discussion about performance of predictive pr78 eos...

DiscussionDiscussion about performance ofabout performance ofpredictive PR78 EOS onpredictive PR78 EOS on PRO/II 9.2PRO/II 9.2DiscussionDiscussion about performance ofabout performance of

predictive PR78 EOS onpredictive PR78 EOS on PRO/II 9.2PRO/II 9.2

SS DESSS DES--0404InvensysInvensys Software ConferenceSoftware Conference

OctoberOctober 1414--1717, 2013, 2013Hilton Anatole HotelHilton Anatole Hotel

Dallas, TexasDallas, TexasMasakazu SasakiMasakazu Sasaki

Toyo Engineering CorporationToyo Engineering Corporation



Dallas, TexasDallas, Texas

DiscussionDiscussion about performance ofabout performance ofpredictive PR78 EOS onpredictive PR78 EOS on PRO/II 9.2PRO/II 9.2DiscussionDiscussion about performance ofabout performance of

predictive PR78 EOS onpredictive PR78 EOS on PRO/II 9.2PRO/II 9.2



Dallas, TexasDallas, TexasMasakazu SasakiMasakazu Sasaki

Toyo Engineering CorporationToyo Engineering Corporation

1



Dallas, TexasDallas, Texas

Brief Overview of History of EOS and Mixing Rule

Model Framework of predictive PR78

Validation Results of pPR78 EOS

Discussion

Conclusion for Validation Work

Further Improvements

AgendaAgenda




Discussion






Discussion



AgendaAgenda

©© 20132013 TOYO ENGINEERING CORPORATIONTOYO ENGINEERING CORPORATION 2




Discussion



VirialVirial ExpansionExpansion

Beattie-Bridgeman (1928) BWR (1940)

Ｉ．Ｉ．BriefBrief Overview of History of EOS and Mixing RuleOverview of History of EOS and Mixing Rule

Cubic EOSCubic EOS

Van der Waals (1873) Berthelot (1899)

Gibbs/Helmholtz Free EnergyGibbs/Helmholtz Free Energy

Span-Wagner (1996)

IAPWS-IF97 (ASME Authorized Steam Tables)

Statistical Thermodynamics (Perturbation Theory)Statistical Thermodynamics (Perturbation Theory)

Barker - Henderson (1967) Carnahan-Starling for Hard Sphere (1969)

SAFT(Statistical Associating Fluid Theory)Chapman SAFT (1988/90), Sadowski SAFT (PC-SAFT) (2001/2002)

VirialVirial ExpansionExpansion

BWRS (1972) LKP (1975/1978)


Cubic EOSCubic EOS

SRK (1972) PR76 (1976) / PR78 (1978)


Gibbs/Helmholtz Free EnergyGibbs/Helmholtz Free Energy

NIST REFFROP / GERG2008 / AGA8

IAPWS-IF97 (ASME Authorized Steam Tables)

Statistical Thermodynamics (Perturbation Theory)Statistical Thermodynamics (Perturbation Theory)

Carnahan-Starling for Hard Sphere (1969)

SAFT(Statistical Associating Fluid Theory)Chapman SAFT (1988/90), Sadowski SAFT (PC-SAFT) (2001/2002)

BACK (1972/75/77)


Mixing Rules of Cubic EOSMixing Rules of Cubic EOS

Van der Waals 1 fluid mixing rule (VdW1f)Random mixing (Lorentz – Berthelot ‘s law) : original SRK(1972), original PR(1976/1978)

Modification of VdW1f mixing ruleAsymmetric kij (≠kji) : SRK-Kabadi-Danner(1985), Harvey – Prausnitz (SRKM/PRM) (1989)Symmetric kij, but component dependency in Kij by introduction second parameter (lij=-lji)

: Schwartzentruber-Renon (1989)

Excess Gibbs Energy (gE) mixing ruleOrigin of gE model : Huron – Vidal (1979)Modification of Huron-Vidal : MHV2 (1991) , Wong-Sandler (1992) , LCVM (1994)Combined with UNIFAC : UNIWAALS (1986) , Schwartzentruber-Renon (1989) ,

predictive SRK (1991) (from PRO/II 9.2)Combined with NRTL Databank : Twu-Bluck-Coon (1998)Combined with group contribution Van Laar gE model : predictive PR78 (2004-2008)




