Air Products and Chemicals, Inc.

Box 538.Allentown, PA 18105

(21~481-4911

LIQUID-PHASE METHANOLPROCESSDEVELOPMENTUNIT:
INSTALLATION, OPERATION, AND SUPPORTSTUDIES

Technical Progress Report No. 2

For the Period 1 January 1982 - 31 March 1982

Contractor
AIR PRODUCTSAND CHEMICALS, INC.
Allentown, PA 18105

and

DOE/PC/30019--T2
DE82 012725

Subcontractor to APC]
CHEMSYSTEMS INC.
Tarrytown, NY 10591
E.
J.
I.
R.

P. Holley Klosek
C. Spector L. Hednick -

APCI Project Manager

APCI Program Manaoer
APCl Program Coordinator
CSI Progra~l Manager

20 April 1982

Prepared for the United States Department of Energy

Under Contract No. DE-AC22-81PC30019
Contract Period 28 September 1982 - 28 March 1985

ABSTRACT
This was the second period of Contract performance. During this period approval
was obtained for the unified design concept, advanced schedule for relocation
of the LPH p i l o t plant, and advanced procurement of long lead delivery equipment
items. The LoPorte LPHeOH PDU Process Flowsheet developed further and the
Eng|neering Flowsil~=~ evolved to the Revision OA preliminaw issue. Eight
cases of point-by-pofnt heat and mass balances were released. Process equipment
specifications were issued f o r 30 of the 33 equipment items. Hechanical
specifications were issued fob 16 equipment items, quotations were received
for the 2 long lead delivew items, the Feed/Recycle Compressor and the Slurry
Circulation Pumps; techntca] evaluations of these bids are underway. Semifinal equipment arrangement and plot plan drawings were prepared. The Preliminary Hazards Review was conducted and the subsequent Design Hazards Review was
i n i t i a t e d . A request for exemption from construction and operating permit
requirements was submitted to the Texas Air Control Board. Progress was made
on the specification of the Data Acquisition System. In the laboratories,
APCI established the priority fOr compositions of new methanol powder catalysts
to be prepared. Construction of the APCI Gas Phase Screening Reactor and
Stirred Autoclave Reactor cnntinued on schedule. Progress was made in evaluating
the potential modification of the Deckwer l i q u i d phase Fisher-Tropsch model to
describe LPMeOHperformance. In the CSI laboratories, a 550-hour l i q u i d fluidized run was completed successfully in the Lab PDU. Preliminary results
indicate that the new catalyst tested is more attrition resistant than any
prior llquid-fluidized catalyst candidate. Testing of in-situ catalyst reduction
procedures continued in the Stirred Autoclave Reactor with successful results
which led CSI to f i l e a Record of Invention form for a potential invention
covering this process. Specifications and quotations for major equipment
items in the CSI liquid-entrained PDU were completed and received. The f i r s t
of the two lab slurry pumps arrived. A preliminary plan for cold flow hydrodynamic modeling was completed. DOE approved submission of the Task 2 deliverable
report on 1 June 1982 in order to increase the accuracy of the program cost
estimate. The I June deliverable report will incorporate and take advantage
of the research achievements and efforts currently underway at APCI and CSI.

TABLE OF CONTENTS

PROJECT DESCRIPTION. . . .
OBJECTIVES .

RESULTS

5
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2.11
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2.2 . . . . . . . . . . . . . . . . . .
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2.3 . . . . . . . . . . . . . . . . . . . . .
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2.3.11
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2.3.2 ......
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12
2.3.3 . . . . . . . . . . . . . . . . .
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2.3.4 . . . . . . . . . . . . . . . . . . .
12
2.3.5 . . . . . . . . . . . . . . . . . .
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2.3.6 . . . . . . . . . . . . . . . . . . . . .
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3. . . . . . . . . . . . . . . . . . . . .
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4. . . . . . . . . . . . . . . . . . . . .
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7 . . . . . . . . . . . . . . . . . . . . . . . . 14
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7.1.3 . . . . . . . . . . . . . . . . .
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7.1.4 . . . . . . . . . . . . . . . . . . . .
15
7.,?. . . . . . . . . . . . . . . . . . . . . . . .
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7.2.1 . . . . . . . . . . . . . . . . .
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7.2.2 . . . . . . . . . . . . . . . . . . .
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7,2.5 . . . . . . . . . . . . . . . . .
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7.2.6 . . . . . . . . . . . . . . . . .
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7.2.7 . . . . . . . . . . . . . . . . . . .
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9 . . . . . . . . . . . . . . . . . . . . . . . 25
10 . . . . . . . . . . . . . . . . . . . . . . . 27
11 . . . . . . . . . . . . . . . . . . . . .
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II. 1 . . . . . . . . . . . . . . . . . . . . . .
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II. 2 . . . . . . . . . . . . . . . . . . . .
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11.3 . . . . . . . . . . . . . . . . . . . . .
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11.4 . . . . . . . . . . . . . . . . . . .
28

Task 1 .
Task 2 .

Task
Task
Task
Task
Task

Task
Task
Task
Task

REFERENCES .

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ACKNOWLEDGEMENTS .

ATTACHMENTS .

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31
32
33

LIST OF TABLES AHD FIGURES

L,

Exhibit No.

,,,,

Item

2.3.1-1

LaPorte LPMeOHPDU Simplified Process Flowshee

2.3,1-2

LaPorte LPMeOHPDU Engineering Flowsheet

2.3.1-3

LaPorte LPMeOHPDU Design Cases & Operating Condition~,

Liquid-Fluidized Operation

2.3.1-4

LaPorte LPMeOHPDU Design Cases & Operating Conditions,

Liquid-Entrained Operation

2.3.1-5

LaPorte LPMeOHPDU Point-by-Point Heat & Mass Balances

2.3.1-6

10.50 Slurry Circulation PumpProcess Specification

2.3. ~7A

01.10 Feed Compressor Process Specification

2.3.1-7B

01.20 Recycle Compressc~' Pw-ocess Specification

2.3.~8

21.20 Slurry Heat Exchanger Process Specification

2.3.1-9A

LaPorte LPMeOHPDU Reactor Schematic Drawing

2.3.~9B

LaPorte LPMeOHPDU Reactor Operating Parameters

2.3.2-1

Engineering Specification Activity, LaPorte LPMeOHPDU

7.1,3-1

APCI Lab Gas Phase Reactor

7.2.2-1

CSI Stirred Autoclave Reactor System

7.2.5-1

CSI Cold-Flow Hydrodynamic Unit

7.2.8-1

Catalyst R71/OF12-02 Activity & Attrition in CSI LiquidFluidized Lab PDU

7.2.8-2

CSI Liquid-Fluidized Lab PDU Run Chronology

7.2.B,-3

CSI Liquid-Fluidized Lab PDU Variable Scans: Preliminary

Results

ii

PROJECT DESCRIPTION:
Jim

On 28 September 1981, Air P~oducts and Chemicals, Inc. (APCI)

began a 42-month contact with the U.S. Department of Energy
(DOE): ==Ltquid Phase Methanol (LPMeOH) Process Development
Unit: I n s t a l l a t i o n , Operation and Support $udies." This
project is aimed to further deve]op the LPMeOHprocess invented
b)" Chem Systems Inc. (CSI). them Systems is performing as a
subcontractor to Air Products.
A DOE-owned, skid mounted p i l o t plant w i l l be transferred from
Chicago, refurbished, expanded f o r service as the LPMeOH Process
Development Unit (PDU), and then relocated and commissioned at
Air Products ~ LaPorte, Texas f a c i l i t y .
Air Products w i l l
supply synthesis feed gas to the LPMeOH PDU and operate the
unit for a planned 24-month peried. Chem Systems is performing
~he major portion of the laboratory support R&D and is providing
.~zhnical management fop the project. Air Products is providing
overall program management and is responsible for engineering
design, construction, and operation.
The program 'is divided into 11 major tasks which are phased to
a]low progress review and approva] to proceed. The 11 major
tasks are:
1.
2.
3.
4,
5.
6.
7.
8.
9.
10.
11.

Program Planning
Engineering and Design Specifications
Equipment Procurement
LPM P | l o t Plant Relocation/Inspection
LaPorte LPMeOH PDU Renovation, I n s t a l l a t i o n and Shakedown
Liquid-Fluidized Operation
Laboratory Support Program
Conversion of the LaPorte LPMeOH PDU from Liquid-Fluidized
to Liquid-Entrained Mode
Shakedown of the Liquid-Entrained Mode of Operation
Liquid-Entrained Operation
Pro~ect Evaluation

The tasks are phased as follows:

Phase
I
II
III

IV
V

Tasks
1,2,4,7,11
3,4,5
6

8
9,10

Schedule
28 September 1981 - 28 March 1985 (Months 1-42)
1 June
1982 - 1 April 1983 (Months 9-18)
1 March
1983 - 1 June 1984 (Months 18-32)
1 January
1984 - 1 April 1984 (Months 28-30)
1 April
1984 - 1 March 1985 (Months 31-41)

-1-

OBJECTIVES:

The overall objective of this program is to demonstrate the

technical feasibility of the Liquid Phase Methanol (LPMeOH)
process at the Process Development Unit (PDU) scale of operation.
On a per task b a s i s , o b j e c t i v e s are to:
Task 1 - Program Planning

Establish a Project Work Plan presenting in detail a11 activities

which will be performed for the successful completion of the
program.
Task2 - Engineering and Design Specifications

a)

Conduct a process engineering/design review and safety examination of the existing Liquid Phase Methanation (LPM) pilot
plant at its present location in Chicago, I l l i n o i s ;

b)

Obtain permits to install and operate the LPMeOHPDU at LaPorte,

Texas;

c)

Develop detailed plans and specifications for the repair,

modification, and expansion of the existing LPM unit to enable
liquid-fluidized (ebu]lated bed) and, subsequently, liquid-entrained (slurry) methanol production; and

d)

Develop a deactivation plan for the LaPorte LPMeOHPDU.

Task 3 - Equipment Procurement

Purchase, lease, or obtaln from DOE inventories the equipment
and systems specified in Task 2.
Task 4 - LPM Pilot Plant Relocation/Inspection
TransFer the existing LPM pilot plant from its present location
in Chlcago to a vendorI s f a c i l i t y for inspection.
Task 5 - LaPorte LPMeOHPDU Renovation~ Irlstallation~ and Shakedown

a)

Renovate the LPM pilot plant to become the LaPorte LPMeOHPDU,

according to the specifications developed in Task 2;

b)

Preparethe laPorte site;

c)

Transfer and install the LPMeOHPDU at LaPorte;

d)

i~ake interconnections and t e s t components; and

e)

Conduct an integrated run without catalyst.

-2-

Task 6 - L!quid-Fluidized Operation

Operate in the liquid-fluidized (ebullated bed) modeto:
a)

Assess the effect of reactor configuration/internals;

b)

Identify catalysts which in short runs have acceptable activity

and a t t r i t i o n characteristics;

c)

Perform process variable scans to determine the effects of

temperature, pressure, space velocity, catalyst loading, circulating oil flewrate, and feed gas composition; and

d)

Perform a 45-day continuous run to demonstrate short-term

process operability, principally at a single set of conditions.

Task 7 - Laboratory Support Program

a)

Conduct literature surveys, develop a bibliography of pertinent

references, and maintain liaison with others working on related
liquld-entrained (slurry) systems.

b)

Develop procedures for in-situ ~eduction of commercial powdered

methanol catalysts slurried in o i i , vapor phase reduction of
commercial granular materials which can subsequently be slurried,
and simultaneously screen commercial catalysts and develop data
for modeling the liquid-entrained reaction;

c)

Synthesizenew liquid-entrained catalysts;

d)

Screen new liquid-entrained catalysts in a gas phase fixed bed

reactor, in a liquid-entrained stirred autoclave reactor, and
in the ChemSystems' Fairfie!d laboratory PDU;

e)

Construct and operate a cold flow model unit to study the

hydrodynamics of the gas-slurry reactor;

f)

Modify the existing Chem Systems' Fairfield laboratory PDU to

allow liquid-entrairled as well as ]iquid-flutdized operation;

g)

Operate the modified CSI lab PDU to perform process variable

scans; and

h)

Support the LaPorte LPMeOHPDU liquid-fluidized and l i q u i d entrained operating modes, p r i n c i p a l l y by screening catalysts.

Task 8 - Conversion of the LaPorte LPHeOH PDU from LiquidTFluidized t q L i q u i d Entrained Node
.....
Perform necessary process adjustments, alterations, and minor
operational tests to f a c i l i t a t e the conversion of the PDU from
the l i q u i d - f l u i d i z e d (ebullated bed} to the liquid-entrained
(slurry) mode.

-3-

Task 9 - Shakedown of the Liquid-Entrained Operation

Test components, conduct an integrated Pun with an inert powder,
and conduct an integrated short Pun with a liquid-entrained
methanol catalyst.
Task 10 -Liquid-Entrained Operation
a)

Conduct short runs with promising liquid-entrained catalysts;

b)

Perform process variable scans to determine the effects of

various operating conditions; and

c)

Perform a 45-day continuous run to demonstrate short-term

process operability.

Task 11 - Project Evaluation

a)

Evaluate data from the LaPorte LPMeOHPDU and the laboratories

to develop models;

b)

Evaluate alternative reactor designs and the two liquid phase

operating modes;

c)

Perform detailed process evaluations for commercial-size plants;

d)

Develop plans for a larger scale demonstration of the LPMeOH

process; and

e)

Report on program a c t i v i t i e s .

