GPA TP-26-2000 Mutual Solubility in Water Methanol Hydrocarbon Solutions《水中 甲醇碳氢化合物溶液中的互溶性》.pdf
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1、Technical Publication TP=26 Mutual Solubility in Water/Methanol Hydrocarbon Systems DB Robinson Research Ltd. Norsk Hydro May, 2000 Gas Processors Association 6526 East 60th Street Tulsa, Oklahoma 74145 Phone: 9181493-3872 * FAX: 9181493-3875 FOREWORD Methanol is commonly used as hydrate inhibitor a
2、nd for hydrate melting in gas production and processing facilities. GPA has funded several projects investigating the hydrate inhibition effects of methanol. Additionally it is important to have a good understanding of the methanol distribution in the hydrocarbon and aqueous phases, when designing t
3、hese systems. The available experimental data for methanol distribution is limited. This Technical Publication (TP) is a summary of work done by Norsk Hydro. The data was compiled by DBR and Associates, the principal investigators for this work. The GPA wishes to thank Norsk Hydro for their willingn
4、ess to share this data with the industry and save the GPA from using their limited research budget for remeasuring similar data. - Subgroup 2 David Bergman/ Chairman Technical Section F “Copyright 2000 by Gas Processors Association. All rights reserved. No part of this Publication may be reproduced
5、without the written consent of the Gas Processors Association.” 1 GPA DISCLAIMER GPA publications necessarily address problems of a general nature and may be used by anyone desiring to do so. Every effort has been made by GPA to assure accuracy and reliability of the information contained in its pub
6、lications. With respect to particular circumstances, local, state, and federal laws and regulations should be reviewed. It is not the intent of GPA to assume the duties of employers, manufacturers, or suppliers to warn and properly train employees, or others exposed, concerning health and safety ris
7、ks or precautions. GPA makes no representation, warranty, or guarantee in connection with this publication and hereby expressly disclaims any liability or responsibility for loss or damage resulting from its use or for the violation of any federal, state, or municipal regulation with which this publ
8、ication may conflict, or for any infringement of letters of patent regarding apparatus, equipment, or method so covered. 11 MUTUAL SOLUBILITY IN WATEWMETHANOL HYDROCARBON SOLUTIONS 1 .O INTRODUCTION In the course of carrying out engineering calculations involving the use of methanol as a dehydrating
9、 agent or as a hydrate depressant, one frequently encounters the problem of knowing the distribution of methanol between the aqueous liquid phase and the hydrocarbon liquid or gaseous phases. Although limited data are available on the mutual solubility of methanol and liquid hydrocarbons or related
10、materials such as hydrogen sulfide and carbon dioxide, little or no data seem to exist on the distribution of the methanol in such a system if it equilibrated with water. In practice, this lack of information creates a problem in calculating the methanol requirements to achieve a specified depressio
11、n. For example, the specified methanol concentration in the aqueous liquid may be 20 wi. percent, but the total methanol that must be added to the flowing system containing liquid condensate to achieve this concentration cannot be reliably calculated. These matters are of obvious concern to Companie
12、s such as Norsk Hydro which have extensive oil and gas operations in the North Sea where all of the conditions necessary for hydrate formation are normally present. In order to advance the technology in this area, Norsk Hydro undertook a systematic investigation of the distribution of water and meth
13、anol between hydrocarbon and aqueous phases. The first part of the study included measurements on simple well defined systems containing the classes of compounds of interest, namely paraffinic, aromatic and naphthenic hydrocarbons. The information on these systems can be used for testing existing mo
14、dels and for model development. The final stage of the study used actual North Sea condensate fluids to provide data on the actual systems of interest to Norsk Hydro and to provide information to evaluate the proposed models. 2.0 SCOPE Part I covered measurements on three hydrocarbon mixtures contai
15、ning constant methane and propane content and varying amounts of toluene, n-heptane and methyl cyclohexane. One mixture was rich in n-heptane, one in toluene and one in methylcyclohexane. They had the following compositions: Mole Fraction Component Mixture I Mixture II Mixture III CH4 C3H8 nC7 O .63
16、 0.07 0.1 6 0.63 0.07 0.07 Methylcyclohexane 0.07 0.16 Toluene 0.07 0.07 0.63 0.07 0.07 0.07 0.16 It was originally planned to study each mixture at temperatures of -100, 200 and 5OoC, at a pressure of 100 bars and at methanol concentrations of nominally 20, 40 and 60 percent by weight. However, the
17、 20 and 40 wi.% methanol mixtures could not be studied at -lOC because of hydrate formation. Consequently, measurements were made about 1C above the hydrate formation temperature. This was 12.30C for the 20 wt.% methanol solution and -1.70C for the 40 wt.% solution. At each experimental temperature/
18、pressure/concentration condition, the composition of the equilibrium hydrocarbon liquid, the aqueous liquid and the vapor phase was determined. Part II covered measurements on three hydrocarbon mixtures. The first mixture contained methane, propane, toluene, n-heptane and methyl cyclohexane; the sec
19、ond mixture contained methane and benzene; and the third mixture contained methane and 1,3,5 trimethyl benzene. These mixtures had the following compositions: 1 Mole Fraction Mixture i Mixture I! Mixture iiJ Component CH4 C3H8 nC7 0.6405 0.6 0.0679 0.0972 Met hy I Cyclohexane 0.0972 Toluene 0.0972 B
20、enzene 0.4 0.6 Mesitylene 0.4 The experimental conditions for mixture I were pressures of 50, 1 O0 and 150 bars, at a temperature of 20C and at methanol concentrations of nominally 20, 40 and 60 percent by weight at each pressure condition. This experiment was to investigate the effect of pressure o
21、n relative phase compositions for each component. It was originally planned to study mixtures II and III at temperatures of -loo, 200 and 50C, at a pressure of 100 bars and at methanol concentrations of nominally 20, 40 and 60 percent by weight. In addition, the amount of methanol-water solution cha
22、rged into the cell for the test was to be kept to a minimum. However, the lowest temperature that could be used for mixture II was OC, in order to avoid hydrate formation and/or freezing of benzene. Similarly, the 20 and 40 wt Y methanol mixtures could not be studied at -10C for mixture III because
23、of hydrate formation. Consequently, a temperature of 3C was used instead. At each experimental temperature/pressure/concentration condition, the composition of the equilibrium hydrocarbon liquid, the aqueous liquid and the vapour phase were determined. However, only the methanol and water concentrat
24、ions in the aqueous phase were determined for the studies on mixture II and 111. This was because the amount of aqueous liquid present in the system was too small for a reliable determination of the hydrocarbons solubility. Part III covered measurements on a stabilized condensate when mixed with two
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