Method of obtaining liquid biohydrocarbons from oils of natural origin

Abstract

In the method of obtaining liquid biohydrocarbons from oils of natural origin, in the first step, the oil and/or waste oil is/are heated in the presence of a mixture of hydrogen and carbon monoxide in the presence of a catalyst in the form of a metal oxide selected from a group comprising CoO, NiO, MoO.sub.3, ZrO.sub.2, or a mixture of such metal oxides, on an oxide support selected from a group comprising SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2, whereupon the product of the first step is contacted with hydrogen gas or with a mixture of hydrogen and carbon monoxide in the presence of a metallic catalyst selected from a group comprising Pd, Pt, Co/Mo, Ni/Mo, Zr on an oxide support selected from a group comprising SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2, P.sub.2O.sub.5, ZrO.sub.2 or on a mixture of such oxides.

Claims

1. A method of obtaining liquid biohydrocarbons from oils of natural origin, carried out in two steps in a coupled flow system in the presence of heterophase catalysts, wherein in the first step, the oils of natural origin are heated at a temperature in a range of 100-500 C., at a pressure in a range of 0.1-5 MPa in the presence of a mixture of hydrogen and carbon monoxide, and in the presence of a catalyst in the form of a metal oxide selected from a group comprising CoO, NiO, MoO.sub.3, ZrO.sub.2, or a mixture of such metal oxides, on an oxide support selected from a group comprising SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2, thereby producing a product of the first step, and wherein in the second step, the product of the first step is contacted with hydrogen gas or with a mixture of hydrogen and carbon monoxide at a temperature in a range of 100-500 C., at a pressure in a range of 0.1-5 MPa, and in the presence of a metallic catalyst selected from a group comprising Pd, Pt, Co/Mo, Ni/Mo, Zr on an oxide support selected from a group comprising SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2, P.sub.2O.sub.5, ZrO.sub.2 or on a mixture of such oxides.

2. The method as claimed in claim 1, wherein the catalyst used in the first step of the process is ZrO.sub.2 or a mixture of ZrO.sub.2 and one or more metal oxides selected from the group consisting of CoO, NiO, and MoO.sub.3.

3. The method as claimed in claim 1, wherein the mixture of hydrogen and carbon monoxide used in the first and second steps of the process is a mixture obtained by a selective decomposition of methanol.

4. The method as claimed in claim 1, wherein the first and/or second step of the process is/are carried out under atmospheric pressure.

5. The method of claim 1, wherein the oils of natural origin are selected from the group consisting of vegetable oils, animal fats, algal oils and lipid fractions of ligno-cellulose waste.

6. The method of claim 1, wherein the mixture of hydrogen and carbon monoxide is in a hydrogen to carbon monoxide molar ratio of 1 to 2.

7. The method of claim 1, wherein the first step produces spatial isomers and/or hexamethylbenzene.

8. The method of claim 1, wherein the first step produces 10-30% by weight of spatial isomers and/or 2-5% by weight of hexamethylbenzene in the product of the first step.

9. The method of claim 5, wherein the mixture of hydrogen and carbon monoxide is in a hydrogen to carbon monoxide molar ratio of 1 to 2; and wherein the first step produces 10-30% by weight of spatial isomers and/or 2-5% by weight of hexamethylbenzene in the product of the first step.

10. The method of claim 1, wherein the first step consists essentially of: heating oils of natural origin at a temperature in a range 100-500 C., at a pressure in a range 0.1-5 MPa in the presence of a mixture of hydrogen and carbon monoxide, and in the presence of a catalyst in the form of a metal oxide selected from a group comprising CoO, NiO, MoO3, ZrO.sub.2, or a mixture of such metal oxides, on an oxide support selected from a group comprising SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2, thereby producing a product of the first step, and wherein the second step consists essentially of: the product of the first step is contacted with hydrogen gas or with a mixture of hydrogen and carbon monoxide, at a temperature in a range of 100-500 C., at a pressure in a range of 0.1-5 MPa, and in the presence of a metallic catalyst selected from a group comprising Pd, Pt, Co/Mo, Ni/Mo, Zr on an oxide support selected from a group comprising SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2, P.sub.2O.sub.5, ZrO.sub.2 or on a mixture of such oxides.

11. The method of claim 10, wherein the oils of natural origin are selected from the group consisting of vegetable oils, animal fats, algal oils and lipid fractions of ligno-cellulose waste.

12. The method of claim 10, wherein the mixture of hydrogen and carbon monoxide is in a hydrogen to carbon monoxide molar ratio of 1 to 2; and wherein the first step produces 10-30% by weight of spatial isomers and/or 2-5% by weight of hexamethylbenzene in the product of the first step.

