ADVANCES IN METHANOL CONVERSION TO PRODUCTS

Transcription

1 THE CATALYST GROUP RESOURCES ADVANCES IN METHANOL CONVERSION TO PRODUCTS A technical investigation commissioned by the members of the Catalytic Advances Program Client Private October 2015 Gwynedd Office Park P.O. Box 680 Spring House, PA USA Phone: Fax: tcgr@catalystgrp.com Web Site:

2 The Catalytic Advances Program (CAP) The Catalytic Advances Program (CAP) is an information resource for research and development organizations in the petroleum, chemical, and polymer industries. By the direction of the member companies (through balloting and other interactive means), the program delivers a range of timely and insightful information and analyses which are accessible exclusively to members and protected by confidentiality agreements. The objective is to provide a technical update on commercially viable advances in catalysis as well as benchmark commercial advances in catalysis and process technology. Members receive three in-depth CAP Technical Reports which are written and peer reviewed by leading scientists and experienced industry professionals in areas selected by the membership (via ballot); weekly CAP Communications (delivered via ) which provide the latest updates on technical breakthroughs, commercial events and exclusive development opportunities; and attendance at the CAP Annual Meeting. The Catalytic Advances Program (CAP) is available on a membership basis from The Catalyst Group Resources (TCGR). For further details, please contact Matthew A. Colquitt at Matthew.A.Colquitt@catalystgrp.com or (x1130). P.O. Box 680 Spring House, PA U.S.A ph: fax: website: Gwynedd Office Park P.O. Box 680 Spring House, PA USA Phone: Fax: tcgr@catalystgrp.com Web Site:

3 CONTENTS EXECUTIVE SUMMARY... xvii 1. INTRODUCTION PATHS IN METHANOL CONVERSION TO PRODUCTS TRADITIONAL AND NEW USES DIRECT UTILIZATION OF METHANOL AND NEW PATHS FOR METHANOL PRODUCTION AUTHORS & CONTRIBUTORS REFERENCES METHANOL TO FUELS AND ADDITIVES INTRODUCTION Conversion Routes New Emerging Opportunities DME Opportunities and Uses Advances in Catalysis and Reaction Mechanism Advances in Processes Process Intensification GASOLINE MTG Process, Status and Recent Developments Advances in Catalysis and Reaction Mechanism Advances in Processes and Alternative Routes in MTG Process Intensification DtG (DME to gasoline) Process MTBE and TAME MTBE Process Status and Recent Advances, Process Optimization Advances in Catalysis and Deactivation Mechanism TAME Synthesis BIODIESEL BY TRANSESTERIFICATION WITH METHANOL Status and Recent Advances Advances in Catalysts Transesterification Reaction Mechanism and Kinetics Process Advances and Process Intensification xxv

4 2.6 METHANOL/DIMETHYL ETHER TO TRIPTANE (MTT) TECHNICAL HURDLES AND PERSPECTIVES CONCLUSIONS AND RECOMMENDATIONS REFERENCES METHANOL TO CHEMICALS INTRODUCTION Conversion Routes New Emerging Opportunities OLEFINS Development in the Process MTO and MTP Technology Advances in the Catalysts, Reaction Mechanism and Deactivation FORMALDEHYDE Formaldehyde Production Options Methanol Oxidation: Status and Advances in Process Methanol Oxidation: Advances in Catalysts Methanol Oxidative Dehydrogenation: Status and Advances in Process Methanol Oxidative Dehydrogenation: Advances in Catalysts ACETIC ACID/ANHYDRIDE Methanol Carbonylation: Process Options and Recent Advances Methanol Carbonylation: Advances in Catalysts and Reaction Mechanism Methanol Carbonylation: Alternative Approaches Coproduction of Acetic Acid and Anhydride METHYL FORMATE ETHANOL Methanol Homologation Direct Hydrogenation of Acetic Acid to Ethanol OTHER ROUTES OF METHANOL CONVERSION AND USE: ADVANCES AND CATALYSTS Methanol to Methyl Chloride by Hydrochlorination Methylamines by Reaction of Methanol with Ammonia Sulfur-Derivatives of Methanol Toluene Alkylation with Methanol Dimethoxymethane xxvi

