Process for producing functionalized organic molecules and uses thereof
A process for producing functionalized organic molecules having 1 to 3 carbon atoms. The method includes the step of contacting carbon dioxide as the only gas, or a gas mixture that includes carbon dioxide and methane, in the presence of water, with a catalyst that includes permanently polarized hydroxyapatite.
1 . A process for producing functionalized organic molecules having 1 to 3 carbon atoms selected from the group consisting of ethanol, methanol, formic acid, acetic acid, malonic acid, acetone and a mixture of at least two of the afore-said functionalized organic molecules, the process comprising the step of:
contacting carbon dioxide as the only gas or a gas mixture comprising or consisting of carbon dioxide and methane in the presence of water with a catalyst comprising or consisting of permanently polarized hydroxyapatite, wherein the gas mixture is free of nitrogen.
2 . The process according to claim 1 , wherein the permanently polarized hydroxyapatite has:
a crystallinity >65% and/or
a proportion of amorphous calcium phosphate <18% by weight, based on the total weight of the permanently polarized hydroxyapatite, and/or
a proportion of β-tricalcium phosphate <36% by weight, based on the total weight of the permanently polarized hydroxyapatite, and/or
a bulk resistance from 10 7 Ω cm 2 to 10 5 Ω cm 2 , wherein the bulk resistance increases by only 4% to 73% after 3 months, and/or
a surface capacitance decreasing less than 8% after 3 months.
3 . The process according to claim 1 , wherein the permanently polarized hydroxyapatite is obtained by a process comprising the steps of:
(a) preparing samples of hydroxyapatite,
(b) sintering the samples prepared in step (a) at a temperature between 700° C. and 1200° C.,
(c) applying a constant or variable DC voltage between 250 V and 2500 V to the samples obtained in step (b) or to shaped bodies thereof or
applying an equivalent electric field between 1.49 kV/cm and 15 kV/cm to the samples obtained in step (b) or to shaped bodies thereof or
applying an electrostatic discharge between 2500 V and 1500000 V to the samples obtained in step (b) or to shaped bodies thereof or
applying an equivalent electric field between 148.9 kV/cm and 8928 kV/cm to the samples obtained in step (b) or to shaped bodies thereof and
(d) cooling the samples obtained in step (c) maintaining the DC voltage or the equivalent electric field or
cooling the samples obtained in step (c) maintaining or without maintaining the electrostatic discharge or the equivalent electric field.
4 . The process according to claim 1 , wherein the permanently polarized hydroxyapatite is obtained by a process comprising the steps of:
(a) preparing samples of hydroxyapatite,
(b) sintering the samples prepared in step (a) at a temperature between 700° C. and 1200° C.,
(c) applying a constant or variable DC voltage between 250 V and 2500 V for at least 1 minute at a temperature between 900° C. and 1200° C. to the samples obtained in step (b) or to shaped bodies thereof or
applying an equivalent electric field between 1.49 kV/cm and 15 kV/cm for at least 1 minute at a temperature between 900° C. and 1200° C. to the samples obtained in step (b) or to shaped bodies thereof or
applying an electrostatic discharge between 2500 V and 1500000 V for less than 10 minutes at a temperature between 900° C. and 1200° C. to the samples obtained in step (b) or to shaped bodies thereof or
applying an equivalent electric field between 148.9 kV/cm and 8928 kV/cm for less than 10 minutes at a temperature between 900° C. and 1200° C. to the samples obtained in step (b) or to shaped bodies thereof and
(d) cooling the samples obtained in step (c) maintaining the DC voltage or the equivalent electric field or
cooling the samples obtained in step (c) maintaining or without maintaining the electrostatic discharge or the equivalent electric field.
5 . The process according to claim 1 , wherein the permanently polarized hydroxyapatite is obtained by a process comprising the steps of:
(a) preparing samples of hydroxyapatite,
(b) sintering the samples prepared in step (a) at a temperature of 1000° C.,
(c) applying an equivalent electric field of 3 kV/cm at a temperature of 1000° C. to the samples obtained in step (b) or to shaped bodies thereof and
(d) cooling the samples obtained in step (c) maintaining the equivalent electric field.
6 . The process according to claim 1 , wherein the permanently polarized hydroxyapatite is obtained by a process comprising the steps of:
(a) preparing samples of hydroxyapatite,
(b) sintering the samples prepared in step (a) at a temperature of 1000° C. for 2 h,
(c) applying an equivalent electric field of 3 kV/cm at a temperature of 1000° C. for 1 h to the samples obtained in step (b) or to shaped bodies thereof and
(d) cooling the samples obtained in step (c) maintaining the equivalent electric field for 30 minutes.
7 . The process according to claim 1 , wherein the contacting step is carried out in the presence of liquid water.
8 . The process according to claim 1 , wherein the contacting step is carried out with a volumetric ratio of the permanently polarized hydroxyapatite to water of 1000:1 to 0.01:1.
9 . The process according to claim 1 , wherein the contacting step is carried out with a volumetric ratio of carbon dioxide to methane of 200:1.
10 . The process according to claim 1 , wherein the contacting step is carried out under a total pressure of 0.1 bar to 100 bar.
11 . The process according to claim 1 , wherein the contacting step is carried out under a pressure of carbon dioxide of 0.035 bar to 100 bar.
12 . The process according to claim 1 , wherein the contacting step is carried out under a partial pressure of carbon dioxide of 0.035 bar to 90 bar.
13 . The process according to claim 1 , wherein the contacting step is carried out with a molar ratio of carbon dioxide to permanently polarized hydroxyapatite of 0.1 to 0.5 and/or with a molar ratio of methane to permanently polarized hydroxyapatite of 0.1 to 0.5.
14 . The process according to claim 1 , wherein the contacting step is carried out under UV irradiation or UV-Vis irradiation having a wavelength from 200 nm to 850 nm.
15 . The process according to claim 1 , wherein the contacting step is carried out under UV irradiation and/or Visible light irradiation having an irradiance from 0.1 W/m 2 to 200 W/m 2 .
16 . The process according to claim 1 , wherein the contacting step is carried out at a temperature of 25° C. to 250° C.
17 . The process according to claim 1 , wherein the process is used for producing ethanol or a mixture comprising or consisting of ethanol and at least one further functionalized organic molecule selected from a group consisting of methanol, formic acid, acetic acid, malonic acid and acetone, or a mixture comprising or consisting of ethanol, methanol, formic acid, acetic acid and acetone or a mixture comprising or consisting of ethanol, methanol, acetic acid, malonic acid and acetone.
18 . The process according to claim 1 , wherein the process is used for removing carbon dioxide from the atmosphere.