Vapor Phase Nitration of Butane in a Molten Salt Reactor Dennis Lee Fear Iowa State University
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Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1964 Vapor phase nitration of butane in a molten salt reactor Dennis Lee Fear Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Chemical Engineering Commons Recommended Citation Fear, Dennis Lee, "Vapor phase nitration of butane in a molten salt reactor " (1964). Retrospective Theses and Dissertations. 3849. https://lib.dr.iastate.edu/rtd/3849 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. This dissertation has been Ç5-4605 microfilmed exactly as received FEAR, Dennis Lee, 1939- VAPOR PHASE NITRATION OF BUTANE IN A MOLTEN SALT REACTOR. Iowa State University of Science and Technology Ph.D., 1964 Engineering, chemical University Microfilms, Inc., Ann Arbor, Michigan VAPOR PHASE NITRATION OF BUTANE IN A MOLTEN SALT REACTOR by Dennis Lee Fear A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OP PHILOSOPHY Major Subject: Chemical Engineering Approved; Signature was redacted for privacy. In Charge of Major Work Signature was redacted for privacy. Head of Major Department Signature was redacted for privacy. Iowa State University Of Science and Technology Ames, Iowa 1964 ii TABLE OF CONTENTS Page ABSTRACT - - —iii INTRODUCTION - — 1 REVIEW OF LITERATURE — 6 Historical 6 Conversion and Yield 8 Types of Reactors 9 Paraffins Nitrated in the Vapor Phase 11 Pressure Effects 15 Temperature Effects 15 Catalysts 16 Mechanism of Reactions in Vapor Phase Nitration 18 EXPERIMENTAL - 30 Description of the Pilot Plant — 30 Operating Procedure 45 Analytical Procedure 47 DISCUSSION 57 Conversion and Yield 57 Analytical Results 68 Nitroparaffin Product Distribution 74 Indicated Reaction Mechanisms 79 Temperatures 83 Economic Evaluation of Process 83 CONCLUSIONS AND RECOMMENDATIONS - 91 BIBLIOGRAPHY - - 93 ACKNOWLEDGEMENTS 101 iii ABSTRACT In this work, butane was nitrated continuously in the vapor phase using a molten salt reactor. Molten salt temperature was varied from 371^C to 482*^0; mole ratio of hydrocarbon to nitric acid from 3.4 to 7.8; and residence time from 0.5 to 0.7 seconds. A statistical design was used to prevent the presence of a linear time trend from affecting comparisons between the dif ferent levels of each variable. Nitroparaffin yields based on hydrocarbon consumed ranged from 26.7% to 84.3%, while conversions based on hydrocarbon fed ranged from 0.86% to 7.3%. Nitroparaffin yields based on nitric acid consumed ranged from 38.7% to 74.4%, while conversions based on nitric acid fed ranged from 8.8% to 30.7%. The mole per cent distribution of the nitroparaffins pro duced ranged as follows: nitromethane, 5.7 - 14.3; nitroethane, 14.4 - 38.7; 2-nitropropane, 0 - 0.12; 2-methyl-2-nitropropane, 0 - 3.0; 1-nitropropane, 2.4 - 13.4; 2-nitrobutane, 5.9 - 64.7; 2-methyl-l-nitropropane, 0 - 1.1; 1-nitrobutane, 10.4 - 40.9. Gas chromatography techniques were developed which provided accurate quantitative analyses of the products. Material bal ances based on these analyses accounted for 99.1% (average) of the nitrogen fed and 96.5% (average) of the carbon fed. An economic evaluation was made for a 14,000,000 Ib./yr. iv nitroparaffin plant. The estimated production cost per pound of product and per cent return on investment were determined as a function of butane cost. As the cost of butane decreased from 14^/gal. to 5//gal., the production cost decreased from 14.43//lb. to 12.87//lb., while the return on investment in creased from 7.53% to 9.24%. 1 INTRODUCTION The nitroparaffins have been known and studied since 1872 when Meyer and Stiiber (66) prepared a nitro derivative of isopentane by reacting amyl iodide and silver nitrite. Commercial prospects for the nitroparaffins were not re alized until the early work of Hass, Hodge, and Vanderbilt on the vapor phase nitration of hydrocarbons appeared in 1936 (36). Several economic considerations in support of this work were: (1) the abundance and low cost of high purity, low molecular weight paraffinic hydrocarbons, (2) low cost tonnage nitric acid, and (3) relatively valuable nitra tion products. A brief cost estimate of the raw materials needed to pro duce one pound of the lowest priced commercial nitroparaffin, 2-nitropropane, shows the economic feasibility of the nitra tion process. It is assumed in these calculations that nitric acid and propane react with 100% yield to produce 2-nitropropane. The calculations are summarized below: Reaction HNO3 + CgHg C3HyN02 + H2O Moles 111 1 lbs. 63 44 89 18 lbs./lb. NP 1.026 0.494 1 0.206 Cost/lb. NP $0.040* $0.00582^ — Selling price/lb. NP $0.16 ^Calculated at current cost, $3.90/100 lbs. of 100% acid (72). ^Calculated at current cost, $0.05/gal. of 100% propane (71) using 4.2 lbs./gal. (23 p. 46). 