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RESULTS:
Task 1 - Program Plannin(]

This task is complete. No activity.

Task 2 - Engineering and Desiqn Specifications
2.1"

APCI ManagementActivities

2.1.1

Project Management Specifications for dismantling the LPM p i l o t plant for relocation
from Chicago were completed and released. Bids were received
and a technical evaluation completed for this contract, and
purchase approval has been requested of the DDE.
Specifications" for shop inspection of the LPM pilot plant
equipment in the Houston area have been completed and technically
approved by the DOE. Receipt of bids is scheduled for 21
April 19B2.
LaPorte commercial f a c i l i t y flowsheets were marked-up to i l l u s trate the eleven piping t i e - i n s required f o r feed gases and
u t i l i t i e s to the LPMeOH PDU. Instructions f o r further d e t a i l i n g
of these tie-ins to the LPMeOHPDU battery l i m i t were transmitted
in coordination of Design Engineering activity.
DOE excess capital equipment and excess property l i s t s for the
Synthoil plant were reviewed to i d e n t i f y potential items for
use in the Liquid Phase Methanol Program. A more detailed
review and physical inspection of t h i s equipment w i l l be conducted
on 21 April 1982.
A review of the Preliminary Hazards Review Report was conducted
and a f i n a l d r a f t is being developed. A Design Hazards Review
Team was organized and assembled to conduct a detailed analysis
of the plot plan, flowsheet, shutdown logic, solids handling
systems, catalyst reduction and product storage.
Based on current schedules f o r receipt of vendor quotations for
new equipment items and for inspection of the LPM equipment,
a request was made to the DOE to revise the submittal date of
the Phase I deliverable report that w i l l include a revised
estimate of the overall program. A revision from 1 May 1982 to
I June 1982 was approved by the DOE, to enhance the usefulness
of the estimate data.

2.1.2

Economic Evaluation - Work was started on revising an internal

Project Scope Report that w i l l consolidate the necessary data
for detailed estimating by each performing group within APCI.

* Refers to Work Breakdown Structure Elements.

-5-

2.1.3

Communications - No Significant Activity.

2.1.4

Permit Fees - No Activity.

2.2

CSI

2.2.1

CSI Assistance to APCI - ChJm Systems provided APCI with review

and comment on preliminary flowsheets for the LaPorte LPMeOH
PDU. A marked-up flowsheet showing suggested process corrections,
control points'and data acquisition points was transmitted to
APCI. This mark-up was reviewed in a meeting at APCl on 19-20
January 1982. Plans for dismantling the LPM p i l o t plant were
also reviewed at this meeting including procedures, equipment
l i s t s , and skid and piping break points. ChemSystems also
participated in the Process Hazards Review held at APCl on i5
March 1982.

2.2.2

Data Acquisition System Specification - The laPorte LPMeOH PDU

flowsheets were reviewed to determine and verify the required
data acquisition and sampling points on the unit. Calculations
to reduce these data points into an operational format were
outlined in order to estimate the size of the data acquisition
computer. Preliminary quotations and leasing arrangements, as
well as catalog information, were received from several vendors
on items required in the analytical (i.e., gas chromatographs,
analytical balances, interfaces, etc.) as well as the computational (computers, data loggers, printers, etc.) sections of
the data acquisition unit. On the basis of this information a
preliminary estimate was prepared and the buy/lease option
evaluated for the data logger/microcomputer option of the data
acquisition system. These results were reviewed with APCI in
Allentown on 25 March 1982, where the associated costs and
leasing arrangements of the minicomputer option were presented.
As a result i t was agreed, in principle, to specify the minicomputer system as the leading option for use in data acquisition,
provided CSI can maintain complete control and responsibility
for the data acquisition task at LaPorte. Final selection of
this option is dependent upon confirmation of system and project
criteria discussed in the 25 March meeting. In addition, the
preliminary configuration and cost estimate for the analytical
portion of the data acquisition system was developed. A l i s t
of acceptable vendors has been established and final specification
sheets are currently beinl developed as a prelude to formal
equipment bid solicitation.

2.3

APCI Design

2.3.1

Integration -

-6-

Process Flowsheet
The Process Flowsheet, Revision P1, dated 5 January 1982 was
attached and described in Technical Progress Report No. 1.
Since that time the following change considerations have developed:
1.

Elimination of Pressure Leaf Filter (22.55)

A more detailed review of the LaPorte LPMeOHPDU shutdown
and the P~essure Leaf Filter operating conditions revealed
the following:

The solids loading is too high for a pressure leaf

filter.
Upon shutdown, the PDU must be quickly evacuated of
the catalyst/oil slurry, otherwise settled catalyst
sludge will build up and cause numsrous blockages.
Catalyst settling in lab slurry samples implies there
may be 15 minutes in which to begin evacuation, and
30 to 60 minutes available to complete the transfer.
(Calculations are required to better determine these
times.)
The oil must be cooled below 180F (80C) for conventional pressure leaf filtration. Standard f i l t e r s
use rubber gasket materials and f i l t e r aid materials
contain some entrapped moisture which could cause
foaming when mixed with hot oil.

I t is now recommended that the slurries be pressure transferred to the Slurry Preparation Tank (28.30) for temporary
holding prior to gravity transfer t . Tote Bins for final
disposal. The Tote Bins mEy be used to decant the slurries
to yield a reuseable oil supernatent. Controlled oxidation
of catalysts may be performed in the Tote Bins to permit
safer handling and direct disposal to a secure landfill.
The need and the methods for catalyst oxidation are under
review. (A plan to evaluate the pyrophoric nature of
spent catalyst/oil slurry is noted in Task 11.4.)
2.

Alternative Water Addition Location

In the Revision PI Process F1owsheet, water addition is
shown upstream of the Three Phase Separator (23.10). An
alternative route has been added to allow water addition
to the top of a small packed section in the vapor outlet
of the Three Phase Separator. This capability allows some
scrubbing of methanol from the purge/recycle gas. Low
methanol content in the recycle gas is desirable in order
to accurately measure net methanol production in the
reactor.

-7-

3.

Catalyst Reduction Vessel (02.81) - (On Hold)

Chem Systems continues to make significant progress in the
stirred autoclave tests to optimize in-situ catalyst
reduction/activation conditions (see Task 7.2.2). Evidence
is mounting that the separate Catalyst Reduction Vessel is
not required. Data is s t i l l needed on other catalysts to
confirm more general abilities to achieve in-situ reduction.

Potential" Elimination of Spare Slurry.Circulation Pump

i(zo. so B)

The flowsheet for the LaPorte LPMeOHPDU has indicated two

Slurry Circulation Pumps (10.50 A & B) since the i n i t i a l
proposal to the DOE for the LPHeOHProgram. The proposal
considered these pumps to each be lOOg design capacity
such that an installed spare would be available on standby during LaPorte PDU operation. This dual pump installation
was justified originally by considering that the costs
associated with a single pump failure leading to the loss
of even one LaPorte PDU run would more than outweigh the
cost for an additional pump.
Progressive development of the LaPorte LPMeOHPDU design
has revealed that three key points of this original j u s t i f i cation are questionable:
Recent developmental experience with hot, high suction
pressure, centrifugal, slurry pumps has lead to the
commercial availability of equipment that may be
considered to have acceptable r e l i a b i l i t y for the
LaPorte LPMeOHPDU operating program.
Failure of the Slurry Circulation Pumpwill not
necessarily lead to loss of a PDU run since the
Slurry Preparation Tank (28.30) will now be used to
maintain the slurry in suspension and at temperature.
I

Due to d i f f i c u l t technical problems associated with

the installation of a stand-by pump in this service,
the incremental costs for a du~l pump installation
over a single pump installation may be several times
greater than originally estimated.

In the final analysis i t is considered desirable to

maintain the slurry circulation loop in the simplest, most
direct flowing arrangement, from both operational r e l i a b i l i t y
and safety standpoints. Therefore, a detailed evaluation
is in progress to evaluate the suitability of a single
Slurry Circulation Pump installation for the LaPorte
1PMeOH FDU.

-8-

A Simplified Process F1owsheet for the LaPorte LPMeOHPDU

is given in Exhibit 2.3.1-1. This simplified version
complements the Revtstoll P1 issue of the Process Flowsheet
by providing a clear, smaller-size schematic of the main
process lines and equipment. Heat and mass balance points
are also given on this flowsheet.
EngineeringFlowsheet
A Revisio~ 0 Engineering Flowsheet for the LaPorte LPMeOH
PDU was issued on 10 March 1982. This was subsequently
marked up during the Design Hazards Review to produce a
Revision OA edition. A preliminary Revision OA Engineering Flowsheet is attached as Exhibit 2.3.1-2. This
preliminary flowsheet has just issued for internal APCI
review and has not yet been approved and slgned-off. The
preliminary flowsheet does show the current state of
development of the P&ID. The next level of development of
the Engineering Flowsheet is the Revision 1 issue, which
w i l l be submitted in the June 1982 Phase I deliverable
report to the DOE.
Heat and Mass Balances

The final design heat and mass balances for the eight (8)
design cases, four (4) for the ]iquid-fluidized mode and
four (4) for the liquld-entrained mode, were completed and
released in January 1982. The operating conditions for
the eight (8) design cases which include the maximum and
minimum methanol production cases for both modes of operation as well as four (4) "normal" operating cases are
given in Exhibits 2.3.1-3 and 2.3.1-4. The detai~ed point
b~/ point heat and mass balances for the design cases were
developed using APCI's process simulator program and are
enclosed as Exhibit 2.3.1-5. The key stream numbers for
the heat and mass balance are shown in Exhibit 2.3.1-1,
the Sin~lified Process Flowsheet for the LaPorte LPMeOH
PDU.
Process, Equipment Design
During this quarter, process equipment specifications were
prepared and issued for 32 equipment items in the LaPorte
LPMeOH PDU. One of these items (Pressure Leaf F i l t e r
22.55) was subsequent]y voided, and two items are considered as one (01.10/01.20 Feed/Recycle Compressor is a
multiservice machine) by Project Engineering. Therefore,
30 of 33 valid process equipment specifications are complete at this time. Of these 30 process specifications, 5
exist as revised specifications resulting from engineering
feedback. The three remaining equipment items are the
Reactor (27.10), the Slurry Preparation Tank.(28.30),and

-9-

the Catalyst Reduction Vessel (02.81). The Reactor is the

existing reactor vessel (R-101) in the LPM pilot plant;
the process specification is being delayed pending further
analysis of the need for internals in the liquid-fluidized
(ebullated bed) and liquid-entrained (slurry) modes. The
Slurry Preparation Tank specification is scheduled for
issue by 25 June 1982. As noted above, the Catalyst
Reduction Vessel is on-hold pending additional experimental confirmation that this vessel is not required.
Some process design characteristics of key equipment items
in the LaPorte LPMeOHPDU are provided in this report as
follows:

1.

Slurry Circulation Pumps (10.50 A & B)

The process equipment specification is attached as
Exhibit 2.3.1-6.

Feed/Recycle Compressor (01,10/01.20)

The process equipment specification is attached as
Exhibits 2.3.1-7A and 2.3.1-7B.

S)urry Heat Exchanger (21.20)

The process equipment specification is attached as
Exhibit 2.3.1-8.

4.

Reactor.(27.10)

A schematic of the reactor and some key operating

parameters are given in Exhibits 2.3.1-9A and 2.3.19B.
Hazards Review
The Preliminary Hazards Review was completed. The subsequent Design Hazards Review progressed to analyze specific
hazards and to document conclusions and recommendations
relevant to each item. The "What If?" method of analysis
was used to review the Engineering Flowsheet, Revision O,
dated 10 March 1982. As a result of this review the
following hazards were recommended for quantification by
Fault Tree analysis:
Description of Hazard
1.

Potentially pyrophoric,
hot, o i l / c a t a l y s t s l u r r y ,

-10-

Preliminary
Recommendation
la.

Use administrative
procedures to assure

exposed to air.

2.

3.

Run-awayreaction.

Major release from

Methanol Tank.

t i g h t shutoff prior to
maintenance on standby equipment in the
slurry mode.
lb.

Monitor errosion
rates in equipment
and piping.

Ic.

Use administrative
controls to prevent
overfill of Tote Bins
for spent slurry
disposal.

2a.

Provide alarms for low

nitrogen flow or high
H~ concentration, specTfically for reduction
gas supply in liquidfluidized catalyst
preparation.

2b.

Utilize administrative
control to eliminate
severe consequences of
temperature rise upon
loss of s l u r ~ circulation duping i n - s i t u
reduction.

2c.

Develop understanding
of catalyst activity
and potential for oil
cracking on temperature
excusions.

3a.

Provide adequate pressure

relieving devices.

3b.

P~ovidehigh liquid
level alarm.