5 3.7.6 Methanol to Aromatics (MTA) Dimethyl Terephthalic Acid Methyl Methacrylate Dimethyl Carbonate TECHNICAL HURDLES AND PERSPECTIVES CONCLUSIONS AND RECOMMENDATIONS REFERENCES INDEX FIGURES Figure 1E Overview of the paths to produce methanol and of the main routes to produce fuels and chemicals from methanol... xviii Figure 1.1 Global methanol demand trend with indication of the major type of conversion products. Note: Excludes integrated methanol demand for methanol to olefins and propylene, which is forecast to grow from 2.2 million tons in 2011 to 18.1 million tons in Figure 1.2 Overview of the paths to produce methanol and of the main routes to produce fuels and chemicals from methanol... 4 Figure 1.3 Methanol: global demand by market segment Figure 2.1a From raw materials to synthesis gas (syngas), methanol, chemicals and fuels Figure 2.1b Overview of the various routes investigated by different companies to produce liquid fuels from syngas, methanol and DME Figure 2.2 Syngas to MeOH/DME equilibrium Figure 2.3 Lurgi s MegaDME process Figure 2.4 Overview of Topsoe process layout in DME synthesis from methanol, including heat integration Figure 2.5 From conventional setup to reactive dividing-wall column (R-DWC) Figure 2.6 ExxonMobil MTG process Figure 2.7 Representation of the paring and side-chain reaction concepts in MTH catalysis Figure 2.8 Shape and connection of the internal surface to the two zeolites that are in industrial use in methanol to hydrocarbon - MTH: H-ZSM-5 (left) and H-SAPO-34 (right) Figure 2.9 Dual-cycle concept for the conversion of methanol over H-ZSM Figure 2.10 Top: role of cyclopentadienium ions in methanol-to-hydrocarbons chemistry. Bottom: beta-scission of an ethyl or propyl group in alkyl- xxvii

6 Figure 2.11 Figure 2.12 Figure 2.13 substituted cyclopentadienium ion resulting in the formation of another cyclopentadienium ion Conversion versus time on stream curves for the MTH reaction over four 3D 10-ring topologies with varying channel intersection size Scheme of ExxonMobil MTG process, with detail on the heavy gasoline treatment unit to isomerize durene Gas to chemicals processing routes, with reference expecially to those developed by Lurgi Figure 2.14 Lurgi s MtSynfuels Figure 2.15 Figure 2.16 Figure 2.17 Figure 2.18 Scheme of ExxonMobil olefins-to-gasoline/diesel (max. distillate mode) MOGD process Effect of the introduction of mesoporosity (by desilication) on the properties of H-ZSM-5 catalyst in conversion of DME to gasoline KIT (Karlruhe Institute of Technology) DtG process in the frame of bioliq (Biomass to Liquid Karlruhe) conversion scheme KIT (Karlruhe Institute of Technology) process scheme to convert methanol to diesel components: oxymethylene ethers Figure 2.19 MTBE and TAME processes in refinery scheme Figure 2.20 CDMtbe process flow diagram Figure 2.21 Simplified flow sheet of the heterogeneous process ESTERFIP-H Figure 2.22 Role of Cu species and effect of CU on catalytic performances in DME conversion to 2,2,3-Trimethylbutane over a Cu/BEA catalyst Figure 3.1 Main routes of chemical utilization of methanol Figure methanol usage, by derivative and by region Figure 3.3a Total/UOP MTO process integrated with olefin cracking process (OCP) Figure 3.3b Yield benefits from OCP integration in Total/UOP MTO process integrated with olefin cracking process (OCP) Figure 3.4 Comparison between SAPO-34 and HZSM-5 characteristics, in relation to MTO reaction Figure 3.5 Model of the active intermediate in MTO reaction present in SAPO-34 cage Figure 3.6 (a) Effect of coke deposition on the methanol conversion and selectivity to light olefins in microscale DMTO fluidized bed reactor at 450 C (b) Typical properties of the DMTO Catalyst Figure 3.7 Scheme of DMTO-II process Figure 3.8 Flowsheet of the SINOPEC S-MTO process Figure 3.9 Methanol to propylene Lurgi MTP process Figure 3.10 Lurgi MTP process: simplified flowsheet xxviii

