Lanthanum-promoted supported metal catalysts and process for producing guerbet alcohols using same
View Patent ↗The present invention relates to novel catalyst compositions and their use in a process for the catalytic conversion of ethanol to a reaction product comprising 1-butanol. The catalysts comprise Group II metal salts selected from the group consisting of oxides, carbonates, bicarbonates, hydroxides, and mixtures thereof, supported on a lanthanum-promoted oxide containing alumina.
1. A process for making a reaction product comprising 1-butanol, comprising the step:
contacting a reactant comprising ethanol with a catalyst composition at a reaction temperature and pressure sufficient to produce said reaction product, wherein said catalyst composition comprises at least one Group II metal salt supported on a lanthanum-promoted oxide containing alumina and has the following empirical formula:
M a [Al (1-b) La b ][A z− ] c
wherein:
(i) M is selected from the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ , and combinations of these;
(ii) A Z− is a monovalent or divalent anion selected from the group consisting of carbonate (CO 3 2− , wherein the charge, “z” is given by z=2), oxide (O 2− , wherein z=2), hydroxide (OH − , wherein z=1), and bicarbonate (HCO 3 − , wherein z=1), or a mixture (A z′− x A z″− y ) of these divalent and monovalent anions wherein A z′− and A z″− are different anions, with the caveat that when A z− is the mixture A z′− x A z″− y , the composite charge “z” is given by z=x(z′)+y(z″), wherein x+y=1;
(iii) a is 0.01 to 0.4, including the endpoints of the range;
(iv) b is 0.0011 to 0.11, including the endpoints of the range; and
(v) c=(2a/z)+[3(1−b)/z]+(3b/z).
2. The process of claim 1 , wherein the temperature is from about 200° C. to about 500° C.
3. The process of claim 1 , wherein the pressure is from about 0.1 mPa to about 20.7 MPa.
4. The process of claim 1 , wherein M is Ca 2+ , Ba 2+ , or Sr 2+ ; A z− is CO 3 2− or O 2− or a mixture of these; a is 0.05 to 0.2; b is 0.005 to 0.05.
5. The process of claim 1 , wherein M is Ca 2+ .
6. The process of claim 1 , wherein M is Sr 2+ .
7. The process of claim 1 , wherein M is Ba 2+ .
8. The process of claim 1 , wherein the alumina is γ-alumina.
9. A catalyst composition comprising:
at least one Group II metal salt supported on a lanthanum-promoted oxide containing alumina and having the following empirical formula:
M a [Al (1-b) La b ][A z− ] c
wherein:
(i) M is selected from the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ , and combinations of these;
(ii) A Z− is a monovalent or divalent anion selected from the group consisting of carbonate (CO 3 2− , wherein the charge, “z” is given by z=2), oxide (O 2− , wherein z=2), hydroxide (OH − , wherein z=1), and bicarbonate (HCO 3 − , wherein z=1), or a mixture (A z′− x A z″− y ) of these divalent and monovalent anions wherein A z′− and A z″− are different anions, with the caveat that when A z− is the mixture A z′− x A z″− y , the composite charge “z” is given by z=x(z′)+y(z″), wherein x+y=1;
(iii) a is 0.01 to 0.4, including the endpoints of the range;
(iv) b is 0.0011 to 0.11, including the endpoints of the range; and
(v) c=(2a/z)+[3(1−b)/z]+(3b/z).
10. The composition of claim 9 , wherein M is Ca 2+ , Sr 2+ , or Ba 2+ ; A z− is CO 3 2− or O 2− or a mixture of these; a is 0.05 to 0.2; b is 0.005 to 0.05.
11. The catalyst composition of claim 9 , wherein M is Ca 2+ .
12. The catalyst composition of claim 9 , wherein M is Sr 2+ .
13. The catalyst composition of claim 9 , wherein M is Ba 2+ .
14. The catalyst composition of claim 9 , wherein the alumina is γ-alumina.