Research Article The Reactants Phase State: A ...downloads.hindawi.com/journals/ijce/2014/405703.pdf · in Tetralin Hydrogenation Catalysts Evaluation ... it decreased dramatically

Research ArticleThe Reactantsrsquo Phase State A Nonnegligible Factorin Tetralin Hydrogenation Catalysts Evaluation

Mingjian Luo12 Qingfa Wang1 Xiangwen Zhang1 and Bing Hu2

1 Key Laboratory for Green Chemical Technology of Ministry of Education School of Chemical Engineering and TechnologyTianjin University Tianjin 300072 China

2 School of Chemistry and Chemical Engineering Northeastern Petroleum University Daqing 163318 China

Correspondence should be addressed to Mingjian Luo luomingjiannepueducn

Received 27 January 2014 Accepted 15 April 2014 Published 13 May 2014

Academic Editor Deepak Kunzru

Copyright copy 2014 Mingjian Luo et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

The effects of reactantsrsquo phase states (gas-liquid and single gas phase) on tetralin hydrogenation were investigated in the fixed bedThe kinetics of tetralin hydrogenation under different phase states was analyzed Results showed that without phase transition thetetralin conversion increased with the rise of temperature However it decreased dramatically around the dew point of the feedat which the reactantsrsquo phase state transferred from gas-liquid phase into gas phase It was also observed that the gas-liquid phasestate was favorable to reduce the deactivation of catalyst in the tetralin hydrogenation

1 Introduction

The deep hydrodearomatization of diesel fuels has beenfocused because of the environmental legislation and theclean-fuel production [1ndash3] The development of catalytictechnology for aromatic saturation and sulfur removal ishighly desirable Since the composition of diesel is complexmodel compounds like toluene tetralin and naphthalenewere commonly used in the evaluation of catalystsrsquo perfor-mancesWithout thermodynamic equilibrium limitation theconversions of these model aromatics should increase withthe rise of reaction temperature However some studies onthe aromatic hydrogenation have found that the conversionsof aromatics increased with the rise of temperature at arelatively low temperature but decreased with the further riseof temperature [4 5] some others have showed an increase-decrease-increase tendency with the rise of temperature [6ndash10] still others showed that hydrogenation depth was deeperat low temperature than at high temperature [5 10ndash14]Generally these phenomena were ascribed to the exothermalcharacter of the hydrogenation reaction In other words thethermodynamic equilibrium constrained the conversion ofaromatics [4 5 7ndash9 11] Nevertheless the calculation results

showed that the equilibrium conversion of naphthalene totetralin could approach 100 under 5MPa and 300∘C evenat 350∘C and 5MPa the equilibrium conversion was alsohigher than 95 (estimated from the figures in [3]) Thehydrogenation of tetralin to decalin had a similar behaviorFurthermore there were also studies with excellent aromaticsconversion under similar reaction conditions [15] Thereforefurther study should be performed to investigate the reasonsthat caused the decrease of aromatics conversion with therise of temperature especially under relatively low reactiontemperature

Another probable reason that affects aromatics conver-sion is the reactantsrsquo phase state The liquid phase vaporizesgradually with the rise of reaction temperature At the dewpoint of the feed all liquid phase vaporizes into vapor phaseWhen the reaction temperature is below the dew point of thefeed the liquid phase is existent and the hydrogen woulddissolve in the liquid phase and react with aromatics on thecatalyst surface (gas-liquid-solid reaction mode) When thereaction temperature is above the dewpoint of the feed all theliquid phase vaporizes into gas phase and reactants react oncatalyst in gas-solid reaction mode The two reaction modesare intrinsically different This difference probably affects the

Hindawi Publishing CorporationInternational Journal of Chemical EngineeringVolume 2014 Article ID 405703 8 pageshttpdxdoiorg1011552014405703

2 International Journal of Chemical Engineering

hydrogenation activity of catalyst and leads to the decreaseof aromatics conversion Generally model compounds arecomposed of aromatics and inert hydrocarbons for examplenaphthalene dissolves in 119899-hexadecane [16ndash19] 119899-tridecane[20 21] 119899-decane [22] 119899-heptane [5 10ndash14 23] and benzene[4] or tetralin dissolves in 119899-dodecane [24] 119899-decane [2225 26] 119899-heptane [6ndash9 12 15 27 28] 119899-hexane [29] andcyclohexane [30 31] The model compounds using lightcomponents as solvents are easier to vaporize and have lowerdew point The reaction mode of these model fuels mightchange from gas-liquid-solid to gas-solid mode Accordinglythe conversion of aromatics might change during the phasetransition

In this work tetralin was diluted in 119899-tetradecane 119899-decane and 119899-octane and then hydrogenated in a fixed bedunder 5MPa 220 to 290∘C and different H

2oil ratios The

effects of reactantsrsquo phase states on tetralin conversion andproducts distribution were discussed

2 Experimental

AmesoporousMCM-41 (SiAl = 24 atom ratio) type catalystcontaining 10 wt of Pt was prepared by incipient wet-ness impregnation of aqueous solution containing requiredamount of Pt(NH

3)4Cl2 After Pt impregnation the sample

was kept at ambient temperature overnight and then dried at110∘C for 3 h and finally calcinated at 400∘C for 4 h

The hydrogenation of tetralin was performed in a fixedbed reactor (inner diameter 12mm length 600mm) 3 gcatalyst (20sim16 mesh) was placed in the isothermal zoneof the fixed bed reactor The reaction temperature wascontrolled by 4 thermocouples placed at the reactor walland monitored with a thermocouple directly placed in thecatalyst bed Before the activity test the catalyst was in situreduced with 100mLmin H

2at 400∘C for 4 h The tetralin

(20wt) dissolved in 119899-tetradecane 119899-decane or 119899-octanewas supplied by a Series II piston pump with the flow rate of03mLmin The H

2flow rate (generally 100mLmin H

2oil

(vv) = 333) was controlled by a mass flow controller Thereaction pressure (5MPa) was adjusted by a back pressurevalve

At each reaction condition the product was collectedafter 35 h in order to achieve steady-state activityThe quanti-tative analysis of the reaction products was carried out usingan Agilent 7890A GC system equipped with a capillary col-umn (HP-PONA 50mtimes 02mmtimes 05 120583m) and FID detectorThe products were preliminarily identified by anAgilent 6890GC-MS system equipped with a capillary column (HP-5MS30m times 025mm times 025 120583m) The hydrogenation productswere 119905-decalin 119888-decalin C