Mixing Rules of Cubic EOSMixing Rules of Cubic EOS

Van der Waals 1 fluid mixing rule (VdW1f)Random mixing (Lorentz – Berthelot ‘s law) : original SRK(1972), original PR(1976/1978)

Modification of VdW1f mixing ruleAsymmetric kij (≠kji) : SRK-Kabadi-Danner(1985), Harvey – Prausnitz (SRKM/PRM) (1989)Symmetric kij, but component dependency in Kij by introduction second parameter (lij=-lji)

: Schwartzentruber-Renon (1989)






II. Model Framework ofII. Model Framework of predictivepredictive PR78PR78

PR 1978 EOS (‘Mather’ Equation of State of pPR78)

Deviation of PR1978 EOS from ‘usual’ PR EOS (PR1976) is calculationprocedures for mi in the alpha function.


PR 1978 EOS (‘Mather’ Equation of State of pPR78)


Deviation of PR1978 EOS from ‘usual’ PR EOS (PR1976) is calculationprocedures for mi in the alpha function.


Mixing Rules of pPR78Van der Waals one fluid mixing rule (Lorentz-Berthelot’s Law, Random Mixing)

Combination of VdW1f mixing rule and Van Laar type gE model (Random Mixingbut it can correspond asymmetric system (molecular size is different)). Thisapproach is originated by Peneloux and his coworkers (1986/1989/1991).


Peneloux’s approach is slightly close to Schwartzentruber-Renon’s approach.


Van der Waals one fluid mixing rule (Lorentz-Berthelot’s Law, Random Mixing)




Peneloux’s approach is slightly close to Schwartzentruber-Renon’s approach.


Mixing Rules of pPR78Jaubert and his coworker’s work (2004-2008)

PR1978 was chosen as a platform EOS of pPR78 model framework Providing a bridge between VdW1f mixing rule and Van Laar gE

based on Peneloux’s approach

Expansion of Van Laar to Group Contribution Method (GCM) Determination of interaction parameters of groups

Paraffin, Aroma, Naphten, CO2, H2S, N2, Mercaptans and Water

Akl (=Alk) and Bkl (=Blk) are interaction parameters for each binary groups.

Jaubert et al. took extra high pressure phase equilibrium data into accountwhen they determined group parameters for hydrocarbon mixtures.


Jaubert and his coworker’s work (2004-2008)

PR1978 was chosen as a platform EOS of pPR78 model framework Providing a bridge between VdW1f mixing rule and Van Laar gE

based on Peneloux’s approach


Expansion of Van Laar to Group Contribution Method (GCM) Determination of interaction parameters of groups

Paraffin, Aroma, Naphten, CO2, H2S, N2, Mercaptans and Water

Akl (=Alk) and Bkl (=Blk) are interaction parameters for each binary groups.

Jaubert et al. took extra high pressure phase equilibrium data into accountwhen they determined group parameters for hydrocarbon mixtures.

III.III. Validation Results of pPR78 EOSValidation Results of pPR78 EOS

Comparisons of published experimental data, pPR78 and other bench markthermo models

Tools : PRO/II ver. 9.2 Beta and ver. 9.2.0Thermo models : pPR78 EOS

PR EOS with default kij databank (SimSci DB)PR EOS with Modified Chueh-Prausnitz kij FillingSRKM EOS with default kij databank (SimSci DB)TBC EOS with default NRTL binary databankNRTL LACT model with default NRTL binary databank



Selected Mixtures for this Validation Study

Major Hydrocarbon Binary Mixtures for Distillation Asymmetric Hydrocarbon Binary Mixture High Pressure VLE for Wide Range Paraffinic Compound Mixtures CO2 Mixtures Water Mixtures


Comparisons of published experimental data, pPR78 and other bench markthermo models







Major Hydrocarbon Binary Mixtures for Distillation Asymmetric Hydrocarbon Binary Mixture High Pressure VLE for Wide Range Paraffinic Compound Mixtures CO2 Mixtures Water Mixtures


Major Hydrocarbon Key Binary Mixtures for DistillationMajor Hydrocarbon Key Binary Mixtures for DistillationMajor Hydrocarbon Key Binary Mixtures for DistillationMajor Hydrocarbon Key Binary Mixtures for DistillationComparisons of pPR78 and PR were carried out for C1-C2, C2-C3, C3-nC4

and C3-iC4 at typical operation pressures of distillation columns. The pPR78indicated almost same results as PR except C3-iC4. The deviation for C3-iC4system was not so significant. It could be expected that pPR78 would showsimilar performance to PR for distillation column study.


