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COAL LIOUEFACTION SUPPORT STUDIES

Tak I. Heat of Reaction of Hydrog*n

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ANL-77-6

ARGONNE NAT IO'L LABORATORY9700 Sou", ss Avenae

Argonne, i:., 3is 60439

COAL LIQUEFACTION SUPPORT STUDIES

Task I. Heat of Reaction of Hydrogenwith Coal Slurries

Task II. Heat Transfer Coefficient

Quarterly Report forOctober--December 1976

by

J. Fischer, R. Lo, T. MulcaheyD. Fredrickson, T. Cannon, and A. Jonke

Chemical Engineering Division

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Previous reports in this series

ANL-76-2ANL-76-47ANL-76-33

October-December 1975January-March 1,'6

April-Ju.ae 1976ANL-76-117 October 1975-September 1976

iIBLIO@RAPHIC DATA I. Report No. 2. 3. Recipient's Ace a.so. No.SHEET ANL-77-6

4. Title tsd Subiste S. fteport oe.Coal Liquefaction Support Studies 1977Task I. Heat of Reaction of Hydrogen with Coal Slurries 4.Task II. Heat Transfer Coefficient

4'9116 J. Fischtr, R. Lo, T. Mulcahev, D. Fredrickson, 6 '. Peforn5 O0'"snea'e'' Rept.T. Cannon. and A. Junke AML 77-6

9. Perform ng OtgSeease s Naee and A4deese I. Protect/Took /ork use, No.

Argonne National Laboratory

9700 South Cass Avenue I. c..esc/Greet No.

Argonne. Illinois 60439W) l-109-ENG;-38

12. Spessoreng Orgaasssseo Name and A4dtess 13. Type of Report a PeriodC Qovered uarterly ReporOc t . -Dec . 1976

11.

IS. Supplemeswary Notes

16. Absetsues

A development program is being carried out to obtain information applicableto the SYNTHOIL process for converting coal to liquid fuel of low sulfur content.This report presents information on (1) a calorimeter to mea-ure heat of reect ionof hydrogen with coal slurries and (2) the construct ion yt.etus .nd . t.%t ;,r-Vr i

for the apparatus for measuring heat transfer coeff itlents of SYNTHOTI feeds andeffluents.

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CoalHeat of ReactionLiquefaction

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Coal LiquefactionSYNTHOIL

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CalorimeterGas AnalysisHeat Transfer CoefficientHydrogenHydrogenat ionSlurriesThermal Measuring Instruments

