Formaldehyde, Supp. A, December 1978
PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL
Abstract
Mod0 Park, California 94025
Process Economics Program Report No. 23A FORMALDEHYDE
This report includes estimates for the capital investment and production costs for making formaldehyde from methanol by two different processes. One process uses a silver catalyst and the other a ferric molybdate catalyst. Each is practiced in eight or more variations, most of which are available fran licensers. Metallic silver is used as a gauze or as crystals. The most modern silver catalyst processes use a thin bed of silver crystals. This report reviews developments in silver catalyst processes, and includes a detailed evaluation of the newest variation practiced by BASF. In the BASF process, the conversions are sufficiently high that the amount of unreacted methanol is negligible. Thus, the usual methanol removal step is omitted. Also, because only a slight excess of air is used, the gas handling equipment is small. The process is simple, and capital is low. The reactors can be very large; thus further economies of scale are achieved. For new plants, the BASF silver catalyst process is economically superior. The second type of process, usually referred to as a ferric molybdate process, uses a mixed oxide catalyst containing iron and molybdenum. Ferric molybdate processes use pelletized catalyst packed in tubes, and are economical to operate in smaller plants. They use a considerable excess of air to obtain very high conversions and high selectivity. This report contains an evaluation of the Formox@process, developed by Perstorp and Beichhold and now used in more than 50 plants around the world. Other processes for methanol dehydration, and processes based on raw materials such as methane, are reviewed but not evaluated in this report. At present, these processes do not appear economically attractive.
Formaldehyde, Supp. A, December 1978
Report No. 23 A
FORMALDEHYDE
by ROBERT H. SCHWAAR
December 1978
A private
report by the
PROCESS ECONOMICS PROGRAM
Menlo Park, California
94025
Formaldehyde, Supp. A, December 1978
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 PETROCHEMICALS 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.
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Formaldehyde, Supp. A, December 1978
CONTENTS
1
INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . .
2
SUMMARY ............................
1
General Aspects ....................... Economic Aspects ...................... Technical Aspects. ..................... Silver Catalyst Processes ................. Ferric Molybdate Process ................. 3
INDUSTRY STATUS ........................ Formaldehyde Production ................... Producers, Plant Locations, Recesses, and Capacities .... Formaldehyde Consumption .................. Licensed Processes ..................... Silver Catalyst ...................... Ferric Molybdate Catalyst ................. Raw Materials and Integrated Manufacture ..........
4
0 0
l
FORMALDEHYDE FROM METHANOL WITH A SILVER CATALYST ....... Review of Processes ..................... Catalyst Development ................... Other Process Variations ................. Effect of Temperature on Yield ............. Effect of Water Addition on Yield ............ Methanol Feed ...................... Methanol Vaporization .................. Air Supply ....................... Inert Gas Addition ................... ...................... Additives.. Reactor Design ..................... Reactor Start-Up .................... Quenching the Reactor Product .............. Absorber Design ..................... Methanol Removal .................... Two-Stage Reactions ................... Low-Conversion Process ................. Commercial Processes .................. Process Jkscription ..................... Process Discussion ..................... Design Alternatives .................... Improved Heat Economy ................... Ion-Exchange Treatment of Formaldehyde Product ...... iX
11 11 11 22 24 24 25 26 29 30 31 40 40 50 51 52 52 53 55 56 57 57 58 58 59 60 61 63 69 69 70 71
Formaldehyde, Supp. A, December 1978
CONTENTS
FORMALDEHYDE FROM METHANOL WITH A SILVER CATALYST (continued) Materials of Construction ................. Waste Treatment. ..................... Cost Estimates ....................... Capitalcosts ....................... Production Costs .....................
71 72 74 74 75
FORMALDEHYDE FROM METHANOL WITH A FERRIC MOLYBDATE CATALYST .....................
83 83
Chemistry .......................... Review of Processes ..................... Ferric Molybdate Catalyst Improvements .......... Catalyst Activity and Selectivity ............ Catalyst Shape ..................... Stronger Unsupported Catalysts ............. Supported Catalysts ................... Fluidized-Bed Processes .................. Formic Acid Production .................. Other Process Improvements ................ Waste Treatment ...................... Commercial Processes ................... Process Description ..................... Process Discussion ..................... Design Alternatives. ................... Catalyst Preparation and Handling ............. Materials of Construction ................. Losses .......................... Cost Estimates ....................... Capital Costs ....................... Production Costs .....................
iPi 94 94 95 95 96 97 98 99 103 108 115 115 117 119 119 120 120 121
FORMALDEHYDE FROM METHANOL WITH OTHER CATALYSTS .......
129
Formaldehyde by Oxidation of Methanol ............ Formaldehyde by Dehydrogenation of Methanol, without Oxidation .....................
129
X
131
Formaldehyde, Supp. A, December 1978
CONTENTS
FORMALDEHYDE FROM OTHER FEEDSTOCKS .............
135
Synthesis Gas Feed ..................... ........................ MathaneFeed Dimethyl Ether Feed .....................
135 136 140
APPENDIX A
DESIGN AND COST BASES.