Major Hydrocarbon Key Binary Mixtures for DistillationMajor Hydrocarbon Key Binary Mixtures for DistillationMajor Hydrocarbon Key Binary Mixtures for DistillationMajor Hydrocarbon Key Binary Mixtures for DistillationComparisons of pPR78 and PR were carried out for C1-C2, C2-C3, C3-nC4

and C3-iC4 at typical operation pressures of distillation columns. The pPR78indicated almost same results as PR except C3-iC4. The deviation for C3-iC4system was not so significant. It could be expected that pPR78 would showsimilar performance to PR for distillation column study.



Asymmetric Hydrocarbon BinaryAsymmetric Hydrocarbon Binary Mixture at Extra High Pressure RangeMixture at Extra High Pressure RangeAsymmetric Hydrocarbon BinaryAsymmetric Hydrocarbon Binary Mixture at Extra High Pressure RangeMixture at Extra High Pressure RangePR w/o Prausnitz : The PRO/II default kij bank does not have kij data. kij=0.0PR w Prausnitz : kij is predicted by mod. Chueh-Prausnitz. kij≠0.0The experimental data on Fig.ii-a-1 show immiscible behaviors for C1-nC16

system at extreme pressure conditions


Asymmetric Hydrocarbon BinaryAsymmetric Hydrocarbon Binary Mixture at Extra High Pressure RangeMixture at Extra High Pressure RangeAsymmetric Hydrocarbon BinaryAsymmetric Hydrocarbon Binary Mixture at Extra High Pressure RangeMixture at Extra High Pressure RangePR w/o Prausnitz : The PRO/II default kij bank does not have kij data. kij=0.0PR w Prausnitz : kij is predicted by mod. Chueh-Prausnitz. kij≠0.0The experimental data on Fig.ii-a-1 show immiscible behaviors for C1-nC16

system at extreme pressure conditions



High Pressure VLE for Wide Range Paraffinic CompoundHigh Pressure VLE for Wide Range Paraffinic Compound MixturesMixturesHigh Pressure VLE for Wide Range Paraffinic CompoundHigh Pressure VLE for Wide Range Paraffinic Compound MixturesMixtures

PR w/o Prausnitz : kij=0.0 for missing binary pairsPR w Prausnitz : kij is predicted by modified Chueh-Prausnitz for missing

binary (kij≠0.0).


High Pressure VLE for Wide Range Paraffinic CompoundHigh Pressure VLE for Wide Range Paraffinic Compound MixturesMixturesHigh Pressure VLE for Wide Range Paraffinic CompoundHigh Pressure VLE for Wide Range Paraffinic Compound MixturesMixtures

PR w/o Prausnitz : kij=0.0 for missing binary pairsPR w Prausnitz : kij is predicted by modified Chueh-Prausnitz for missing

binary (kij≠0.0).



CO2CO2 Mixtures ~ MethaneMixtures ~ Methane –– CO2CO2 –– Ethane ternary systemEthane ternary systemCO2CO2 Mixtures ~ MethaneMixtures ~ Methane –– CO2CO2 –– Ethane ternary systemEthane ternary system


CO2CO2 Mixtures ~ MethaneMixtures ~ Methane –– CO2CO2 –– Ethane ternary systemEthane ternary systemCO2CO2 Mixtures ~ MethaneMixtures ~ Methane –– CO2CO2 –– Ethane ternary systemEthane ternary system



CO2CO2 Mixtures ~ CO2Mixtures ~ CO2 –– HeptadecaneHeptadecane system at High Pressure Rangesystem at High Pressure RangeCO2CO2 Mixtures ~ CO2Mixtures ~ CO2 –– HeptadecaneHeptadecane system at High Pressure Rangesystem at High Pressure Range


CO2CO2 Mixtures ~ CO2Mixtures ~ CO2 –– HeptadecaneHeptadecane system at High Pressure Rangesystem at High Pressure RangeCO2CO2 Mixtures ~ CO2Mixtures ~ CO2 –– HeptadecaneHeptadecane system at High Pressure Rangesystem at High Pressure Range