10products (the ring opening

products and the isomers of decalin) and cracking products(C3to C9hydrocarbons these compounds were ignorable

at temperature below 270∘C) About 001sim002 of C20

compounds which were ascribed to the oligomerization ofC10

component were also detected at 290∘C Although theamounts of C

20compounds were ignorable they might affect

the deactivation of catalyst

200 220 240 260 280 30020

30

40

50

60

70

All liquid vaporized

Tetr

alin

conv

ersio

n (

)

Temperature (∘C)

n-Tetradecanen-Decane

n-Octanen-Octane-666

Figure 1 Tetralin conversion versus temperature in different sol-vents Reaction conditions 3 g catalyst 5MPa 03mLmin tetralinsolvent and H

2

oil (vv) = 333 (666 in 119899-octane-666)

3 Results

Figure 1 showed the effects of different solvents on the tetralinconversion at the temperature range from 220∘C to 290∘CThe tetralin conversion in 119899-tetradecane increased with therise of temperature However there were transition pointswhen 119899-decane and 119899-octane were used as solvents When 119899-decane was used as solvent the tetralin conversion decreasedat 290∘C When the solvent was alternated to 119899-octane thetetralin conversion decreased at 260∘C and then increasedwith the further temperature rise Tetralin conversions in 119899-octane and 119899-decane are similar at 290∘C But the values aremuch lower than in 119899-tetradecane Increasing theH

2oil ratio

from 333 to 666 led to the increase of tetralin conversionand resulted in a lower temperature (250∘C) at which tetralinconversion began to decrease

Figures 2 and 3 showed the influence of solvent on theC10yield and the 119905-decalin119888-decalin ratio respectively Both

the C10yield and the 119905-decalin119888-decalin ratio increased with

the rise of temperature in all the solvents Differently fromthe results in 119899-tetradecane two increased stages of C

10yield

and 119905-decalin119888-decalin ratio were observed in 119899-octane Thetemperature transition points of the two stages were similarto that of tetralin conversion in Figure 1The transition of C

10

yield and 119905-decalin119888-decalin ratio in 119899-decane can also beobserved at 270∘C but not as obviously as in 119899-octane

Figure 4 showed the tetralin conversion in 119899-octaneunder different hydrogen flow rates at 250∘C Firstly thetetralin conversion increased with the increase of the H

2oil

ratio and then it decreased dramatically between the H2oil

ratios = 555 and 666 Further increase in H2oil ratio led to

the increase in tetralin conversion again The retested valuesat H2oil ratios = 333 and 666 were lower than the values in

Figure 1 which indicate the deactivation of the catalyst Theyield of tetralin in naphthalene hydrogenation with the rise

International Journal of Chemical Engineering 3

0

1

2

3

4

5

6

7

220 240 260 280 300Temperature (∘C)

C 10

yiel

d (

)



Figure 2 C10

yield versus temperature in different solvents

09

12

15

18

220 240 260 280 300Temperature (∘C)

t-de

calin

c-d

ecal

in



Figure 3 119905-Decalin119888-decalin ratio versus temperature in differentsolvents

of hydrogennaphthalene ratio also exhibited the increase-decrease-increase tendency [28]

4 Discussion

41 Effect of Phase State on the Catalytic Activity

411 Relationship of Dew Point and Catalytic Activity Withthe rise of temperature the liquid phase vaporized graduallyuntil all the liquid changed into gaseous phase at the dewpoint of the feed The reaction modes below and abovethe dew point were intrinsically different as illustrated inScheme 1 Liquid phase exists at the temperature below thedew point of the feed The hydrogen was dissolved in liquid

300 450 600 750 900

36

38

40

42

Tetr

alin

conv

ersio

n (

)

H2oil (vv)

Figure 4 Tetralin conversion in 119899-octane under different H2

oilratio (250∘C)

Table 1 Dew points of feeds with different solvents

Solvent n-Tetradecanea n-Decanea n-Octanea n-Octane-666b

Dewpoint∘C

356 297 266 239

aReaction conditions 3 g catalyst 5MPa 03mLmin tetralin solvent H2oil= 333 and bH2oil = 666

phase and reacted with tetralin molecule on the catalystsurface In other words the reaction took place in the gas-liquid-solid mode or the trickle bed mode Tetralin andsolvents are all vaporized into gas phase at the temperatureabove the dew point Thus hydrogen and tetralin moleculesdiffused to the catalyst surface in gaseous phase adsorbedon the active sites and reacted with each other in the gas-solidmodeThe difference between these two reactionmodesmight affect the catalytic activity

The dew points of reactants under the given conditionsof pressures liquid flow rates and H

2oil ratios can be

calculated by equation of state PR and SRK [32] equations ofstates are commonly used in phase equilibria modelingTheywere compared in hydrogen-hydrocarbon phase equilibriacalculation with experiment data The SRK equation of stateis a little more accurate than the PR equation of state Thusthe dew points were calculated using SRK equation of state(1) as follows and the results were listed in Table 1

119901 =

119877119879

119881 minus 119887

minus

119886

119881 (119881 + 119887)

119886 = 119886119888sdot 120572 (119879 120596)

119886119888= 042748

1198772

119879119888

2

119901119888


Gas-liquid-solid mode Gas-solid mode

AromaticsHydrogen

SolventCondensed molecule

Scheme 1 Illustration of gas-liquid-solid and gas-solid reaction modes

119887 = 008664

119877119879119888

119901119888

120572 (119879 120596) = 1 + (048 + 1574120596 minus 01761205962

) (1 minus 119879119903

05

)

(1)

The dew point of tetralin119899-tetradecane system is 356∘Cwhich is much higher than the experimental temperaturesLiquid phase existed all through the experiment temperaturerange and only gas-liquid-solid reaction mode takes placeThus the conversion of tetralin increased with the rise oftemperature as shown in Figure 1Thedewpoint of tetralin119899-decane system is 297∘C which is close to the experimentaltemperature 290∘C At this temperature the reaction takesplace in gas-solid mode and thus the tetralin conversiondecreased Similarly the dew point of tetralin119899-octane(H2oil ratio = 333) is 266∘C and the conversion of tetralin

decreased at 260∘C Further rise in temperature can speed upthe reaction and lead to the increase of tetralin conversionagain Increasing the H

2oil ratio from 333 to 666 would

bring down the dew point (from 266 to 239∘C)Therefore thetemperature at which tetralin conversion began to decreasealso shifted to low (from 260 to 250∘C) In Figure 4 thetetralin conversion decreased between the H

2oil ratio = 555

and H2oil ratio = 666 The calculated dew point of the feed

at H2oil ratio = 555 and pressure 5MPa was 2466∘C which

was close to the experiment temperature 250∘CThese resultsindicated that there is substantial relationship between thereactants phase state and the catalytic activity

