Determining the Ionic Dew Point

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1 OLI Systems, Inc. Determining the Ionic Dew Point Amine Surveys in Refinery Overhead Chemistry using OLI Studio Rasika Nimkar May 5, 2017

2 Copyright 2017 OLI Systems, Inc. All rights reserved. The enclosed materials are provided to the lessees, selected individuals and agents of OLI Systems, Inc. The material may not be duplicated or otherwise provided to any entity without the expressed permission of OLI Systems, Inc. 240 Cedar Knolls Road STE (Fax) Disclaimer: This document was produced using the OLI Studio version As time progresses, new data and refinements to existing data sets can result in values that you obtain being slightly different than what is presented in this manual. This is a natural progress and cannot be avoided. When large systematic changes to the software occur, this document will be updated. 1

3 Amines survey in Refinery Overhead Chemistry OLI Added MSE parameters for the pure, binary and multicomponent systems of the targeted species. A list of amines and amine s in the existing OLI V9.5.2 database Descriptive name Alkyl amines Chemical formula OLI Formula OLI Tag Cation name Amine Hydrochloride name OLI Tag Name for Methylamine CH 3 NH 2 CH3NH2 MEAMINE MEAMINEHION Dimethylamine (CH 3 ) 2 NH C2H7N DMEA DMEAHION Trimethylamine (CH 3 ) 3 N C3H9N TRIMEAMINE TRIMEAMHION Ethylamine CH 3 CH 2 NH 2 C2H7N ETAMINE ETAMINEHION Diethylamine CH 3 CH 2 NHCH 2 CH 3 C4H11N DIETHYLAMN DIETHYLAHION Propylamine CH 3 (CH 2 ) 2 NH 2 C3H9N PROPYLAMN PROPAMHION Butylamine CH 3 (CH 2 ) 3 NH 2 C4H11N BUTYLAMINE BUTYLAMHION 2 Butanamine CH 3 CH 2 CH(CH 3 )NH 2 C4H11N SECBUTYAMN SECBUAHION Cyclohexylamine c (CH 2 ) 5 CHNH 2 C6H13N CYCLHEXAMN CHEXAMNHION Ethylenediamine H 2 N(CH 2 ) 2 NH 2 C2H8N2 ENAMN2 ENAMN2HION Table 1 Methylamine Dimethylamine Trimethylamine Ethylamine Diethylamine n Propylamine Butylamine 2 Butylamine Cyclohexylamine Ethylenediamine di MEAHCL DMEAHCL TMEAHCL EAHCL DEAHCL PROPAMHCL BUTAMHCL SECBAHCL CHEXAHCL ENAMN2HCL Alkanolamines Ethanolamine HO(CH 2 ) 2 NH 2 NH2C2H4OH MEXH MEXH2ION Diethanolamine Dimethylethano lamine Diglycolamine Dimethylisoprop anolamine Methyldiethanol amine Table 2 Oxygenated amines HO(CH 2 ) 2 NH(CH 2 ) 2 OH HN(C2H4OH )2 DEXH DEXH2ION (CH 3 ) 2 N(CH 2 ) 2 OH C4H11NO DMEXH DMEXH2ION HO(CH 2 ) 2 O(CH 2 ) 2 N H 2 HOCH(CH 3 )CH 2 N(C H 3 ) 2 NH2C2H4OC 2H4OH DGXH DGXH2ION C5H13NO DMIPA DMIPAHION CH 3 N(C 2 H 4 OH) 2 C5H13NO2 MDEXH MDEXH2ION Ethanolamine Diethanolamine Dimethylisopropano lamine MEXHCL DEXHCL DMIPAHCL 2

3 Methoxypropylamine H 2 N(CH 2 ) 3 OCH 3 C4H11NO MOPA MOPAHION Morpholine c (CH 2 ) 2 O(CH 2 ) 2 NH C4H9NO MORPHOLN MORPHHION N Methylmorpholine N Ethylmorpholine Table 3 c (CH 2 ) 2 O(CH 2 ) 2 NCH

refinery overhead type of application, traditionally the chemistry of interest has been CO 2, H 2 S, H 2 O, HCl, NH 4 Cl, hydrocarbons and amines.