Fault trees on the above items w i l l be completed and

quantified upon release of the Revision OA Engineering
Flowsheet and the preliminary shutdown logic diagrams
resulting from the "What If?" review.
Environmental Permit Action
A request for exemption from construction and operating
permit requirements was submitted to the Texas Air Control

Board (TACB) on 17 March 1982. I t ts believed that the

PDU f a c t l t t y w i l l not make a significant contribution of
air contaminants to the atJ~osphere. The request to TACB
included a report on the emission sources and quantities.
The emission sources are the flare stack, storage tank
vents, pressure leaf f i l t e r purge, and fugative hydrocarbons. The continuous process vents of hydrocarbons and
CO along with emergency or r e l i e f valve vents w i l l be sent
to a single smokeless flare designed for complete combustion.
Working lbsses from the storage tanks along with controlled
fugative hydrocarbon emissions are estimated to tota|
about 14 T/Y.
The water discharge (treated rainwater runoff from the
process area) w i l l be directed to the existing f i r e pond

at APCI's commercial facilities at LaPorte. This water

discharge increment is being included in renewal applications for APCI's overall water discharge permit at
LaPorte.
Permits w i l l not be required by APCI for handling of
hazardous wastes on site. However, c~adle-to-grave

accounting will be required on all used catalyst/oil

preparations requiring disposal.
Methanol product w111 be disposed of as a fuel and therefore is exempt from EPA regulation.
2.3.2

Equipment - Exhibit 2.3.2-1 summarizes engineering specification

a c t i v i t y for the process equipment items in the LaPorte LPMeOH
PDU. Process specifications have been issued for 30 of the 33
equipment items. Mechanical specifications have been issued
for 16 items, including 15 of the new equipment items (18 total
new items). Quotations have been received on the 2 long lead
delivery items (01.10/01.20 Feed/Recycle Compressor and 10.50 A
& B Slurry Circulation Pumps) and technical evaluations are
underway. Requests for purchase approval for these ] = t i e r
items are expected to be submitted to the DOE by 30 April 1982.

2.3.3

Site/Structural - A site v i s i t was made to LaPorte to verify

conditions for t t e - t n pipe racks, roads and underground road
crossing designs.

2.3.4

Piping A site v i s i t was made to LaPorte to v e r i f y existing piping

systems for t i e - i n . Upon return, design drawings were prepared
detailing the required t i e - i n consturction. These drawings
w i l l be u t i l i z e d for the preparation of take-off estimates to
be incorporated into the 1 June !982 deliverable report.

-12-

Semi-final equipment arrangement and p l o t plan drawings were

prepared based on information from the Design Hazards Review.
These drawings and the Revision OA Engineering Flowsheet w i l l
form a basis for the LaPorte LPMeOHPDU renovation and i n s t a l l a tion estimates to be incorporated into the I June 1982 deliverable
report.

2.3.5

Electrical Specification~ have been prepared for switchgear additions to

the LaPorte commercial f a c i l i t y that would provide a source of
600 kVA service for the LPMeOH PDU.
Two alternate specifications have been prepared for motor
control fop the LPMeOH PDU to allow evaluation between matching
and ltne up with the existing LPM p i l o t plant motor control,
and t o t a l new purchase of motor control equipment.

2.3.6

Instrumentation - Support was provided in the development of

control loop requirements on the Revision 0 and Revision OA

Engineering Flowsheets.

Task 3 - Equipment Procurement

No Activity.
Task 4 - LPM Pilot PlAnt Relocation/Inspection
4.1

APCI Management A c t i v i t i e s

4.1.1

Warehousing - No A c t i v i t y .

4.1.2

T r a f f i c Services - No A c t i v i t y .

4.2

CSI Management A c t i v i t i e s

4.2.1

On 11 February 1982, a meeting was held at IGT in Chicago,

Illinois to inspect the LPM pilot plant with regard to its
relocation to a fabricator shop in Texas. A Chem Systems
representative was on hand for discussions with IGT personnel
and to answer question~ pertaining to the pilot plant, them
Systems also reviewed the APCl specifications fo~ dismantling
the pilot plant.

4.3

Field Eng|neering - A s i t e inspection was conducted by an APCI

f i e l d instrument technician on the LPH p i l o t p l a n t instrument a t i o n . Several loops were energized, and pneumatic valves
stroked to establish a l i s t of reuseable instrument items for
incorporation into the detailed ship inspection plans.

4.4

LPM Pilot Plant Relocation

-13-

4.4.1

Disassembly - A technical evaluation of bids was conducted and

purchase approval has been sought from the DOE f o r award of
t h i s contract, Site a c t i v i t y in Chicago is expected during May
1982.

4.4.2

Inspection - No Activity.

4.4.3

Rehabilitation - No A c t i v i t y .

Task

LaPorte LPMeDHPDU Rbnovation~ Installation~ ahd Shakedqwn

No Activity.

T_aask 6 - Liquid-Fluidized Operation

No Activity.
Task 7 , Laboratory Support Program

7. I

APCI R&D

7.1,3

Catalyst Screening and Testing APCI Stirred Autoclave (Bench Scale Slurry) Reactor Set-UR
Major items ordered for construction of the I000 ~L Stirred
Autoclave Reactor were delivered. Items which were ordered and
not delivered as of this writing include:
I.
2.
3.
4.
5.
6.

Fittings and valves from Autoclave Engineers, Inc. (l lot).

Pressure transducers and demodulator~ (3 ea.).
Multipoint chart recorder ( l e a . ) .
Pressure regulator ( l e a . ) .
Gas inlet flow integrators.
Miscellaneous solenoid valves and fittings.

The construction of the main control panel began, with cut-out

holes f o r missing instrumentation items made from dimensions
supplied by the manufacturers. The 1000 mL Stirred Autoclave
Reactor was moved into the operations cell and plumbing operations
w i l l begin during April 1982. The reactor construction is
proceeding on schedule; back-ordered items should not affect
the schedule i f promised shipping dates are met.
The operation cell area, which was newly constructed, was
completed and was checked-cut for proper v e n t i l l a t i o n with
smoke bombs. The area is monitored with recently i n s t a l l e d
carbon monoxide alarms. The principal lab area is monitored at
4 points. The gas supply !ines are located external to the lab
and are monitored at 3 points for carbon monoxide. With the
f i n a l check on the cell operation area v e n t i l ] a t i o n and the
i n s t a l l a t i o n of the CO monitor, the lab area is now operational.

-14-

High-pressure piping of i n l e t CO and Ho gases from the external

gas supply area was completed and leak=checked. The high
pressure piping for inert and CO~ gas supplies was completed;
however, the gas cylinder manifo)d has not been installed.
Work on t h i s manifold is scheduled at a l a t e r date.

APCI Gas Phase Screening Reactor

Final specifications for this unit were given to Chemical Data
Systems, Inc. and construction of this unit began at CDS's
facility. Monitoring of progress continued and shipment of the
completed unit is expected by 30 April 1982. Exhibit 7.1.3-1
shows a simplified schematic of the unit along with critical
measurements and capacities.
7.1.4

Catalyst Preparation The methanol catalyst literature search to cover the program
needs was initiated and is nearly complete. Discussions with
APCI's Corporate Development Department and other Process
Systems Group personnel have indicated that one-pound quantities of catalyst in the 45-75 ~,icron range will be provided for
testing. The f i r s t five catalysts for the program will be
prepared for delivery before 30 May 1982. The catalysts w i l l
be characterized as to pore size, surface area, analytical
composition, and bulk density, although only the composition
ai:d particle size distribution will be controlled in the i n i t i a l
preparations.
The preparation priority, from high to low, with respect to
cnmposition type is:
I.

Supported CuO/ZnO, CuO/MgO, CuD/ZnO/Ceria.

2.

CuO/Ceria (Ce+3 and Ce+4), CuO/Ceria/Alumina.

3.

CuO/MoO3 or CuO/WO3 types.

4.

Raney alloys of Cu plus Zn and aluminum and copper plus

cerium and aluminum.

Copper-thorium alloys have been dropped from consideration at

present. This is due to the practical problems associated with
handling radioactive materials. Copper-ceriumand/or copperlanthanum alloys may be recommended as substitutes after further
analysis.
Mixed heterogeneous-homogeneous catalyst systems have been
Puled out due to potential metal carbonyl v o l a t i l i t y problems.

-15-

7.2

CSI R&D

7.2.1

Literature Review Cold Flow Hydrodynamics of Three-Phase Systems

The following paragraphs discuss some of the literature reviewed
prior to scoping a system for cold flow modeling of the LPMeOH
process.
The performance of a chemical reactor with respect to conversion
and selectJvil~y depends on the i n t r i n s i c kinetics of the various
chemtcal reactions, various physical rate processes such as
tnterphase transfer, and inter and intra p a r t i c l e heat and mass
transfer. The effects of these physical rate processes on the
reaction performance have been shown to depend on the dynamics
of the various phases involved. While there are numerous
publications about backmixing in liquid-gas bubble c~!u~ns ~nd
in s o l i d - f l u i d systems (References 1-5), much less material has
been published on three-phase ebullated bed/liquid entrained
systems (References 6-8).

Experimental data on Peclet numbers due to axial dispersion in

chemical reactors are also very limited. Most of the work has
been limited to single phase packed bed reactors. Moreover,
data on such systems are only reliable when applied to systems
resembling those of the experimental studies (Reference 9).
At the present time, an extensive effort is being directed
toward the measurement and evaluation of backmixing in multiphase
systems through residence time distribution (RTD) studies
(References lO-ll). One major problem encountered is that
separate RTD measurements are required to evaluate the mixing
characteristics of each phase. Although there are numerous
methods available to obtain RTDs in complex multiphase syste=s,
measurement problems have been encountered by all recent investigators. Flowmaldistribuion of the phases can especially
impede evaluation of RTD data.
7.2.2

CSI Stirred Autoclave Tests The program for optimizing in-situ catalyst reduction techniques
for catalyst powders suspended in inert hydrocarbon liquids
continued during this quarterly period. To date, seven runs
have been completed including five in-situ reduction conditions,
one replicate run and a base case. vapor-phase reduction condition.
I.

Description of Stirred Autoclave Reaction System

A process schematic of the CSI lab Sticred Autoclave
System is shawn in Exhibit 7.2.2-1. The heart of the
system is a two-liter autoclave equipped with a top entering

-16-

magnedrtve agitator assembly and water cooled by an automatic

temperature controller. The autoclave is a Model A F P - 2 0 0 5
from Autoclave Engineers. The agitator has a 3/8-inch

diameter hollow shaft with two 3/16-inch diameter draft

tube inlet holes located ten inches above the l-I/4-inch
diameter impeller. The system is set up in such a way
that feed gas, reduction gas and make-up oil can be introduced under controlled pressure and flow conditions. The
reactor effluent passes through a shell and tube heat
exchanger b~fore i t enters the vapor-liquid separator.
Auxiliary equipment on the V/L separator a11ow for sampling
of vapor and liquld streams and measurements of flows,
temperature and pressure.
2.

Catalyst Reduction Test Pr,,ocedures

This section contains potentially patentable material and
has therefore been issued in the Supplement to the Technical
Progress Report, marked "Not For Publication".

3.

Run Pr_ocedures and Preliminary Results

This section contains potentially patentable material and

has therefore been issued in the Supplement to the Technical
Progress Report, marked "Not For Publication".
4.

Calculation Methods
The feed gas contained approximately 15 mole percent of
argon as an internal standard for calculation purposes.
The calculated data include vapor hourly space v e l o c i t y
(VHSV), hydrogen and carbon oxides conversions, s e l e c t i v i t y

and methanol productivity.

The VHSV is calculated as follows:
Ve
Ar e
VHSV =~C x ~
x
Where:

273.;5
Pe
273.15 + Te x L101.3S

(Eq. 1)

Wc

= Space Velocity in l " h r ' l . k g -1

= Volume flow of effluent, 1/hr (at STP)
= Mole percent argon in effluent
= Hole percent argon in feed
= Oxided catalyst charge, kg

Te

VHSV
Ve
Ar e
Arf

Effluent Temperature, C
Effluent Pressure, kPa

-17-

The percentage conversions of feed gas components (H2, CO and

CO2) are calculated as follows:

Arf
Ci =

If

X I00

(Eq. 2)

= Percent conversion of component I

"= Mole percent of I in feed gas
= Mole percent of I in effluent gas

Where Ci
If
Ie
I

H2, CO or CO2

I f the feed gas has a low CO9 concentration (less that three
percent), then net COo w i l l be produced, and the percent select i v i t y to CO2 (Sc02) ~an be calculated as follows:

(o,
SC02

Arf

Mf"

Arf
--- )
Are

(MeX

x 100

(Eq. 3)

Where D = Mole percent of carbon dioxide

M = Mole percent of carbon monoxide
Ar = Mole percent of argon
Subscript e refers to reactor effluent
Subscript f refers to reactor feed
The methanol productivity is calculated as follows:
Mp

Where:

VHSV
22'4 x lO0

(Mf x CM + Df x CD)

(Eq. 4)

Mp = calculated methanol p r o d u c t i v i t y ; gmol/hr/kg

oxidized catalyst.

When a low CO~ content feed gas is used, part of the CO is

converted to CO~ as well as to methanol. For t h i s case, the
s e l e c t i v i t y to CO~ would have to be subtracted from the term in
the parenthesis ih Equation (4) in order to calculate the
methanol p r o d u c t i v i t y .

-18-

7.2.5

Cold-Flow Model The i n i t i a l scoptng of equipment requirements and experimental

techniques was conducted in order to determine costs and timing
associated wtth cold flow hydrodynamic modeling of the LPMe~H
process.
A cold flow hydrodynamic u n i t was designed which could be
operated as e i t h e r a l i q u i d - f l u i d i z e d reactor or a l i q u i d entrained reactor. In the l t q u i d - f l u i d i z e d mode, the process
l i q u i d velocity is controlled over a narrow range in order to
fluidize a fixed quantity of cataly;t particles within the
confines of the reactor. For liquid-entrained operations,
smaller catalyst particles are intentionally suspended in the
process liquid and are circulated throughou'c the liquid circulation loop. The process flows and physical dimensions of the
hydrodynamic unit broadly resemble that of the LaPorte LPHeOH
PDU. A conceptual process flow diagram of the cold flow hydrodynamic unit is shown in Exhibit 7.2.5-1.

