Process for producing guerbet alcohols using water tolerant basic catalysts
View Patent ↗A process is provided for making a reaction product comprising 1-butanol by contacting a reactant comprising ethanol containing a significant amount of water with a decomposed hydrotalcite catalyst. The catalyst may be 1) hydrotalcites which have been thermally decomposed, either partially or fully, to form catalytically active species; 2) combinations of hydrotalcites (optionally containing transition metals) and metal carbonates; and 3) hydrotalcites (optionally containing transition metals) surface-impregnated with a transition metal nitrate, where catalysts 2) and 3) have also been thermally decomposed, either partially or fully, to form catalytically active species. The catalyst, at a selected reaction time, has greater activity when the ethanol contains water as compared to when the ethanol is anhydrous.
1. A process for making a reaction product comprising 1-butanol, comprising:
contacting a reactant comprising ethanol containing water with a catalyst at a reaction temperature and pressure sufficient to produce said reaction product, wherein said catalyst is derived from a hydrotalcite of Formula I:
[M 2+ 1−x M 3+ x (OH) 2 ][{(M′A′) n′− } a A n− (1−a)(n′/n) ] x/n′ .yH 2 O Formula I
wherein
M 2+ is divalent Mg, or a combination of divalent Mg and at least one divalent member selected from the group consisting of Zn, Ni, Pd, Pt, Co, Fe, and Cu;
M 3+ is trivalent Al, or a combination of trivalent Al and at least one trivalent member selected from the group consisting of Fe and Cr;
x is 0.66 to 0.1;
M′ is one or more divalent members selected from the group consisting of Ni and Co;
A′ is the anion of ethylenediaminetetraacetic acid;
n′ is the absolute value of the sum of the oxidation state of M′ and the oxidation state of the anion of ethylenediaminetetraacetic acid (−4);
A n− is CO 3 2− with n=2 or OH − with n=1;
a=0.001 to 1; and
y=0 to 4;
wherein the hydrotalcite catalyst is partially decomposed;
and wherein the Wet:Dry Activity Ratio obtained by the Relative Conversion Test is greater than 100% after 70 minutes of time on stream.
2. A process for making a reaction product comprising 1-butanol, said process comprising:
contacting a reactant comprising ethanol containing water with a catalyst at a reaction temperature and pressure sufficient to produce said product, wherein said catalyst is derived from a hydrotalcite of Formula II:
(M 2+ 1−x M 3+ x (OH) 2 )(A n− x/n ).yH 2 O Formula II
wherein
M 2+ is divalent Mg and at least one divalent member selected from the group consisting of Ni and Co;
M 3+ is trivalent Al, or a combination of trivalent Al and at least one trivalent member selected from the group consisting of Fe and Cr;
x is 0.66 to 0.1;
A n− is CO 3 2− with n=2 or OH − with n=1; and
y is 0 to 4;
wherein the hydrotalcite catalyst is partially decomposed;
and wherein the Wet:Dry Activity Ratio obtained by the Relative Conversion Test is greater than 100% after 70 minutes of time on stream.
3. A process for making a reaction product comprising 1-butanol, comprising:
contacting a reactant comprising ethanol containing water with a catalyst at a reaction temperature and pressure sufficient to produce the reaction product, wherein the catalyst is derived from a hydrotalcite of Formula III:
[[(Me 2+ 1−x M 3+ x (OH) 2 )(A n− x/n )].yH 2 O][M′A′] z Formula III
wherein
M 2+ is divalent Mg, or a combination of Mg and at least one divalent member selected from the group consisting of Zn, Ni, Pd, Pt, Co, Fe, and Cu;
M 3+ is trivalent Al, or a combination of trivalent Al and at least one trivalent member selected from the group consisting of Fe and Cr;
x is 0.66 to 0.1;
A n− is CO 3 2− with n=2, or OH − with n=1;
M′A′ is a carbonate of at least one divalent metal M′ selected from the group consisting of Ni and Co; and A′ is carbonate;
z is any number between 0.001 and 0.5 inclusive; and
y is 0 to 4;
wherein the hydrotalcite catalyst is partially decomposed;
and wherein the Wet:Dry Activity Ratio obtained by the Relative Conversion Test is greater than 100% after 70 minutes of time on stream.
