1、STDOGPA TP-24-ENGL 1997 3824699 00199494T4 = Addendum To GPA TP-24 Solubility and Vapor-Liquid Equilibrium Data for Systems Containing Diamondoids, Gas Mixtures, Feed Stock Oil and Triethylene Glycol Gas Processors Association 6526 East 60* Street Tulsa, Oklahoma 74145 Phone 918-493-3872 Fax 918-493
2、-3875 Diamondoid Hydrocarbons in Deep Gas Accumulations Diamondoid hydrocarbons occur in crude oils and condensates, and certain post-mature natural gas accumulations which partly derive 6om the natural cracking of oils. The chemical structures of diamondoid hydrocarbons are based on progressively l
3、arger fiagments of the diamond lattice. For this reason, they are a class of extremely stable compounds that appear to survive late-stage catagenesis, metagenesis, and thermochemical sulfate reduction. Diamondoid hydrocarbons survive after oil accumulations have been geologically transformed into dr
4、y methane and pyrobitumen. Diamondoids also display unusual physical characteristics compared to other petroleum and natural gas hydrocarbons, exhibiting melting points hundreds of degrees higher than n- parafns of comparable molecular weight. These unusual properties can cause severe gas field prod
5、uction problems as diamondoid solids plate-out inside surface production facilities. However, the great stability of the diamondoids is also beig used to develop new source, correlation, and thermai maturity parameters valuable in oil and gas exploration. The first member of the diamondoid hydrocarb
6、on family is adamantane, a CIO hydrocarbon. Each higher member of the family has four additional carbons added as a three-dimensional cage, hence, we have diamantane CI), triamantane (CIS), and so on. Adamraitane c1fi16 Triamaniane 1 SH24 “anti“ Tetramautane (me of thra isomers) c22H28 While the fir
7、st three members of the diamondoid family have oniy a single form, tetramantane (CU) and higher members show exploding numbers of isomers. The higher diamondoids are extremely diiicult to synthesize in the laboratory. The largest diamondoid hydrocarbon synthesized so far is one of the tetramantanes.
8、 However, not oniy the tetramantanes, but also pentamantanes (C,) and hexamantanes (C,) occur naturally in some deep gas accumulations. These hard-to-synthesize, high molecular weight diamondoid hydrocarbons may represent an important, and valuable resource. Some diamondoid hydrocarbons have melting
9、 points over 4F, yet have relatively high vapor pressures, giving these compounds high solubility in gas at bottom-hole pressures and temperatures. As gas is produced, diamondoid hydrocarbons can condense as whitish crystalline solids in surface production pipes and separators, causing costly produc
10、tion shutdowns if preventative measures have not been taken. However, other naturally occurring, methylated diamondoids remain liquids at ambient temperatures. Furthermore, STD*GPA TP-24-ENGL 1997 = 3824699 0039953 052 9 diamondoid concentrations in gas reservoirs can vary greatiy. Extraordinarily h
11、igh concentrations (up to -100 lb per MCF) of scale-forming diamondoid hydrocarbons can occur in dry gas produced fiom deep Norphlet sandstone reservoirs (20,000 A) in the Gulf of Mexico. Therefore, accurate identication and quantSication of diamondoid hydrocarbons in production gas streams can be c
12、ritical for proper facilities design and production management. Diamondoid hydrocarbon scaling problems can be expected to become more common as naturai gas drilling operations focus on progressively deeper horizons. STDmGPA TP-24-ENGL 3997 3824b99 0039952 T99 = Technical Pu bl cat ion TP-24 Solubil
