -
I! ae-
(/i
o J 0.5 -
? 0.4-
2
0.3 -
0.2 -
0.1 -
0 -
8
Figure 26. MeOH & DME outputs, A L -5207.
^°^\
\
1
\
\

A
/ \
^^^ -a — a
i i i i i i i i i i i i i i i i
3 1 00 1 20 140 1 60 1 80 200 220 240







Temperature
D MeOH + DME
Figure 27. MeOH & DME outputs, AL-5407 E 1/16.
   RTI 4-13

-------
                                                                                4.  RESULTS
      1.1
£
a
a
  o

  "
o
01
2
  1 -




0.9 -




0.8 -




0.7 -




0.6 -




0.5 -




0.4 -




0.3 -




0.2 -




0.1 -




  0
            1—i	1	1	1	1	1	1	1	1	1	r	1	1	1	1	1—

         80      100     120     HO     160      180      200      220      240


                                     Temperature

                               D   MeOH        •*•   DME



                        Figure 28. MeOH & DME outputs, LZ-20.




£
a
a^
J c
a o
§|
it
o
01
2









i . t
.1 -
0.9 -
0.8 -

0.7 -

0.6 -

0.5 -


0.4 -


0.3 -
0.2 -
0.1 -
. 0 -
LJ~X\
\
\
\
a
%
\
\
\
\
\

\ i 	 	
V "•" "~^"™™"™""~— | - L .
y*a _ ~_+ 	
/ \ ~~~
/ \
S/ \ 	 	 	 g^ 	 a—
~*
i i i i i i i i i i i 	 1 	 1 i 	 1 	 1 	



















80 100 120 140 160 180 200 220 240
Temperature
D MeOH + DME
Figure 29. MeOH & DME outputs, M-8.
                                                                                    RTI  4-14

-------
                                                         4.  RESULTS
                    160     180     200     220
80
       100     120
140
                Temperature
           D   MeOH        +   DME
                                                           240
Figure 30. MeOH & DME outputs, Z6-06-02 1/16.
                                                            RTI 4-15

-------
                                                         4. RESULTS
Table 9.  Ranking of All Candidate Catalysts Tested According to T3Q

Catalyst                Catalyst family             T3Q (°C)
LZ-M8
CS-331-4
AL-5407
MCG-8
CS 331-1
AL-5307
AL-3945
AL-5207
LZ-20
MCG-7
Z6-06-02
AL-3996R
LZ-Y-72
7913-S K306
T-317
T-314
ZR-0304T
Z6-06-02, B6980
T-312
Zeolite
Alumina
Alumina
Zeolite
Alumina
Alumina
Alumina
Alumina
Zeolite
Zeolite
Zeolite
Alumina
Zeolite
Metal oxide
Metal oxide
Metal oxide
Metal oxide
Metal oxide
Metal oxide
118
131
135.5
136.5
138
142
142.5
142.5
145
145
146
148.5
164
171.5
178
186
188
215
216.5
       Catalysts Which did not Convert 30% of the Feed Methanol
              Under the Conditions of the Screening Test

TT-0720                 Metal oxide
T-1502B                 Metal oxide
T-1502A                 Metal oxide
                                                            RTI 4-16

-------
                                                                             5. DISCUSSION
SECTION  5
DISCUSSION
                    The results given in Table 9, in which all the catalysts tested are ranked
                    according to their activity for 30% conversion of the feed methanol, are useful
                    in separating some of the candidate catalyst families. In particular, the metal
                    oxide catalysts are less active than either the alumina or zeolite. Even those
                    catalysts in which the metal oxide is supported by an alumina or zeolite
                    (e.g., Z6-O6-O2-B6980) shows significantly higher T30 values than their non-
                    metallic counterparts (e.g. Z6-06-02).

                    It is also interesting to note that the T-317 catalyst showed virtually no metha-
                    nol (see Figure 20) at higher conversions while all of the other catalysts showed
                    a maximum of roughly 90% methanol conversion. This non-equilibrium value
                    of methanol conversion on the T-317 catalyst indicates that further reaction of
                    DME was occurring. Indeed, upon inspection of the gas chromatographic data
                    some lighter compounds were detected although no identification was made.

                    Among the aluminas and zeolites no such  clear definition exists. The most
                    active catalyst was found to be the ammonia exchanged zeolite M-8 provided
                    by the Union Carbide Corporation.  It is known that a mixture of acid and base
                    sites, perhaps provided by the zeolite and ammonia respectively, is necessary
                    for a favorable dehydration catalyst. The alumina catalysts, CS-331-1 and -4
                    provided by United Catalyst Incorporated are primarily alumina oxide with
                    higher surface  area than the Harshaw AL-series (see Tables 3-8). Although the
                    inspection properties of the AL-5207, -5307 and -5407 catalyst are very similar
                    (see Table 3), other literature not reported here shows that the pore volume
                    distribution of the three catalysts are slightly different. In particular, the pore
                    size distribution of the AL-5407 is slightly narrower with the majority of pore
                    volume attributable to pores less than 150 A Both AL-5207 and AL-5307
                    exhibit pores larger than 1,000 A  Whether this narrow pore size distribution
                    provides a larger number of adjacent sites in the sense of the unimolecular
                    mechanism proposed by Swabb and Gates [5] is unknown.  The catalyst litera-
                    ture provided by Harshaw (makers of 5207,5307,5407) does state that this group
                    of alumina catalysts is designed for dehydration reactions.  They go on to say
                    that these aluminas have a slightly alkaline nature. Indeed  all three of these
                    catalysts provide significant activity.