I t is anticipated that the hydrodynamic test unit would be

constructed of materials that are compatible with a range of
organic solvents. The process liquids will be selected to have
properties similar to those of the hot process I~quids. Solvents
of differing physical properties would be used in 1:he determination of the density, viscosity and surface tension effects on
the hydrodynamic character of the process fluid.
1.

Process Equipment
In the liquid-entrained gas/liquid upflow configuration,
gas and slurry are co-fed to the bottom of :,,~ reactor
(TW-IO0). Gas is introduced through a suitable d i s t r i bution device while the slurry is introduced below the gas
distributor. Catdlyst particle size and process liquid
flows would be selected so as to intentionally suspend the
catalyst in the process liquid and circulate the solids
throughout the liquid circulation loop. By design, the
catalyst solids and process liquids must remain a homogeneous mixture everywhere within the liquid circulation
loop. Gas/solids/liquids are taken overhead out of the
reactor to the V/L separator (VT-IOO) where phase separation between gas and slurry phases occurs. The separated slurry phase is recirculated to the reactor inlet
through a pump (CP-IO0). The gas phase passes through a
demister (VT-IOI) to de-entrain any liquid droplets. The
gas can then be vented or recycled back to the compressor
(GC-lO0). The gas compressor would be equipped with a
water cooled aftercooler (HE-IO0). The gas then flows
into a surge tank in order to damp out pressure (or flow)
fluctuations prior to passing to the reactor gas d i s t r i bution system.

-19-

Reactor,
The reactor used fop tlle hydrodynamic study would be
constructed of a combination of flange-connected
glass and metal sections. The column dimensions
( i d e n t i c a l to the LaPorte LPMeOH PDU reactor) w i l l be

0.56 meters inside diameter by4.6 meters long. The

reactor piping connections at the top and bottom will
be flexible. The bottom metal spool piece is designed
to support the entire cold flow reactor assembly,
Each metal spool piece would be constructed so as to
allow for the introduction of sample probes, pressure
taps, and other instrumentation as required. The
sample probes would be constructed and operated so as
to obtain s l u r r y concentration data along the radial

and axial direction. A Plexiglass or Lexan shield

would be used to enclose the glass column for personnel
protection. Sections of the plastic shield would be
made removable to allow access to the various sample
and pressure taps. Finally, an x-ray source and
detector will be mounted so as to traverse the length
of the reactor, l~Iternately, a series of fixed
source/detector pairs may be mounted along the vertical
length to obtain the density profile.

Pumpsand Compressors
A rotary screw air compressor with a water cooled
aftercooler would be used for supplying gas. The
present design requires a compressor capable of up to
2.8 m~ per minute at standard conditions and 790 kPa
outlet pressure. The compressor discharges into a
surge tank to damp out pressure and flow fluctuations.
Magnetically coupled centrifugal pumps will be selected
for the slurry feed and circulation loop. These
pumps are magnetically coupled to their motor so as
to eliminate problems of liquid or gas leakage across
a dynamic seal. In addition, these pumps do not
require a seal flush flow. The present design requires
a pump capable of 830 liters per minute maximum flow
at 23 meters total dynamic head.
Catalyst Recove~ Filter
A plate and frame f i l t e r press is included in the
design to be used in determining solids hold1~p within
the column. Additional use would be made of the
f i l t e r in recovering "used" catalyst upon completion
of testing.

-20-

Vessels

The slurry feed tank (VT-IOE) was sized at II00

liters to hold the entire contents of the cold flow
hydrodynamic test unit. I t is baffled at 90 and
supplied with an agitator to maintain the catalyst
slurry in suspension. Liquid inventory can be monitored
by placing the unit on a weigh cell or by using a DP
cell. I f a DP cell is used, an inert purge gas must
be s~pplied to the high side of the cell to prevent
plugging by catalyst. A slurry feed pump (CP-I02) is
used to transfer the slurry to the main test unit
circulating loop.
The slurry preparation tank (VT-I03) has a capacity
of 400 l i t e r s and was sized for slurry addition and
makeup in multiple batches. I t is also baffled at
90 and supplied with an agitator. Inventory control
would be accomplished by placing the unit on a weight
eel1. Slurry is transferred from the vessel to the
feed tank or the main circulation loop through the
slurry transfer pump (CP-lOl).
2.

ExperimentaI Techniques
Test methods for determining hydrodynamic system characteristics can be categorized as being either external or
internal monitoring techniques. External techniques are
preferential in that they do not interfere with established
flow patterns. Internal methods involve the insertion of
devices through the test cell wall, consequently inducing
flow disturbances downst~-eam of the saaple location.

External Methods
Sonic probes and gamma-ray scan techniques have been
used to obtain data on the average bulk density in
multiphase systems. Gamma-raytechniques make use of
differential absorption of radiation by various
materials. Being an external technique, i t is an
excellent method for determining the average density
of a multiphase syste~ without creating a flow disturbance. A movable density gauge could traverse the
length of the reactor and give point bed density
measurements directly. Thesemeasurements combined
with fluldized bed height measurements give a direct
evaluation of the relative liquid, gas and solid
phase volume fraction.
Sonic techniques are alternate external methods for
determining densities of multiphase systems, using
sound rather than radiation. In sing|e-phase systems,

-21-

phase-time and dual-path sonic probes (which measure

sonic impedance) can be used to determine density.
These devices can also be used in two-phase, liquidsolid slurry systems, provided that the sonic impedance
of the two-phase mixture is a very weak function of
slurry concentration. These devices cannot be used
when a bulk gas phase is present because discrete gas
bubbles give rise to interfering sonic reflections.
I t can measure vertical bubble rise velocity or
slurry velocity.

Internal Methods
Several tracer testing methods are known for determining residence time distributions, flow rates and
relative phase volumes in multiphase reactors. The

techniques employed involve use of a tracer component

with an internal or external monitoring device.
External detection systems are preferred as they w i l l
not interfere with established flow patterns.

In genera], flow patterns can be studied by injecting

a tracer into a vessel i n l e t stream and observing the
subsequent concentration p r o f i l e at the outlet. At
steady state, methods used consist of injecting a
continuous tracer into the i n ] e t of a studied interval
and measuring the upstream concentration. For large
diameter columns, problems are encountered in obtaining
a homogeneous dispersion of the tracer. Further,
attempts to obtain an average sample profile across
the column can be d i f f i c u l t without disturbing the
original flow patterns within the column. When
continuous sample withdrawal is employed, sample t!me
effects may d i s t o r t the measured response. Unsteady
state methods of measuring residence time distributions
consists of injecting a momentary tracer pulse at the
reactor i n l e t and measuring the response function at
the outlet. Pulse injection methods are preferred to
step or frequency response methods since inputs
requiring large quantities of tracer are impractical
on large units. Pulse injection techniques are
simple, inexpensive, and require only small quantities
of tracer material.
In performing a tracer study, proper tracer selection

is extremely important. The hydrodynamic response

must be characteristic of the flowing phase and not a
function of the tracer component. Any tracer employed
should be miscible and have pl~sical properties
similar to the bulk f l u i d phase. The tracer must not
be transferrable to the other phases of the system.
All tracers under consideration should be accurately

-22-

detectable in low concentrations to minimize disturbances in the established reactor flow patterns.
To enable tracer detection in fast moving streams,
the data recording equipment must o~fer exceptional

sensitivity with a minimal detection response time.

For simplicity and accuracy, the response of this
equipment should be linear.
Gas/liquid or solid tracers can be injected into a
flow system to determine the responses for each
phase. For the gas phase, a tracer gas injected into
a multi-phase reactor would have i t s concentration
measured by a thermal conductivity or infrared
absorption cell. Alternately, a radioisotope is
substituted. In using gas ~hase tracers, absorption
into the liquid phase precludes an accurate determination of the gas phase mixing and holdup without an
independent measurement of tracer content in other
phases. The differing rise velocities of individual
bubbles further complicate the detector response.
Because of these inherent difficulties in using gas
pi;sse tracers, only qualitative data concerning gas
phase mixing are available in the literature.
The use of liquid tracers are well accepted industrial
practices. Problems associated with their use are
the familiar ones of sampling induced errors when
internal techniques are used. External techniques
employed include the use of dyes coupled with high
speed photography and radioactive tracer methods.
Unfortunately, photographic techniques relying on
photochromatic dyes or particle luminescence cannot
be used i f the color change is obsured by the catalyst
particles. In larger diameter columns wall effects
can also obscure the events from photographic interpretation.
For the solid phase, a magnetic tracer can sometimes
be used. The concentration of a solid phase tracer
may be measured by a capacitance probe if the dielectric
constant of the tracer material is substantially
different than that of the solid phase. In general,
for solid phases, a suitable radioactive tracer is
often the most convenient to ,~se. If proper precautions
are observed, a radioactive tracer ilas a distinct
advantage over other tracers i. that the tracer

detection devices can be mounted externally. In this

way, no disturbances in the established flow patterns
resulting from the presence of probes or sampling
devices are encountered. The use of a radioactive
tracer permits the time distribution function of a

-23"

rapidly moving phase to be accurately determined,

since scintillation detectors can be Interfaced with
high speed recorders or wlth multi-channel analyzers
with data storage capabilltles.
7.2.6

CSI Lab PDU Modifications

Tile request to purchase the f i r s t of two slurry pumps was

approved. Meanwhile, all responses on the RFq for fabrication

of vessels and'skid equipment for the CSI lab PDU were received
and evaluated. I t was decided, however, at a meeting held in
Fairfield on 25 February with APCI personnel not to hire a
contractor to build a complete skid-mounted unit. Instead,
only major equipment items, such as process vessels and heat
exchangers, will be fabricated outside with the majority of
engineering, skid design and assembly handled by CSI In-house.
Thls change has been necessitated to allow more project flexib i l i t y , lower overall costs and improved scheduling. Work
began on the assembly of a technical package which will serve
as sufficient documentation for required purchases of equipment
or services. This package will contain process flowsheets,
heat and material balances and a description of the liquidentrained CSI Lab PDU. The process flowsheets w i l l eventually
evolve into complete engineering flowsheets. This package when
assembled will accompany any requests for approval sent to
APCI/DOE.
7.2.7

CSI Lab PDU Experimental Program - This subtask will not be

initiated until the CSI Lab PDU modifications are completed.

7.2.8

LaPorte LPMeOHPDU Support Overview

United Catalysts Inc. has developed under EPRI support (Reference
12) a methanol synthesis catalyst for the liquid-fluidized
(ebullated bed) mode. This material represents a catalyst
candidate with potentially better attrition resistance than any
catalyst tested under the prior EPRI contract (Reference 13).
A 10 Ib sample of this catalyst (CSI Identification Number
R71/OF12-02) was shipped to CSI's Fairfield Research Center for
evaluation in a test in the CSI Lab PDU. The catalyst was
charged to the reactor on 16 Feb1'uary 1982 and was reduced
u t i l i z i n g a vapor-phase reduction technique over a three-day
period. Two days of t e s t i n g concentrated on the three-phase
f l u t d i z a t t o n properties of the c a t a l y s t suspended in Witco
mineral o i l , p r i o r to the actual synthesis t e s t .
The c a t a l y s t
was brought on-stream w i t h a 2/1 H~/CO feed gas, and operating
conditions were maintained constant f o r a period of about 370
hours.

-24-

During this period, CO conversion and settled catalyst b~d

height were monitored. Fines generation, as determined by
pressure drop buildup in the o i l f i l t e r s and decrease in
settled bed height, was higher in the f i r s t two days on-stream
time than during the later part of the run. Both factors were
lower than experienced previously with another catalyst (FX2/
1F15-02) tested under a previous EPRI contract (Reference 13).
A measure of the a t t r i t i o n resistance characteristics of the
catalyst w i l l be obtained upon inspection and post-mortem
analysis of the catalyst recovered from the reactor at the
conclusion of the run.
During the Lab PDU operation, a process variable scan was also
made to study the effect of temperature, space velocity, pressure
and synthesis gas composition on catalyst activity and product i v i t y to methanol.
CSl Lilquid-F1uldized Lab..PDU Description
The CSI Lab PDU reactor is 0.092 m I.D. x 2.13 m high, and the
catalyst bed height can be varied from 0.6 to 1.5 meters. The
detailed engineering design of the CSI Lab PDU has been presented
elsewhere (Reference 14). The premixed synthesis gas feed is
delivered to the laboratory in a tube t r a i l e r . A gas compressor
is used to feed the gas to the reactor. In this manner, the
pressure ~n the tube t r a i l e r can be reduced to 2170 kPa before
a new supply is required. Two compressors are provided to
allow f l e x i b i l i t y in feed gas rate. Product methanol and small
amounts of vaporized oii are condensed out of the product
gas/vapor stream. Phaseseparation occurs at ambient temperature
with a typical residence time in the product separator of one
hour. The oil is recycled back to the process oil circulating
loop. The product gases, following analysis, are sent to an
incinerator. Sufficient instrumentation is provided for automatic
control and monitoring from a remote control room. The system
is designed for pressure up to 7000 kPa and temperatures up to
400C. All necessary gas streams are connected to a common
manifold and are constantly purged to reduce sampling time
lags. The selected gas stream may be directed to each chromatograph column, in turn, to analyze for components of interest.
Preliminary Analysis of Short-Term Attrition Test

After the CSI Lab PDU was pressure tested, the reactor was
loaded wtth fresh oxided catalyst (R71/OF12-02) and reduced
over a three-day period. The system was put on-stream at
conditions similar to those used in the previous EPRI-funded
test made in No~@mber, 1978: 250C reactor temperature, 7000
kPa and 3000 hr * VHSV (Reference ]3). These conditions were
held constant for 370 hours before process variable scans
proceeded. The complete run chronology is shown in Exhibit
7.2.8-2.

