Report No. 106 AMINO ACIDS by WING S. FONG Contributions by Victor E. Althouse November 1976 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I I MENLO PARK, CALIFORNIA
For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD HYDROCARBONS Program covers major hydrocarbons and their derivatives on a worldwide Basis. In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States and Western Europe. ii
TABLE OF CONTENTS 1 INTRODUCTION.......................... 1 2 SUMMARY... 3 Glutamic Acid and Monosodium Glutamate... 3 L-Lysine... 4 and Methionine Hydroxy Analogue... 7 3 INDUSTRY STATUS... 9 Monosodium Glutamate... 9 Methionine... 10 Lysine... 18 4 GLUTAMIC ACID AND MONOSODIUM GLUTAMATE BY FERMENTATION... 23 Biochemistry... 23 Review of Processes... 25 Composition of Medium... 26 Microorganisms... 26 Carbon Sources... 55 Nitrogen Sources... 57 Inorganic Salts... 57 Biotin and Other Growth Factors... 57 Other Additives... 58 Fermentation... 59 Aeration and Agitation... 59 Yield and By-Product... 59 Fermenters... 60 Continuous Process... 60 Recovery and Purification... 61 Process Description... 62 Process Discussion... 69 Cost Estimates... 71 5 GLUTAMIC ACID AND MONOSODIUM GLUTAMATE BY Introduction... Chemistry From.... From Acrolein... Review of Processes... Process Description... Process Discussion... Cost Estimates... CHEMICAL SYNTHESIS.. 79... 79... 79... 79... 91... 92... 103... 113... 115 Vii
TABLE OF CONTENTS 6 L-LYSINE BY FERMENTATION... 125 Introduction... 125 Biochemistry... 125 Review of Processes... 129 Composition of Medium... 129 Microorganisms... 129 Carbon Sources... 142 Additives... 144 Fermentation... 145 Recovery and Purification... 146 Equipment... 147 Process Description... 147 Process Discussion... 153 Cost Estimates... 154 7 L-LYSINE BY CHEMICAL SYNTHESIS... 163 Introduction... 163 Chemistry...16 3 Review of Processes... 174 Process Description... 190 Process Discussion... 201 Cost Estimates... 203 8 DL-METHIONINE AND METHIONINE HYDROXY ANALOGUE... 215 Introduction... 215 Chemistry...21 6 Review of Processes... 219 From Acrolein... 232 From Other Materials.. 234... 235 Process Description... 235 Process Discussion... 243 Cost Estimates... 244 Calcium Salt of Methionine Hydroxy Analogue... 253 Process Description... 253 Process Discussion... 261 Cost Estimates... 262 Economic Comparison of and Calcium Salt of Methionine Hydroxy Analogue... 263 APPENDIX DESIGN AND COST BASIS.................. 271 CITED REFERENCES........................ 273 PATENT REFERENCES BY COMPANY................... 313 viii
ILLUSTRATIONS 4.1 4.2 4.3 4.4 5.1 5.2 5.3 5.4 6.1 6.2 6.3 6.4 Glutamic Acid Fermentation Pathway.............. 24 Flow Scheme.. '...................... 327 Effect of Molasses Price, Chemical, Nutrient and Packaging, Labor, Capital and Utilities Costs or Requirements and Process Yield on Production Cost.................. 77 Effect of Operating Level and Plant Capacity on Production cost... 78 Monosodium Glutamate by Chemical Synthesis from Flow Scheme................,........ 331 Monosodium Glutamate by Chemical Synthesis from Effect of, Sodium Hydroxide, Sulfuric Acid and Synthesis Gas Prices and By-Product Disposal Charge on Production Cost,,,,,,,.,,,,,,,.,,,,,,. 121 Monosodium Glutamate by Chemical Synthesis from Effect of Labor, Capital and Utilities Cost or Requirement and Process Yield on Production Cost............ 122 Monosodium Glutamate by Chemical Synthesis from Effect of Operating Level and Plant Capacity on Production Cost............................23 L-LySine Fermentation Pathway via o-aminoadipic Acid..... 126 L-Lysine Fermentation Pathway via Diaminopimelic Acid, and Feedback Regulation..................... 127 L-Lysine by Fermentation Flow Scheme......................... 335 L-Lysine by Fermentation Effect of Molasses, Hydrolyzed Soybean Meal, and Aqua Ammonia Prices, Labor, Capital and Utilities Costs or Requirements and Process Yield on Production Cost............ 160 ix
ILLUSTRATIONS 6.5 7.1 L-Lysine by Fermentation Effect of Operating Level and Plant Capacity on Production cost............................ 161 L-Lysine from Cyclohexene, Using Cyclohexanol and Enzyme- Flow Scheme......................... 337 7.2 7.3 L-Lysine from Cyclohexene, Using Cyclohexanol and Enzyme- Effect of Raw Material Prices on Production Cost...... L-Lysine from Cyclohexene, Using Cyclohexanol and Enzyme- Effect of By-Product (Ammonium Sulfate) Credit and Labor, Capital, Utilities and Nutrients Prices and Requirements on Production Cost...................... 212 213 7.4 8.1 8.2 8.3 8.4 8.5 L-Lysine from Cyclohexene, Using:Cyclohexanol and Enzyme- Effect of Operating Level and Plant Capacity on Production cost............................ 214 Flow Scheme......................... 343 Effect of Various Raw Materials Prices and By-Product Disposal Charge on Production Cost............. 250 Effect of Labor, Capital or Utilities Cost or Requirement and Process Yield on Production Cost.............. 251 Effect of Operating Level and Plant Capacity on Production cost............................ 252 Calcium Salt of Methionine Hydroxy Analogue Flow Scheme......................... 345 X
