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Synthesis of Methyl Methacrylate From Coal-Derived Syngas
Final Report October 1 - November 30, 1999 - 1999

Jang, B. W. L.
Gogate, M. R.
Spivey, J. J.
Zoeller, J. R.
Colberg, R. D.
Choi, G. N.

Research Triangle Institute

In the pdf format this document has 106 pages and is 1369kb

Table of Contents

1

 Executive Summary 1

2

 Introduction 5
  2.1 Step 1: Propionate Synthesis 8
2.2 Step 2: HCHO-Propionate Condensation 9

3

 Experimental 10
 

3.1

 Task 1 - Propionate Synthesis 10
  3.1.1 Generation of Propionic Anhydride [(CH3CH2CO)2O] 10
3.1.2 Generation of Propionic Acid [CH3CH2COOH] 12

3.2

 Task 2 - Condensation Catalysts 13
  3.2.1 Catalyst Preparation 13
3.2.2 Catalyst Testing 13
3.2.3 Product Analysis 14
3.2.4 Catalyst Characterization 15

3.3

 Task 3 - Slurry Reactor Studies 15

3.4

 Task 4 - DME Condensation Study 17

4

 Results and Discussion 18
 

4.1

 Task 1 - Propionate Synthesis 18
  4.1.1 General Description of the Catalyst 18
4.1.2 Mo Catalyzed Carbonylation of Ethylene to Propionic Anhydride 19
4.1.3 Mechanistic Interpretation 31
4.1.4 Conceptual Design and Economic Analysis of Propionate Synthesis 34
4.1.5 Summary of Propionate Synthesis 38

4.2

 Task 2 - Condensation Catalysis 39
  4.2.1 Catalyst Characterization of V-Si-P Catalysts 39
4.2.2 Formalin as an Alternative Feedstock 45
4.2.3 Characterization with TGA, XRD, and ESCA 47
4.2.4 Long-term Tests on V-Si-P (1:10:2.8) and Ta/SiO2 Catalysts 56
4.2.5 Acid-Base Properties of V-Si-P Catalysts 58
4.2.6 Extended Activity and Stability Tests of Niobium Catalysts 62
4.2.7 Summary 66

4.3

 Task 3 - Slurry Reactor Studies 67

4.4

 Task 4 - Conceptual Design and Economic Analysis: "External" Formaldehyde - Propionic Acid Condensation Route 68
  4.4.1 Process Description/Design Basis 68
4.4.2 Formaldehyde and Propionic Acid Condensation - Design and ASPEN Simulation 72
4.4.3 Simplified Overall Process Flow Diagram and Material Balance 80
4.4.4 Cost Estimation 80
4.4.5 Process Economics 80

4.5

 Task 5 - DME Condensation Study (RTI and Eastman) 83
  4.5.1 HCHO-MP Condensation 86
4.5.2 DME Partial Oxidation 87
4.5.3 In-situ DME Oxidation and Condensation with MP 88

5

 Conclusions 91
  5.1 Propionate Synthesis 91
5.2 Condensation Catalysis 91
5.3 Slurry Reactor Studies 92
5.4 Economics 92
5.5 DME Condensation 92
6 Recommendations 93
7 References 94