412 Kinetic Analysis The kinetic of tetralin hydrogenationwas analyzed to investigate the effects of reactantsrsquo phase stateon the catalytic activity The Weisz-Prater parameter 119862WPunder the experimental conditions is estimated to be about003 (with the method described in [33]) thus the diffusionlimitations can be neglected The reverse reaction can alsobe neglected since the tetralin conversions are far from theequilibrium values [3]With the existence of the liquid phasethe mass balance of tetralin can be expressed as

minus119889 (120592119871119862THN119871 + 120592119866119862THN119866) = 119896

0119890minus119864119886119877119879

119862119899

H2119871

119862119898

THN119871119889119881

(2)

Without the existence of the liquid phase the massbalance of tetralin can be expressed as

minus119889 (120592119866119862THN119866) = 119896

0119890minus119864119886119877119879

119862119899

H2119866

119862119898

THN119866119889119881 (3)

Assuming vapor-liquid equilibrium is achieved at theinlet and every point of the catalyst bed then the gas phasetetralin concentration 119862THN119866 = 119870119862THN119871 and 119870 = 119870

0=

1198620

THN1198661198620

THN119871The reaction order of the tetralin119898 is chosenas 1 according to the previous reports [3 24 34 35] Thevariations of 120592

119871 120592119866 119862H

2119871 and 119879 are neglected to simplify

the discussion though they vary along the reactor due to theconversion of the reactant and the generation of heat duringthe reaction Then the conversion of tetralin can be derivedfrom integrating (2) and (3) with the boundaries 119881 = 0119862THN119871 = 119862

0

THN119871 (or 119862THN119866 = 1198620

THN119866) and 119881 = 119881119862THN119871 = 119862THN119871 (or 119862THN119866 = 119862THN119866) For gas-liquid-solidmode

minus ln(119862THN119871

1198620

THN119871)

= minus ln (1 minus 119909) = 1198961015840

0

119890minus119864119886119877119879

1

120592119871+ (1198620

THN1198661198620

THN119871) 120592119866119862119899

H2119871

(4)

and for gas-solid mode


1198620

THN119866) = minus ln (1 minus 119909) = 119896

1015840

0

119890minus119864119886119877119879

1

120592119866

119862119899

H2119866

(5)

with

1198961015840

0

= 1198960119881 (6)

Equations (4) and (5) imply that the tetralin conversionincreases with the increase of the hydrogen concentrationin liquid phase 119862H

2119871

(gas-liquid-solid reaction mode) orhydrogen concentration in gas phase 119862H

2119866

(gas-solid reac-tion mode) The tetralin conversion also increases with thedecrease of 120592

119871+(1198620

THN1198661198620

THN119871)120592119866 (gas-liquid-solid reactionmode affected by volumetric flow rate of liquid and gasphase and the tetralin concentration in liquid and gasphase) or 120592

119866(gas-solid reaction mode) The 120592

119866and 120592

119871+

(1198620

THN1198661198620

THN119871)120592119866 can be related to the practical residencetime of tetralinThe greater the 120592

119866or 120592119871+(1198620

THN1198661198620

THN119871)120592119866


Table 2 Parameters for (4) and (5)

119864119886

times 104 Jmolminus1 119899

1198961015840

0

times105minmmolminus1 mLminus1 mLcat

minus1

119899-Tetradecane 119899-Decane 119899-Octane 119899-Octane-6665 3 6082 3817 3507 5797

220 240 260 280 300

030

035

040

075

090

105

120

Gas phase

Liquid phase

Temperature (∘C)

266∘C

297∘C

CH2(m

mol

mL)

n-Tetradecane

n-Decanen-Octane

Figure 5 The hydrogen concentration in gas and liquid phases ofdifferent solvents calculated by SRK equation of state

02

03

04

05

4

5

6

Gas phase

Liquid phase

266∘C

297∘C

220 240 260 280 300Temperature (∘C)

120592L+(C

0 THNGC

0 THNL)120592

Gor

120592G

(mL

min

)

n-Tetradecane

n-Decane

n-Octane

Figure 6 The 120592119871

+ (1198620

THN1198661198620

THN119871)120592119866 and 120592119866 of different solventscalculated by SRK equation of state

the lower the practical residence time of tetralinThese valuescan also be calculated by SRK equation of state [32] Theresults were illustrated in Figures 5 and 6 Without phasetransfer the values of hydrogen concentration and 120592

119871+

(1198620

THN1198661198620

THN119871)120592119866 or 120592119866change smoothly The gas phase

hydrogen concentrations are about 2sim3 times as large as theliquid phase ones which benefits the tetralin conversionHowever the 120592

119866was about 8sim25 times as large as the 120592

119871+

(1198620

THN1198661198620

THN119871)120592119866 and had a negative effect on the tetralinconversion The combined effects of hydrogen concentrationand 120592119866(or 120592119871+ (1198620

THN1198661198620

THN119871)120592119866) lower down the tetralinconversion when all liquid is transferred into gas phase abovethe dew point

210 240 270 3000

20

40

60

80

100

Mod

elin

g te

tral

in co

nver

sion

()

Temperature (∘C)

266∘C

297∘C

239∘C



Figure 7 The tetralin conversion calculated by (4) and (5)

Table 3 Tetralin conversion after gas-liquid-solid or gas-solidreaction manner

Temperature ∘C 250 290 250 (after 290)Tetralinn-octane 4451 4987 4161Tetralinn-tetradecane 4079 6484 3918

The 119864119886 119899 and 119896

1015840

0

of (4) and (5) were listed in Table 2The activation energy 119864

119886was set to 50 kJmol which was

referred to as the values ofmostmonocyclic aromatics [3 36]The 11989610158400

were regressed with experiment data for each reactionsystem Without phase transition the changes of hydrogenconcentration can be neglected Thus the reaction order 119899with respect to hydrogenwas set to zero inmost of the studies[24 35]The 119899was set to 3 in this study because the hydrogenconcentrations in liquid phase and gas phase were greatlydifferent Figure 7 showed the tetralin conversion calculatedby (4) and (5) Similar tendencies can be observed in Figures7 and 1 though the calculation values could not exactlymatchwith the experiment valuesThe errorsmight be caused by theerror of phase equilibrium calculation The same activationenergies and reaction rate constants that were used for bothgas-liquid-solid and gas-solid reaction modes might alsocause the deviation

42 Effect of Phase State on Catalyst Deactivation The retesttetralin conversions (tetralin119899-octane) at H

2oil ratio = 333

and H2oil ratio = 666 in Figure 4 were lower than the values

in Figure 1 These decreases might be caused by the deac-tivation of catalyst Fresh catalyst was loaded to investigate