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TABLE OF CONTENTS

PageAbstract . . . . . . ........ 1

Summary . . . . .. . . . . . . . . . . . -.......- . . . 2

Project Plan and Status . . . .. - - . . . . . . . . .-.. . . . . . 2

Task I. Heat of Reaction of Hydrogen with Coal Slurries . . . . . . . . 5

fask II. Heat Transfer Coefficient . . . . . . . . . . . . . . . 6

A. Heat Transfer Test Unit ..- .-. . . . . . . . . 6

B. Test Module . . . . . . . . . . . 7

C. Test Program . . . . . . . . . . . . . . . . . 9

1. Test Module Characterization Tests . . . . . , . . .... 9

2. Tests of Gas Heat Transfer Coefficients at BaseConditions .. - - .. . . . . . . . . . . . . . . . . . 9

3. Liquid/Gas Flow Characteristics at BaseConditions . - - - - - - - - - - -

..... . . . . .10

4. SYNTHOIL Effluent Tests . . . . .. . .. . . . .. . .. 10

5. SYNTHOIL Slurry Feed Tests . . . . . . . . . . . . . . . . 10

Ref--rence .....---........... ... . ........ 10

1i

LIST OF FIGURES

No. Title Page

1. SYNTHOIL Mixer Lying on its Side . . . . . . . . . . . . . . . . . 8

2. Helix Cooler, Partially Assembled . . . . . . . . . . . . . . . . 8

3. Helix Cooler Partial Assembly Prior to Helix Installation . . . . 8

4. Thermocouple Assembly on Straight Tube Cooler . . . . . . . . . . 8

5. Heater . . . . . . . . . . . . . .. . . .. . . . . . . . . . 9

LIST OF TABLES

1. TasK I. Heat of Reaction of Hydrogen with Coal Slurries,Work Plan FY-1977 . . . . . . . . . . . . . . . . .... .. 3

2 Task II. Heat Transfer Coefficient, Work Plan, FY-1977 . . 4

iv

COAL. LIQUEFACTION SUPPORT STUDIES

.. rischer, R. Lo, T. Mulcahey,D. Fredrickson, T. Cannon, and A. Jonke

ABSTRACT

This work is in support of the development- of processessuch as the SYNTHOIL process for converting coal to a liquidfuel that has a low sulfur content and is suitable for use inpower production.

In the SYNTHOIL process for converting coal to a low-sulfur fuel oil, coal is liquefied and hydrodesulfurized ina turbulent-flow, catalytic packed-bed reactor. A slurry ofcoal in recycled oil is reacted with hydrogen at 450 C and2,000-4,000 psi in the presence of Co-Mo/Si0 2-A1 203 catalyst.Turbulent flow of fluid prevents the coal's mineral matterfrom settling and plugging the reactor. In a 1/2 ton per daypilot plant at PERC, the gross liquid product is centrifugedto remove unreacted solids, producing a low-sulfur, low-ashliquid fuel.

The work for the remaining portions of this program includestasks I and II, started in September 1975.

Task I, Heat of Reaction of Hydrogen with Coal SlurriesThe heat of reaction of coal-oil slurries with hydrogen will

be determined in the presence and absence of catalysts at 2,000-4,000 psi and 400-475*C, using a calorimeter. Calorimeter construc-tion is complete, and performance evaluation and calibration havebeen started.

Task II, Heat Transfer CoefficientThe coefficients of heat transfer from SYNTHOIL reactor

fluids to heat exchangers will be determined in the followingranges of conditions: pressures of 2,000-4,000 psi and tempera-tures to 465*C. The test unit has been installed. Acceptancetesting will be done during January 1977.

I

2

SUMMARY

Task I, Heat of Reaction of Hydrogen with Coal Slurries

A calorimeter has been built by Calcrimetrics Inc. of Boulder, Colorado,

to be used to obtain heat of reaction data for the hydrogenation of coal

slurries typical of those found in the reactant stream of the SYNTHOIL process.

Calibration tests are now being performed in Boulder prior to shipment of the

calorimeter to Argonne in January 1977.

Task II, Heat Transfer Coefficient

An experimental unit, which will be used to obtain measured coefficients

of heat transfer from both SYNTHOIL coal slurry process feed and product stream

to container valls, for use in future design of heat transfer equipment for

the process, is near completion. The test unit will have feed capacity ofslurry and hydrogen flow rates comparable to those in a plant designed for

1/2 ton/day capacity. All individual modules for the test unit have been

delivered to the facility at Argonne and interconnection of the various

modules has been completed by the contractor.

Fabrication of the heater and cooler components of the heat transfer

test section is complete, and assembly of the components to form the test

section module is almost complete. Preliminary testing and calibration ofthe components were done prior to assembly.

PROJECT PLAN AND STATUS

The project plans are depicted in Tables 1 and 2 for the two active

tasks.

Task I, Heat of Reaction of Hydrogen with Coal Slurries

At the end of this report period (December 31, 1976), final testing of

the calorimeter was being done by the vendor before shipment of the test unitto Argonne in January.

Task II, Heat Transfer Coefficient

At the end of this report period (December 31, 1976), installation of

the test unit was 90% complete. Completion of the test facility is expected

to be accomplished before the end of January 1977.

