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PROPYLENE GLYCOL from GLYCERIN (December 2007)

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PROPYLENE GLYCOL from GLYCERIN (December 2007) Abstract Process Economics Program Report 262 PROPYLENE GLYCOL FROM GLYCERIN (December 2007) A variety of economic, environmental and technical factors have encouraged industry attention on producing industrial chemicals from bio-feedstocks, rather than from crude oil derivatives. One such example is producing propylene glycol (PG) from glycerine (GLY), rather than the conventional routes starting with propylene monomer. Propylene glycol has historically been produced in commercial quantities either via the chlorohydrin process or by peroxidation, both using propylene monomer as the starting material. Both routes produce propylene oxide (PO) as an intermediate chemical, which is then hydrated to propylene glycol. The peroxidation routes have evolved from those processes (Arco Chem/Lyondell, Repsol, Shell, BASF) producing a significant amount of by-product (PO/styrene monomer, PO/tertiary butyl alcohol, PO/ methyl tertiary butyl ether), to more recent processes developed by Solvay, Dow and BASF that eliminate the by-product by using hydrogen peroxide as the oxidizing agent. As of 2007, Degussa has announced the design and construction of a commercial scale PG plant using glycerine as its feedstock. Other companies have announced processes to use glycerine to produce polyols and epichlorohydrin. The combination of high crude oil prices and governmental subsidies to produce biofuels (bio-ethanol, bio-diesel) have resulted in an enormous increase in bio-diesel production, resulting in a glut of by-product glycerine (which represents 10% of biodiesel mass). As a result, glycerine market prices have fallen from $US 2/kg down to fuel value ($US 200/mt), or less. The low cost of glycerine combined with the high price of PG offers an opportunity to develop industrial scale processes converting glycerine to propylene glycol. This report presents preliminary process engineering design information and the corresponding production economics for converting GLY to PG using the Davy process and a process developed at the University of Missouri by Galen Suppes. In addition to these two processes this report also provides a detailed design of the glycerin purification section that is needed to allow these processes to take advantage of lower cost crude glycerin which is readily available form may bio-diesel production facilities. © SRI Consulting PEP Report 262 SRI Consulting PROCESS ECONOMICSPROGRAM A privatereportbythe Menlo Park,California 94025 PROPYLENE GL FROM GL by ANTHONY December 2007 Report No.262 YCERIN YCOL P A VONE SRIC agrees to assign professionally qualified personnel to the preparation of the Process Economics Program’s reports and will perform the work in conformance with generally accepted professional standards. No other warranties expressed or implied are made. Because the reports are of an advisory nature, neither SRIC nor its employees will assume any liability for the special or consequential damages arising from the Client’s use of the results contained in the reports. The Client agrees to indemnify, defend, and hold SRIC, its officers, and employees harmless from any liability to any third party resulting directly or indirectly from the Client’s use of the reports or other deliverables produced by SRIC pursuant to this agreement For detailed marketing data and information, the reader is referred to one of the SRI Consulting 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 PETROCHEMICALS PROGRAM covers major hydrocarbons and their derivatives on a worldwide basis. In addition the SRIC DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Western Europe, Canada, and East Asia, South America and Mexico. CONTENTS 1 INTRODUCTION ........................................................................................................ 1-1 SOURCE OF GLYCERIN FROM BIO-DIESEL MANUFACTURE............................. 1-2 ALTERNATIVE COMMERCIAL ROUTES TO PG VIA PO ........................................ 1-3 VALUE PROPOSITION FOR PROPYLENE GLYCOL FROM GLYCERIN ............... 1-6 2 SUMMARY ................................................................................................................. 2-1 UPGRADING FUEL GRADE GLYCERIN .................................................................. 2-2 AVAILABLE LICENSED TECHNOLOGIES ............................................................... 2-3 KEY TECHNOLOGY ATTRIBUTES........................................................................... 2-3 ATTRACTIVENESS OF GLYCERIN TO PROPYLENE GLYCOL............................. 2-3 3 PROCESS SAFETY................................................................................................... 3-1 PROCESS SAFETY CONCERNS ............................................................................. 3-1 MAJOR SAFETY CONCERN FOR PG FROM GLY.................................................. 3-1 PRODUCT SAFETY CHARACTERISTICS OF PROPYLENE GLYCOL AND GLYCERIN ................................................................................................................. 3-1 Glycerin....................................................................................................................... 3-2 Hydrogen .................................................................................................................... 3-3 Acetol.......................................................................................................................... 3-3 Acrolein....................................................................................................................... 3-3 Propylene Glycol ........................................................................................................ 3-4 Ethylene Glycol........................................................................................................... 3-4 Methanol ..................................................................................................................... 3-5 CATALYSTS............................................................................................................... 3-5 BRIEF PROCESSING PERKS................................................................................... 3-6 MAJOR PROCESSING RISKS .................................................................................. 3-6 MATERIALS OF CONSTRUCTION ........................................................................... 3-6 © SRI Consulting iii PEP Report 262 CONTENTS (Continued) 4 VALUE PROPOSITION FOR CONVERTING GLYCERIN TO PROPYLENE GLYCOL..................................................................................................................... 4-1 HISTORICAL PRICING ENVIRONMENT .................................................................. 4-1 GLYCERIN PRODUCTION LEVEL FROM BIO-DIESEL........................................... 4-4 SUBSIDY ECONOMICS FOR BIO-DIESEL............................................................... 4-5 LONG TERM VIABILITY OF METHYL ESTER BIO-DIESEL .................................... 4-6 BIO-DIESEL FEEDSTOCK OPTIONS ....................................................................... 4-8 ALTERNATE CHEMISTRIES FOR CONSUMING GLYCERIN................................. 4-9 5 INDUSTRY STATUS.................................................................................................. 5-1 PROPYLENE GLYCOL .............................................................................................. 5-1 PG--Physical Properties ............................................................................................. 5-1 PG--Chemical Properties............................................................................................ 5-2 PG--Uses.................................................................................................................... 5-2 PG--Integrated Supply Chain ..................................................................................... 5-3 PG--Commercial Grades............................................................................................ 5-4 PG--Methods of Manufacture ..................................................................................... 5-5 PG--SUPPLY AND DEMAND..................................................................................... 5-5 PG--DEMAND GROWTH........................................................................................... 5-7 PG--By-Product Production........................................................................................ 5-7 PG--COMPETITORS.................................................................................................. 5-8 HISTORICAL PRICES FOR PROPYLENE GLYCOL ................................................ 5-11 GLYCERIN ................................................................................................................. 5-14 Glycerin Physical Properties....................................................................................... 5-14 Glycerin Chemical Properties..................................................................................... 5-15 COMMERCIAL USES FOR GLYCERIN .................................................................... 5-15 PRODUCTION OF GLYCERIN.................................................................................. 5-16 © SRI Consulting iv PEP Report 262 CONTENTS (Continued) GLOBAL
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