                    The catalysts provided by the Mobil Research & Development Corporation
                    (MCG-7 and -8) were sent without literature so that their composition is
                    unknown. It is thought that these are examples of the ZSM-5 catalyst used by
                    Mobil in their MTG second stage reactor wherein the DME is converted to
                                                                                     RTI 5-1

-------
                                                           5.  DISCUSSION
higher hydrocarbons for gasoline production. No difference between MCG-7
and -8 was indicated by Mobil.

Again, the metal oxide catalysts show a significantly lower activity as evidenced
by T30 values of more than 20° C above the least active alumina. Of particular
note are the T-1502A and B catalysts which are silica supported rather than alu-
mina supported catalysts. Although silica-alumina  is highly acidic, silica by it-
self exhibits no acidity. The titanium oxide catalyst 0720 also has no acidic
support and exhibits virtually no activity.
                                                                   RTI 5-2

-------
                                                                6.  PHASE II PLAN OF WORK
SECTION 6
PHASE I! PLAN OF WORK
                    In light of the data presented as Phase I of this contract it is likely that a
                    suitable commercial candidate exists for the initiation of Phase II. The goal of
                    this phase is the design and construction of a prototype dehydration reactor ca-
                    pable of providing a combustible mixture of methanol  and DME (> 15% vol.
                    DME) at a mass flowrate sufficient to start a spark-ignition engine.
                    Calculations (see Appendix C) show that if an energy flow of 6 kcal/sec is
                    needed to start an engine, a volumetric flowrate of liquid methanol of roughly
                    89.8 cm3/min must be fed to the dehydration reactor. This value can be used in
                    a simple reactor  design.  A practical constraint on the design of the prototype is
                    one of size.  The need to mount this unit in the engine  compartment of most
                    vehicles limits  total reactor volume. To illustrate this point a maximum unit
                    size will be assumed as a tube 10 cm I.D. and 35 cm in  length. If the catalyst
                    were to occupy 70% of the internal volume of this reactor, its LHSV is

                                        3
                        T rrqy _ 5388 cm  (liquid methanol)                           /y>
                                 hr (0.70 (ir) (5 cm)2  (35)

                             =  2.8 hr"1

                    This should be compared with the LHSV of the microreactor system used in
                    Phase I:
200 cm3
min
60 min
hr
1000 cm MeOH3
10
6
3
cm
total
22
mol
,400
cm (liql
3
cm
0.
025
mol
                    LHSV =
                                            (0.70)  (ir)  (.2 cmr  (4 cm)

                         =  6.08 x 10"2  hr                                           (8)

                    It is seen that a LtlSV of more than two orders of magnitude greater than that
                    used in Phase I will be needed in the prototype. For 30% conversion, the feed
                    methanol will have to be at a higher reactor temperature. Referring to the data
                    published by Chang et al. [1] shown in Figure 1, the space time (1/LHSV)
                    required for the prototype (1/2.8 hr"1 = 0.36 hr) is greater than the space time
                    needed for 30% conversion (roughly 10"3 hr) measured by those investigators.
                    This means that the temperature, T30, for the prototype unit must be higher
                    than the 150° C measured in the Phase I  but lower than the 371° C studied by
                    Chang et al.
                                                                                   RTI  6-1

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                                              6.  PHASE II PLAN OF WORK
Some problems exist in simply raising the reactor temperature for 30% conver-
sion at the higher LHSV in the prototype.  The methanol dehydration reaction
is considerably exothermic.  Therefore, the heat that evolves during the conver-
sion of methanol in the reactor must be carried away at a sufficient rate to
prevent a significant rise in the reactor  temperature. Otherwise, the  higher
temperature will raise the reaction rate and, consequently, the heat of reaction,
which thereby liberated, leads to yet higher temperatures. The maximum
temperature, Tad, is that which would result in an adiabatic system and can be
calculated using a standard expression  as given by Kramers and Westerterp [7].
The calculation (given in Appendix D)  shows that Tad would equal 377° C.

Thus, if the prototype reactor is allowed to operate adiabatically, the gas phase
temperature will rise approximately 177° C over the length of the unit. Exactly
where the rise will occur is not readily calculated although some approximate
results will be discussed shortly.

The selectivity of the methanol dehydration will suffer dramatically if such a
temperature rise occurs. It was shown in equation (7) that the LHSV required
to start a cold engine is 2.8 hr"1 or a space time (1/LHSV) of 0.36 hr. This is
much longer than the approximately 10"3 hr Chang et al. used to achieve a 30%
conversion of methanol at 371° C on ZSM-5. Hence, a significantly  lower reac-
tor  temperature would suffice in the case of the automobile prototype (say,
200° C).  If, on the other hand, such a unit experienced a 177° C temperature
rise at its midpoint, the remainder of the reactor would operate at 377° C.  The
space time for this reactor would be 0.36 * 2 = 0.18 hr. From Figure 1, a re-
actor operated at 371° C and space time of 0.18 hr will produce primarily
higher hydrocarbons. This, in turn, will lead to significant coking with
subsequent catalyst deactivation.