13、ity and Vapor-Liquid Equilibrium Data for Systems Containing Diamondoids, Gas Mixtures, Feed Stock Oil and Triethylene Glycol Heng-Joo Ng DB Robinson Research Ltd. Edmonton, Alberta, Canada December, 1997 Gas Processors Association 6526 East 60th Street Tulsa, Oklahoma 74145 Phone: 918/493-3872 9 FA
14、X: 9181493-3875 STD-GPA TP-24-ENGL 1997 3824b99 0019953 925 = Solubility and Vapor-Liquid Equilibrium Data for Systems Containing Diamondoids, Gas Mixtures, Feed Stock Oil and Triethylene Glycol Heng-Joo Ng Di3 Robinson Research Ltd. Calgary, Alberta, Canada December 1997 FOREWORD In 1990, the GPA b
15、egan a joint project with GRI on solid deposition in hydrocarbon systems, Project 905. During this project with GRI, the importance of understanding Diamondoid deposition directly from il gas phase in production equipment and pipelines became apparent. Although no project funds were used to measure
16、data on Diamondoids, a number of member companies either had measured data or were in the process of measuring data. This Technical Publication (TP) is a summary of that work donated by those companies. The data was compiled by DBR and Associates as they were the principal investigator for these com
17、panies with some data measured at Wiltec. The GPA wishes to thank Exxon, Chevron, Mobil and Unocal for their willingness to share this data with the industry and to save the GPA from using their limited research budget for remeasuring similar data. teering Committee Dave Bergman Chai ririan Technica
18、l Section F Technical Data Development “Copyright O 1998 by Gas Processors Association. Ail rights reserved. No part of this report may be reproduced without the written consent of the Gas Processors Association.“ i STDOGPA TP-24-ENGL 3997 3824b99 0039955 7T8 = GPA DISCLAIMER This Technical Publicat
19、ion was prepared by DB Robinson Research Ltd. in Co-ordination with the GPA Phase Equilibria Steering committee. Neither GPA, DB Robinson Research Ltd., nor any person acting on behalf of either makes any warranty, guarantee or representation, express or implied, with respect to the accuracy, comple
20、teness, or usefulness of the information contained in this report. The GPA and DB Robinson Research Ltd. hereby expressly disclaim any liability or responsibility for loss or damage resulting from the use of any apparatus, method, or process disclosed in this report; and for the infringement or any
21、patent or the violation of any federal, state or municipal law or regulation arising from the use of, any information, apparatus, method, or process disclosed in this report. ii AUTHORS INTRODUCTION All experimental works except the vapor pressure measurements described in this publication were carr
22、ied out at DB Robinson Research Ltd. in Edmonton, Alberta, Canada during the period from September 1988 to May 1993. The experimental measurements were carried out by Mr. Hans Nerenberg and Mr. Helmut Schroeder under the direction of Dr. Heng-Joo Ng. The vapor pressure measurements were carried out
23、at Wiltec Research Company, Inc. in Provo, Utah during June, 1992. . 111 STDOGPA TP-24-ENGL 3997 I 3824699 0039957 570 W TABLE OF CONTENTS Page Foremrd i GPA Disclaimer ii Authors Introduction . iii Table of Contents iv List of Tables v, vi List of Figures .vi . . 1.0 RESULTS AND DlSCUSSIONS 1 1.1 1
24、.2 1.3 1.4 1.5 I Diamondoid Solubility Data 1.1.1 1.1.2 1.1.3 1.1.4 System System System System I I 111 . 6 II 18 IV 26 Vapor-Liquid Equilibrium Study . 36 1-21 System v . 36 1-22 System VI 49 Vapor-Liquid Equilibrium Diamondoids in TEG Solution (System Vil) . 69 Vapor pressure of 1,3-Dimethyl Adama