Both tasks are scheduled for completion in September J977. A final

report will be completed by the end of that month

Table 1. Task 1. Heat of Reaction of Hydrogen with Coal Slurries, Work Plan FY-1977

1976 19_ _ _ ___ _ _ _ _ _ _ __ _ _ _ _ _ __ _ _ _ _ _ _

ISOCT l.NOV DEC AN FEB MAR APR MAY liNE JULY AUG SEPT

Fir fraten Deemntos ____----

P rf o mn p T afing -1

2000 pa4 450OC - -- - -

Hlydrngen and Coal Slurry --- - --- ~ - -- -

2000 pal 4SC-e

- 2110pal 450

1.2000 1a 450

4Q00 pal 450eCftggi~n + Coal Sluryy4000 Dui 450eC

His+SYNTol lr+ Catalyst-4000 palf 450C

arted May 1976.

Task II. Heat Transfer Coefficient, Work Plan, FY-1977

1977

--C NL DE JAL EB 1977Heat Transfer Test Unit w rd rc 97

Fabrication, Installation j -j v -Installation CompleteAccetance Tests

Test ModuleFabricationInstallation CompleteInstrument TestsC'uu lete Calibrations

Heat Transfer CoefficientDeterminations

Gas FlowLiquid-Gas FlowSYNTHOIL Effluent FlowSlurr -Gas Flow

Coal ACoal BCoal C

Final Report - 7

-T~izaznzziiinzzz - -- - - -

I i I I I I - -

Table 2.

1976

TASK I. HEAT OF REACTION OF HYDROGEN WITH COAL SLURRIES(D. Fredrickson)

A calorimetric system, described previously in ANL 76-117, has been builtby Calorimetrics, Inc. of Boulder, Colorado, for determination of the heat ofreact ion of hydrogen with i .al ,lurrtes typical of those used in coal lque-f.act ion processes. The basic components of the system are a drop tube, aht.ated pressure vessel (in which the react ion takes place), and a calorimetersurrounding the pres - - v. ;e I.

Calibrat.ion tests ire ,'. conducted at Calorimetrics in order to meetthe .Iceptance criteria . ed in the contract. These include electricalcalibrations with a precision (standard deviation) of 1% or better as deter-mined by replicate electrical calibrations. These have been completed success-fully. A second calibration test requires that the calorimeter be capable of.in accuracv of 1% in a determination of the enthaIpv of svnthetic sapphire.The latter is near completion, and delivery of the heat of reaction calorim-eter is scheduled for the end of January 1977. A packaging plan has beenreceived from Calorimetrices for shipping of the calorimeter. The plan isto ship the Lpparatus directly to ANI. in a panel truck driven by Calorimetricspers.onnet .

The calorimeter will be installed in a laboratory in the ChemicalEngineering Division building. This laboratory has a separate shielded areafor the calorimeter.

To accomplish the goal of this task, we need (1) to know t'ie energyreleased during the reaction and (2) to determine the extent of the reaction.The energy release will be measured in the calorimeter. Extent of reaction(hyvdiogen consumption) will be obtained from the hydrogen balance betweenthe reactants and products. Upon completion of an experiment, liquid andgas products must be analyzed. Liquid products will he analyzed by conven-tional means. We are working on procedures for handling and analyzing thegaseous products.

Auxiliary equipment has been set up to determine the optimum conditionsfor collecting gases in cold traps after a reaction in the calorimeter hasbeen completed. The equipment includes a 2-liter autoclave, with a vesselidentical to that used in the calorimeter and a gas-handling manifold. Aseries of experiments are under way to develop procedures for quantitativedetermination of hydrogen in the reaction products. The determination ofhydrogen in the gaseous products is difficult because hydrogen gas must beseparated from the other gases. Most of the gaseous components can betrapped using liquid nitrogen as a coolant. The separation of hydrogen frommethane is particularly difficult since methane has a partial pressure ofabout 1.0 kPa (10 Torr) at liquid N., temperature.

In a preliminary test, the autoclave was charged to 6.9 MPa (1000 psi) witha He-5.38% CH4 mixture and slowly discharged through the two liquid nitrogentraps to condense CH4. The traps were then warmed, and the collected metnanewas passed over hot CuO, where it was converted to H20. The H20 was collectedin a U tube containing magnesium perchlorate and weighed. We are developingthis method to be used for the H2-CH4 mixture expected in 3 calorimeterexperiment. At present, the limiting factor in this procedure is the vapor

C

6

pressure of CH4 at liquid nitrogen temperatures, around 1.0 kPa (10 Torr).We are evaluating molecular sieves as a method for collecting the portion ofthe CH4 which is not condensed at liquid nitrogen temperature.

