Production of acrylic acid and ethanol from carbonaceous materials
A process for producing acrylic acid from carbonaceous materials such as biomass. The carbonaceous material, such as biomass, is gasified to produce synthesis gas. The synthesis gas then is subjected to a plurality of reactions to produce acrylic acid.
1. A process for producing acrylic acid and ethanol from biomass comprising:
(a) contacting said biomass with an oxidizing gas comprising oxygen and steam, thereby oxidizing said biomass;
(b) treating, in a first stage, at least a portion of said oxidized biomass produced in step (a) with an oxidizing gas comprising oxygen and steam to heat and reform said oxidized biomass, and provide an oxidized biomass containing residual carbon in char particles entrained in said oxidized biomass, and low molecular weight alkyl and aromatic hydrocarbons and phenolics in said oxidized biomass;
(c) treating, in a second stage, at least a portion of said oxidized biomass containing residual carbon in char particles entrained in said oxidized biomass, and low molecular weight alkyl and aromatic hydrocarbons and phenolics in said oxidized biomass, produced in step (b) with an oxidizing gas comprising oxygen and steam to heat said oxidized biomass to a temperature from about 800° C. to about 1500° C., thereby producing a crude synthesis gas;
(d) purifying the crude synthesis gas to provide a purified synthesis gas;
(e) reacting at least a portion of the carbon monoxide from said purified synthesis gas with hydrogen from said purified synthesis gas to provide a product stream containing dimethyl ether;
(f) separating said dimethyl ether from said product stream of step (e) and reacting said dimethyl ether to provide a product comprising propylene and ethylene;
(g) reacting said ethylene to produce ethanol; and
(h) subjecting said propylene to one or more reaction steps to produce acrylic acid.
2. The process of claim 1 wherein step (c) is conducted in one or more tubular flow reactors.
3. The process of claim 2 wherein, in step (c), said oxidized biomass is heated to a temperature of from about 925° C. to about 1,300° C.
4. The process of claim 1 wherein said dimethyl ether is reacted in step (f) in the presence of an acid catalyst.
5. The process of claim 4 wherein said acid catalyst is a zeolite.
6. The process of claim 1 wherein, in step (h), said propylene is reacted in a partial oxidation reactor to produce acrylic acid in the presence of a cobalt and nickel molybdate containing catalyst.
7. The process of claim 1 wherein, in step (h), said propylene is oxidized to produce acrolein, and said acrolein is reacted in an oxidation reactor to produce acrylic acid.
8. The process of claim 1 wherein, prior to step (a), said biomass is admixed with at least one additive material which neutralizes impurities which may be present in said biomass.
9. The process of claim 8 wherein said impurities are selected from the group consisting of chlorine, fluorine, and sulfur.
10. The process of claim 8 wherein said at least one additive material is at least one adsorbent material.
11. The process of claim 8 wherein said at least one adsorbent material is selected from the group consisting of calcium oxide, calcined limestone, ash materials, olivine, and mixtures of calcium and magnesium oxides.
12. The process of claim 1 wherein steps (a) and (b) are conducted in a gasifier, said gasifier having a fluidized bed section and a freeboard section, and wherein step (a) is conducted in said fluidized bed section and step (b) is conducted in said freeboard section.
13. The process of claim 2 wherein, in step (c), said oxidized biomass is heated to a temperature of from about 925° C. to about 1,500° C.
14. The process of claim 1 wherein, in step (f), said product further comprises methane and aromatics.
15. The process of claim 1 wherein, in step (f), the propylene selectivity is between 70% and 95%.
16. The process of claim 1 wherein step (e) is completed in a single reactor, and wherein step (e) comprises:
reacting at least a portion of the carbon monoxide from said purified synthesis gas with hydrogen from said purified synthesis gas in the presence of an integrated methanol synthesis and dehydration catalyst, suspended in an inert oil, whereby said hydrogen and said carbon monoxide are reacted to produce methanol, and said methanol is reacted to produce dimethyl ether and water.
17. The process of claim 1 wherein, in step (c), said carbon in said char is converted to carbon monoxide.
18. The process of claim 1 , and further comprising:
prior to step (c), converting said phenolics of step (b) into simple aromatics.
19. The process of claim 12 wherein said oxygen and steam are introduced into the freeboard section of said gasifier in amounts that provide a reaction time of from about 4 seconds to about 8 seconds.
20. The process of claim 2 wherein said one or more tubular flow reactors include reflectorized and insulated carbon steel pipes.
21. The process of claim 2 wherein, in step (c), the reaction time is 1 to 3 seconds.
22. A process for producing acrylic acid and ethanol from biomass, comprising:
(a) contacting said biomass with an oxidizing gas comprising oxygen and steam, thereby oxidizing said biomass;
(b) treating, in a first stage, at least a portion of said oxidized biomass produced in step (a) with an oxidizing gas comprising oxygen and steam to heat and reform said oxidized biomass, and provide an oxidized biomass containing residual carbon in char particles entrained in said oxidized biomass, and low molecular weight alkyl and aromatic hydrocarbons and phenolics in said oxidized biomass;
(c) treating, in a second stage, at least a portion of said oxidized biomass, containing residual carbon in char particles entrained in said oxidized biomass, and low molecular weight alkyl and aromatic hydrocarbons and phenolics in said oxidized biomass, produced in step (b) with an oxidizing gas comprising oxygen and steam to heat said oxidized biomass to a temperature of at least 1,500° C., thereby producing a crude synthesis gas;
(d) purifying the crude synthesis gas to provide a purified synthesis gas;
(e) reacting at least a portion of the carbon monoxide from said purified synthesis gas with hydrogen from said purified synthesis gas to provide a product stream containing dimethyl ether;
(f) separating said dimethyl ether from said product stream of step (e) and reacting said dimethyl ether to provide a product comprising propylene and ethylene;
(g) reacting said ethylene to produce ethanol; and
(h) subjecting said propylene to one or more reaction steps to produce acrylic acid.