-25-

At the onset of the run, CO conversion was 34 percent and then

dropped ~tnearly to the 28 percent level within 100 hours.
During this time period, the ~ettled catalyst bed height decreased
to 93 percent of i t s i n i t i a l height. For the remaining time,
270 additional hours, the CO conversion hovered at the 28
percent level while the settled catalyst bed height decreased
to 81 percent of i t s i n i t i a l height. These results are shown
graphically in Exhibit 7.2.8-1.
The next 70 ho~rs of running time were utilized in performing a
process variable scan. The preliminary results of these tests
are shown in Exhibit 7.2.8-3. At the termination of these
scans (440 total hours on-stream time), the settled bed height
had dropped to 78 percent of its i n i t i a l height. Setting the
system back to the i n i t i a l run conditions gave a slightly lower
CO conversion (27.5 percent) than the value just prior to the
start of the variable scan.
With 460 hours logged on the catalyst, a short scan was performed
using a low CO~ (1.5 percent) content 2/1 H~/CO feed gas. This
synthesis gas ~esulted in essentially the s~me CO conversion as
the 10 percent CO~ gas with the exception that a small percentage
of CO had apparently shifted to CO2.
The synthesis gas used for the i n i t i a l conditions was put back
on-line resulting in a CO conversion of 27.5 percent. The
settled catalyst bed height at this point was 75 percent of its
i n i t i a l height. After a total of 555 hours on-stream time, the
settled catalyst bed height was 73 percent of the inital height
and CO conversion was 27 percent. A short test using a 0.6/I
H2/CO feed was then performed before the unit was shut down.
The unit w i l l be disassembled to recover the catalyst and then
cleaned up and placed in a stand-by condition. Catalyst and
oil samples will be analyzed. The analysis of the non-hydrocarbon liquid products is not complete at this time but indicates
a 96I weight percent methanol content with the remainder being
Witco 40 o i l , water and a small amount of higher alcohols ethanol through hexanols.
Task 8 - Conversion of the LaPorte LPMeOHPDU from Liquid-F1uidized to Liqb;uEntrained Mode

No Activity'.
Task 9 - Shakedown for Liquid-Entrained Operation
No Activity.

-26-

Task 10- L|quld~EntrainedOperatlon

No Activity.
Task 11 - Project Evaluation
11.1

APCI Management Activities

ii. I.i

Project Management The

ProjectStatus Reports, Format 5 Reports, and quarterly
Technical Progess Report No. I were coordinated.
An arrangeaent was made to provide closer liaison between APCI
design engineers and CSI's laboratory personnel following
review of CSI's requisitioning material for a skidded assembly
for modification of the Laboratory PDU to permit liquid-entrained operation. The specification, design, and erection of
this unit remains in CSI's subcontract scope; however, APCI
will take a more active role in engineering assistance and
specification review. A rough project plan was worked out to
establish requirements for future purchase requests by CSI in
this area.
A meeting among APCI, CSI and DOE was held in Pittsburgh on 18
March 1982 to clar';fy procurement and approval procedures. A
brief presentation was made by APCI and CSI owl the program
status.

11.1.2

Economic Evaluation - No Activity.

11.1.3

Travel and Living - AP1 and CSI met on several occasions in

A11entown and Fairfield and once in Pittsburgh. APCI's Operations Manager from LaPorte attended meetings in Allentown and
Chicago. Two trips were made to Chicago by APCI and CSI personnel
to review LPM pilot plant relocation specifics.

11.2

CSI Activities

II. 2. I

Data Evaluation - Information from the CSI Lab Stirred Autoclave and the CSI liquid-fluidized PDU runs was evaluated and
reported under the corresponding subtasks. Thorough analysis
of data from both of these units will continue into the next
reporting period.

11.2.2

Design and Economics - No A c t i v i t y .

11.2.3

Process Scaleup - No A c t i v i t y .

11.2.4

Reporting - Monthly Project Status Reports, management reports

and the f i r s t q u a r t e r l y Technical Progress Report were issued.
Work was completed on a paper f o r presentation.
A meeting was

held et PETC on 18 March 1982 to discuss current project status

and equipment review/purchase procedures. Work began on updating
the CSI Project Work Plan including schedule, manpower and
cost~. This w i l l be part of the 1 June deliverable to DOE from
APCI.
11.3

APCI Design

11.3.1

Integration APCI reviewed a.d technically approved CSI~s f i r s t Laboratory

PDU slur~ pump purchase. A technical difference exists between
recommendat'lons of the International Coal Refining Co. and
Lawrence PumpCo. regarding the most appropriate ~eal arrangement for this application. Due to the experienced position
Lawrence has with various pilot plant operations in hot, high
pressure, slur~ service these recommendations are being given
thoughtful consideration.
Technical review and approval were given by APCI on CSI specifications fop pressure vessels and a slurry heat exchanger
required for modification of CSI's Laboratory PDU for liquidentrained operation,,

11.4

APCI R&D Activities

11.4.1

Corporate Development Department - Input was provided to the

Monthly Status Reports and Technical Progress Report No. 1.
Meetings were held with the CSI Fairfield laboratory staff to
strengthen the technical liaison between the research organizations.

11.4.2

Process Systems Group R&D Preliminary Viscosity and Density Data

In support of the LaPorte LPMeOH PDU design e f f o r t , preliminary
v i s c o s i t y measurements of klitco 40 oil/MC-2 catalyst s l u r r y
were carried out using a Brookfield LVT viscometer with an
u l t r a low viscosity adapter attachment and spindle. The variables
included:
Temperature
Slurry Concentration

67F to 482F (!9 to 250C)

0 Vl~, 12 wt~ and 25 wt~

Immediately before measurement for slurries, the U.L. adapter

was removed and shaken vigorously to ensure a uniform solids
suspension during the viscosity measurement. Preliminary
results indicated that 25 wt% s l u r r y viscosity showed a strong
shear-rate dependence. These results are suspect from several
points of view. The data are currently being evaluated and the
f u l l report and conclusions w i l l be included in the next quarterly

-28-

report. In addition to the viscosity data, the densty, the

volulne X and ~ vhlume c~ange of 12wt~ and 25 w l ~ s l u r r y w e r e
measured at 71-72F (22uC).
Pyropho~ic Nature of Spent.Catalyst

An experimental plan was developed to assess the wrophoric

nature of o i l / c a t a l y s t slurries. Three types of experiments
have been considered:
I.

Qualitative observation of oil/catalyst slurries in an

open a i r environment (hood).

Differential Thermal Analysis (DTA) of oil/catalyst slurries

(1-5 mg) to determine quantitatively the timing and the
temperature at which auto-ignition would occur.

Heat of combustion measurements of o i l / c a t a l y s t slurries

(1 g sample) to verify the theoretical calculations for
the largest posstble energy release.

This plan is ready for circulation within APCI for review and
comment.

Fundamental Hodel for LPHeOH

Progress was made in exploring fundamental modeling of the
LPMeOH reactor and reaction kinetics. A computer model written
by Professor W. D. Oeckwer of gniversitat Hannover (West Germany)
for Fischer-Tropsch synthesis in a slurry phase reactor was
tested. (This computer program is not generally available to
the public but was made avai]able by Professor Deckwer under a
pr|vate agreement with APCI. I t is planned to report results
from the computer model; the software programming w i l l not be
reported without p r i o r agreement with Professor Deckwer.) The
Deckwer model is well described in Reference 15. The computer
program was made operational and the results of computations
published in Reference 25 were duplicated. The strategy is
now being developed to model the LPHeOH fluidized (ebullated
bed) and entrained (slurry) reactors by modifying the rate
expressions, modifying the mass balances to allow both solids
and liquid to flow in and out the reactor, and by incorporating
appropriate hydrodynamic parameters at high liquid velocities.
Liquid PflaseReactor Patents
A preliminary patent search on 3-phase slurry reactor designs
was made P~garding possible infringements of the LaPorte LPMeOH
PDU reacto~ design on the prior patents. The search revealed
that the current simple reactor design~ at LaPorte probably do
not infringe any p r i o r patent because the p r i o r 3-phase reactor
patents are largely process-oriented.

Input was provided to the Monthly Status Reports and the

Technical Progress RepoPt No. 1. Meetings were organized
and held with the CSI F a i r f i e l d laboratoPy s t a f f to enhance
technical communications.

-30-

REFERENCES
(1) Mashelkar, R. A., Brtt. Cl!em. Eng., 15__~, 1297 (October 1970).
(2) Shu]man, H. L., et al., IEC, 42(6), 1060 (June 1950).
(3) Argo, W. B., eL a]., I EC Proc. Des. & Dev., ~ ,
(4) Stiege], G. J., e t a ] . ,

352 (October 1965).

IEC Proc. Des. & Oev., 1 6 ~ ,

37 (1977).

(5) Mashelkar, R. A., e t a ] . , Trans. Inst. Chem. Eng., 48, T162 (1970).
(6) Ostergaard, K., AIChE Sym.. Set. 176(74), 82 (1978).
(7) Kim, S. D., et al., Can. J. Chem. Eng., 50, 695 (1972).
(8) Blass, K. E., et al., J. Multiphase Flow, 4, 459 (1977).

(9) Levenspie], 0., Chemical Reaction Engineerinq, J. Wiley & Sons (1962).
(10} Ostergaard, K., Adv. Chem. Eng., 71 (1968).
(11) Shah, Y. T., e t a ] . ,

AIChE J., 24(3), 369 (1978).

(12) EPRI Contract RP 1656-1. Final report not yet published.

(13) Liquid Phase Methanol, Prepared by them Systems Inc., EPRI Project 317-2,
EPRI Report AF-1291 (December 1979).
(14) Liquid Phase Methanation, R & D Report No. 78, ERDAReport Fe-1505-2.
(15) Deckwer, W. D., et al., IEC Proc. Des. & Dev., 2]_~, 231-241 (1982).

-31-

ACKNOWLEDGEMENTS
The Chem Systems' research work ts under the direction of M. I.
Greene, C$! Research Manager. At Air Products the responsible
Research Managers ere S. A. Butter and M. $. Chen. Lead engineering performers at AiT. Products a~'a D. J. Si]kworth - Project
Engineering, T. R. Tsao -Process Engineering, and J. L. Henderson LaPorte Operations. Commercial support at Air Products is
provided by W. J. Keller of the PSG Synfuels Department.

-32-

ATTACHMENTS
Exhibits 2 . 3 . 1-1
2.3. 1-2
2.3. 1-3
2.3. 1-4
2.3. 1-5
2.3. 1-6
2.3. 1-7A
2.3. l'-7B
2.3. 1-8
2.3. 1-9A
2.3. 1-9B
2.3. 2-1
7.1. 3-1
7.2. 2-1
7.2. 5-1
7.2. 8-1
7.2. 8-2
7.2. B-3

E. P. HolleyJ
Project Man~,~ger

K]osek
Manager
~J J.Program

"

i'

-33-

ATTACHMENTS

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PAGE
1 of 2
DA'rE
!/.29/82
REVISED

EXHIBIT 2 . 3 . 1 - 6
CENTRIFUGAL PUMP S P E C I F I C A T I O N SHEET
~USTOMER APCI
YENDOR
Bv Elec. Mech,
ENERAL INFORMATIO N
i.
I T E N No.
,
2.
No. REQU.',RED

UNIT LP.Me0H PDU

S l u r r y C i r . c u l a t i o n Pump

'i'

4',
5.

.. I 0 . 5 0 A &B.

Two ( 2 ) - one .on,jj;r.eam & one spa't~e

T,YpE

UOUS.
DUTY ( CONTI~UOUS

INTERMITTENT )

SERVICE

',R0CESS

_ 7,
8.

..... 2 3 ,

25,
- 2 6 ,
__2?.

and hot o~l-catalvst slurry

"LiQuid E n tra in e d Mo d e ~
HvdrocaPhon Flutd-Catal w t
S l u r r y & Di ssol ved Syngas &CH30

LiQuid F l u i d i z e d Mode

INFORMATION

*Hydrocarbon Fluid & Dissolved Svnaas+CH~0H .

FLUID
CORROSIVE. COMPOUNDS

Minimum FIowGPM
Solid ....C,oncentration".Wt,%

HYDRAULIC

2z

Continuous

".',To
10 q~rculate
q~rculal;e hot o i l

9,
SOL z DS
O.
TEMPERATURE. OPERATING. ~F
11,
TEMPERATURE. MAXIHUM. ~F
I I~
VAPDR PRESSU.RE. OPERATING
'1_3'~. . S P E C I F I C G R A V I T Y . OPERATING
. 14,
.SP.EC1FIC G R A V I T Y , a .E0F
....I S .
V I $ O S I T Y , . . OPERATING
....
I~,0,
_VISCOSITY. a 6 o ' F
.....
1i 7,
NORMAL FLOW . GPM
__:
18,
MAXI MUM FLOW .. G.P.M

i 1~,
20,

PROJECT NO. 87.7-1533

. . .