TASK II. HEAT TRANSFER COEFFICIENT(T. P. Mulcahey, R. Lu, T. Cannon)

The objectives of this task are to determine heat transfer coefficientssu.t for the design of process feed heat exchangers and product effluentheat changerss used in coal liquefaction processes and to identify mechanismsfor the heat transfer process. Heat transfer film coefficients for mixturesof gas, liquids, and solids in a turbulent flow will be measured for (a)reactor effluent cooled by a stainless steel surface and (b) feed heated bya stainless steel surface. The experimental work will be carried out ina test module in a nominal 1/2-ton-per-day Heat Transfer Test Unit, whichwill include a slurry makeup system; slurry feed system; heaters; coolers;pressure letdown tanks; and power, flowrate, and temperature instrumentation.

The following ranges of conditions will be covered:

Pressure: 2,000-4,000 psig (14-28 MPa)

Temperature 200-465*C

Three different coals suitable for liquefaction will be studt.ed in theinvestigation. Slurries will be used having the compositions of SYNTHOILInross product (unfiltered oil) and SYNTHOIL feed containing 30% by weightof finely ground coal.

A. Heat Transfer Test Unit*

All modules and the unit control console have been delivered to us fromthe commercial firm that is building the test unit. Integration of thevarious modules is completed. Intrumentation and power wiring will becompleted by January 15, 1977.

*Described in detail in ANL 76-117. The basic operation of the unit is asfollows: A coal slurry consisting of an oil with physical properties similarto those of SYNTHOIL and a 200-mesh coal is mixed and heated in the 140-galslurry make-up tank. A mixer and a rotating cavity recirculation pump main-tain the slurry in suspension; the pump also provides the pressure to transferthe slurry to the 10-gal slurry feed tank. A mixer and recirculation pumpconnected to the slurry feed tank maintain slurry suspension, and the pumpprovides slurry at pressure to the suction side of the piston-type high-pressure pump. The high-pressure pump supplies the slurry to the entranceof the test module at 4,000 psi.

Hydrogen supplied to the unit at 500 to 1,000 psi, is compressed to4,000 psi and merged with a recirculating hydrogen stream. The recircu-lating hydrogen is merged with the slurry before it enters the test section.The gas/slurry mixture passes into the heaters where a heat transfer coeffi-cieat is measured; the mixture then passes into the coolers where anotherheat transfer coefficient is measured.

The oas and liquid solid phases are separated in the high-pressurereceiver. The gas stroam is washed and cooled and returned via another gascompressor as the recirculating hydrogen stream. The liquid SYNTHOIL typeeffluent and water wash are collected in low-pressure receivers andperiodically sampled and removed from the system.

7

In order to protect other equipment and personnel in the building duringoperation, interior steel walls have been erected around apparatus containinghigh-pressure gas.

Blast mats are to be placed along the exterior blow-out walls of thebuilding to prevent any debris or flying pieces from being shot through thewall in case of an explosion. The exterior walls will be covered by mattingup to the 10-ft level except where the high-pressure receivers extend theneeded coverage up to the 15-ft level.

B. Test Module

Fabrication of the test module, which contains the heating and coolingtest components, is almost complete. All parts for the heaters, mixers, andcoolers have been manufactured by the ANL shops or procured, and most of theindividual heaters, mixers, and coolers have been fabricated. Assembly ofthe heaters into one leg of the L-shaped test module has been initiated.Fabrication of the control and instrumentation racks has been initiated andthe shunts to be used for power calibration of the individual heaters havebeen mounted. Testing and electrical calibration of the test module and dataacquisition systems were initiated, using a dummy test section heater. Theblower that supplies compressed air to the coolers was delivered, and instal-lation of the blower and compressed air piping is completed. Installation ofthe air flowmeters and piping connection for the test section coolers willbe completed by January 15, 1977.