CO2CO2 Mixtures ~ CO2Mixtures ~ CO2 –– CumeneCumene –– nC9 ternary system at High Pressure RangenC9 ternary system at High Pressure RangeCO2CO2 Mixtures ~ CO2Mixtures ~ CO2 –– CumeneCumene –– nC9 ternary system at High Pressure RangenC9 ternary system at High Pressure Range


CO2CO2 Mixtures ~ CO2Mixtures ~ CO2 –– CumeneCumene –– nC9 ternary system at High Pressure RangenC9 ternary system at High Pressure RangeCO2CO2 Mixtures ~ CO2Mixtures ~ CO2 –– CumeneCumene –– nC9 ternary system at High Pressure RangenC9 ternary system at High Pressure Range



WaterWater Mixtures ~ Solubility of water moisture into supercritical CO2Mixtures ~ Solubility of water moisture into supercritical CO2WaterWater Mixtures ~ Solubility of water moisture into supercritical CO2Mixtures ~ Solubility of water moisture into supercritical CO2


WaterWater Mixtures ~ Solubility of water moisture into supercritical CO2Mixtures ~ Solubility of water moisture into supercritical CO2WaterWater Mixtures ~ Solubility of water moisture into supercritical CO2Mixtures ~ Solubility of water moisture into supercritical CO2



WaterWater Mixtures ~ WaterMixtures ~ Water –– nC8 (VLLE) atnC8 (VLLE) at AAtmospheric Pressuretmospheric PressureWaterWater Mixtures ~ WaterMixtures ~ Water –– nC8 (VLLE) atnC8 (VLLE) at AAtmospheric Pressuretmospheric Pressure

All of the thermo models (pPR78, NRTL, SRKM, TBC) show good agreements withthe experimental data except water solubility into liquid octane. The pPR78 andSRKM indicate lower solubility in comparisons of the experimental data.


WaterWater Mixtures ~ WaterMixtures ~ Water –– nC8 (VLLE) atnC8 (VLLE) at AAtmospheric Pressuretmospheric PressureWaterWater Mixtures ~ WaterMixtures ~ Water –– nC8 (VLLE) atnC8 (VLLE) at AAtmospheric Pressuretmospheric Pressure

All of the thermo models (pPR78, NRTL, SRKM, TBC) show good agreements withthe experimental data except water solubility into liquid octane. The pPR78 andSRKM indicate lower solubility in comparisons of the experimental data.



WaterWater Mixtures ~ WaterMixtures ~ Water –– nC8 (LLE at Low to high pressure)nC8 (LLE at Low to high pressure)WaterWater Mixtures ~ WaterMixtures ~ Water –– nC8 (LLE at Low to high pressure)nC8 (LLE at Low to high pressure)

There are two groups in experimental data. One is Tu and Englin. The other is Heidman andBudantseva. NRTL and TBC seems to be following Tu and Englin. SRKM and PR with freewater agree Heidman group. The pPR78 is predicting significantly lower solubility values.


WaterWater Mixtures ~ WaterMixtures ~ Water –– nC8 (LLE at Low to high pressure)nC8 (LLE at Low to high pressure)WaterWater Mixtures ~ WaterMixtures ~ Water –– nC8 (LLE at Low to high pressure)nC8 (LLE at Low to high pressure)

There are two groups in experimental data. One is Tu and Englin. The other is Heidman andBudantseva. NRTL and TBC seems to be following Tu and Englin. SRKM and PR with freewater agree Heidman group. The pPR78 is predicting significantly lower solubility values.


IV. DiscussionIV. Discussion~ Conclusion Remarks for Validation Work~ Conclusion Remarks for Validation Work


Major Hydrocarbon Binary Mixtures

The pPR78 shows almost same results as the existing PR with SSI kij bank. Itcould be expected that pPR78 would show similar performance to PR fordistillation column study.

Asymmetric Hydrocarbon Binary Mixture

The pPR78 shows pretty good performance for asymmetric hydrocarbon binary(the sizes of molecules are different) at extra high pressure conditions (ex.reservoir pressure).


High Pressure VLE for Wide Range Paraffinic Compound Mixtures

The pPR78 shows good results for estimation phase envelop curve, especiallybubble point curve. This would be a big advantage of pPR78.