4. A process for making a reaction product comprising 1-butanol, comprising:
contacting a reactant comprising ethanol containing water with a catalyst at a reaction temperature and pressure sufficient to produce the reaction product, wherein the catalyst is derived from a hydrotalcite of Formula IV:
[[(M 2+ 1−x M 3+ x (OH) 2 )(A n− x/n )].yH 2 O][M′(A′) 2 ] z Formula IV
wherein
M 2+ is divalent Mg, or a combination of Mg and at least one divalent member selected from the group consisting of Zn, Ni, Pd, Pt, Co, Fe, and Cu;
M 3+ is trivalent Al, or a combination of trivalent Al and at least one trivalent member selected from the group consisting of Fe and Cr;
x is 0.66 to 0.1;
A n− is CO 3 2− with n=2, or OH − with n=1;
M′(A′) 2 is a nitrate or hydroxide of at least one divalent metal M′ selected from the group consisting of Ni and Co; and A′ is nitrate or hydroxide;
z is any number between 0.001 and 0.5 inclusive;
y is 0 to 4;
wherein the hydrotalcite catalyst is partially decomposed;
and wherein the Wet:Dry Activity Ratio obtained by the Relative Conversion Test is greater than 100% after 70 minutes of time on stream.
5. The process of claim 1 , 2 , 3 , or 4 wherein the hydrotalcite decomposition is achieved by heating for a time and at a temperature sufficient to cause a diminution in the hydrotalcite powder X-ray diffraction pattern peak intensities between 2θ angles of 10 degrees and 70 degrees using CuKα radiation.
6. The process of claim 1 , 2 , 3 , or 4 wherein the ethanol contains about 0.5 weight percent to about 20 weight percent water.
7. The process of claim 1 , 2 , 3 , or 4 wherein the reaction temperature is from about 200° C. to about 500° C. and the pressure is from about 0.1 MPa to about 20.7 MPa.
8. The process of claim 1 , 2 , 3 , or 4 wherein the Wet:Dry Activity Ratio is greater than 100% after 90 minutes of time on stream.
9. The process of claim 1 , 3 , or 4 wherein M 2+ is divalent Mg.
10. The process of claim 1 , 2 , 3 , or 4 wherein M 3+ is trivalent Al.
11. The process of claim 1 , 2 , 3 , or 4 wherein A n− is CO 3 2− or OH − .
12. The process of claim 1 , wherein M 2+ is divalent Mg; M 3+ is trivalent Al; x is 0.2; a is 0.1; A′ is the anion of ethylenediaminetetraacetic acid; M′ is Ni; A n− is OH − ; n′ is 2; n is 1; and y is 0 to 4.
13. The process of claim 2 , wherein M 2+ is divalent Mg and at least one divalent member selected from the group consisting of Ni and Co; M 3+ is trivalent Al: and A n− is CO 3 2− or OH − .
14. The process of claim 2 , wherein M 2+ is divalent Mg and at least one divalent member selected from the group consisting of Ni and Co, and x is 0.35 to 0.1.
15. The process of claim 3 , wherein M 2+ is divalent Mg; M 3+ is trivalent Al; A n− is CO 3 2− or OH; z is any number between 0.001 and 0.5; and M′ is selected from the group consisting of Ni and Co.
16. The process of claim 15 , wherein z is any number between 0.01 and 0.25.
17. The process of claim 4 , wherein M 2+ is divalent Mg; M 3+ is trivalent Al; x=0.25; A n− is CO 3 2− ; M′ is Ni; A′ is nitrate; and z=0.06; and y is 0 to 4.