Figure 1 is a Photograph of a SYNTHOIL mixer lying on its side. Theslurry-gas mixture will enter the left end and be mixed, the bulk temperaturewill be measured by a thermocouple inserted into the thermal well at the topnear the right-hand end, and the mixture will exit at the right end. Figure 2is a photograph of a partially assembled helix cooler; the five wires at eachend are thermocouples which are attached to the outside wall of the 3/8-in.stainless tubing containing the slurry-gas mixture. Eight of the thermocouplewires are embedded in grooves of the inner flow surface of the tube which issurrounded by the hel: % The thermocouples are held in place by a high-temperature chlorine-free epoxy as shown in Fig. 3, which shows the coolerprior to helix installation.

Figure 4 is a photograph of the internal assembly of the straight tubecooler; eight thermocouples are attached to the 3/8-in. tube for monitoringthe external wall temperature. Figure 5 is a photograph of one of the sixheaters prior to assembly into the test section and prior to installationof any thermocouples.

8

Fig. 1. SYNTHOIL Mixer Lying on its Side

Fig. 2. Helix Cooler, Partially Assembled

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Fig. 3. Helix Cooler. Part ial Assembly Prior to lelix Installat ion

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Fig. 4. Thermocouple Assembly on Straight Tube Cooler

9

Fig. 7 Heater

C. Test Proeram_

The Heat Transfer Coefficient Measurement Test Unit SYNTHOIL testingprogr-: is divided into five main phases as described below.

i. Test Module Characterization Tests

Objective: These tests are designed to obtain calibration and heat lossdata :or the test module components so that compensation can be made forinstrument errors and heat losses in the calculation of heat transferrates.

Program

a. Calibration will be performed on the following:

(1) electrical shunts used to measure the current to thetest module heaters

(2) thermocouples mounted on the mixers, heaters, andcoolers

(3) high-pressure liquid pump flow

(4) air flow monitors for the cooling air supply

(5) data logging system

(6) hydrogen recirculation and makeup flow monitor

b. Heat loss determinatior

The heaters, mixers, coolers, and piping will have heat lossesassociated with the transmission of heat through the insulation.The values of the heat losses of the various components must bedetermined to assess their significance and to allow correction,if necessary, for these losses.

2. Tests of Gas Heat Transfer Cofficients at Base Conditions

Objective: Heat transfer coefficients for hydrogen, helium, and nitrogenwill be determined for the "clean" system. These coefficients willserve as a base to which the heat transfer for SYNTHOIL fluid can laterbe compared and as a base for monitoring the fouling of the heat transfersurface during the remainder of the test program.

10

Program: Heat transfer coefficients of the pure gases will be run onthe initial clean system and periodically after each major step throughoutthe course of the test program.

3. Liquid/Gas Flow Characteristics at Base Conditions

Objective: These tests are designed to provide information aboutthe physical nature of the flow (e.g., slug, annular) as a function ofthe expected flow parameter variations.

Program: Fluids of different viscosities will be circulated throughthe system under different gas flow rates to ascertain characteristicsassociated with different flow regimes.1

4. SYNTHOIL Effluent Tests

Objective: These tests are to determine the heat transfer coefficientsof the SYNTHOIL effluent.

Program: The heat transfer coefficient will be determined in thefollowing range of parameters.

a. pressure: 2,000-4,000 psig

b. temperature: 200-465*C

5. SYNTHOIL Slurry Feed Tests

Objective: These tests are to determine the heat transfer coefficientsof the slurry feed material, using three different coals.

Program: The heat transfer coefficients will be determined over the

range of parametnrs listed in 4. above.

REFERENCE

1. K. Javdani, S. Schwalbe, and J. Fischer, "Multiphase Flow of Gas-Liquidand Gas-Coal Slurry Mixtures in Vertical Tubes," Argonne NationalLaboratory, January 1977, ANL 76-116.