Of course, the prototype will not be operated adiabatically. The temperature
rise of the gas phase reactants will then depend on a balance between the rate
of heat production (via reaction) and the rate of heat transferred away from the
reactor. Probably the simplest configuration of such a non-adiabatic methanol
dehydration reactor is shown below:
                                     *• Gaseous Products


                           Cold Methanol Fuel
  Vaporization
This reactor utilizes the methanol fuel as a coolant while vaporizing and
preheating it as reactant to the dehydrator.  The heat requirements for this
process will be described below. For now, however, it is important to focus on
the reactor itself. Gaseous methanol will enter at a temperature of roughly

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                                              6.  PHASE II PLAN OF WORK
200° C. The dehydration reaction will be initiated thereby generating heat. It
was shown above that a temperature rise of 177° C is possible with no heat
exchange resulting in the rapid deactivation of the catalyst. As the rate of heat
exchange is increased (from zero), however, the maximum temperature, Tmax,
reached in the reactor will drop. At sufficiently high values of heat transfer, the
reaction will proceed in a controlled fashion resulting in prolonged catalyst life
and proper product selectivity. It has been shown [8] that the transition from
controlled operation (with small Tmax) to a rapid and severe temperature rise
(with large Tmax) is a critical phenomenon. Bilous and Amundson [9]
demonstrated the profound effect small changes in the coolant stream temper-
ature had on the gas phase temperature in an exothermic reaction system (see
Figure 31). The region of parameter sensitivity can be estimated without resort
to an exact solution of the relevant heat and mass balances by a method due  to
Barkelew [10]. This analysis showed that a relationship between two
dimensionless parameters exists which defines the region of reactor sensitivity.
The first of these parameters is defined as,
N j =
ad
RT2
I c J

' AH '
r1
p
which is related to the adiabatic temperature rise (see Appendix B).  Here Tc is
the coolant temperature.  The second parameter describes the cooling (heat
transfer) capacity of the system.
                                                                    (10)
where 1^ is the rate constant as defined in Appendix D, p is the gas density, C
is the specific heat capacity, U is the overall heat transfer coefficient and Rt is
the radius of the tubular reactor.' The relationship between these two
dimensionless parameters is shown in Figure 32.

Using the kinetic data calculated in Appendix D, the values of these parameters
may be computed for the prototype system. The following values will be used:

  E  =  2.7 x 104 cal/mol
AHv  =  -2.2 xlO3 cal/mol
  Cp  =  12.4 cal/mol K
  R  =  1.987 cal/mol K
  Tc  =  375 K
  U  =  5.4 cal/cm2 hr.K
  1^  =  1.2 x 104 cm3/cm3 hr (at 140° C)
   p  =  9.92 x ID'4 g/cm3
  Rt  =  5 cm

                                                                 RTI  6-3

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                                              6. PHASE II PLAN OF WORK
   300
                    10             20




                    Residence time
30
Figure 31.  Effect of Tc on the temperature profile of a PFTR [9].
                                                                RTI 6-4

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                                               6.  PHASE II PLAN OF WORK
   u
      (0
2.5-

2.0-

1.5-

1.0-

0.5

  0
                      Insensitive
                                 Sensitive
                        10    20
                            50
100
200
                                 N
                                  ad
 Figure 32.  Relationship between two dimensionless parameters.

 Note the assumed coolant temperature, TC, of 102° C. This temperature will
 vary in the reactor configuration shown in Figure 5, from the boiling point of
 methanol, 65° C, to the reactor inlet temperature.  This latter value was
 assumed to be 140° C. Tc was assumed to be the average of these two or
 102° C. Using these values,

    Nad =17
     Nc =0.47
         = 2.8xlO-2.
 This value is clearly in the sensitive region in Figure 32 indicating that a
 runaway temperature excursion is possible.
 The reactor system described by the above values must be changed.
 Unfortunately, not all of the parameters that make up Nad and NC an
 ble. In particular, U/Rt and k^, could be effectively varied.
 The overall heat transfer coefficient, U, describes the heat transfer from the
-reacting gas through the reactor vessel to the coolant medium (in this case,
 liquid methanol).  The rate limiting step in this exchange is that of the gas to re-
 actor vessel. While little  can be done to improve this rate, using the reactor
 configuration shown in Figure 31, the surface area over which the heat is trans-
 ferred can-be increased.  That is, Rt can be decreased. In fact, even if ten 3.2
 cm I.D. reactors were used in a shell and tube arrangement (i.e. ten tubes
 surrounded by the liquid (boiling) methanol all housed in a larger diameter
 vessel), Nc would only be increased to 1.5.  The ratio of Nc/Nad would only be
 9 x 10~2 which is still clearly in the sensitive region.
                                                                  RTI 6-5

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                                              6.  PHASE II PLAN OF WORK
Alternatively, a less active catalyst could be used thereby reducing k^, and
decreasing Nad. Equation (D.7) shows, however, that a decrease in ^ would re-
quire an increase in Vcat for a constant level of conversion and feedrate thereby
requiring a larger reactor vessel. This would be unacceptable from a volume
standpoint.