4 3 Methoxypropylamine H 2 N(CH 2 ) 3 OCH 3 C4H11NO MOPA MOPAHION Morpholine c (CH 2 ) 2 O(CH 2 ) 2 NH C4H9NO MORPHOLN MORPHHION N Methylmorpholine N Ethylmorpholine Table 3 c (CH 2 ) 2 O(CH 2 ) 2 NCH 3 c (CH 2 ) 2 O(CH 2 ) 2 NC 2 H 5 C5H11NO NMM NMMHION C6H13NO NEM NEMHION 3 Methoxypropylamine Morpholine N methylmorpholine N Ethylmorpholine MOPAHCL MORPHHCL NMMHCL NEMHCL Amines and amine s: In refinery overhead type of application, traditionally the chemistry of interest has been CO 2, H 2 S, H 2 O, HCl, NH 4 Cl, hydrocarbons and amines. Our goal in demonstrating the following parametric survey in OLI Studio is to demonstrate OLI s capability in predicting the overhead chemistry behavior at various temperature ranges. Process: In the following example, we will mix two different streams together in a Mixer and export the output of the mixer as a molecular stream. We will then perform a survey on it. Step1: Adding an Assay stream: Figure 1 Add a stream Rename is to Crude Assay Change the Stream amount and Inflows units to lb/hr Change the Temperature unit to F. Add an Assay with the shortcut Shift +Enter Change the Assay Data type to TBP Curve 3

curve: Figure 2 Assay Parameters: Select the Average Bulk Density Type as

5 Leave all other items with their default values. Step 2: Adding the Distillation Data: Add the following data set for the TBP curve: Figure 2 Assay Parameters: Select the Average Bulk Density Type as Specific Gravity and use as the value. Input 10 as the number of Distillation Curve Cuts. The Thermo Method is API 8. 4

6 Step 3: Additional Components stream: Add a second stream and rename it as Additional Components. The conditions: T ( C) 230 P (atm) 3.05 Table 4 Inflows in lb/hr H2O HCL 6.99 NH3 1.90E 05 C2H6 9.93E 03 C2H4 1.00E 03 C3H C3H6 5.63E 04 H2 1.80E 04 C6H C4H TBUTEN 3.76E 05 BUTENE1 5.51E 05 CBUTEN 1.75E 05 ISOBUTANE ISOBUTENE 5.51E 05 C5H E 03 IPENTAN N2 0 MEXH Table 5 The stream will look like the following: 5

7 Figure 3 Step 4: Add a Mixer: Add both the streams in this Mixer. Figure 4 Perform a Single Point Mix calculation at 121 C and 1 atm. 6

8 Figure 5 Click on Add as Stream button circled above. Rename the exported stream as a Mixed Stream. Figure 6 7

9 Step 5: Add a survey: Figure 7 Click on Specs and select the survey by Temperature. Put the range in from 65.5 C to C with an increment of

10 Figure 8 Click OK. 9

12 Figure 10 Analysis of the Plot: These plots are conventionally read from high temperature to low temperature because in the refinery overhead process this type of behavior has highest probability of occurring at the top trays of a distillation column. The formation of the Ionic phase starts at 105 C. Below 94 C, we observe high concentrations of MEXHION and CLION. The above phenomenon indicates the initial formation of the aqueous phase corresponding with a high ion concentration in that phase. In this specific example, the formation of a concentration solution of ions should be identified as the separation of a liquid salt. It should also be noted that the liquid salt will practically never be pure because the ionic amine liquids are freely miscible with water. Thus, we term this behavior as identification of ionic dew point. Solid forming Amine: Now that we observed the ionic dew point phenomena, we will plot an amine which does have a distinctive salt point. For this calculation, we will modify the Additional Components Stream and add 0.5 lb/hr of Ethylenediamine which has OLI tag name ENAMN2. Repeat Step 4 to Step 6, which involves adding a mixer and adding the Crude stream along with the modified Additional Components stream and exporting the output at a new stream. Once a survey is added to the above stream which we can name as Salt Point, we can see the following plot. Remember to change the Y axis to Logarithmic Scale by right clicking on the Y Axis. 11

Figure 11 The salt point plot can be seen below: Figure 12 Analysis of the Plot: Because we have both the ion forming amine as well as the solid forming amine, we can identify both the ionic dew

13 Figure 11 The salt point plot can be seen below: Figure 12 Analysis of the Plot: Because we have both the ion forming amine as well as the solid forming amine, we can identify both the ionic dew point and the salt point in the above plot. The water dew point (WDP) in such cases is the temperature where a large amount of H2O is condensing from the vapor stream. The mole fraction of H2O in this phase is largest concentration as a rule. 12

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Amine hydrochlorides in refinery overheads: Solving corrosion problems through electrolyte process simulation Prodip Kundu

Amine hydrochlorides in refinery overheads: Solving corrosion problems through electrolyte process simulation Prodip Kundu OLI Systems Inc. 2014 Software Global Customer Conference September 30 - October