The pPR78 shows almost same results as the existing PR with SSI kij bank. Itcould be expected that pPR78 would show similar performance to PR fordistillation column study.

Asymmetric Hydrocarbon Binary Mixture




High Pressure VLE for Wide Range Paraffinic Compound Mixtures

The pPR78 shows good results for estimation phase envelop curve, especiallybubble point curve. This would be a big advantage of pPR78.


Selected Mixtures for this Validation Study CO2 Mixtures

The pPR78 shows pretty good agreements with experimental data at lowtemperature and high pressure range for Methane – CO2 – Ethane ternary VLE.The pPR78 shows better results for VLE of CO2 – Heptadecane system and

phase envelop curve for CO2 – Cumene – Nonane system.The pPR78 shows poor performance for prediction of solubility of water moisture

into supercritical CO2. This testing assumes dehydration operation for CO2pipeline.

Water Mixtures




The pPR78 shows poor performance for prediction of solubility of water into liquidoctane. The current pPR78 admit of further improvements for water –hydrocarbon mixtures. Otherwise, it would not be easy to apply pPR78 for highpressure VLLE calculation for gas – gas condensate – water system.










The pPR78 shows poor performance for prediction of solubility of water into liquidoctane. The current pPR78 admit of further improvements for water –hydrocarbon mixtures. Otherwise, it would not be easy to apply pPR78 for highpressure VLLE calculation for gas – gas condensate – water system.


Comparisons of possibility of pPR78 and PRO/II PR-HV for VLE calculation

Succeeded bypPR78 exceptwater system

Non

-idea

l

Non

-Idea

l Beh

avio

r in

Vapo

r Pha

se

(Ope

ratin

g P

ress

ure)

Original SRKOriginal SRKand PRand PR

Succeeded bypPR78

pPR78


Non-Ideal Behavior in Liquid PhaseIdeal Non-ideal

Non

-Idea

l Beh

avio

r in

Vapo

r Pha

se

Idea

l

(Ope

ratin

g P

ress

ure)

(Clustering, configuration of long chainmolecule etc.)


Combination with the existing P2modified alpha is a better choice foraccurate VP Calc. (ex. Mercaptanes)

A big advantage of pPR78 is GC modelwhich is tuned at extra high pressure range.


Comparisons of possibility of pPR78 and PRO/II PR-HV for VLE calculation


Non

-idea

l

Non

-Idea

l Beh

avio

r in

Vapo

r Pha

se


Not yet proven.Probably, possible.

Possible, buttuning isrequired.

PRO/II PR-HV



Combination with the existing P2modified alpha is a better choice foraccurate VP Calc. (ex. Mercaptanes)

Non-Ideal Behavior in Liquid PhaseIdeal Non-ideal

Non

-Idea

l Beh

avio

r in

Vapo

r Pha

se

Idea

l


Possible, buttuning isrequired.

The alpha of PRO/II PR-HVhas already been modifiedalpha formulas.

A big advantage of pPR78 is GC modelwhich is tuned at extra high pressure range.

IV. DiscussionIV. Discussion~~ Further ImprovementsFurther Improvements

A preliminary notice from Invensys for updating of pPR78 group parameters

The Current PRO/II (Ver. 9.2.0)1 (CH3) / 2 (CH2) / 3 (CH) / 4 (C) / 5 (CH4) / 6 (C2H6) / 7 (CHaro) /8 (Caro) / 9 (Cfused~arom) / 10 (CH2,cyclic) / 11 (Chcyc or Ccyc) / 12 (CO2) /13 (N2) / 14 (H2S) / 15 (SH) / 16 (H2O)

The Next PRO/II (Ver. 9.2.X)CH3 (group 1) / CH2 (group 2) / CH (group 3) / C (group 4) / CH4 (group 5) /C2H6 (group 6) / CH, aro (group 7) / C, aro (group 8) /Cfused aromatic rings (group 9) / CH2,cyclic (group 10) /CHcyclic or Ccyclic (group 11) / CO2 (group 12) / N2 (group 13) /H2S (group 14) / SH (group 15) / H2O (group 16) / C2H4 (group 17) /CH2,alkene/CH,alkene (group 18) / C,alkene (group 19) /CH,cycloalkene/C,cycloalkene (group 20) / H2 (group 21)

