Apparatuses and methods for deoxygenating biomass-derived pyrolysis oil
Apparatuses and methods for deoxygenating a biomass-derived pyrolysis oil are provided herein. In one example, the method comprises of dividing a feedstock stream into first and second feedstock portions. The feedstock stream comprises the biomass-derived pyrolysis oil and has a temperature of about 60° C. or less. The first feedstock portion is combined with a heated organic liquid stream to form a first heated diluted pyoil feed stream. The first heated diluted pyoil feed stream is contacted with a first deoxygenating catalyst in the presence of hydrogen to form an intermediate low-oxygen pyoil effluent. The second feedstock portion is combined with the intermediate low-oxygen pyoil effluent to form a second heated diluted pyoil feed stream. The second heated diluted pyoil feed stream is contacted with a second deoxygenating catalyst in the presence of hydrogen to form additional low-oxygen pyoil effluent.
1. A method for deoxygenating a biomass-derived pyrolysis oil, the method comprising the steps of:
dividing a feedstock stream comprising the biomass-derived pyrolysis oil and having a first temperature of about 60° C. or less into portions including a first feedstock portion and a second feedstock portion;
combining the first feedstock portion with a heated co-feed organic liquid stream comprising alcohols, ethers, phenolic compounds, or mixtures thereof to form a first heated diluted pyoil feed stream;
contacting the first heated diluted pyoil feed stream with a first deoxygenating catalyst in the presence of hydrogen in a first reaction zone at first hydroprocessing conditions effective to form a first intermediate low-oxygen pyoil effluent;
combining the second feedstock portion with the first intermediate low-oxygen pyoil effluent to form a second heated diluted pyoil feed stream; and
contacting the second heated diluted pyoil feed stream with a second deoxygenating catalyst in the presence of hydrogen in a second reaction zone at second hydroprocessing conditions effective to form additional low-oxygen pyoil effluent, and wherein the first and second deoxygenating catalysts are the same type or different types of catalyst.
2. The method of claim 1 , wherein the step of combining the first feedstock portion comprises combining the first feedstock portion with the heated co-feed organic liquid stream and a hydrogen-rich gas stream to form the first heated diluted pyoil feed stream prior to the step of contacting the first heated diluted pyoil feed stream with the first deoxygenating catalyst.
3. The method of claim 2 , wherein the hydrogen-rich gas stream comprises a hydrogen-rich recycle gas stream, and the method further comprises the step of:
passing the hydrogen-rich recycle gas stream through a heater to heat the hydrogen-rich recycle gas stream prior to the step of combining the first feedstock portion with the heated organic liquid stream and the hydrogen-rich gas stream.
4. The method of claim 2 , wherein the heated co-feed organic liquid stream comprises a heated recycle organic liquid stream.
5. The method of claim 4 , further comprises the step of:
passing a recycle organic liquid stream through a heater to form the heated recycle organic liquid stream prior to the step of combining the first feedstock portion with the heated co-feed organic liquid stream and the hydrogen-rich gas stream to form the first heated diluted pyoil feed stream.
6. The method of claim 5 , wherein the hydrogen-rich gas stream comprises a hydrogen-rich recycle gas stream, and the method further comprises the step of:
combining the recycle organic liquid stream and the hydrogen-rich recycle gas stream to form a combined recycle stream, and wherein the step of passing comprises passing the combined recycle stream through the heater to form a heated combined recycle hydrogen-containing organic liquid stream, and wherein the step of combining the first feedstock portion comprises combining the first feedstock portion with the heated combined recycle hydrogen-containing organic liquid stream to form the first heated diluted pyoil feed stream.
7. The method of claim 1 , wherein the step of combining the first feedstock portion comprises forming the first heated diluted pyoil feed stream having a second temperature of from about 100 to about 300° C.
8. The method of claim 1 , wherein the step of contacting the first heated diluted pyoil feed stream comprises contacting the first heated diluted pyoil feed stream with the first deoxygenating catalyst at a reaction zone temperature of from about 100 to about 350° C.
9. The method of claim 1 , wherein the step of combining the second feedstock portion comprises forming the second heated diluted pyoil feed stream having a third temperature of from about 120 to about 350° C.