Apparently a more sophisticated reactor design would be required to improve
U in NC in an effort to de-sensitize the dehydration reactor. A number of
options exist, one of which would be a series of tubular reactors with interstage
cooling.
                             Catalyst
    Feed
                           V  Cold
                             Methanol
Here, each reactor stage allows the gas phase temperature to rise due to the
heat of reaction. Before the temperature reaches a point which would degrade
product selectivity and catalyst life, however, the reactants pass through a non-
catalyst cooling section before entering a second reactor stage. The tempera-
ture history of the gas-phase reactants would be
         si
        Js
        £ |
         »E
        o §
 Inlet
 Condition
                          Product
                          Stream
Distance or Time
As the concent-ration of methanol decreases along space (or time), the space
(or time) needed to reach the maximum allowable temperature will increase.
Thus, proper design would provide increasingly longer reactors.
                                                                RTI  6-6

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                                                                  6.  PHASE II PLAN OF WORK
                    It should be noted that the optimization of any reactor design will require some
                    mathematical modeling of the reaction network and reactor system. This will
                    require some limited kinetic data which can be obtained using the present
                    microreactor apparatus already operational. By operating in a low conversion
                    ("differential mode"), initial rate data can be measured relatively easily. This
                    data can then be used in conjunction with the appropriate reactor model to
                    evaluate its optimal design.
Dissociation Reaction
                    In the case of the exothermic dehydration reaction, it was shown that the system
                    could develop a runaway temperature excursion detrimental to both product
                    selectivity and catalyst life. To maintain a (parameter insensitive) system,
                    however, a completely novel reactor concept may be sought.  One such
                    concept, originally brought forth by the U.S. Environmental Protection Agency
                    (EPA), uses an endothermic catalytic reaction which could provide an in situ
                    heat sink to limit a temperature excursion. The methanol dissociation reaction,

                               CH3OH  + CO  +  2H2                                      (11)

                    is a highly endothermic reaction yielding CO and H2. These products are suit-
                    able for cold starting combustion requirements in that they are volatile and
                    have high octane values.  Work previously by EPA dealing with this reaction for
                    a different application has identified a dissociation catalyst with favorable
                    properties. Preliminary work with this catalyst was performed using the same
                    equipment and procedure discussed in Section 3. A 4 cm bed of this dissocia-
                    tion catalyst was found to have a T30 of 152.5° C (see Figure 33). A 50/50 (by
                    volume) mixture of the dissociation catalyst with AL-3996R (T30 = 148.5° C)
                    exhibited a T30 of 150° C (see Figure 34). Although  the product gas analyzer
                    could not detect CO and H2, the two catalysts appear to be compatible in that
                    the effective activity of the 50/50 mixture as measured by T30 lies between the
                    T30's of the two pure catalyst  beds. Hence, no inhibition was measured.

                    Such a mixture makes a multi-reaction system possible
                           2CH3OH  + CHgOCHg + HgO  •» higher  hydrocarbons            (12)

                                CO, H2

                    Note that conversion of DME to CO and H2 is also indicated. Tests analogous
                    to the methanol dehydration but using DME demonstrated that the conversion
                    of DME (presumably via dissociation) was equally feasible (Figure 35).
                                                                                     RTI 6-7

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                                                                6.  PHASE II PLAN OF WORK
i
o
01
2
c
0
o
X
o
1)
c
o
u
                                         I    I  <-" I    I    I

                                        160     180     200
         80
0.9 -



0.8 -



0.7



0.6



0.5



0.4



0.3



0.2



0.1 -
                                     Temperature


                   Figure 33. MeOH conversion, dissociation catalyst.
                       -O-T — "?-
                                     1	1	1	1	r
         80      100      120      140     160     180     200      220     240


                                    Temperature


                Figure 34.  MeOH conversion, dissociation and AL 3996R.
                                                                                    RTI  6-8

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                                                           6.  PHASE II PLAN OF WORK
      0.9 -
      0.8 -
      0.7 -
r
o
I
'o
c
0
0
         80
200
                                                            220
                    160     180
                Temperature

Figure 35. MeOH conversion, dissociation in DME.
                                                                    240
             The advantage of providing both dehydration and dissociation reaction
             pathways lies in relative heating requirements. The dissociation reaction
             requires approximately 20 kcal/mol of methanol consumed while methanol de-
             hydration releases 2.2 kcal/mol. If a dehydration catalyst .considerably more
             active than the dissociation catalyst was mixed with the dissociation catalyst, an
             in-situ safety net would be provided. As the dehydration reaction rate
             increased due to  the liberation of heat, the dissociation reaction rate would be-
             gin to utilize more heat in the formation of CO  and Hr

             A situation would exist which is analogous to the so-called predator (wolf) -
             prey (rabbit) system. In this scenario, the  rabbit population is kept in check by
             an ever-present wolf population. In times of large rabbit proliferation (rapid
             dehydration rate) the wolf (dissociation rate) population grows due to the
             growing food supply. In turn, the wolf population is held in balance because
             the rabbit supply is consumed at a greater rate.