Metal oxlde~ nnwder-~-50/~',~.

None
430~'530
550
@5300F,

430~530
55O

n~ta

~4R0?F"
~4Rnop .~p~
CPS
20U

5 ~ a t ' d wlH~
0.63
~,R~
0,7
6

250
150D.

0.89
1.15..
] .0
9
2O0

,:

INFORMATION

NPSH REQUIRED
...
B}' E!ec. Mech.
NPSH AVA I.LABLE
..
SUCTION PRESSURE P S I
..... 495/695/895
DISCHARGE PRESSURE P S I
545/7_45/945
HEAD REQUIRED PSI
50 = 185..ft. @ 480F
HEAD AVAI.LABLE PSI
A v a i l . Condensed Oil f o r Seal F1ush.'~PH@280F. Min/Nr.x= 0_l/1.

M3X_ _~lllPrv Cnn~Lit~nns

250
33 Max..{8~ by vol. @IO0F
~6% by .vol @480F
Bv Elec, ..Mech,
49516951895
54517,451945
50 = 1 3 0 , f t ,

@ 480F

(1 1H).7

28..

~ONSTRUCT ION
_~9,
MATERIAL OF CON$.TRUCTION
UON~.TRU;T.IOI ............
_CONNECTIONS
{ I N C L U D E F I G , R A T I N G ) 3-117" ~ n l 3 - 1 / ~ " n - ~ nr_hu vpnHn~
,. 30.
PACKING AND/OR SEALS Seal fl,Jsh requirement sh~uld'b~-min~mtz~d-tn i ~
J 31,
i,

" ~2.
33,
34.
.~..35.
,

IMPELLER TYPE.

if_possible,

th~n N_I RPM

The use o f water as supplment seal flush sho.ld

STUFFING BOX
0nlv be considered as the l a s t alternat~,ve when nther m~an~ tn
SMOOTHERING GLAND
provide adequate seal f l u s h f a i l .
Vendne shnuld ~ n e c i f v th~
MANUFACTURERS MODEL NO, desired Q u a l i t y o f .,;eal f l u s h _ a l l n w a h l B ~ n l i d lnRdinn:
1

oartlcle ~iz~: etc.

~,,

"IpRIVER
.[. 3 7 .

TYPe

FI p c t r ~ r

38.
39

CURRENT C H A R A C T E R I S T I C S
MOTOR C L A S ~
R~M & HORSEPOWER RATI'NG

41,

PHP B REQUIRED CAPACITY

MANUFACTURE MODEL NO.

4;~,

M,~tnr

FORM 8 2 4 3

(REV.

11/75)

*See attached Table I

SPECIFIED BY

T. R,. T~ao I / 2 g l R 2

SPECIFZCATION SHEET

2 of 2
29 Januar? 82

For Slurry, Ctrcul,~tton Pump :0.50 A&~

EXHIBIT 2.3.1-6

RELEASED FOR PROJECT

I
.'
:,ROPERX Or .zTco

ox,

1..Composition - (72I pin'aff|nlc, 28I naphthentc)

Component

[ 1414"C1]5
C16-C17
C18-C19
C2o-C21
>c21 ..
Sulfur

S
15
20
2S
20
lS
1 ppm

Vtscostl~,
Kinematic - 4.2 cSt 0100F
Sa.vbolt
- 40-43 SUS GIOOOF

3.

Vapor Pressure~O.OO2mmH9 0100F

4.

Speciftc Gravtty= 0.810 0 60F

Denstty
= 0,810 9/cc @IO0F

5.

~nttiai Botl|n9 P o t n t - 471F @ 1 a ~ .

6.

$ o l u b t l | t y tn Kethanol:
7.2 wt. ~ o t l ~ O wt. ~ ~20 tn methanol and 120F
2.9 wt. ~ otl @ Owt. ~ H20 tn methanol and 70F
2.1 wt. ~ o t l ~ S vt. S H2O tn methanol and 120F
(Insoluable In.Water)

7.

H.W. - 2 6 8 . 5 l b . l l b ~ role

8.

ASTHPour P o t n t - -35F, max|mum

9.

Surface Tens|on = 32 dynes/cm. ~ 6 8 F

= 13 dynes/cm. ~ 4 6 4 F

10.

ASTHCloud Point = +40F, 14axtmum

11.

Saybolt Color - +30

12.

Odor or Taste-)None

13.

U.V. Absorbance-~ Passes FDA Requirements

14.

USP Actd Test-) Passes

~K
29-1-82

PAGE ....
DATE _

COMPRESSOR SPECIFICATION SHEET

REVISED

EXHIBIT 2.3.1-7A
~CUSTDMER APCI
VENDQR
B.vE1ec. Mech.
GENERAL

INFORMATION

,,,UNIT LP Me0H PDU

Feed Compr'ess6"r

one {I )
Reclprocatlng.Compressor expected
Continuous
Compress Dry Synthesis Gas (Hp, CO, C0p, Np, CHa)

DUI.Y.
5,
~ E R V I C E ..
PROCE.SS INFORMAT I 0'N

6.
7,
8.
9,

! ~10.

11~
,t2,
%).
14,
~s,

1
l
I

S.ynthesi s_Gas
(see pa~e 212 I
". (see page 2 / 2 )

FLU/D
COMPOSITe.ON - MO~X
AVERAGE MOLECULAR WEIGHT
CORROSIVE ~QMPQUN~S
R E L A T I V E HUMIDITY
SUCTION TEMPERATURE F,
SUCTION PRESSU.,.R.R - PSXA
DISCH,A~GE PRESSURE - . . p S I A ~
DISCHARGE TEMP~RATUR~ " F ,
NORMAL SUtT~.0N FLOW RATE

A... A..F,M,
...B, POUNDS/H0~R
16.
STANDARD CUBI.C FEET/MINUTE
17.
COQL, IHG WATER SUPPLY F,
18.

COOLING WATER RETURN F ,

~o.

P/~V

PROJECT NO. 87-7-1533

'111113

i ITEM NO'
.....No. REQUIRED
!

I/2
29 January 1982

~ON$TRUCTION
20.
.T.YPE OF COMPRESSOR
. 2__!_. . M A T E R I A L OF .CONSTRUCTION. ,
SUCTION CONNECTIONS
22.
,,23.
~)I.SCHARGE ~ONNECTI_ONS

7% (7~O'4LB Hp'0/]b .o_.1

= Gas, D.P. = 27'F.')
100 Norm., 125 Max.
150
150
150
550*
750**
950***
C
,,,,

see paqe 2/2

90 Nor.~.105.Max, @ 43 psiq$
120 Nor., 105 Max. @ I0 psiq~

~,
'

2,5,.
ii~l 6 ,
27~

i 28.
29,

3o,

2 - 1 / 2 " or by vendor

....
2-l/2" or bv vendorlinterstage r e l i e f valve inlet flanae
2-I/2" with 450 psi 9 design pre~s

TYpE .OF ~UB~!CATION

COMPRESSOR SPEED
Intercooler & rsrycle cooler design for 100% recycle
AFTERCOO~ER R~OUIRE D
COp.F ~TAMP FOR AFTERCOOLER Yes. ASMESec. VIII
Intercooler by compressor vendor: recycle cooler by proce
AFTERCOOLER SURFACE FT2
By vendor **Coolin9 water Is a premium
WATER REQ~XREPGPM
Minimize coolin 9 water requirement
Utility

~CCESSORXES
3] .
F I.I~.TER
.
32.
CLE.ARAN~ POCKE.TS
33,
UNI~OADERS
.. 34~

3S,
36,
D_RI VER
37.
TYPE
POWER ,CHARACTER I__STI $
_3B
39.
. A0,
...
41.
MOTOR__CLAsS
42,
MD.TOR TYPE
.........
43.
POWER F A ~_T_QR

.44,

M, G,. SE.7

45,
~ T -A R TE R
__~46, . T y p e ._
-. 4 7 .
ENCLOSURE
48,
.....
FORM 8 2 4 0

(REV.

2/76)

Flectric

Mntnr

.+Vendor to specify Lhe i n l e t condition o f recycle cooler

~Design/Elec.Mech, should confirm that the ma. di~charoe
pressure,..950 nsig = 935 osig ts att~inoble when the
r e l i e f valves o f the compressor is set at 1000 psig,.
. . . . the design pressure o f the PDU.
*For cases operating at 500 psi 9
**Foe c~$e~ operatin 9 a t 700 P$ig
***For cases operating a t 900 psig
.... ~ProJect should confirm temo. and o r ~ = * e - n~
cool in 9water in w r i t i n g . "
~
- "
T. R. Tsao

1/29/82

pag~ 2 of 2

EXHIBIT 2.3.1-7A
LPHeOII PDU; FEED COHPRESSOR.01.10
87-7-1533
For Lurgt-type Reactor'
Feed, Hol
H2
CO

For KT-type Reactor

.....Feed, Hol

~ r Balanced ~esh
Feedp ~ 1 . . .
65 N 6 7

50 ~

63

38 ~

25 N

29

49 ~ 6 0

30~33

0~2

0~3

CO2

4 ,,~, 10

N2
CH4

0 ,"~ 15

trace

02

L|ghtest
Hol %

51

0 ~1

~-'1

Heavies~
Mol

Lightest
Hol ~

99.99

trace
trace

trace
trace

0 .,",-.~5

N2
Hol

Heaviest
Hol

Lightest
Hol %

trace

Heaviest
P~I Z

H2

63

50

51

38

67

67

CO

29

25

49

60

33

29

CO2
N2

4
4

1O
15

99.99

CH4

--

._:160

._:100

02
Total
H.W.

Suctton
Flow Rate

12.3

100

16.6

.
100

14.7

18.5

Trace

100

I00

10.6

100

11.1

28

Hfn

Nor

Max

Htn

Nor

Flax

Hin

Nor

Max

Nor

Hax

18
12
220

60
40

100
67

18
12

40
27

55
37

18

50

80

20

12

34

54

13

30
20

870

1660

265

660 1020

190

540

890

560

840

SCFH@1 azm.
70OF :~
i 16

387

644

116

258

116

322

516

129

193

lb-mollhr
A.C.F.H.

lb/hr

354

386.6B SCF/lb-mol
T. R. Tsao
1129192

COMPRESSOR SPECIFICATION SHEET

EXHIBIT 2.3.1-7B

ICUSI'OMER APCI
VENDOR
By Elec, Mech.
~GENER~L
B

NIT LP He0H PDU

PROJECT.NO,
ecycl e compressor
01.20
one (1)
Reciprocatinq Compressor Expected
, ..Cont.lnu0us
Compress Rec.ycle. Gas

INFORMA~IDN

~I

ITEM

2.
3.

NO. REQUIRED
TYPE

...........

NO

PAGE
DATE _
REVISED

....

SERVICE

1/2
2 9 aanu:ary _I982

87-7-1,533

PROCESS IHFQRMATIOH
, , 6~
FLUID
.Unco.n.ve~ted S.ynthesis Gas or Nltroqen
CDMPO$1TION - M'OIL~
(see pa.qe 2/2)
....
7,
8,,
AV.ER.AGE MO~_EqUI_AR WEIGHT .. (see pa{le 212)
CORROSIVE COMPOUNDS
H~0,=C0~, CH~0H., CpHsOH.& Hiqher Alcqhol s
RELATIVE HUMIP.ITY
100~...Saturoted
wlH?0 & CH30H
11
SUCTION TEMPERATURE "F.
II0 Norm.. 125 Max.
I~,,
~UCTION PRESSURE - P.C,.IA
i~85"
685**
BB5**~
I ] 3.
950
DISCHARGE PRESSURE -- P.5~,~" 550
750
141 DISCHARGE TEMpERATUR~ " F ,

t,'o:

.....)61
17,
...18,

B.
POUNDS/HOUR
I
STANDARD CUBIC FEET/MINUTE
COOLING WATER ~,,UPPLY F..
COOLING WATER RETURN F.

i C0NSTRUCT..ION

see page 2/2

90 Nor.. 105 Max. @ 43 psi-q

]20 Nor.. 105 ~ X I @ 10 DSig~

..............
.
.
.
.
.
.
20, TYP~ OF COMPRESSOR ...........
21.
MATERIA~ OF CONSTRUr'C~;N
22.
SUCTION CONNECTIONS.
2-112, 10T b.y vendor
2-I/2" lOt by vendor
...23... DISCHARGE CONNEC~IONS....
24. TYPE OF LUBRI.CATIQN
i 9. ~ P , / C V

25,
COMPRESSOR S~EEO
26.
AFTERCOO~ER REQU.IRFD
27.
~0OE STAMP FOR AFTERCO~LER
i~B.
AFTERC.QOLER SURFAC~ F T ~ _
2~.
WATER R~QUIRED GPM
....
30.
IJtilitv
ACCES$0RXES
31,
F|~TER
3~,
CLEARANq~ POCKETS
.331
UNLOADERS ....
341
35,.
361
D_R,I.VER
37,
TYPE
IIW~R~.CHARA~ERXSTICS
'__38,
POW~
39.