180 182 184 186 188 190 192 194 196 198 200

183 225171129

136145

158

268

67121

C

A81 95

91 115

4155

67

183

81 95

136

129

121

171

136

145

158 268

274

274

D

B

Time (min)

4155

4155

6781

95

6741

0 50 100 150 200 250 300 0 50 100 150 200 250 300

0 50 100 150 200 250 300 0 50 100 150 200 250 300

A C20H34

B C20H28

C C20H34

D C20H28

C20 extracted from used catalyst

C20 in hydrogenation product

mzmz

mz mz

Figure 8 GC-MS spectra of C20

components in product and used catalyst

the effect of gas-liquid-solid or gas-solid operating mode oncatalyst deactivation The results were listed in Table 3 Thetetralin conversion at 250∘C decreased from 4451 to 4161after the gas-solid reaction at 290∘C (tetralin119899-octane) whileit decreased from 4079 to 3918 after gas-liquid-solidreaction at 290∘C (tetralin119899-tetradecane) The deactivationof triphase mode was much slighter than the previous one

The decalin dimers were detected in hydrogenation prod-uct at 290∘C and in the used catalyst (extracted with 119899-tetradecane and the obtained liquid was analyzed with GC-MS) They might adsorb on the catalyst surface or activesite and cause the deactivation [37 38] Figure 8 showed theGC-MS spectra of the C

20components in the hydrogenation

product and the used catalyst The MS results showed thatthe C

20components were composed of multialicyclics and

aromatic cycle This indicated that more than two aromaticmolecules condensed into a large molecule during the hydro-genation process As illustrated in Scheme 1 the liquid solventmight dissolve these large molecules and carry them awayHowever with the gas-solid mode the large molecules weredifficult to be desorbed andmight occupy the active siteThusthe deactivation in the gas-solid reaction mode was muchseverer than in the gas-liquid solid one

Similar to our experiment results the available literatureswhich used light hydrocarbon (benzene [4] 119899-heptane [5ndash14] or cyclohexane [31]) as solvents are likely to show aro-matics conversion transition with the increase of the reaction

temperatureGenerally the ones that use heavy hydrocarbonslike 119899-hexadecane 119899-tridecane and 119899-dodecane as solventsare likely to show that the conversion of aromatics increaseswith the rise of temperature In addition the light hydro-carbons were not the typical components of diesel fuel Wesuggest that the model compounds for the evaluation ofaromatic hydrogenation catalysts (especially the diesel fuelhydrodearomatization catalysts) should use suitable heavyhydrocarbons as solvents Otherwise the reactantsrsquo phasestate should be taken into consideration during the catalystevaluation

5 Conclusions

The reactantsrsquo phase state had a significant effect on the cat-alytic activity of hydrogenation catalyst The hydrogenationconcentration that was available to the catalyst surface of gas-solid reaction mode is 2sim3 times as high as that of gas-liquid-solid reaction mode while the 120592

119866(gas-solid mode) is about

8sim25 times as large as the 120592119871+(1198620

THN1198661198620

THN119871)120592119866 (gas-liquid-solidmode)The combined effects of hydrogen concentrationand 120592119866(or 120592119871+(1198620

THN1198661198620

THN119871)120592119866) cause tetralin conversionto dramatically decrease at the dew point of the feedThe gas-liquid-solid mode was preferred to reduce catalystdeactivationModel compounds for aromatics hydrogenationcatalysts evaluation should be absent in components thatmight bring in phase transfer under the test condition


Notations

119862 Concentration mmolmLminus1119864119886 Activation energy JmoLminus1

1198960 Reaction rate constant minmmoLminus1mLminus1

1198961015840

0

Reaction rate constantminmmoLminus1mLminus1mLcat

minus1

119877 Ideal gas constant 8314 JmoLminus1 Kminus1119879 Temperature K120592 Volumetric flow rate mLminminus1119881 Catalyst bed volume mL

Subscripts

0 Initial condition119866 Gas phase119871 Liquid phase119898 119899 Reaction orderH2 Hydrogen

THN Tetralin

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

The financial supports by the National Natural Science FundofChina (Grant no 90916022)were gratefully acknowledged

References

[1] C Song ldquoAn overview of new approaches to deep desulfuriza-tion for ultra-clean gasoline diesel fuel and jet fuelrdquo CatalysisToday vol 86 no 1ndash4 pp 211ndash263 2003

[2] B H Cooper and B B L Donnis ldquoAromatic saturation ofdistillates an overviewrdquo Applied Catalysis A General vol 137no 2 pp 203ndash223 1996

[3] A Stanislaus and B H Cooper ldquoAromatic hydrogenationcatalysis a reviewrdquo Catalysis ReviewsmdashScience and Engineeringvol 36 no 1 pp 75ndash123 1994

[4] S R Kirumakki B G Shpeizer G V Sagar K V R Chary andA Clearfield ldquoHydrogenation of Naphthalene over NiOSiO

2

-Al2

O3

catalysts structure-activity correlationrdquo Journal of Catal-ysis vol 242 no 2 pp 319ndash331 2006

[5] S Albertazzi G Busca E Finocchio R Glockler and AVaccari ldquoNew PdPt on MgAl basic mixed oxides for thehydrogenation and hydrogenolysis of naphthalenerdquo Journal ofCatalysis vol 223 no 2 pp 372ndash381 2004

[6] A Infantes-Molina J Merida-Robles E Rodrıguez-CastellonJ L G Fierro and A Jimenez-Lopez ldquoEffect of molybdenumand tungsten on CoMSU as hydrogenation catalystsrdquo Journalof Catalysis vol 240 no 2 pp 258ndash267 2006

[7] D Eliche-Quesada J M Merida-Robles E Rodrıguez-Castellon and A Jimenez-Lopez ldquoInfluence of theincorporation of palladium on RuMCM hydrotreatingcatalystsrdquo Applied Catalysis B Environmental vol 65 no 1-2pp 118ndash126 2006

[8] A Infantes-Molina J Merida-Robles E Rodrıguez-CastellonB Pawelec J L G Fierro and A Jimenez-Lopez ldquoCatalystsbased on Cozirconium doped mesoporous silica MSU for thehydrogenation and hydrogenolysishydrocracking of tetralinrdquoApplied Catalysis A General vol 286 no 2 pp 239ndash248 2005

[9] D Eliche-Quesada J M Merida-Robles E Rodrıguez-Castellon and A Jimenez-Lopez ldquoRu Os and Ru-Ossupported on mesoporous silica doped with zirconiumas mild thio-tolerant catalysts in the hydrogenation andhydrogenolysishydrocracking of tetralinrdquo Applied Catalysis AGeneral vol 279 no 1-2 pp 209ndash221 2005