25、ntane . 75 Experimenta I Detai 1s 78 1.5.1 1.5.2 1.5.3 1.5.4 1.5.5 1.5.6 1.5.7 Gas MixhJre Preparation 78 Equipment . 78 Solubility Data . 78 Vapor-Liquid Equilibrium Data . 79 Analysis . 79 Density MeaslJl-ements . 80 Vapor pressure Data 80 iV List of Tables Page Table 1.1 Table 1.2 Table 11.1 Tabl
26、e 11.2 Table 11.3 Table 11.4 Table 111.1 Table 111.2 Table 111.3 Table 111.4 Table IV.l Table IV.2 Table IV.3 Table IV.4 Table IV.5 Table V.l Table V. 1 a Table V.2 Table V.2a Table V.3 Table V.3a Table V.4 Table V.4a Table V.5 Table V.5a Compositions of Supplied Adamantane and Diamantane Samples So
27、lubility of Adamantane andlor Diamantane in the Gas Mixture 3 4 . . Solubility of Diamondoid Mixture in the Prepared Gas Mixture 8 9 Il . Solubility of Diamondoid Mixture in the Prepared Gas Mixture Solubility of Diamondoid Mixture in the Prepared Gas Mixture . 10 Solubility of Diamondoid Mixture in
28、 the Prepared Gas Mixture . Compositions of Diamondoid Field Samples . 20 Diamantane) in Sour Gas . 21 Diamantane) in Sour Gas . 22 Solubility of Diamantane (Field Sample) in Sour Gas 23 Solubility of Diamondoid (1.8:l Field Sample of Adamantane to Solubility of Diamondoid (2:l Field Sample of Adama
29、ntane to Compositions of Gas Mixtures and Diamondoid Mixture . 27 Compositions of 150N Basestock and #5 Fuel Oil 28 Solubility of Diamondoids in Gas Mixture No. 1 . 29 Solubility of Diamondoids in Gas Mixture No. 2 . 30 Solubility of Diamondoids in Gas Mixture No. 2 . 31 Compositions of VLE Study fo
30、r 5 wt % Diamondoids in Solvent Compositions of VLE Study for 5 wt % Diamondoids in Solvent 150N Basestock with the Gas Mixture at 100F and 1414 psia 38 Compositions of VLE Study for 5 wt % Diamondoids in Solvent Compositions of VLE Study for 5 wt % Diamondoids in Solvent 150N Basestock with the Gas
31、 Mixture at 280F and 1414 psia 40 Compositions of VLE Study for 5 wt % Diamondoids in Solvent 150N Basestock with the Gas Mixture at 100F and 1414 psia 41 Compositions of VLE Study for 15 wt % Diamondoids in Solvent 150N Basestock with the Gas Mixture at 100F and 1414 psia 42 Compositions of VLE Stu
32、dy for 5 wt % Diamondoids in Solvent Compositions of VLE Study for 5 wt % Diamondoids in Solvent Compositions of VLE Study for 5 wt % Diamondoids in Solvent Compositions of VLE Study for 5 wt % Diamondoids in Solvent Of #5 Fuel Oil with the Gas Mixture at 280F and 1414 psia . 46 150N Basestock with
33、the Gas Mixture at 100F and 1414 psia 37 150N Basestock with the Gas Mixture at 280F and 1414 psia 39 Of #5 Fuel Oil with the Gas Mixture at 100F and 1414 psia . 43 Of #5 Fuel Oil with the Gas Mixture at 100F and 1414 psia . 44 Of #5 Fuel Oil with the Gas Mixture at 280F and 1414 psia . 45 V Table V
34、I. 1 Table V1.2 Table V1.3 Table V1.4 Table V1.5 Table V1.6 Table V1.7 Table V1.8 Table V1.9 Table V1.10 Table VII.l Table V11.2 Table V11.3 Table VIL4 Table VIL5 Table VIII.l Compositions of Sour Gas, CIO and CIO-Diamondoid . 50 Equilibrium Phase Compositions for Sour Gas-CIO System at 170F and 120
35、0 psis 51 Equilibrium Phase Compositions for Sour Gas-CIO-Diamondoid System at 170F and 1200 Psis . 52 Equilibrium Phase Compositions for Sour Gas-CIO-Diamondoid Equilibrium Phase Compositions for Sour Gas-CIO-Diamondoid Equilibrium Phase Compositions for Sour Gas-CIO-Diamondoid Compositions of Sour
36、 Gas and Separator Sample 110-1 Reservoir Oil 56 Equilibrium Phase Compositions for Sour Gas-1 10-1 Oil at Equilibrium Phase Compositions for Sour Gas-1 10-1 Oil at 100F and 1200 psis 58 59 Equilibrium Phase Compositions for Sour Gas 1 10-1 Oil at 70F and 1200 psis : System at 1 7OoF and 900 psis .
