Preparation of polyoxymethylene dimethyl ethers by acid-activated catalytic conversion of methanol with formaldehyde formed by dehydrogenation of methanol

• US 20020007089A1
• Filed: 07/11/2001
• Published: 01/17/2002
• Est. Priority Date: 11/12/1998
• Status: Active Grant

• Current Assignee: BP Corporation North America Incorporated (BP PLC)
• Original Assignee: BP Corporation North America Incorporated (BP PLC)
• Inventors: Hagen, Gary P., Spangler, Michael J.
• Granted Patent: US 6,437,195 B2
• Time in Patent Office: Days
• US Class Current: 568/472
• CPC Class Codes: C07C 41/56 by condensation of aldehydes, paraformaldehyde, or ketones
• CPC Class Codes: C07C 43/30 Compounds having groups
• CPC Class Codes: C07C 45/002 by dehydrogenation
• CPC Class Codes: C07C 47/04 Formaldehyde
• CPC Class Codes: C10L 10/02 for reducing smoke development
• CPC Class Codes: C10L 10/08 for improving lubricity; for reducing wear
• CPC Class Codes: Y02P 20/10 Process efficiency

Abstract

A particularly useful process which includes the steps of providing a feedstream comprising methanol, a soluble condensation promoting component capable of activating a heterogeneous acidic catalyst and a source of formaldehyde formed by conversion of methanol in the presence of a catalyst comprising copper and zinc; and heating this feedstream with the heterogeneous acidic catalyst in a catalytic distillation column to convert methanol and formaldehyde present to methylal and higher polyoxymethylene dimethyl ethers and to separate the methylal from the higher polyoxymethylene dimethyl ethers is disclosed. Advantageously, methylal and higher polyoxymethylene dimethyl ethers are formed and separated in a catalytic distillation column. By including within the column a section containing an anion exchange resin, an essentially acid-free product is obtained. Products can be used directly as a blending component, or fractionated, as by further distillation, to provide more suitable components for blending into fuel.

Claims

1. A process for the catalytic production of a mixture of oxygenated organic compounds suitable as a blending component of fuel for use in compression ignition internal combustion engines, which process comprises providing a feedstream comprising methanol, a soluble condensation promoting component capable of activating a heterogeneous acidic catalyst, and a source of formaldehyde formed by the conversion of methanol in the presence of a catalyst comprising copper and zinc as catalyst components which source of formaldehyde comprises from about 30 to about 85 percent by weight formaldehyde in methanol solution containing less than about 5 percent water;

heating the feedstream with the heterogeneous acidic catalyst under conditions of reaction sufficient to form an effluent of condensation comprising water, methanol, methylal and one or more polyoxymethylene dimethyl ethers which methylal and polyoxymethylene dimethyl ethers have structures represented by the formula

CH₃O(CH₂O)_nCH₃

where n is a number from 1 to about 10; and

contacting at least a liquid portion of the effluent with an anion exchange resin to form an essentially acid-free mixture comprising methylal and polyoxymethylene dimethyl ethers having values of n greater than 1.

2. The process according to claim 1 wherein the soluble condensation promoting component capable of activating the heterogeneous acidic catalyst comprises at least one member of the group consisting of low boiling, monobasic organic acids, and the heating of the feedstream with the heterogeneous acidic catalyst employs at least one catalytic distillation column having internal and/or external stages of contact with the acidic catalyst.

3. The process according to claim 1 which further comprises dehydrating the acid-free mixture using a molecular sieve to obtain an essentially water-free mixture of polyoxymethylene dimethyl ethers, and fractionating the water-free mixture as by distillation to obtain an overhead fraction containing methylal and an essentially methylal-free bottom fraction containing polyoxymethylene dimethyl ethers having values of n greater than 1.

4. The process according to claim 2 wherein the acidic catalyst comprises at least one cation exchange resin of the group consisting of styrene-divinylbenzene copolymers, acrylic acid-divinylbenzene copolymers, and methacrylic acid-divinylbenzene copolymers, and the soluble condensation promoting component capable of activating the heterogeneous acidic catalyst comprises at least one member of the group consisting of formic acid and acetic acid.

5. The process according to claim 2 wherein the acidic catalyst comprises a sulfonated tetrafluoroethylene resin derivative, and the soluble condensation promoting component capable of activating the heterogeneous acidic catalyst comprises at least one member of the group consisting of formic acid and acetic acid.