[10] S Albertazzi N Donzel M Jacquin et al ldquoRole of the organicfeed and the support acidity in hydrotreating reactions on Pd-Pt on MCM-41 catalystsrdquo Catalysis Letters vol 96 no 3-4 pp157ndash164 2004

[11] S Albonetti G Baldi A Barzanti et al ldquoNanosized PdPtand PdRh catalysts for naphthalene hydrogenation andhydrogenolysisring-openingrdquo Catalysis Letters vol 108 no 3-4 pp 197ndash207 2006

[12] S AlbertazziM JacquinD J JonesM Lenarda L Storaro andA Vaccari ldquoActivity of Rh-containing catalysts in naphthalenehydrogenation under pressurerdquo Reaction Kinetics and CatalysisLetters vol 83 no 1 pp 11ndash17 2004

[13] S Albertazzi R Ganzerla C Gobbi et al ldquoHydrogenation ofnaphthalene on noble-metal-containing mesoporous MCM-41aluminosilicatesrdquo Journal of Molecular Catalysis A Chemicalvol 200 no 1-2 pp 261ndash270 2003

[14] M Mandreoli A Vaccari E Veggetti M Jacquin D J Jonesand J Roziere ldquoVapour phase hydrogenation of naphthaleneon a novel Ni-containing mesoporous aluminosilicate catalystrdquoApplied Catalysis A General vol 231 no 1-2 pp 263ndash268 2002

[15] D Eliche-Quesada J Merida-Robles P Maireles-Torres et alldquoEffects of preparation method and sulfur poisoning on thehydrogenation and ring opening of tetralin onNiWzirconium-dopedmesoporous silica catalystsrdquo Journal of Catalysis vol 220no 2 pp 457ndash467 2003

[16] V L Barrio P L Arias J F Cambra M B Guemez B Pawelecand J L G Fierro ldquoHydrodesulfurization and hydrogenationof model compounds on silica-alumina supported bimetallicsystemsrdquo Fuel vol 82 no 5 pp 501ndash509 2003

[17] V L Barrio P L Arias J F Cambra M B Guemez BPawelec and J L G Fierro ldquoAromatics hydrogenation onsilica-alumina supported palladium-nickel catalystsrdquo AppliedCatalysis A General vol 242 no 1 pp 17ndash30 2003

[18] B Pawelec R Mariscal R M Navarro S Van Bokhorst SRojas and J L G Fierro ldquoHydrogenation of aromatics oversupported Pt-Pd catalystsrdquo Applied Catalysis A General vol225 no 1-2 pp 223ndash237 2002

[19] H Yasuda T Sato and Y Yoshimura ldquoInfluence of the acidityof USY zeolite on the sulfur tolerance of Pd-Pt catalysts foraromatic hydrogenationrdquo Catalysis Today vol 50 no 1 pp 63ndash71 1999

[20] H Liu X Meng D Zhao and Y Li ldquoThe effect of sulfurcompound on the hydrogenation of tetralin over a Pd-PtHDAYcatalystrdquo Chemical Engineering Journal vol 140 no 1ndash3 pp424ndash431 2008

[21] K Ito M-A Ohshima H Kurokawa K Sugiyama and HMiura ldquoEffect of residual Cl- derived from metal precursorson catalytic activity in the hydrogenation of naphthalene oversupported Pd catalystsrdquo Catalysis Communications vol 3 no11 pp 527ndash531 2002


[22] P A Rautanen M S Lylykangas J R Aittamaa and AO I Krause ldquoLiquid-phase hydrogenation of naphthaleneand tetralin on NiAl

2

O3

kinetic modelingrdquo Industrial andEngineering Chemistry Research vol 41 no 24 pp 5966ndash59752002

[23] S J Ardakani X Liu and K J Smith ldquoHydrogenation and ringopening of naphthalene on bulk and supportedMo

2

C catalystsrdquoApplied Catalysis A General vol 324 no 1-2 pp 9ndash19 2007

[24] R C Santana S Jongpatiwut W E Alvarez and D EResasco ldquoGas-phase kinetic studies of tetralin hydrogenationonPTaluminardquo Industrial and Engineering Chemistry Researchvol 44 no 21 pp 7928ndash7934 2005

[25] H Li B Shen X Wang and S Shen ldquoAssembly of thepresynthesized crystalline AIPO

4

structure with alumina andits promotion for aromatic hydrogenationrdquo Energy and Fuelsvol 20 no 1 pp 21ndash25 2006

[26] PA Rautanen J RAittamaa andAO I Krause ldquoLiquid phasehydrogenation of tetralin on NiAl

2

O3

rdquo Chemical EngineeringScience vol 56 no 4 pp 1247ndash1254 2001

[27] HMa X Yang GWen et al ldquoCoupled hydrogenation and ringopening of tetralin on potassium modified PtUSY catalystsrdquoCatalysis Letters vol 116 no 3-4 pp 149ndash154 2007

[28] M Jacquin D J Jones J Roziere et al ldquoNovel supported RhPt Ir and Ru mesoporous aluminosilicates as catalysts for thehydrogenation of naphthalenerdquo Applied Catalysis A Generalvol 251 no 1 pp 131ndash141 2003

[29] S G A Ferraz F M Z Zotin L R R Araujo and J LZotin ldquoInfluence of support acidity of NiMoS catalysts inthe activity for hydrogenation and hydrocracking of tetralinrdquoApplied Catalysis A General vol 384 no 1-2 pp 51ndash57 2010

[30] M A Arribas P Concepcion and A Martınez ldquoThe role ofmetal sites during the coupled hydrogenation and ring openingof tetralin on bifunctional Pt(Ir)USY catalystsrdquo Applied Catal-ysis A General vol 267 no 1-2 pp 111ndash119 2004

[31] R Contreras J Ramırez R Cuevas-Garcıa et al ldquoPreparationand characterization of PtHMFI-SBA-15 hybrid catalyst fortetralin transformationrdquo Catalysis Today vol 148 no 1-2 pp49ndash54 2009

[32] G Soave ldquoEquilibrium constants from a modified Redlich-Kwong equation of staterdquo Chemical Engineering Science vol 27no 6 pp 1197ndash1203 1972

[33] H S Fogler Elements of Chemical Reaction Engineering Pear-son Education 4th edition 2005

[34] J Chen V Mulgundmath and N Wang ldquoAccounting forvapor-liquid equilibrium in the modeling and simulation of acommercial hydrotreating reactorrdquo Industrial and EngineeringChemistry Research vol 50 no 3 pp 1571ndash1579 2011