             The selection of the appropriate dehydration catalyst (the wolfs food supply)
             will  depend upon the relative effect of flow rate, heat transfer and both dehy-
             dration and dissociation reaction kinetics. To design and construct the
                                                                               RTI 6-9

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                                                                  6.  PHASE II PLAN OF WORK
                    optimum reactor utilizing a dehydration/dissociation reaction system would re-
                    quire both the measurement of dehydration and dissociation kinetics and a re-
                    actor analysis based on the predator-prey model. Many of the latter theoretical
                    descriptions exist in. the applied mathematics literature so that no new model-
                    ing development is required.  These models provide a steady state analysis
                    which would be extremely useful in determining relative catalyst mixtures.
Process Energetics
                    Regardless of whether a pure DME catalyst or a mixture of methanol dehydra-
                    tion and dissociation catalyst are considered, an ultimate application of this
                    contract is to design a prototype reactor system capable of starting a cold
                    engine. If the liquid methanol fuel is initially at a very low temperature (say
                    -10° C), the cold start apparatus must vaporize this liquid methanol and
                    preheat it to the initial inlet condition needed for the dehydration reaction
                    (approximately 200° C). Once in the reactor,  the parameter sensitivity
                    described in the previous section can be important due to the exothermicity of
                    the dehydration reaction. It may be beneficial in this regard to add some disso-
                    ciation catalyst. In any event, the heat given off by complete conversion of
                    methanol to DME is given by:
                                 =    89-8  CI°3  0-7914 g   mol  2.2  x  103 kcal
                    dehydration        min         cm      32g       mol
                                 =   4.9 x  103     .
                                                mm

                    The amount of heat required to bring the initially cold methanol to the inlet
                    condition of the reactor (200° C) is given by


                    Total  heat  {*£} =  h*at ?f ded, to ™ jse  +  vaporization
                                            liquid methanol to        methanol  to
                                                                                        (14)
                                              heat needed to                ,  f   «
                                               raise  gaseous     =  25 x 10   ~r~
                                             reactor  condition

                    Obviously, considerably more warm-up heat is consumed than is released by
                    the dehydration reaction, even at a 100% conversion. Consequently, some ad-
                    ditional heat must be made available before this apparatus can be used effi-
                    ciently.  This energy could conceivably be provided by the battery of the vehicle
                    although given this energy availability it could be argued that the dehydration
                    reactor itself is superfluous. That is, if the battery can provide 20 x 103 cal/min,
                    it could certainly provide the additional 4.9 x 103 cal/min, thereby delivering a
                                                                                   RTI  6-10

-------
                                             6.  PHASE II PLAN OF WORK
stream of vaporized methanol at 200° C to the engine. Even so, this is unlikely
to be feasible; an alternative process should be considered.  This process is
shown schematically as:
        Warm Gaseous
        Products
T
                               Cold Methanol
                               Fuel
                                              :> Phase
                                                         •>-To Engine
In this system the reactor products are assumed to be vapors at 200° C
consisting of unconverted methanol, water, DME and perhaps a mixture of CO
and hydrogen. The reactor exchanges heat with the incoming  methanol feed
stream, preheating it. The products are then passed through a condenser which
liberates a significant amount of heat forming now a two-phase mixture. The
vapor phase of this stream would consist of CO, H2, some DME, water and
methanol. The liquid stream would consist of liquid methanol, some water and
DME. The proportions of DME in the vapor and liquid phases are dictated by
the vapor-liquid phase equilibrium. A simple vapor-liquid equilibrium
calculation is provided in Appendix E for the two component  system of DME
and methanol. The results show a liquid stream between 10 - 30° C should
contain a DME mole fraction of roughly 10-20% DME. Since this mixture
would exist under its own vapor pressure in the product phase separator, the
liquid stream could be then pumped to the fuel system (i.e., fuel injectors).
Once the mixture was sprayed in the cylinders or in the air intake, the DME
would readily vaporize producing a combustible mixture suitable for starting
the engine. This is very similar to  the concept of winterized gasoline in which
the lighter component of the gasoline is increased during the winter months.
                                                               RTI 6-11

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                                                                        7.  REFERENCES
SECTION 7
REFERENCES
                   1.  Chang, C.D., and AJ. Silvestri, /. Catal., 47:249-259,1977.
                   2.  Persona] communication between RTI and Mobil Research and
                      Development Co., 1988
                   3.  Panzar, J., "Characteristics of Primed Methanol Fuels for Passenger Cars,"
                      SAE paper 831687.
                   4.  Winterbottom, J.M., "Hydration and Dehydration by Heterogeneous
                      Catalysts," in Catalysis-Specialist Periodical Report, Vol. 4, Royal Society of
                      Chemistry, London,  141-174,1981.
                   5.  Swabb, E.A., and B.C. Gates, Ind. Eng. Chem. Fund., 11(4), 1972.
                   6.  Levenspiel, O. "Chemical Reaction Engineering," 2nd ed., Wiley, 1972.
                   7.  Kramers, H., and K.R. Westerterp, Elements of Chemical Reactor Design
                      and Operation, Academic Press, 1963.
                   8.  Froment, G.F., and  K.B. Bischoff, Chemical Reactor Analysis and Design,
                      Wiley, 1979.
                   9.  Bilous, O., and N.R. Amundson, AIChE Journal, 2,117, (1956).
                  10.  Barkelew, C.H., Chem. Eng. Prog. Symp. Series No. 25,55, p. 37 (1959).
                                                                                RTI  7-1