37、53 System at 100F and 1200 psis . 54 System at 1OOoF and 900 Psis . 55 170F and 1200 psis 57 Compositions of Prepared Gas and Supplied Condensate . 70 Compositions of Selected Streams at 1200 psia and 90F (97 wt % TEG Solution) 71 Compositions of Selected Streams at 1200 psia and 120F (97 wt TEG Sol
38、ution) 72 Compositions for Vapor Phase and Ci O+ Fraction of Liquid Phase By Flashing Saturated 97 wt % TEG Phase Compositions of Selected Streams at 1200 psia and 1200F (1200 psis and 120F) at 200F and 50 psis . 73 (98.5 wt ?4 TEG Solution) . 74 Measured and Correlated Vapor Pressures for 1 v3-Dime
39、thyl Adamantane 76 vi STD-GPA TP-Z4-ENGL 3997 3824699 00L9b0 Ob5 m List of Figures Page . Figure 1.1 Chromatogram of Adamantane and Diamantane Samples 5 Figure II . 1 Chromatogram of Adamantane 12 Figure 11.2 Figure 11.3 Figure 11.4 Chromatogram of l-MethYl Achmantane . ; . 13 Chromatogram of 1 v3-D
40、imethyl Adamantane 14 Chromatogram of Diamantane . 15 Figure 11.5 Figure 11.6 Typical Chromatogram of Diamondoid in the Mixture 16 Typical Chromatogram of Diamondoid in the Mixture 17 Figure 111.1 GC Chromatogram for Adamantane Field Sample 24 Figure 111.2 GC Chromatogram for Diamantane Field Sample
41、 . 25 Figure IV.l Chromatogram of Supplied Diamondoids Sample .i . 32 Figure IV.2 Chromatogram of the Supplied 150N Basestock . 33 Figure IV.3 Chromatogram of the Supplied #5 Fuel Oil 34 Figure IV.4 Chromatogram of Cio+ in Vapor Phase for Typical Solubility Study 35 Figure V. 1 Figure V.2 Chromatogr
42、am of C1 O+ Fraction of the Vapor Phase for Typical Chromatogram of CIO+ Fraction of the Liquid Phase for Typical VLE Study 47 VLE Study 47 . . Figure Vi.1 Figure V1.2 Figure V1.3 Figure V1.4 Figure V1.5 Figure V1.6 Figure V1.7 Figure V1.8 Figure V1.9 Chromatogram of CIO Chromatogram of ClO-Diamondo
43、ids Mixture 61 Chromatogram of Liquid from the Vapor Sample by Freezing Method Using the Megabore Column 63 Chromatogram of GOR Liquid Sample 64 Chromatogram of 110-1 Reselwir Oil . 65 Chromatogram of Gas Sample Using Megabore Column . 66 Chromatogram of Liquid from the Vapor Sample by Freezing Meth
44、od Using Megabore COhmn 67 Chromatogram of GOR Liquid Sample Using the Capillary Column . 68 Chromatogram for GOR Gas Using Megabore Column 62 Figure VIM Vapor Pressure of 1,3-Dimethyl Adamantane . 77 Figure IX.1 Figure IX.2 Figure X. 1 Schematic of Phase Behavior CeIl . 81 Vapor pressure Apparatus
45、. 82 Principal Diamondoid Compound Structures and Their Physical Properties 83 . vii STD-GPA TP-24-ENGL 1997 3824b99 00199bl TTL II 1 .O RESULTS AND DISCUSSIONS The experimental work consisted of four parts. The first part dealt with the solubility of diamondoid compounds in four selected gasdiamond
46、oid systems. The first three gas- diamondoid systems were in the vapor-solid region while the fourth system was in the vapor-liquid region. The second part dealt with a vapor-liquid equilibrium study for systems containing a gas mixture, diamondoids, 150N basestock, #5 fuel oil, corrosion inhibitor
47、oil (CIO) or 100-1 reservoir oil. The third part dealt with a vapor-liquid equilibrium study for systems containing a sour gas mixture, condensate and triethylene glycol. The fourth part dealt with vapor pressure determination for I ,3dimethyl Adamantane. 1.1 Diamondoid Solubility Data 1.1.1 System
48、I (i) Scope The experimental program for this system involved the following studies. (a) The preparation of a suitable amount of gas mixture having the following specified composition: Component Mole % CH4 C2H6 CO2 90 5 5 (b) The determination of the solubilities of the adamantane andlor diamantane
49、at specified pressures and temperatures as follows: AdamantanelDiaman tane Tem pera tu re by wt. “F l:o o: 1 1:l 1:1 1:l 1:l 1:l 1:l 180 180 180 180 120 50 300 300 Pressure psia 3000 3000 3000 1200 1200 1200 3000 7000 1 STD-GPA TP-ZLi-ENGL 1977 3824b99 00199b2 938 ( II ) Results and Discussions , The compositions of the supplied adamantane and diamantane samples are given in Table 1.1. The analysis was carried out using the gas chromatographic method. The samples were divided into four components for adamantane and two components for diamantane. The chr
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