[35] S Dokjampa T Rirksomboon S Osuwan S Jongpatiwut andD E Resasco ldquoComparative study of the hydrogenation oftetralin on supported Ni Pt and Pd catalystsrdquo Catalysis Todayvol 123 no 1ndash4 pp 218ndash223 2007

[36] JWThybautM Saeys andG BMarin ldquoHydrogenation kinet-ics of toluene on PtZSM-22rdquoChemical Engineering Journal vol90 no 1-2 pp 117ndash129 2002

[37] D Kubicka N Kumar P Maki-Arvela et al ldquoRing opening ofdecalin over zeolites I Activity and selectivity of proton-formzeolitesrdquo Journal of Catalysis vol 222 no 1 pp 65ndash79 2004

[38] M Guisnet and P Magnoux ldquoCoking and deactivation ofzeolites Influence of the pore structurerdquo Applied Catalysis vol54 no 1 pp 1ndash27 1989

International Journal of

AerospaceEngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014


Active and Passive Electronic Components

Control Scienceand Engineering

Journal of



RotatingMachinery


Hindawi Publishing Corporation httpwwwhindawicom

Journal ofEngineeringVolume 2014

Submit your manuscripts athttpwwwhindawicom

VLSI Design



Shock and Vibration


Civil EngineeringAdvances in

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Electrical and Computer Engineering

Journal of

Advances inOptoElectronics


Volume 2014

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

SensorsJournal of


Modelling amp Simulation in EngineeringHindawi Publishing Corporation httpwwwhindawicom Volume 2014


Chemical EngineeringInternational Journal of Antennas and

Propagation




Navigation and Observation



DistributedSensor Networks



hydrogenation activity of catalyst and leads to the decreaseof aromatics conversion Generally model compounds arecomposed of aromatics and inert hydrocarbons for examplenaphthalene dissolves in 119899-hexadecane [16ndash19] 119899-tridecane[20 21] 119899-decane [22] 119899-heptane [5 10ndash14 23] and benzene[4] or tetralin dissolves in 119899-dodecane [24] 119899-decane [2225 26] 119899-heptane [6ndash9 12 15 27 28] 119899-hexane [29] andcyclohexane [30 31] The model compounds using lightcomponents as solvents are easier to vaporize and have lowerdew point The reaction mode of these model fuels mightchange from gas-liquid-solid to gas-solid mode Accordinglythe conversion of aromatics might change during the phasetransition

In this work tetralin was diluted in 119899-tetradecane 119899-decane and 119899-octane and then hydrogenated in a fixed bedunder 5MPa 220 to 290∘C and different H

2oil ratios The

effects of reactantsrsquo phase states on tetralin conversion andproducts distribution were discussed

2 Experimental

AmesoporousMCM-41 (SiAl = 24 atom ratio) type catalystcontaining 10 wt of Pt was prepared by incipient wet-ness impregnation of aqueous solution containing requiredamount of Pt(NH

3)4Cl2 After Pt impregnation the sample

was kept at ambient temperature overnight and then dried at110∘C for 3 h and finally calcinated at 400∘C for 4 h

The hydrogenation of tetralin was performed in a fixedbed reactor (inner diameter 12mm length 600mm) 3 gcatalyst (20sim16 mesh) was placed in the isothermal zoneof the fixed bed reactor The reaction temperature wascontrolled by 4 thermocouples placed at the reactor walland monitored with a thermocouple directly placed in thecatalyst bed Before the activity test the catalyst was in situreduced with 100mLmin H

2at 400∘C for 4 h The tetralin

(20wt) dissolved in 119899-tetradecane 119899-decane or 119899-octanewas supplied by a Series II piston pump with the flow rate of03mLmin The H

2flow rate (generally 100mLmin H

2oil

(vv) = 333) was controlled by a mass flow controller Thereaction pressure (5MPa) was adjusted by a back pressurevalve

At each reaction condition the product was collectedafter 35 h in order to achieve steady-state activityThe quanti-tative analysis of the reaction products was carried out usingan Agilent 7890A GC system equipped with a capillary col-umn (HP-PONA 50mtimes 02mmtimes 05 120583m) and FID detectorThe products were preliminarily identified by anAgilent 6890GC-MS system equipped with a capillary column (HP-5MS30m times 025mm times 025 120583m) The hydrogenation productswere 119905-decalin 119888-decalin C

10products (the ring opening

products and the isomers of decalin) and cracking products(C3to C9hydrocarbons these compounds were ignorable

at temperature below 270∘C) About 001sim002 of C20

compounds which were ascribed to the oligomerization ofC10

component were also detected at 290∘C Although theamounts of C

20compounds were ignorable they might affect

the deactivation of catalyst

200 220 240 260 280 30020

30

40

50

60

70

All liquid vaporized

Tetr

alin

conv

ersio

n (

)

Temperature (∘C)



Figure 1 Tetralin conversion versus temperature in different sol-vents Reaction conditions 3 g catalyst 5MPa 03mLmin tetralinsolvent and H

2

oil (vv) = 333 (666 in 119899-octane-666)

3 Results

Figure 1 showed the effects of different solvents on the tetralinconversion at the temperature range from 220∘C to 290∘CThe tetralin conversion in 119899-tetradecane increased with therise of temperature However there were transition pointswhen 119899-decane and 119899-octane were used as solvents When 119899-decane was used as solvent the tetralin conversion decreasedat 290∘C When the solvent was alternated to 119899-octane thetetralin conversion decreased at 260∘C and then increasedwith the further temperature rise Tetralin conversions in 119899-octane and 119899-decane are similar at 290∘C But the values aremuch lower than in 119899-tetradecane Increasing theH

2oil ratio

from 333 to 666 led to the increase of tetralin conversionand resulted in a lower temperature (250∘C) at which tetralinconversion began to decrease

Figures 2 and 3 showed the influence of solvent on theC10yield and the 119905-decalin119888-decalin ratio respectively Both

the C10yield and the 119905-decalin119888-decalin ratio increased with

the rise of temperature in all the solvents Differently fromthe results in 119899-tetradecane two increased stages of C

10yield

and 119905-decalin119888-decalin ratio were observed in 119899-octane Thetemperature transition points of the two stages were similarto that of tetralin conversion in Figure 1The transition of C

10

yield and 119905-decalin119888-decalin ratio in 119899-decane can also beobserved at 270∘C but not as obviously as in 119899-octane

Figure 4 showed the tetralin conversion in 119899-octaneunder different hydrogen flow rates at 250∘C Firstly thetetralin conversion increased with the increase of the H

2oil

ratio and then it decreased dramatically between the H2oil

ratios = 555 and 666 Further increase in H2oil ratio led to

the increase in tetralin conversion again The retested valuesat H2oil ratios = 333 and 666 were lower than the values in