CH3 (group 1) / CH2 (group 2) / CH (group 3) / C (group 4) / CH4 (group 5) /C2H6 (group 6) / CH, aro (group 7) / C, aro (group 8) /Cfused aromatic rings (group 9) / CH2,cyclic (group 10) /CHcyclic or Ccyclic (group 11) / CO2 (group 12) / N2 (group 13) /H2S (group 14) / SH (group 15) / H2O (group 16) / C2H4 (group 17) /CH2,alkene/CH,alkene (group 18) / C,alkene (group 19) /CH,cycloalkene/C,cycloalkene (group 20) / H2 (group 21)

The group 17 to 21 are new added groups. And, water group would be revised at futureversion.


A preliminary notice from Invensys for updating of pPR78 group parameters

1 (CH3) / 2 (CH2) / 3 (CH) / 4 (C) / 5 (CH4) / 6 (C2H6) / 7 (CHaro) /8 (Caro) / 9 (Cfused~arom) / 10 (CH2,cyclic) / 11 (Chcyc or Ccyc) / 12 (CO2) /13 (N2) / 14 (H2S) / 15 (SH) / 16 (H2O)




The group 17 to 21 are new added groups. And, water group would be revised at futureversion.


Further improvements of water group are required. Revising of water group New thermo framework is required if the current pPR78 model is not enough for water

system.

Importance for modeling of gas hydrate equilibrium inhibitors Adding of typical gas hydrate equilibrium inhibitors (Methanol, MEG, DEG and TEG) Creating of new group for the above compounds

Possibility of creating of new thermo model framework based on pPR78 technology Can we handle pPR78 as a kij generator ? Can we fill out

missing kij or overwrite existing kij of original PR/SRK andHurvey-Prausnitz (SRKM / PRM) ?

pPR78 kij = Function (T)Schwartzentruber-Renon (SR-Polar) kij = Function (T,x)

The kij of pPR78 is relatively easy to combine with otherVdW1f mixing rule since it is function of only T.Can we integrate pPR78 kij into PR-HV since HV mixing

rule is a flexible mixing rule for polar system ?


Further improvements of water group are required. Revising of water group New thermo framework is required if the current pPR78 model is not enough for water

system.

Importance for modeling of gas hydrate equilibrium inhibitors Adding of typical gas hydrate equilibrium inhibitors (Methanol, MEG, DEG and TEG) Creating of new group for the above compounds

Invensys announced a concreteplan for revision of water group ofpPR78 at the next patch in winter.


Possibility of creating of new thermo model framework based on pPR78 technology Can we handle pPR78 as a kij generator ? Can we fill out

missing kij or overwrite existing kij of original PR/SRK andHurvey-Prausnitz (SRKM / PRM) ?

pPR78 kij = Function (T)Schwartzentruber-Renon (SR-Polar) kij = Function (T,x)

The kij of pPR78 is relatively easy to combine with otherVdW1f mixing rule since it is function of only T.Can we integrate pPR78 kij into PR-HV since HV mixing

rule is a flexible mixing rule for polar system ?

pPR78 kij vs. Tr (Heavier), Jaubert et al. (2004)

C1-C3

C1-nC6

C1-nC10

AttachmentAttachment

1) J.-N. Jaubert and F. Mutelet, Fluid Phase Equil., 224, 285-304 (2004)2) J.-N. Jaubert, S. Vitu, F. Mutelet and J.-P. Corriou, Fluid Phase Equil., 237, 193-211

(2004)3) S. Vitu, J.-N. Jaubert and F. Mutelet, Fluid Phase Equil., 243, 9-28 (2006)4) R. Privat, J.-N. Jaubert and F. Mutelet, Ind. Eng. Chem. Res., 47, 2033-2048 (2008)5) R. Privat, J.-N. Jaubert and F. Mutelet, Ind. Eng. Chem. Res., 47, 10041-10052 (2008)6) S. Vitu, R. Privat, J.-N. Jaubert and F. Mutelet, J. Supercritical Fluids, 45, 1-26 (2008)7) R. Privat, J.-N. Jaubert and F. Mutelet, J. Chem. Thermodynamics, 40, 1331-1341 (2008)

Original Papers of pPR78



AttachmentAttachment






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