2 This shows a profit of $0,160 - $0,046 or $0,114 per pound of 2-nitropropane produced not counting conversion costs. The approximate distribution of the products produced from the commercial nitration of propane and their current market prices are shown in Table 1. It can be seen from the table that the production of nitroparaffins other than 2- nitropropane will further increase profits. Table 1. Current prices and typical nitroparaffin product distribution from the nitration of propane Nitroparaffin Distribution,^ Current price,^ cents (NP) weight % per lb. in carload lots Nitromethane (NM) 19 28 Nitroethane (NE) 9 29 1-Nitropropane (1-NP) 28 27 2-Nitropropane (2-NP) 44 16 ^Approximate, typical, calculated from (12). ^As of May 4, 1964 (72). The only major U. S. producer of nitroparaffins using vapor phase nitration is the Commercial Solvents Corporation. Their plant started in 1955 has a rated capacity of 10,000,000 pounds of nitroparaffins per year (21). Propane and constant boiling (67%) nitric acid are the feed materials. 3 Since nitroparaffins have become available commercially, many new uses have been developed for these compounds, and it seems certain that many more will be adopted. Nitroparaffins are of value as industrial solvents since they are miscible with most organic substances. They are potentially useful as components in engine and rocket fuels. A large number of useful compounds are derived from the nitroparaffins. Among these are the aminoalcohols, nitroalcohols, nitroolefins, hydroxylammonium salts, amines, alkaterges and oximes. A great many combinations' of hydrocarbon, nitrating agent, and reactor design are possible in the vapor phase nitration of the lower paraffinie hydrocarbons. Several con siderations led to the choice of the particular system used in this research. Butane was selected for use as the hydrocarbon. One ad vantage of using butane instead of propane is that the same nitroparaffins are obtained from butane as from propane plus four additional nitroparaffins. These additional products are: 1-nitrobutane (1-NB), 2-nitrobutane (2-NB), 2-methyl-l- nitropropane (2-M-l-NP), and 2-raethyl-2-nitropropane (2-M- 2-NP). The nitrobutanes thus produced may be very useful as chemical intermediates. Studies of butane nitration in tubular reactors have been made by Hass, Hodge, and Vanderbilt (36) and by Bachman, Hass, and Addison (8), and a study of butane nitration in a molten salt reactor has been made by 4 Adams (1), These provide data for comparison purposes. Butane has not been as fully investigated as propane presumably because of the difficulties involved in analyzing the nitration products. In some of the previously published research only the average molecular weight of the bulk nitro- products has been reported because of the difficulty of separa tion, identification, and quantitative determination of in dividual compounds. Adams (1) determined the distribution of nitroparaffin products with good success by employing gas- liquid partition chromatography techniques. A portion of the present work has been devoted to developing highly sensitive chromatography techniques which will permit the complete quantitative analysis of all possible reaction products from the nitration of butane. Such an analysis could also provide suitable information for determining some of the reaction mechanisms. i Nitrating agents which have been used by previous investi gators are nitrogen dioxide (9, 24, 34, 89), nitric oxide (33), and nitric acid (12, 38). Some difficulty has been experi enced with corrosion of equipment used to vaporize nitric acid (21, 50, 62). To avoid this problem the acid can be vaporized in the reaction zone where its heat of vaporiza tion can be used to help control the reaction temperature. This technique is used successfully in commercial production of the nitroparaffins (21). The water introduced with the 5a nitric acid adds to the analytical difficulties and compli cates the calculations. However, conversions based on ni trating agent are higher when nitric acid is employed. This information along with the facts that nitric acid is used in the commercial process and is readily available in the laboratory led to its selection as the nitrating agent to be used in this research. Tubular reactors constructed from ordinary materials have exhibited corrosion and a gradual poisoning effect (3). To avoid these effects, pyrex, gold-lined, platinum-clad, and silica apparati have been used but these materials are ex pensive for large scale vessels. The majority of the laboratory scale vapor phase nitration studies have utilized pyrex tubular reactors. Several patents describe the use of alkali and alkaline earth materials which, when introduced into the reaction vessel, prevent reaction inhibiting effects from occurring (44, 45, 61).