Figure 1 which indicate the deactivation of the catalyst Theyield of tetralin in naphthalene hydrogenation with the rise


0

1

2

3

4

5

6

7

220 240 260 280 300Temperature (∘C)

C 10

yiel

d (

)



Figure 2 C10


09

12

15

18

220 240 260 280 300Temperature (∘C)

t-de

calin

c-d

ecal

in





4 Discussion



300 450 600 750 900

36

38

40

42

Tetr

alin

conv

ersio

n (

)

H2oil (vv)


oilratio (250∘C)



Dewpoint∘C

356 297 266 239




2oil ratios can be


119901 =

119877119879

119881 minus 119887

minus

119886

119881 (119881 + 119887)

119886 = 119886119888sdot 120572 (119879 120596)

119886119888= 042748

1198772

119879119888

2

119901119888



AromaticsHydrogen



119887 = 008664

119877119879119888

119901119888

120572 (119879 120596) = 1 + (048 + 1574120596 minus 01761205962

) (1 minus 119879119903

05

)

(1)





2oil ratio = 555





minus119889 (120592119871119862THN119871 + 120592119866119862THN119866) = 119896

0119890minus119864119886119877119879

119862119899

H2119871

119862119898

THN119871119889119881

(2)


minus119889 (120592119866119862THN119866) = 119896

0119890minus119864119886119877119879

119862119899

H2119866

119862119898

THN119866119889119881 (3)


0=

1198620

THN1198661198620


119871 120592119866 119862H



0

THN119871 (or 119862THN119866 = 1198620



1198620

THN119871)

= minus ln (1 minus 119909) = 1198961015840

0

119890minus119864119886119877119879

1

120592119871+ (1198620

THN1198661198620

THN119871) 120592119866119862119899

H2119871

(4)



1198620


1015840

0

119890minus119864119886119877119879

1

120592119866

119862119899

H2119866

(5)

with

1198961015840

0

= 1198960119881 (6)


2119871


2119866


119871+(1198620

THN1198661198620



119866and 120592

119871+

(1198620

THN1198661198620


119866or 120592119871+(1198620

THN1198661198620

THN119871)120592119866



119864119886


1198961015840

0


minus1


220 240 260 280 300

030

035

040

075

090

105

120

Gas phase

Liquid phase

Temperature (∘C)

266∘C

297∘C

CH2(m

mol

mL)

n-Tetradecane

n-Decanen-Octane


02

03

04

05

4

5

6

Gas phase

Liquid phase

266∘C

297∘C

220 240 260 280 300Temperature (∘C)

120592L+(C

0 THNGC

0 THNL)120592

Gor

120592G

(mL

min

)

n-Tetradecane

n-Decane

n-Octane

Figure 6 The 120592119871

+ (1198620

THN1198661198620



119871+

(1198620

THN1198661198620




119871+

(1198620

THN1198661198620


THN1198661198620


210 240 270 3000

20

40

60

80

100

Mod

elin

g te

tral

in co

nver

sion

()

Temperature (∘C)

266∘C

297∘C

239∘C






The 119864119886 119899 and 119896

1015840

0






2oil ratio = 333




180 182 184 186 188 190 192 194 196 198 200

183 225171129

136145

158

268

67121

C

A81 95

91 115

4155

67

183

81 95

136

129

121

171

136

145

158 268

274

274

D

B

Time (min)

4155

4155

6781

95

6741

0 50 100 150 200 250 300 0 50 100 150 200 250 300

0 50 100 150 200 250 300 0 50 100 150 200 250 300

A C20H34

B C20H28

C C20H34

D C20H28



mzmz

mz mz











5 Conclusions




THN1198661198620


THN1198661198620



Notations



1198961015840

0


minus1


Subscripts


THN Tetralin



Acknowledgment


References





2

-Al2

O3





















2

O3



2




4



2

O3
















RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










0

1

2

3

4

5

6

7

220 240 260 280 300Temperature (∘C)

C 10

yiel

d (

)



Figure 2 C10


09

12

15

18

220 240 260 280 300Temperature (∘C)

t-de

calin

c-d

ecal

in





4 Discussion



300 450 600 750 900

36

38

40

42

Tetr

alin

conv

ersio

n (

)

H2oil (vv)


oilratio (250∘C)



Dewpoint∘C

356 297 266 239




2oil ratios can be


119901 =

119877119879

119881 minus 119887

minus

119886

119881 (119881 + 119887)

119886 = 119886119888sdot 120572 (119879 120596)

119886119888= 042748

1198772

119879119888

2

119901119888



AromaticsHydrogen



119887 = 008664

119877119879119888

119901119888

120572 (119879 120596) = 1 + (048 + 1574120596 minus 01761205962

) (1 minus 119879119903

05

)

(1)





2oil ratio = 555





minus119889 (120592119871119862THN119871 + 120592119866119862THN119866) = 119896

0119890minus119864119886119877119879

119862119899

H2119871

119862119898

THN119871119889119881

(2)


minus119889 (120592119866119862THN119866) = 119896

0119890minus119864119886119877119879

119862119899

H2119866

119862119898

THN119866119889119881 (3)


0=

1198620

THN1198661198620


119871 120592119866 119862H



0

THN119871 (or 119862THN119866 = 1198620



1198620

THN119871)

= minus ln (1 minus 119909) = 1198961015840

0

119890minus119864119886119877119879

1

120592119871+ (1198620

THN1198661198620

THN119871) 120592119866119862119899

H2119871

(4)



1198620


1015840

0

119890minus119864119886119877119879

1

120592119866

119862119899

H2119866

(5)

with

1198961015840

0

= 1198960119881 (6)


2119871


2119866


119871+(1198620

THN1198661198620



119866and 120592

119871+

(1198620

THN1198661198620


119866or 120592119871+(1198620

THN1198661198620

THN119871)120592119866



119864119886


1198961015840

0


minus1


220 240 260 280 300

030

035

040

075

090

105

120

Gas phase

Liquid phase

Temperature (∘C)

266∘C

297∘C

CH2(m

mol

mL)

n-Tetradecane

n-Decanen-Octane


02

03

04

05

4

5

6

Gas phase

Liquid phase

266∘C

297∘C

220 240 260 280 300Temperature (∘C)

120592L+(C

0 THNGC

0 THNL)120592

Gor

120592G

(mL

min

)

n-Tetradecane

n-Decane

n-Octane

Figure 6 The 120592119871

+ (1198620

THN1198661198620



119871+

(1198620

THN1198661198620




119871+

(1198620

THN1198661198620


THN1198661198620


210 240 270 3000

20

40

60

80

100

Mod

elin

g te

tral

in co

nver

sion

()