6. The process according to claim 1 wherein the heating of the feedstream with the acidic catalyst is carried out at temperatures in a range from about 45°

to about 90°

C. and employs at least one catalytic distillation column having internal and/or external stages of contact with the acidic catalyst and internal zones to separate methylal from higher polyoxymethylene dimethyl ethers.

7. The process according to claim 6 wherein at least a liquid portion of the effluent containing polyoxymethylene dimethyl ethers is contacted with an anion exchange resin disposed within a section of the distillation column below the stages of contact with the acidic catalyst to form an essentially acid-free mixture.

8. The process according to claim 6 wherein a source of methanol is admixed with the feedstream, and/or into the stages of contact with the acidic catalyst.

9. The process according to claim 1 which further comprises formation of the feedstream by a process comprising continuously contacting methanol in the vapor phase with a catalytically effective amount of a catalyst consisting of copper, zinc and a member selected from the group consisting of sulfur, selenium and tellurium as catalyst components at elevated temperatures to form a gaseous dehydrogenation mixture comprising formaldehyde, dimethyl ether, dihydrogen and carbon monoxide;

cooling the gaseous dehydrogenation mixture with a liquid comprising methanol and collecting formaldehyde therein; and

separating a gaseous mixture, comprising predominantly dihydrogen and carbon monoxide, from resulting liquid comprising dimethyl ether, methanol, formaldehyde and formic acid.

10. A process for the catalytic production of a mixture of oxygenated organic compounds suitable as a blending component of fuel for use in compression ignition internal combustion engines, which process comprises providing a feedstream comprising methanol, a soluble condensation promoting component capable of activating a heterogeneous acidic catalyst, and a source of formaldehyde formed by the conversion of methanol in the presence of a catalyst comprising copper and zinc as catalyst components which source of formaldehyde comprises from about 30 to about 85 percent by weight formaldehyde in methanol solution containing less than about 5 percent water;

heating the feedstream with the heterogeneous acidic catalyst under conditions of reaction sufficient to form an effluent of condensation comprising water, methanol, methylal and one or more polyoxymethylene dimethyl ethers which methylal and polyoxymethylene dimethyl ethers have structures represented by the formula

CH₃O(CH₂O)_nCH₃

where n is a number from 1 to about 10;

contacting at least a liquid portion of the effluent of condensation with an anion exchange resin to form an essentially acid-free mixture; and

fractionating the acid-free mixture as by distillation to obtain an overhead fraction containing methylal and an essentially methylal-free bottom fraction containing polyoxymethylene dimethyl ethers having values of n greater than 1, and further comprises formation of the feedstream by a process comprising continuously contacting methanol in the vapor phase with a catalytically effective amount of a catalyst consisting of copper, zinc and a member selected from the group consisting of sulfur, selenium and tellurium as catalyst components at elevated temperatures to form a gaseous dehydrogenation mixture comprising formaldehyde, dihydrogen and carbon monoxide;

cooling the gaseous dehydrogenation mixture with a liquid comprising methanol to take up and hold formaldehyde therein; and

separating a gaseous mixture, comprising predominantly dihydrogen and carbon monoxide, from resulting liquid comprising methanol, formaldehyde and formic acid.

11. The process according to claim 10 wherein the catalyst comprises copper, zinc and selenium or tellurium as catalyst components in atomic ratios of 1:

0.05-0.5;

0.01-0.5 with the proviso that the amount of zinc is at least equal to the amount of selenium or tellurium present in the catalyst, and wherein the elevated temperatures are in a range from about 500°

to about 750°

C.

12. The process according to claim 10 wherein the catalyst comprises copper, zinc and selenium as catalyst components in an atomic ratios of 1:

0.05-0.5;

0.05-0.4 with the proviso that the amount zinc is at least equal to the amount of selenium present in the catalyst, and wherein the elevated temperatures are in a range from about 600°

to about 700°

C.

13. The process according to claim 10 wherein the collecting of formaldehyde is carried out at temperatures in a range downward from about 100°

C. to about 25°

C. in at least one continuous separation column.

14. The process according to claim 10 wherein the elevated temperatures are maintained in a range from about 600°

to about 700°

C. using a source of heat derived at least in part from the gaseous mixture comprising dihydrogen and carbon monoxide by combustion thereof.