10. The method of claim 1 , wherein the step of contacting the second heated diluted pyoil feed stream comprises contacting the second heated diluted pyoil feed stream with the second deoxygenating catalyst at a reaction zone temperature of from about 160 to about 360° C.
11. A method for deoxygenating a biomass-derived pyrolysis oil, the method comprising the steps of:
separating a low-oxygen pyoil effluent and optionally selectively heating to form a low-oxygen pyoil product stream, a heated co-feed recycle organic liquid stream comprising alcohols, ethers, phenolic compounds, or mixtures thereof, and a hydrogen-rich recycle gas stream;
dividing a feedstock stream comprising the biomass-derived pyrolysis oil and having a first temperature of about 60° C. or less into portions including a first feedstock portion and a second feedstock portion;
combining the first feedstock portion with the heated co-feed recycle organic liquid stream and the hydrogen-rich recycle gas stream to form a first heated diluted pyoil feed stream;
introducing the first heated diluted pyoil feed stream to a first reaction zone that contains a first deoxygenating catalyst and that is operating at first hydroprocessing conditions effective to form a first intermediate low-oxygen pyoil effluent;
combining the second feedstock portion with the first intermediate low-oxygen pyoil effluent to form a second heated diluted pyoil feed stream; and
introducing the second heated diluted pyoil feed stream to a second reaction zone that contains a second deoxygenating catalyst and that is operating at second hydroprocessing conditions effective to form additional low-oxygen pyoil effluent, and wherein the first and second deoxygenating catalysts are the same type or different types of catalyst.
12. The method of claim 11 , wherein the step of separating comprises forming the heated co-feed recycle organic liquid stream having a second temperature of from about 150 to about 400° C.
13. The method of claim 11 , wherein the step of combining the first feedstock portion comprises combining the first feedstock portion with the heated co-feed recycle organic liquid stream at a predetermined pyoil to recycle oil ratio of from about 1:5 to about 1:40, wherein the predetermined pyoil to recycle oil ratio is defined by a pyoil mass flow rate of the first feedstock portion to a recycle oil mass flow rate of the heated recycle organic liquid stream.
14. The method of claim 11 , wherein the step of combining the first feedstock portion comprises combining the first feedstock portion with the heated co-feed recycle organic liquid stream and a hydrogen-rich gas stream that comprises the hydrogen-rich recycle gas stream, wherein the first feedstock portion is combined with the hydrogen-rich gas stream at a predetermined pyoil to hydrogen ratio of from about 1:1 to about 1:5, and wherein the predetermined pyoil to hydrogen ratio is defined by a pyoil mass flow rate of the first feedstock portion to a hydrogen-rich gas mass flow rate of the hydrogen-rich gas stream.
15. The method of claim 11 , wherein the step of dividing comprises dividing the feedstock stream into the portions including a third feedstock portion, and wherein the method further comprises:
combining the third feedstock portion with a second intermediate low-oxygen pyoil effluent to form a third heated diluted pyoil feed stream; and
introducing the third heated diluted pyoil feed stream to a third reaction zone that contains a third deoxygenating catalyst and that is operating at third hydroprocessing conditions effective to form the low-oxygen pyoil effluent.
16. The method of claim 15 , wherein the step of dividing comprises dividing the feedstock stream to form the first feedstock portion having a first pyoil mass flow rate of from about 10% to about 35% of the feedstock stream, the second feedstock portion having a second pyoil mass flow rate of from about 15% to about 35% of the feedstock stream, and the third feedstock portion having a third pyoil mass flow rate of from about 15% to about 50% of the feedstock stream.
17. The method of claim 15 , wherein the first deoxygenating catalyst, the second deoxygenating catalyst, or the third deoxygenating catalyst is a more active and/or increased quantity of catalyst than the other of the first deoxygenating catalyst, the second deoxygenating catalyst, or the third deoxygenating catalyst, and wherein the method further comprises:
operating the first reaction zone, the second reaction zone, or the third reaction zone that is associated with the more active and/or increased quantity of catalyst at a reaction zone temperature less than the other of the first reaction zone, the second reaction zone, or the third reaction zone.