Temperature (∘C)

266∘C

297∘C

239∘C






The 119864119886 119899 and 119896

1015840

0






2oil ratio = 333




180 182 184 186 188 190 192 194 196 198 200

183 225171129

136145

158

268

67121

C

A81 95

91 115

4155

67

183

81 95

136

129

121

171

136

145

158 268

274

274

D

B

Time (min)

4155

4155

6781

95

6741

0 50 100 150 200 250 300 0 50 100 150 200 250 300

0 50 100 150 200 250 300 0 50 100 150 200 250 300

A C20H34

B C20H28

C C20H34

D C20H28



mzmz

mz mz











5 Conclusions




THN1198661198620


THN1198661198620



Notations



1198961015840

0


minus1


Subscripts


THN Tetralin



Acknowledgment


References





2

-Al2

O3





















2

O3



2




4



2

O3
















RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation











AromaticsHydrogen



119887 = 008664

119877119879119888

119901119888

120572 (119879 120596) = 1 + (048 + 1574120596 minus 01761205962

) (1 minus 119879119903

05

)

(1)





2oil ratio = 555





minus119889 (120592119871119862THN119871 + 120592119866119862THN119866) = 119896

0119890minus119864119886119877119879

119862119899

H2119871

119862119898

THN119871119889119881

(2)


minus119889 (120592119866119862THN119866) = 119896

0119890minus119864119886119877119879

119862119899

H2119866

119862119898

THN119866119889119881 (3)


0=

1198620

THN1198661198620


119871 120592119866 119862H



0

THN119871 (or 119862THN119866 = 1198620



1198620

THN119871)

= minus ln (1 minus 119909) = 1198961015840

0

119890minus119864119886119877119879

1

120592119871+ (1198620

THN1198661198620

THN119871) 120592119866119862119899

H2119871

(4)



1198620


1015840

0

119890minus119864119886119877119879

1

120592119866

119862119899

H2119866

(5)

with

1198961015840

0

= 1198960119881 (6)


2119871


2119866


119871+(1198620

THN1198661198620



119866and 120592

119871+

(1198620

THN1198661198620


119866or 120592119871+(1198620

THN1198661198620

THN119871)120592119866



119864119886


1198961015840

0


minus1


220 240 260 280 300

030

035

040

075

090

105

120

Gas phase

Liquid phase

Temperature (∘C)

266∘C

297∘C

CH2(m

mol

mL)

n-Tetradecane

n-Decanen-Octane


02

03

04

05

4

5

6

Gas phase

Liquid phase

266∘C

297∘C

220 240 260 280 300Temperature (∘C)

120592L+(C

0 THNGC

0 THNL)120592

Gor

120592G

(mL

min

)

n-Tetradecane

n-Decane

n-Octane

Figure 6 The 120592119871

+ (1198620

THN1198661198620



119871+

(1198620

THN1198661198620




119871+

(1198620

THN1198661198620


THN1198661198620


210 240 270 3000

20

40

60

80

100

Mod

elin

g te

tral

in co

nver

sion

()

Temperature (∘C)

266∘C

297∘C

239∘C






The 119864119886 119899 and 119896

1015840

0






2oil ratio = 333




180 182 184 186 188 190 192 194 196 198 200

183 225171129

136145

158

268

67121

C

A81 95

91 115

4155

67

183

81 95

136

129

121

171

136

145

158 268

274

274

D

B

Time (min)

4155

4155

6781

95

6741

0 50 100 150 200 250 300 0 50 100 150 200 250 300

0 50 100 150 200 250 300 0 50 100 150 200 250 300

A C20H34

B C20H28

C C20H34

D C20H28



mzmz

mz mz











5 Conclusions




THN1198661198620


THN1198661198620



Notations



1198961015840

0


minus1


Subscripts


THN Tetralin



Acknowledgment


References





2

-Al2

O3





















2

O3



2




4



2

O3
















RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation











119864119886


1198961015840

0


minus1


220 240 260 280 300

030

035

040

075

090

105

120

Gas phase

Liquid phase

Temperature (∘C)

266∘C

297∘C

CH2(m

mol

mL)

n-Tetradecane

n-Decanen-Octane


02

03

04

05

4

5

6

Gas phase

Liquid phase

266∘C

297∘C

220 240 260 280 300Temperature (∘C)

120592L+(C

0 THNGC

0 THNL)120592

Gor

120592G

(mL

min

)

n-Tetradecane

n-Decane

n-Octane

Figure 6 The 120592119871

+ (1198620

THN1198661198620



119871+

(1198620

THN1198661198620




119871+

(1198620

THN1198661198620


THN1198661198620


210 240 270 3000

20

40

60

80

100

Mod

elin

g te

tral

in co

nver

sion

()

Temperature (∘C)

266∘C

297∘C

239∘C






The 119864119886 119899 and 119896

1015840

0






2oil ratio = 333




180 182 184 186 188 190 192 194 196 198 200

183 225171129

136145

158

268

67121

C

A81 95

91 115

4155

67

183

81 95

136

129

121

171

136

145

158 268

274

274

D

B

Time (min)

4155

4155

6781

95

6741

0 50 100 150 200 250 300 0 50 100 150 200 250 300

0 50 100 150 200 250 300 0 50 100 150 200 250 300

A C20H34

B C20H28

C C20H34

D C20H28



mzmz

mz mz











5 Conclusions




THN1198661198620


THN1198661198620



Notations



1198961015840

0


minus1


Subscripts


THN Tetralin



Acknowledgment


References





2

-Al2

O3





















2

O3



2




4



2

O3
















RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










180 182 184 186 188 190 192 194 196 198 200

183 225171129

136145

158

268

67121

C

A81 95

91 115

4155

67

183

81 95

136

129

121

171

136

145

158 268

274

274

D

B

Time (min)

4155

4155

6781

95

6741

0 50 100 150 200 250 300 0 50 100 150 200 250 300

0 50 100 150 200 250 300 0 50 100 150 200 250 300

A C20H34

B C20H28

C C20H34

D C20H28



mzmz

mz mz











5 Conclusions




THN1198661198620


THN1198661198620



Notations



1198961015840

0


minus1


Subscripts


THN Tetralin



Acknowledgment


References





2

-Al2

O3





















2

O3



2




4



2

O3
















RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation










Notations



1198961015840

0


minus1


Subscripts


THN Tetralin



Acknowledgment


References





2

-Al2

O3





















2

O3



2




4



2

O3
















RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation











2

O3



2




4



2

O3
















RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation











RoboticsJournal of





Journal of



RotatingMachinery





VLSI Design



Shock and Vibration







Journal of



Volume 2014


SensorsJournal of





Propagation









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