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                                                            8.  SUMMARY AND FUTURE WORK
SECTION  8
SUMMARY AND FUTURE WORK
                    The research done in Phase I of this contract shows that there are commercial
                    catalysts potentially suitable for the methanol dehydration reaction.  This is
                    evidenced by the wide range of dehydration activities as measured by T30 given
                    in Table 2. Some problems exist, however, in the development of a prototype
                    dehydration reactor.  These were discussed in the Phase 2 plan of work.
                    Primarily, the exothermicity of the methanol dehydration reaction can result in
                    a runaway temperature excursion within the reactor.  This can lead to loss of
                    product selectivity by the formation of higher hydrocarbons with the
                    concomitant formation of coke (carbonaceous material) which can lead to
                    catalyst deactivation. Although more sophisticated reactor designs can be used
                    to minimize the likelihood of these excursions, the reaction system is quite
                    sensitive to slight changes in operating conditions. It is proposed to  study the
                    kinetic rates of both the methanol dehydration reaction over a limited group of
                    candidate catalysts as well as the methanol dissociation reaction over the
                    dissociation catalyst explored in Phase I. With this information, a relatively
                    simple theoretical analysis is feasible by which a  dehydration/dissociation mix-
                    ture reactor could be designed. The dissociation reaction pathway would be
                    provided only as a heat sink to prevent reactor runaway.  Finally, it was noted
                    that the process energetics would require the condensation of the product
                    stream in order to allow operation without a significant amount of external
                    power requirements. The condensed product stream is believed to be suitable
                    for cold starting an internal combustion engine in a mechanism completely
                    analogous to winterized gasoline.

                    It is recommended that the design parameters of a methanol dehydration/
                    dissociation reactor be pursued to enable the design  of a  stable cold start
                    apparatus. To that end the following work is proposed:

                    •  study the reaction kinetics of the methanol dehydration over a select
                       number of candidate catalysts

                    •  study the reaction kinetics of the dissociation reaction over the dissociation
                       catalyst explored in Phase I

                    •  complete the reactor analysis required for optimal reactor designs and
                       catalyst mixture proportions
                                                                                    RTI  8-1

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                                        8. SUMMARY AND FUTURE WORK
•  complete a more rigorous thermodynamic calculation of the multi-phase
   equilibrium formed by water, DME and methanol

It should be noted that the measurement of the chemical kinetic rates is a
relatively simple task for which the equipment used for Phase 1 can be used
with only slight modification (to include CO and hydrogen detection).

Although it is perhaps possible to design a prototype based exclusively on the
methanol dehydration reaction using the data made available through Phase I,
it is felt that the level of sophistication needed to control that reaction would be
high making the expense of the ultimate reactor prohibitively large. Alter-
nately, the dehydration/dissociation concept appears to be inherently stable,
permitting a simpler design.
                                                                 RTI 8-2

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                                                                      APPENDIX A
APPENDIX A
SOLICITATION FOR COMMERCIAL METHANOL DEHYDRATION

CATALYSTS

    Dear

        Research Triangle Institute  is involved with the developement of a system
    for the dehydration of methanol  vapor to a mixture of dimethanol ether in
    water.  The purpose of this  research is to overcome cold start  problems in
    methanol powered vehicles.   The  ultimate application of the catalyst and
    system which we will develop will be for such vehicles.  Our immediate goal is
    twofold:

             •  Screening of a number of catalysts that are suitable for the
                dehydration of methanol to dimethanol ether.

             •  The assembly of  a system using the best catalyst from our
                screening test to be tested on a stationary methanol powered
                automobile.

        Our review of the literature on this reaction indicates that the
    dehydration of methanol is an intermediate step over acid catalyst with the
    ultimate products being light olefins and hydrocarbons.  However, in contrast
    to processes such as the methanol to gasoline process,  we wish  to develop a
    catalyst that will produce dimethanol ether selectively.  The literature also
    seemed to indicate that desirable catalyst characteristics are  strong lewis
    acidity, little or no bromstead  acidity, and weak lewis basicity.  Conditions
    of interest for our  study are atmospheric pressure, temperatures below about
    350*C, and high space velocities.

        We would appreciate your recommendations for catalyst that  you may produce
    which could meet the objectives  of our program.  Specifically,  we would
    appreciate your providing us with roughly 100 grams of  candidate catalyst that
    you feel would work.   In return, we will keep you advised of the results of
    our screening tests.

        We plan to begin  our  screening in mid-December  and  would appreciate your
    providing  samples  for our use by then,  if possible.  We  greatly appreciate
    your cooperation in this  effort.