Onlv reautred for the compressor recycle stream. Desiqn

Yes: ASME_.SQc.,.VI I I
100% Rec,vcle
By Process. vendor t9 specify i n l e t condition o f rec,ycle
By vendor, **C.oo..ling water is a premium
cooler
Minimi.z...e.~;O01i n9 water reaui rement

F1 ectric Motor

401
41.

42,
4,3,,

MOTORCLASS
MOTORTYP,
POWER FAC~_!OR

44,

M, G, SET

46,
47,

TYp E
~NCLOSURE

45~
~TARTER

4.81
FORM 8240 (REV. 2/?6)

~Desiqn/Elec. Mech. should confirm that the max.

discharge pressure, 950 psia = 935 psig~ is.attainable
...... when the r e l i e f valves of...the compressor is set at
lD00. p~ig, the design pressure o.f the PDU..
*For cases operating at 500 psig
**For cases operating at 700 psiq
.***.For cases operatinq at 900 psiq..
~Projec~"should confirm temp. and pressure of
cooling water in writing.
T.R. Tsao

page 2 o f 2

LPHeOH PDU; RECYCLE COHPRESSOR, 01.20

EXHIBIT 2.3.1-7B

87-7-1533
For Lurgt-type Reactor
Feed, He1Z

For KT-type Reactor

Feed, No1. g
25t-~51

40N50

60-~-'70

20~-'25

H2
CO

45~63
22~29

CO2

ION15

1 ~

N2

15 ,,'~18

0 ~ 2

CH4

15 "~'18

CH30H

..

1 ,,v2

C2H50H

(200 .,,~1ooo ppmv)

02
Nitco #40 Oil

trace
trace

Ltghtest
Hol %

Heavtest
Hol ~

10,"~20

99.99

trace

lO~v20

1 ...~,2

1 ,...,.~2

ppmv)

(0~1200

(200 . ~ 1 0 0 0 ppmv)
trace
trace

(200~1000
trace
trace

Lightest
No1%

Np
HoT %

10 ~ J 2 0

(0~1200

( 0 . , v 1 2 0 0 ppmv)

H20

For Balanced Fresh

Feed, Uol ~

Heaviest
Hol %

Lightest
No1%

ppmv)
ppmv)
trace
trace

Heaviest
Hoi %

N
Ho~ %

H2

63

45

51

25

67

40

C0

29

22

4g

70

33

20

CO2

]5

19

N2

16

19

99.99

CH4
CH30H
C2HsOH
H20

02

..

..

..

_~-

--

100

100

1 O0

100

100

100

Total

.
2
1200 ppmv
1000 ppmv

H.g.

12.3

18.8

.
2
1200 ppmv
1000 ppmv

14.7

22.1

.
-

2
1200 ppmv 1000 ppmv -

10.6

trace
100

20.7

28

Suction
Row Rate

H|n

Nor.

Hax

Ntn

Nor

Hax

Hin

Nor

Flax

Nor

Max

lb.mol/hr
A.C.F.M.

50
*

150
*

300
*

50
*

100
*

250
*

50
*

150
*

300
*

150
.

330
*

2333

5640

735

1840 5525

530

2348

6210

4200

9240

967

1933

322

644 !511

322

967

1933

967

2127

lb/hr
615
SCFH @1atm.
70F #
322
*A.C.F.N. =

(Suctton Flow, Lb-HollHr) x (10.73) (460 + S u c t t o n T~ F)

60
(Suction Press, psia)

:J:386.68 SCF/lb-ml

T. R. Tsao
1129/82

VENDOR:

EXHIBIT 2 . 3 . 1 - 8
HEAT EXCHANGER SPECIFICATION SHEET
12 1 Customer

APCIIDOE LPMe0H PDU

[%ddresa
LaPbrte, IX
4 1 P~ant.._Local,on
.~L~c.~-~,
_,
S I Servlu of
~I l i t e r H e ~ l : x r ~ h a n n m r
~:~-~
"
~vp,
Y.or/V..) V e r t i c a I
? . Surf/Unit (km,/Zfl. BR ~t 2.
S= r t : Shelle'Un'lt
l

I~ofetence No.
Pmposm! NO.

9 Fluid Allocation
Ailo
I
]0 Fluid Name
I1 Fiu!.~ qumntlty.,!o~.1
i
12
Vapor (in'Out)
I
,,, Uquld
13
14
SIeo m
Water
]S
16
Nonzondenxable
17 Temperature (in/Out)
t8

.I~i

tJlitv

....

Serlisl
sq,,FI

5L~*

T,,b, sad, " '

O i l / C a t a ] v s t S l u r r y ',
75~ 90
0
J
0

0il

55~.o

~g~qn

7~.~qn

.,

~9

Cp

"

_ _ _ ~ ~
,

~'7"~-~
.... 0.048
.

5.65

o...o~_l

M l

- 40/100

" .5

o~o_

ma X . }

(6" 0

4.~Q/_95O

___~__~___

5 ( I 0 max..}

(M!n.) Hr. f t ~ / - E . T D -

~17_
_,
(1_80

258

..... z e r o

25 [ Inlet Pres~
pressur, (minlmax.~
e,l,l
26 _'V'elocity
it~ m.inimum-(not~_3~_F.t.'s]
27 Pressure
.re IOro~, A,,o.. Cole.
~--~i7

51.o.

47
_
A.AD

O_fir~

0-~5

Btu/Lb *F
~,HrS.," F _ _ _ _ ~ 0 ~ 8 _

p c t sSi
. 1~s

51[.5

55~,3'

. Lh/FL,

Fouling:
,, R~
...lst."c'

Parallel

)9 Viscosity, Liquid,
20 Molecular Weight, Vapor
21 Moleeu,a.,Wa'=ht, L'iquid
22 Specific Halt
~e..., Cnndu~l.l,~
.,.

28

ConneCted In
Sut//Shzll (m""_./Eff,)

6rlpgrl

Ar)p~rt

ty

m~TSTb-~
.....

6OZZO

LblHr

O-- l

....... 'tern No. 21-20

PERFORMANCE OF ONE UNIT

Shell Side

0.,.3"/22182n.,.

".~..-l~-

~.uo3

._

29 H o l t Exi:~
Exchan,ed
1 23
~
note..L~
etulHr: MTO(Correctem
"F
Trinzfor Rate, SOtNit:t.~,
t = . = ~
Cle~'k
e t ~
]1
CONSTRUCTION OF ONE SHELL
Sketch (Bundle "Nozzle Orientation)
32
Shell Side
1
Tube Side
33 Oeslgn,'rest Pressure
Psi~ " ~ 8
/
]ODD '
See sheet 4
34 Design Temperature
" F,
(~0~)
35 [NO, Paste2, p e r Shell ,
l
] max _
36 :Corrosion Allowance
In:
bY desiqn
by destgn
In
4 m.*
~ ll'k
3? Connections
S!zo &
Out
~"w
~,'*
38
39
Rating
Intermediate
40 X . b , No
42*
On 3 ~ n : T h k (M~'AvE)
1 GG/In" LQngth ..Z~_ It:..
~
~41 Tube T_.~ype14_.~_~,~.l~[~.~.0_..V.~.t.f,,yl~_____
Material
C.._SteeL
I
42 s , , ,
C. S t e ~ l " NnmeoIN*
In She---1"~--Cn~r.
.
.
.
(,ntel.}mtm~.l'
43 chi..,,orBnnne,
Coqlc~l
44 "rub_aLbeit:St _utionary
H e a d Coy__e.r_.__._ . . . .
45 ._Final_.ing
46 Baffles.Cross

[ s e e note ~
.

channelco,r

._.

Tubeshezt-Floetinl~
' Impinemznt Protection
_ , , % Cut (Diam_/Arn)
Seal Type

Tx~j_b~_~endor

47 Baffles.Long
48 Su~portl.Tube
49 Bypass Semi Arrmnsement
50 Expansion Joint
St e,v'- Inlet Nozzle
52 Gaskets.Shell Side
53
.FIoMInB..Heed
b4 Code Require.___nixn_ta
55, Weight/Shell
..
56 Remarks

U.Bend

5micing: /

Inlet

In,

Type
Tube-Tubeshmtt Joint
Type

Bundle EntranCe

Bundle Exit
Tube Side

Filled with Water

T[MA Class
Bundle

I.

58 a

59
61 ~

.,

~)1978 by t:~e Tubular Exchanger Manufacturer Association

FORM 8304 (RV. 12180)

Specified

by:

L. W. Bonne11 22 Mar 82
T. R. Tsao 22 Mar 82
P~E

I OF 2

EXHIBIT 2.3.1-B

H E A T EXCHANGER SPECIFICATION SHEET

A D D I T I O N A L INFORMATION REQUIRED BY A I R PRODUCTS & CHEMICALS, INC.
5.1
7.I

_Sir'vice of U n i t
qNumber Qf Units

............ A D D I T I O N A L P R O C E S S D A T A
~- Coole~'
nr
Heater~'~
Rebnller

Vaporizer

.iC(~nden~

~:~iquJr~ nnP_ ( 1 ~

.....

Shmll Side
OUT

IN

> gt I ( l F
oF
II
17.1 _ . r ' f ~ m ~ / B u b b l 0 Point
LI)lt~Cu. Ft.
t8,1 J:)anlltv, V/',,
Cp
19.1 Vlscoslt~ V/1.
Lbl./M~ll~'
20.1 Molecular Weight, V / L
Btu~Lb.-'F
22.1 Specific Hoat t V / L
~AJ F t . ~ I b ' T ~ F t , O F
23.1 T h e r m l l C o n ~ u ( : t | v i ~ l l l v / L .
" 1~'0
25.1 t41ghest (:)piratlng Prelsufe~ psl a
3.1 ~
Ft~,
26.1 . VelPcltv. in/Out
30.1 Pleat T r l n ~ e r Coeff~[~an 13tu/Hr. Sq. Ft. OF I
30.2 ~rrAnsfAr Rate F~UV~, 9tu/Hr, sq, Ft~l= fl0mt n i l
~l'lm'J t l r ~ l
~0.3 T r a n s f l f R i t e C A A n . 9 t u / H r , S q , F.t, F
Includes 40% Process
=0A Transfer Rate Servlr.~. Dtu/Hr. Sq. Ft. F

IN

I '~

,, O U T

Saturated Liquid
I

II

ag~
39.~

60',~
BB*
5afey

220*

~cor),,,,,43"

ADDIlTIONAL MECHANICAL DATA n

, Vents= Numl~r
S'lze & Reran0,
Dr|ins: Number
Size & Rating
Rupture Discs: Number
, . Size & Rating ....

Additional Connections,.
....

3+.3
,

40.1
40.2
403
40A
40.5

950

ii, ,m

Finned or ~xt~nd*<l Surface-. ' t ' v ~

Surfact,or Bundle Mfr.
Fin Count
FPl
Fin Thick
Bunlle Linden I
in
Hel0ht II
In

Area Ritln A o l A I
Model & Description
I It
Dmpth

In

Fin M l t ' l .
Face Area

Coating
Ft~-4

Seat Type..& ArranBement (OelcrlbA)

,,,,.

44.1
44.2

T U ~

S h ~ t

..,,

Stationary

MltArlll

ThickneSs

In.

Corrosion Allowance

In.

I~ i n l t l r l a

~l~lltnrlel

"rhtr.knn.

In.

P-nrrntlnn

In

Baffle Thk:kn~u

Diametrical ClearanCell
Bunel! to Sh,lll

In.

In.

Allnw.nrm

Mothod o1 Fastening (Describe|

Affloto halt

file Hol

I;)lm~fter. Peleorated PlAte or Condensate Removal Device "l"vnl & Descrlutlon:

Lifting Lugs
Cleaning RequlrGmentl
~.~?~.~ulrnmentR
j E v c h k . ~ OrtwlnQ N u m b e r
Detail Method & RatFno I-rent "f'rinsfar Coefrlelen)
Detail Method i t CalCulltlna MTD
RemarkS;.

I Paint

SEE REMARKS PAGE 3 ....

i II

FORM 8304-1 (REV. 12/80)

II

,,I

PAGE2 oF 4

L. W. Bonne11 3/22/B2
T, R. Tsao 3/22/82

L. W, B o n n e ] l
191~rch
1982

EXHIBIT 2.3.1-8

21.20 Slurry Heat Exchanger Remarks

87-7-1533

'l.

APCI Design Case: EK-2571 with 150 MBTU/hr. heat leak.

process duty safety facto~r has been applied.

2.

40 percent

Shell and Tube flowrate design ranges (gpm)

Min.

Shell (oli)
Tube {slurry)

I00
200

Normal I.~x.
200
200

210
260

Hinimum tubeside velocities must be maintained between 5 and lO ft/sec

for above flow range.

Due to slurry service and erosion concerns, one tube pass strongly
recommended, with vertical upflow of slurry In normal operation.
I n l e t (front) head should be cone-shaped, to eliminate dead spaces
where solids can gather.

Data marked with an asterisk ("*") on pp. 1 & 2 are given for estimate
purposes only, and do not constrain the vendor's design.

See p. 4 for sketch of 21.20 and utility oii system. 21,20 will
function as both heater and cooler. Design Eng. and the vendor to
ensure that exchanger is designed to handle large shell-to-tube
temperature differences.

7.

Catalyst particle size (typical): 60 microns

Page 3 o f 4

Page 4 of 4
UTILITY OIL SYSTEft

q~O

~,

........
1 5BOF,J
011

"1

EXHIBIT 2.3.1-8

21.4o

cw

lOOF
J ....