143
APPENDIX B
CONVERSION, SELECTIVITY, AND YIELD
7
. . . . . . . . . . . . . . . . . . . . . .
145
CITEDREFERENCES........................
147
PATENT REFERENCES BY COMPANY.
157
. . . . . . . . . . . . . . . . .
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Formaldehyde, Supp. A, December 1978
ILLUSTRATIONS
0
4.1 Formaldehyde from Methanol with a Silver Catalyst Process Flow Diagram . . . . . . . . . . . . . . . . . . .
161
4.2 Formaldehyde from Methanol with a Silver Catalyst Effect of Plant Capacity on Total Fixed Capital . . . . . .
78
4.3 Formaldehyde fran Methanol with a Silver Catalyst Effect of Operating Level and Plant Capacity on Production Cost. . . . . . . . . . . . . . . .
. .
79
Formaldehyde from Methanol with a Ferric Molybdate Catalyst Process Flow Diagram . . . . . . . . . . . . . . . . . . .
163
5.2 Formaldehyde fran Methanol with a Ferric Molybdate Catalyst Effect of Plant Capacity on Total Fixed Capital . . . . . .
125
5.3 Formaldehyde from Methanol with a Ferric Molybdate Catalyst Effect on Operating Level and Plant Capacity on Production Cost. . . . . . . . . . . . . . . . . . . .
128
l
5.1
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Formaldehyde, Supp. A, December 1978
TABLES
l 0
Summary of Cost Estimates for Formaldehyde Manufacture . .
4
3.1 Formaldehyde Producers United States . . . . . . . . . . . . . . . . . . . . . . .
13
3.2 Formaldehyde Producers Western Hemisphere . . . . . . . . . . . . . . . . . . . .
14
3.3 Formaldehyde Producers Europe . . . . . . . . . . . . . . . . . . . . . . . . . .
16
3.4 Formaldehyde Producers Japan...... . . . . . . . . . . . . . . . . . . . . .
19
3.5 Formaldehyde Producers Africa, Asia, and Australia . . . . . . . . . . . . . . . .
20
2.1
4.1
l
Formaldehyde fran Methanol with a Silver Catalyst Summary of Patents on Catalyst Developments . . . . . . . .
32
4.2 Formaldehyde fran Methanol with a Silver Catalyst Summary of Patents on Other Process Developments . . . . .
41
4.3 Formaldehyde from Methanol with a Silver Catalyst Bases and Assumptions . . . . . . . . . . . . . . . . . . .
64
4.4 Formaldehyde from Methanol with a Silver Catalyst Major Equipment and Utilities Summary . . . . . . . . .
.
66
4.5 Formaldehyde from Methanol with a Silver Catalyst StreamFlows . . . . . . . . . . . . . . . . . . . . . . .
68
4.6 Formaldehyde Absorber Off-Gas, Silver Catalyst Processes Typical Flow Fates and Compositions . . . . . . . . . . . .
73
4.7 Formaldehyde fran Methanol with a Silver Catalyst Capital Investment . . . . . . . . . . . . . . . . . . . .
76
4.8 Formaldehyde from Methanol with a Silver Catalyst Major Capital Equipment Costs . . . . . . . . . . . . . . .
77
4.9 Formaldehyde from Methanol with a Silver Catalyst Production Costs . . . . . . . . . . . . . . . . . . . . .
80
5.1 Formaldehyde fran Methanol with a Ferric Molybdate Catalyst Patent Summary . . . . . . . . . . . . . . . . . . . . . .
85
5.2 Formaldehyde Absorber Vent Gas Typical Flow pates and Compositions . . . . . . . . . . . .
100
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Formaldehyde, Supp. A, December 1978
TABLES
5.2 Formaldehyde Absorber Vent Gas Typical Flow Fates and Compositions . . . . . . . . . . . . 5.3 Treatment
100
of Waste Gases from Formaldehyde
Manufacture Patent Summary . . . . . . . . . . . . . . . . . . . . . .
101
5.4 Treatment of Aqueous Wastes from Formaldehyde Manufacture Patent Summary . . . . . . . . . . . . . . . . . . . . . .
104
5.5 Formaldehyde from Methanol with a Ferric Molybdate Catalyst Bases and Assumptions . . . . . . . . . . . . . . . . . . .
109
5.6 Formaldehyde from Methanol with a Ferric Molybdate Catalyst Major Equipment and Utilities Summary . . . . . . . . . . .
112
5.7 Formaldehyde fran Methanol with a Ferric Molybdate Catalyst StreamFlows . . . . . . . . . . . . . . . . . . . . . . .
114
5.8 Formaldehyde from Methanol with a Ferric Molybdate Catalyst Capital Investment . . . . . . . . . . . . . . . . . . . .
123
5.9 Formaldehyde from Methanol with a Ferric Molybdate Catalyst Major Capital Equipment Costs . . . . . . . . . . . . . . .
124
5.10 Formaldehyde from Methanol with a Ferric Molybdate Catalyst Production Costs . . . . . . . . . . . . . . . . . . . . .
126
7.1 Formaldehyde from Methane Patent Summary . . . . . . . . . . . . . . . . . . . . . .
138
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