        Please contact me at  (919)  541-7272  to discuss  any  details of our goals
    and how your catalyst might be evaluated.
                                                   Sincerely,


                                                   James J. Spivey, Ph.D.
                                                                          RTI  A-1

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                                                                          APPENDIX B
APPENDIX B
CALCULATION OF ADIABATIC TEMPERATURE RISE IN A
TUBULAR REACTOR
The maximum temperature reached in a tubular reactor occurs when the
reactants are completely converted under adiabatic conditions. This
temperature known as the adiabatic temperature (T ,) can be calculated using
a standard expression as given by Kramers and Westerterp [1].

            T               £
             ad  dT = AH   /f  d£                           (B.I)
                               /
                               T
                  where C is the specific heat capacity of the gas stream, TQ is the temperature of
                  the incoming stream, x is the molar fraction of the reacting species, AHr is the
                  heat of reaction and f is the fractional conversion.  The maximum Tad occurs
                  when £f = 1 (100% conversion). Although the equilibrium conversion of
                  methanol to DME alone is limited to 85%, the  DME can react further for
                  higher hydrocarbons. This will allow complete  depletion of the methanol.

                  Equation (B.I) can now be evaluated to yield

                                           AH
                            Tad - To = -« of *,                              (B-2)

                  For pure methanol forming DME (the heat of reaction due to the further
                  reaction of DME is also exothermic but will be neglected),
                       Cf  = 1

                        x  = 1

                      AHr  = -2.2 x 103
                       C  = 12.4
                        p        mo

                       T  = 200° C (assumed inlet temperature)

                   Tad is calculated to be 377° C. If a feedstream of 1,000 ppm of methanol in
                   nitrogen is converted,
                                                                             RTI  B-1

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                                                                              APPENDIX B
Reference
                                               x = 1 x ID'3

                   which yields a Tad - T0 of 0.18° C.
                   1.   Kramers, H., and K.R. Westerterp, Elements of Chemical Reactor Design
                       and Operation, Academic Press, 1963.
                                                                                  RTI B-2

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                                                                         APPENDIX C
APPENDIX C
CALCULATION OF METHANOL REQUIRED TO START AN ENGINE
                  For the preliminary design of a prototype catalytic dehydrator, an estimate of
                  the required methanol throughput is needed. To this end, the combustion
                  energy required to start a spark ignition engine was assumed to be 6 kcal/sec
                  (EPA). To satisfy cold starting requirements a product stream of 15% DME is
                  needed [1] which corresponds to 30% conversion of methanol. To provide 6
                  kcal/sec assuming 15 mole % DME, the volumetric flow rate of gas from the
                  dehydrator can be found as follows:

                                                       o
                           Q _   6 kcal/sec    22.400 cm
                           * ~ E x. (-AH .)       mol
                                 3.     Cl

                  where
                        Q  = volumetric flowrate of gas from the dehydrator, cm3/sec

                        x-  = mole fraction of component i, dimensionless

                     AH •  = heat of combustion of component i, calculated herein at 25 ° C with
                         1   all reactants and products as gases, kcal/mol

                  For our system

                      AHC(CH3OH) =-160.3 kcal/mol

                     AHC (CH3OCH3) = -331  kcal/mol

                         AHc(H,O) =0 kcal/mol

                  Substituting

                                 Q = 829 cm3 STP/sec

                  To result in 829 cm3 STP/sec of gas containing 15% DME, 15% FLO, and 70%
                  methanol, the volume of liquid methanol, Qm, that must be fed to the
                  dehydrator is thus:

                             3                      3
                  n  -  goo cm       mol gas       cm  (liquid)   32 g  60 min
                   m ~     sec   22,400 cm3  STP      °'7914 g     ™*     min

                              3
                  Q  =  89.8 ££_  liquid methanol
                  xm       mm   ^

Reference
                  1.  Panzar, J., "Characteristics of Primed Methanol Fuels for Passenger Cars,"
                     SAE paper 831687.

                                                                            RTI  C-1

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                                                                             APPENDIX D
APPENDIX D
ESTIMATION OF GLOBAL KINETICS OF METHANOL DEHYDRATION
                    It is possible to use data presented in Section 3 to estimate the overall chemical
                    kinetics of the methanol dehydration reaction,

                            2CH3OH   *  CH3OCH3  +  HgO                             (D.I)

                    at an approximation for use in preliminary design. At low conversions (< 50%)
                    reaction D.I is far from equilibrium (see Section 2) so that only the forward
                    reaction should be considered. For heterogeneous reaction systems a first
                    order expression based on the volume of catalyst (m  cat) can be assumed to
                    approximate this reaction's rate,

                                      r = kyC                                     (D.2)

                    where r is the rate of methanol conversion (m3/hr m3cat), k^, is the rate constant
                    (m3/hr m3cat) and C is the concentration of methanol (M) in the feed (fd)
                    (m3M/m3fd).