140F~

cw ~
120F - .

Q = 750 MBTU/hr
I (~
BTU .
UA (min.) = 2300 h--~

21.20

q : 750 MBTU/hr
UA = 19,230

200 gpm
,,

i.

10.53
I.

C~se EB-X954 (deslgn case for 21.40)

Y
T

158F

483F
250 gpm
~6 vol. pct. solids
950 psla

26 kw
)"~',s oil system heat leak
Q = 88 HBTUIhr)e'=
. . . . .
~I
%=

"5 40

.,
Sl urry

F
cw

200 gpm~
554OF "
(290C)

cw '~

q=o

21.20

q = 88 NBTU/hr
BTU .
UA (min,) = 2500h--~ ~

!
; 10.53
2. Ca~eEK-2571 LdesTgn-c~se-~o~ 21.20)

T516F
200 gpm
~O1 vol. pct, solids
450 psia
LWB
5 March 1982

EXHIBIT

2,3.1-9A

27.10 LPMeOH REACTOR

(LIQUID-ENTRAINED OPERATING MODE)
OUTLET
~

CATALYST

4"

c_

__]
15 FT.

4
r~ ....

.-.

-22-1/2'" '

'"

<

15-1/2"...
)
VAPO-RURI NG SPA RG"ER ~'~

~'0 o o o o o ooo~p,~ooo

oo

1 FT.

DEF LECTO R~=~'~ 8" " - - ~ , ~

PLATE
I
II'
CIRCULAR)
4"
.

(-- 4'-.,~

,=221

____,L

CATA L Y S T ~ ~ ~ "
tll~
OUT
DRAIN

I'
VAPOR INLET
I'
SLURRY INLET
LWB

12 MAR. 82

EXHIBIT 2.3.1-9B
LaPorte LPMeOHReactor Operating Parameters
Case EB-X954
Case FB-4930
(Max. Production, (Max. Production
Liquid-Entrained) Liquid Fluidized)
Superficial Vapor Velocity, ftlsec

0.39

0.26

Superficial Liquid Velocity, ft/sec

0.21

0.17

Space Velocity, acfh/ft 3.

Space Velocity, scfh/ft ~
Space Velocity, Std. l i t e r s / h r - k 9 cat oxide

Catalyst Loading, lb
Catalyst Particle Size, inches
Catalyst Particle Size, microns

93.6
3270
9770
909
0.0024
60

62.4
2300
3975

1387

0.107
2718

* i t 3 refers to reactor free volume.

LWB
16 April 1982

EXHIBIT 2.3.2-1
~neerlng

Specification Activity . for Process Equlpment/LaPorte LPMeOHPDU

Equipment
Item

Process
Specification

Mechanical quotations Existing

Specification
Received Equipment

O1.1010~ .ZO Feed/Recycl e

X (Note 1)
Compressor
X
Of.13 Feed Surge Tank
X
01.14 Feed Compressor Recycle
X
Cooler
01.24 Recycle Compressor Recycle
Cooler
X
02.50 Sulfur Trim Bed
X
X
02.51 Sulfur Trim Bed A f t e r f i l t e r
02.81 Catalyst Reduction V~ssel
02.83 Reduction Gas Heater
X
02.91A&B Water Pumps
X
02.92 Water Feed Tank
X
I0.50 A&B Slurry Circulation Pumps
X
I0.52 A&B Condensed Oil Pumps
X
I0.53 A&B Hot Oil Pumps
X
10.54 Process Oil Make-up Pump
X
15.40 0i1 Heater
X
21.I0 Feed/Product Exchanger
X
21.20 Slurry Heat Exchanger
X
2i.30 Product ~s Cooler
X
21.40 Oil Cooler
X
21.53 Hop Seal Flush Cooler
X
22.10 Three-phase Separator
X
22.II Methanol Degasser
X
22.12 Demister
X
22.50 A&B Side Stream Filters
X
22.51 A&B Condensed Oil Filters
X
27.10 Reactor
(Note 3)
27.13 Primary VIL Separator
X
27.14 Intermediate V/L Separator
X
28.I0 Product Storage Tank
X
28.20 Process Oil Storage Tank
X
28.30 Slurry Preparation Tank
(Note 4)
28.40 Maintenance DumpTank
X
28.53 Oil Expansion Tank
X
Total Items = 33
NOTES: (1)
(2)
(3)
(4)

Total = 30

X
X

X
X

X
X
X

X (Note 2)
X

X
X
X
X
X

Total = 16

Total = 2 Total = 15

Two process specifications issued, counted here as one for multiservice

machine.
Existing vessel D-lO1 considered marginally acceptable for use on
LaPorte LPMeOHPDU. Evaluation of modification costs versus new
equipment fabrication must be made,
Process specification covering LaPorte LPMeOH reactor based on
existing LPM vessel R-IO1, delayed pending determination of internals,
Slurry Preparation Tank required for liquid-entrained modifications
only. Process specifications scheduled for 25 June 1982.

.............

..............

S:teLUl s~6 I ~ X I W . ~

'Iliiii. !iii
~

.,-~

,-'~

xr,.

P
I

Ill

II

nn,lnl

,I

II

II III

II

I ill

i I

rd

n~
.f-

U~o;

~o-

l,j .F. i w

. . - - o

,p,,, j , ~

~ I ~
iil

bJ
m

lu

0
n~.

b.

u
~'bJ
-JI-

!I

n-

e~
I ~
u

~E

, ~L,

~:;~,,-~,/

fr

ji

l
a

W
mmm

I~

I m ~'j~
m
I ~ -q

~
I~

, 0
;

b,. ~-a i I g

hi
=j v

Z
0
I

---'II
1 0 t::~ I - -

i ~r

.~ . . I . r ' , , J

--

~D

,~.~

~__.~
IAI

'

....

Fql

[~lster
VT-I01

*W
Slurry Feed ]
Tank
Surge
Tank

Dryer

CP-]02

Trace.__r

I'|

Slur.
Preo.
Tank

Ro~ry Compressor

wr~

.,.%

~;~ CP-IO0
~ t n Circulating
S l u r . Pump

CP-I01

51.try Feecl
Slur.
Pu,~
Transfer Pu~
"~
I ~. LIqu~d
C l HT-lOO

i;~a.k

S l u r . Transfer
~USTID

T..._.._~" FTnal TTI ter

. .T.~.~
~

E.~HIBIT 7 . 2 . 5 --

CN(ll ~;TST[II|II1~.
-w v , ~ , . q.'.

~.O-FLOW . ~ R O D T . ~ ;

-.,.
U.;T
3

IHg13H

"IVlJ.INI

.-I0 IN33~3d

a.IHgl3H

()3"lJ.J.3~

Q38

0
0

0
J O ID

. 8t'-

=.. ,~ o
tD

=,

,I a

=o~

~g.

oo'.
oo=

,.=,
~.

X
X
X

-...

..o

Iv,,,,e

oU

PiJr~

X
X

2.S-I

Ot

0
0

0
U

X
o

--0

II1
X
!

I
0

i
0

I
0

0
!

N30~13cl

i. NOIS~I3ANOO

O0

.,

CHEMSVSEMSINC.
EXHIBIT 7.2.8-2

C$I LIQUID-FLUIDIZED PDU RUN CHRONOLOGY

Page ! of 2

WITH CATALYSTRTl/OF12-02

Date

Cumulative
Reaction
Time
Time
(Hours)

2116182

0900
1600

2117182

--

2118182

0
0

Milestone

4.4 K9 exided catalyst (R71/OF12-02) loaded into reactor.

2% H2/N2 reduction 9~s in; catalyst heating to 1BOOt.
Reduction continuing

Two Al203-filled guard chambers put on-line.

0300

0400
1100
1200
1300

0
0
0
0

First sight of H2 break through; a total of 45.0 9mol

H2 has passed over catalyst at this point.
Begin heating catalyst @ lOOC per hour to 240oc.
Catalyst at 240oc.
Catalyst cooling to 200oC,
Oil circulating on reactor by-pass; heating to 200oc;
pressurizing system to 3500 kPa with nitrogen,
Reactor f i l l e d w/Witco 40 o i l .
0 i l flow started through reactor; f i l t e r s placed in-service.

1630
1745

0
0

2100

Oil through reactor @15 liters/min.

Fluidization tests at various oil flow rates at 7000 kPa
and 250oc.
Gas flow started through reactor.
Fluidization tests @ 15 liter~/min oil and various gas flows
started at 7000 kPa and 250oc.
Gas fluldization tests complete and establishment
of run conditions.

2121182

0800

11

At steady-state conditions of 3000 VHSV, 7000 kPa, 250oc;

draining 2L methanol product each hour; fluidized bed height
taken every 4 hrs, and settled bed height taken every 24 hrs.

2122182

180q

45

Change filter.

2/23/82

1400

65

Change filter.

2126/82

0230

125

Change filter.

2128/82

0230

173

Change filter.

312182

1400

233

Change filter.

3/5/82

OlO0

292

Change filter.

318/82

0500

368

Change filter.

2/19/82

1630
1830
2120182

0600

I000

CNCM SVSTEMSIMC.
EXHIBIT 7.2.8-2

(Continued)

CSI LIQUID-FLUIDIZED PDU RUNCHRONOLOGY

Page 2 of 2

WITH CATALYSTR71/OF12-02
Cumulative

Reaction
Time

Dat.___~e

Time

3/8/82

1315
1330
1400
1900

376
376
377
382

Switch oil pumps due to excessive leaking.

Begin process variables scan.
7000 kPa, 250oc, 2000 VHSV, 2/1H2/CO feed gas.
7000 kPa, 230oc, 2000 VHSV, 2/1H2/CO feed gas.

3/9/82

0100
0700
1300
1400
1800

3B8
394
399
400
404

7000 kPa, 270oC, 2000 VHSV, 2/1H2/CO

7000 kPa, 270oc, 4000 VHSV, 2/1H2/CO
Change f i l t e r .
7000 kPa~ 250oc, 4000 VHSV, 2/1H2/CO
7000 kPa, 230oc, 4000 VHSV, 2/1H2/CO

3/10/82

0100
0600
II00
1700
2200

411
416
421
427
432

3500 kPa,
3500 kPa,
3500 kPa,
3500 kPa,
3500 kPa,

3111182

0600
1400
1500
2000

440
448
449
454

3500 kPa, 250oc, 1000 VHSV, 2/1H2/CO feed gas.

Change f i l t e r .
3500 kPa, 250oc, 3000 VHSV, 2/1H2/CO feed gas.
Back to original conditions of 7000 kPa, 250oc,
3000 VHSV, 2/1H2/CO feed gas.

3/12/82

1130

469

1800

476

Start low C02-content 2/1H2/CO feed gas @7000 kPa, 250oc,

3000 VHSV.
7000 kPa, 270oc, 3000 VHSV, low C02 211H2/CO feed gas.

0200
0800
1200
1800

484
494
500

7000 kPa, 270oc, 4000 VHSV, low C02 2/1H2/CO feed gas.
Change f i l t e r .
7000 kPa, 250oc, 4000 VHSV, low CO2 2/1H2/CO feed gas.
Back to original with 2/1H2/CO feed gas at 7000 kPa, 250oc,
300O VHSV.

3/14/82

0500

511

Change filter,

3/15/82

1000
1100
1700
1800

540
541
547
548

211H2/CO feed off, K/T gas on-line.

Start K/T run; 7000 kPa, 250oc, 3000 VHSV.
End K/T run.
Shutdown; feed gas switched to N2; all heats off; circulating
through oil cooler on reactor bypass; depressurize system
and seal flush over 2 hr period; pumpoff when oil at 200OFt
cooling water left on overnight.
overnighto

3/13/82

(Hours)

490

Milestone

feed gas.
feed gas.
feed gas.
feed 9as.

230oc, 4000 VHSV, 2/1H2/CO feed

250oc, 4000 VHSV, 2/1H2/CO feed
270oc, 4000 VHSV, 2/1H2/CO feed
270oc, 2000 VHSV, 2/1H2/CO feed
230oC, 2000 VHSV, 2/1H2/CO feed

gas.
9as.
gas.
gas.
9as.

CHEM SVSTEMSIMC
EXHIBIT 7.2.8-3

CSILIQUID-FLUIDIZED
PDU VARIABLE SCANS: PRELIMINARYRESULTS

H2/CO
Feed

Ga__E~

Temp., C

VHSV*
L/HP.Kg

......
CO
__

Conversion~ %

._2_

C02_

2/1

7000

250

2000

33.1

34.6

3.3

2/1

7000

230

2000

31.1

33.6

61

2/1
2/1

7000
7000

270
270

2000
4000

29.8
23.8

30.0
24.2

1.5
4.5

2/1

7000

250

4000

24.1

24.6

5.3

2/1

7000

230

4000

20.3

21.4

6.8

2/1
2/1
2/1
2/1
2/1
2/1
211

3500
3500
3500
3500
3500
3500
3500

230
250
270
270
230
250
250

4000
4000
4000
2000
2000
1000
3000

9,4
10.2
8.7
12.8
17.3
17.4
11.9

10.3
10.5
9.7
13.Z
21.5
18.~
13.Z

1.9
1.7
2.3
2.3
5.2
0.7
3.0

*Based on weight of oxided catalyst (R7110F12-02) charged at start of run