7 Figure 3.11 Figure 3.12 Figure 3.13 The influence of the relative density of internal defects on catalyst deactivation for MTH reaction over HZSM-5 catalysts MTO catalytic results for SAPO-34 catalysts as a function of time on steam (TOS) Schematic diagram of the crystallization process of SAPO-34 with Si distribution in the crystals. The dot density in the square stands for the Si concentration in the crystals Figure 3.14 Catalytic performance of nano-sapo Figure 3.15 The reaction mechanism of the MTO reaction Figure 3.16 (a) PolyMB cycle (top) and alkene cycle (bottom) proposed for MTO over the H-MCM-22 zeolite used to unravel the catalytic roles of the supercages, pockets, and sinusoidal channels. Via the polymb cycle, polymethylbenzenes act as the active hydrocarbon pool species, whereas via the alkene cycle, alkenes are the active hydrocarbon pool species. (b) Framework of the H-MCM-22 zeolite with three types of pores: upercages, pockets, and sinusoidal channels Figure 3.17 Olefin-based catalytic cycle proposed to be the primary reaction pathway during the early stages of the MTO reaction over H-SAPO Figure 3.18 Methanol conversion and selectivity to light olefins with time-on-stream over nano SAPO catalysts. In the inset, SEM image of the most stable S3 sample. Experimental conditions: WHSV = 2 h -1, T = 400 C, catalyst weight =300 mg Figure 3.19 (a) BASF process for formaldehyde production from methanol. (b) Formaldehyde production through incomplete conversion and distillative recovery of methanol Figure 3.20 Flow-sheet of CT-ACETICA process Figure 3.21 Scheme of BASF process to prepare methyl formate by methanol carbonylation Figure 3.22 Catalytic oxidation of methanol on np-au. (A) Methyl formate: gray squares CO 2 blue rhombuses. (B) Selectivity to methyl formate. Low oxygen partial - 1 vol.%: blue rhombuses; elevated oxygen partial pressures - 50 vol.%: red squares Figure 3.23 Stability investigation of in situ thermally activated 1 wt% Au Pd/TiO 2 water-refluxed treated catalyst undergoing methanol oxidation at reaction temperatures of 30 and 70 C for 20 h Figure 3.24 Model of titanium-chabazite active in methanol oxidation to methyl formate with H 2 O Figure 3.25 Model of methanol photo-coupling on TiO Figure 3.26 Paths of methanol oxidation into methyl formate on rutile TiO 2 (110): methoxy and formaldehyde to produce the intermediate hemiacetal, which leads to methyl formate xxix

8 Figure 3.27 Figure 3.28 DMM productivity over the various catalysts as a function of temperature with poor (open symbols) and rich (filled symbols) feedes (a) Effect of reaction temperature on the oxidation of methanol over a monolayer V 2 O 5 /TiO 2 catalyst. The feed consisted of methanol, oxygen, and helium in the 1:1:23 M ratio. (b) Proposed mechanism for the oxidation of methanol over highly dispersed vanadia supported on TiO Figure 3.29 Methanol-derived products Figure 3.30 Methanol is at the crossroads between energy and chemistry, and between the current use of fossil fuels (FF) and the future scenario based on the extended use of FF and the use of new renewable raw materials and energy sources. On the left an estimation of the share methanol on petrochemical raw materials (% wt.) in 2030 with respect to current use TABLES Table 1.1 MTO Plants Planned or Under Construction Table 1.2 Newly Started MTG Plants... 7 Table 2.1 Comparison of Process Intensification Technologies for Continuous Biodiesel Production with Conventional Stirred Tank Reactors Table 2.2 Novel Reactors for Biodiesel Process Intensification Table 3.1 Selectivity and Yield to Light Olefins in MTO Reaction Using SAPO Table 3.2 SAPO-34 vs. SSZ-13 Performances in MTO Reaction Table 3.3 Average Results of DMTO-II Demonstration Unit Table 3.4 MTO Reaction Results over SAPO-34 Synthesized with and without HF Table 3.5 (top): Lifetime and Product Distribution of SAPO-34s in the MTO Reaction (middle): SEM Images of Calcined Samples (bottom): Synthesis Conditions, Yields and Composition of Products Table 3.6 World Acetic Acid Capacity Additions Table 3.7 Comparison of Technical Methanol Carbonylation Processes xxx SCHEMES Scheme 2.1 Alternative route to convert methane to liquid fuels via halomethane Scheme 2.2 Scheme 3.1 Reaction mechanism proposed for MTT (starting with propylene for simplicity) Formation mechanism of the original C-C bond in MTO reaction over HSAPO Scheme 3.2 Proposed cycles for the iridium/iodide catalysed WGS reaction Scheme 3.3 Mechanism for ruthenium-promoted, iridium-catalyzed methanol carbonylation... 97