ILLUSTRATIONS 8.6 Calcium Salt of Methionine Hydroxy Analogue Effect of Acrolein, Methyl Mercaptan and Hydrogen Cyanide Prices and By-Product Disposal Charge on Production Cost... 268 8.7 Calcium Salt of Methionine Hydroxy Analogue Effect of Labor, Capital or Utilities Cost or Requirement and Process Yield on Production Cost............ 269 8.8 Calcium Salt of Methionine Hydroxy Analogue Effect of Operating Level and Plant Capacity on Production Cost...........................,270 xi
TABLES 2.1 3.1 3.2 3.3 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 5.1 5.2 Cost Estimate Summary.................... 5 MSG Producers........................ 11 Producers................... 16 L-Lysine Monohydrochloride Producers............ 21 Glutamic Acid and Patent Summary....................... 27 Recovery and Purification of Glutamic Acid and Monosodium Glutamate Obtained by Fermentation Patent Summary....................... 47 Major Equipment and Utilities Summary............ 65 Stream Flows........................ 67 Total Capital Investment.................. 73 Battery Limits and Utilities Cost by Process Section.... 74 Total Production Cost.................... 75 Total Direct Operating Cost by Process Section....... 76 Glutamic Acid and Monosodium Glutamate by Chemical Synthesis Patent Summary....................... 8o Recovery, Purification, Resolution, and Racemization of Glutamic Acids and Sodium Glutamates Obtained by Chemical Synthesis Patent Summary....................... 93 xiii
TABLES 5.3 Monosodium Glutamate by Chemical Synthesis from Design Bases and Assumptions................ 107 5.4 Monosodium Glutamate by Chemical Synthesis from Major Equipment and Utilities Summary........... 108 5.5 Monosodium Glutamate by Chemical Synthesis from Stream Flows........................ 110 5.6 Monosodium Glutamate by Chemical Synthesis from Total Capital Investment.................. 117 5.7 Monosodium Glutamate by Chemical Synthesis from Battery Limits and Utilities Cost by Process Section.... 118 5.8 Monosodium Glutamate by Chemical Synthesis from Total Production Cost................... 119 5.9 Monosodium Glutamate by Chemical Synthesis from Total Direct Operating Cost by Process Section....... 120 6.1 L-Lysine by Fermentation Patent Summary....................... 131 6.2 L-Lysine by Fermentation Major Equipment and Utilities Summary........... 149 6.3 L-Lysine by Fermentation Stream Flows........................ 151 6.4 L-Lysine by Fermentation Total Capital Investment.................. 156 6.5 L-Lysine by Fermentation Battery Limits and Utilities Cost by Process Section.... 157 xiv
TABLES 6.6 L-Lysine by Fermentation Total Production Cost................... 158 6.7 L-Lysine by Fermentation Total Direct Operating Cost by Process Section...... 159 7.1 Lysine by Chemical Synthesis Patent Summary...................... 175 7.2 Purification, Resolution and Racemization of Lysine Obtained by Chemical Synthesis Patent Summary...................... 184 7.3 L-Lysine from Cyclohexene, Using Cyclohexanol and Enzyme- Design Bases and Assumptions............... 194 7.4 L-Lysine from Cyclohexene, Using Cyclohexanol and Enzyme- Major Equipment and Utilities Summary........... 195 7.5 L-Lysine from Cyclohexene, Using Cyclohexanol and Enzyme- Stream Flows........................ 198 7.6 L-Lysine from Cyclohexene, Using Cyclohexanol and Enzyme- HydrolysisfRacemization Total Capital Investment................. 206 7.7 L-Lysine from Cyclohexene, Using Cyclohexanol and Enzyme- Battery Limits, Utilities and Tankage Investment by Process Section......................... 207 7.8 L-Lysine from Cyclohexene, Using Cyclohexanol and Enzytne- HydroLysis/Racemization Total Production Cost................... 209 7.9 L-Lysine from Cyclohexene, Using Cyclohexanol and Enzyme- Total Direct Operating Cost by Process Section...... 210 xv
TABLES 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 8.10 8.11 8.12 8.13 and Methionine Hydroxy Analogue or its Salts by Chemical Synthesis Patent Summary,...................... Design Bases and Assumptions................ Major Equipment and Utilities Summary........... Stream Flows........................ Total Capital Investment.................. Battery Limits and Utilities Cost by Process Section... Total Production Cost................... Total Direct Operating Cost by Process Section...... Calcium Salt of Methionine Hydroxy Analogue Design Bases and Assumptions................ Calcium Salt of Methionine Hydroxy Analogue Major Equipment and Utilities Summary........... Calcium Salt of Methionine Hydroxy Analogue Stream Flows........................ Calcium Salt of Methionine Hydroxy Analogue Total Capital Investment.................. Calcium Salt of Methionine Hydroxy Analogue Battery Limits and Utilities Cost by Process Section.... 220 238 239 241 246 247 248 249 256 257 259 264 265 xvi
TABLES 8.14 Calcium Salt of Methionine Hydroxy Analogue Total Production Cost................... 266 8.15 Calcium Salt of Methionine Hydroxy Analogue Total Direct Operating Cost by Process Section...... 267 xvii