                    In estimating the rate constant from data measured in the tubular microreactor,
                    an analysis similar to that given by Kramers and Westerterp [1, p. 25] will be
                    used. That analysis shows that, at steady state, the extent of conversion, £, of a
                    reactant varies with distance along the axis of the reactor, z, according to,
                                                                                   (D.3)


                    where Scat is the cross-sectional area of catalyst and $v is the volumetric
                    flowrate of methanol (m3 hr) fed to the reactor at reactor conditions. This
                    expression can be rearranged and integrated to give


                           ^  idf  .  /"'S^d,                            (D.4)
                           o               o

                    where f, is the extent of conversion at the reactor outlet and V „ is the total
                         31                                              Cat
                    volume of catalyst in the reactor. According to reaction (D.I) the gas mixture's
                    density should remain constant. The rate expression (D.2) can be rewritten in
                    terms of the extent of reaction as.
                                                                                 RTI D-1

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                                                            APPENDIX D
               r = kyCo  (1-0                                     (D.5)

where C0 is the concentration of methanol in the feedstream at the reactor
inlet.  Equation E.I can now be integrated to yield,
         v o

This expression can be solved for k^,,
                              -  ef)                               (°-7)
                 o  cat

For the catalyst screening tests described in Section 3 the following values apply

                   0V  = 1.2 x ID'5 rr^/hr

                  Co  =1.0xlO-3m^/m3fd

Vcat  = (1 - e)Vr = (1 - 0.3)(5.03 x 10'7 m3) = 3.52 x 10-7m3cat .

Here Vr is the total reactor volume (4 mm I.D., 40 mm long) and e is the
approximate void fraction in the reactor.

In this manner the first order rate constant can be calculated for any catalyst
tested  under Phase I. For the purpose of the preliminary design work
presented here, the results of catalyst AL-5207 (Harshaw) presented in
Figure 28 will be used:

                      (1.2 x  10~5(m2/hr)
k  = -- 3   o  3 - - - n-t -  ln(l-0.25)   (D.8)
 v      (1.0 x 10 <5(mu/mdfd)(3.52 x 10  m cat)
                       M

The  rate constant is a function of reactor temperature

                ky =  Ae~E/RT                                      (D.9)

where  A is the pre-exponential factor, E is the activation energy of the reaction
on the particular catalyst, R is the gas constant and T the temperature in
Kelvin. The activation energy can be estimated by plotting the In k vs 1/T for a
number of reactor temperatures, as follows:
                                                                RTI  D-2

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                                                                                 APPENDIX D
                               JL

                               o.i
                               0.2
                               0.25
                               0.3
3.6 x 103
7.6 x 103
9.8 x 103
1.2 x 104
Ink

8.2
8.9
9.2
9.4
1/T(K4)

2.51 x lO'3
2.46 xlO'3
2.44 x ID'3
2.42 x lO'3
                10.0 - -
                 9.0--
                 8.0--
                          2.4    2.42     2.44    2.46    2.48     2.5

                                            1  (K~1) X 103
                    The slope of this curve is, then, E/R =  13.6 x 103 K.  The apparent activation
                    energy E, of this reaction on AL-5207 is approximately 27 kcal/mol.
Reference
                    1.  Kramers, H., and K.R. Westerterp, Elements of Chemical Reactor Design
                        and Operation, Academic Press, 1963.
                                                                                    RTI  D-3

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                                                                      APPENDIX E
APPENDIX E
CALCULATION OF THE VAPOR-LIQUID EQUILIBRIUM (VLE)
DATA FOR A TWO-COMPONENT MIXTURE OF DME AND METHANOL*
                 A first approximation to the vapor-liquid equilibrium relationship for a binary
                 mixture of dimethyl-ether (DME) in methanol (MeOH) at 1 atm pressure is
                 given by:

                    For DME,    YDM£  = KDM£ XDM£                      (E.I)
                 where y is the vapor-phase mole fraction, K is the proportionality constant to be
                 determined, and X is the liquid phase mole fraction.
                    For MeOH,   YMeQH = KMeQH XMcQH                   (E.2)


                  The addition of (E.I) and (E.2) yields
                             XDME
                  Two methods will be used:

                  Method 1:  Assume Henry's Law for
                           Assume Raoult's law for
                             KDME = 7°°DME PDME
                                      MeOH

                 The infinite dilution activity coefficient for DME, 7°°DME, was calculated using
                 UNIFAC (Universal Quasi Chemical Functional-Group Activity Coefficient
                 model) while Psat, the vapor pressure of both components, was calculated by
                 Antoine's equation.

                 The VLE results are given in Table E-l for both 10° C and 30° C.
* Source: Tony Rogers, RTI.
                                                                         RTI E-1

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                                                            APPENDIX E
                              Table E-1
Temperature (°C)
10
30
7«DM
1.47
1.5
psat
DME
3.81
7.08
XDME(%)
16.8
7.6
Method 2:  Assume Raoult's law for both DME and MeOH

                 y    _  pSa,t
                         rMeOH
The VLE results are given in Table E-2 for both 10° C and 30° C.
                              Table E-2
Temperature (°C)
10
30
psat
DME
3.81
7.08
XDME(%>
24.7
11.5
The actual liquid-phase DME concentration will likely be between the
extremes shown in the above tables. Because the target reactor conversion of
methanol is roughly 30%,othe DME concentration at the phase separator will
be approximately 15'%'.° T^ais js;substantially above infinite dilution of DME in
methanol, so the Raoult's law-results are thought to be more accurate. Note,
however, that the proportionality constant, K, is concentration dependent and a
more involved iterative procedure should be used to predict XDME with greater
accuracy.
                                                                RTI E-2

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