Description

Example 1

(1) The process was carried out in a flow-type catalytic system. The process was carried out using the following catalysts: in step I10% ZrO.sub.2//Al.sub.2O.sub.3 in the amount of 0.5 kg, in step II10% Pd/(Al.sub.2O.sub.3) in the amount of 0.25 kg, after their activation at high temperatures. Temperature in the reactors in step I and step II was then lowered to 100 C. and the reactor in step I were fed with a mixture of hydrogen and carbon monoxide in a molar ratio of 1:2, respectively, at a rate of 4 dm3/h and with Feedstock I after heating it to a temperature of 60 C. at a rate of 0.2 dm.sup.3/h. At the same time, the mixture of hydrogen and carbon monoxide was continued to be introduced at the same molar ratio in a continuous manner in Step II. Temperature was then increased successively to 420 C. (step I) and 300 C. (step II) and, as soon as the reaction conditions stabilized (approx. 1 h), the final product was collected. A pressure of 0.1 MPa was applied in the both steps.

(2) At a 100% conversion of the acids, the content of saturated C.sub.6-C.sub.19 n- and iso-paraffins in the product was 87% by weight, of which C.sub.12-C.sub.17 constituted 82% by weight, and unsaturated C.sub.6-C.sub.19 in the amount of 8% by weight, of which C.sub.12-C.sub.17 constituted 2% by weight, and aromatics in the amount of 5% by weight, including 3% of hexamethylbenzene. The product after step I was found to have a content of 20% by weight of the spatial isomers of C.sub.16-C.sub.17.

Example 2

(3) The process was carried out in a flow-type catalytic system. The process was carried out using the following catalysts: in step I10% NiO.sub.//Al.sub.2O.sub.3 in the amount of 0.5 kg, in step II10% Pd/(Al.sub.2O.sub.3+SiO.sub.2+P.sub.2O.sub.5) in the amount of 0.25 kg, after their activation at high temperatures. Temperature in the reactors in step I and step II was then lowered to 100 C. and the reactor in step I were fed with a mixture of hydrogen and carbon monoxide in a molar ratio of 1:2, respectively, at a rate of 4 dm.sup.3/h and with Feedstock I after heating it to a temperature of 60 C. at a rate of 0.2 dm.sup.3/h. At the same time, hydrogen gas was continued to be introduced in a continuous manner in Step II. Temperature was then increased successively to 420 C. (step I) and 300 C. (step II) and, as soon as the reaction conditions stabilized (approx. 1 h), the final product was collected. A pressure of 0.1 MPa was applied in the both steps.

(4) At a 100% conversion of the acids, the content of saturated C.sub.6-C.sub.19 n- and iso-paraffins in the product was 88% by weight, of which C.sub.12-C.sub.17 constituted 80% by weight, and unsaturated C.sub.6-C.sub.19 in the amount of 6% by weight, of which C.sub.12-C.sub.17 constituted 2% by weight, and aromatics in the amount of 6% by weight, including 2% of hexamethylbenzene. The product after step I was found to have a content of 10% by weight of the spatial isomers of C.sub.16-C.sub.17.

Example 3

(5) The process was carried out in a flow-type catalytic system. The process was carried out using the following catalysts: in step I15% ZrO.sub.2//Al.sub.2O.sub.3 in the amount of 0.5 kg, in step II10% Pd/(Al.sub.2O.sub.3+SiO2+P.sub.2O.sub.5) in the amount of 0.25 kg, after their activation at high temperatures. Temperature in the reactors in step I and step II was then lowered to 100 C. and the reactor in step I were fed with a mixture of hydrogen and carbon monoxide in a molar ratio of 1:2, respectively, at a rate of 4 dm.sup.3/h and with Feedstock II at a rate of 0.2 dm.sup.3/h. At the same time, the mixture of hydrogen and carbon monoxide was continued to be introduced at the same molar ratio in a continuous manner in Step II. Temperature was then increased successively to 420 C. (step I) and 300 C. (step II) and, as soon as the reaction conditions stabilized (approx. 1 h), the final product was collected. A pressure of 0.1 MPa was applied in the both steps.

(6) At a 100% conversion of the acids, the content of saturated C.sub.6-C.sub.19 n- and iso-paraffins in the product was 87% by weight, of which C.sub.12-C.sub.17 constituted 80% by weight, and unsaturated C.sub.6-C.sub.19 in the amount of 5% by weight, of which C.sub.12-C.sub.17 constituted 2% by weight, and aromatics in the amount of 8% by weight, including 4% of hexamethylbenzene. The product after step I was found to have a content of 25% by weight of the spatial isomers of C.sub.16-C.sub.17.

Example 4

(7) The process was carried out in a flow-type catalytic system. The process was carried out using the following catalysts: in step I15% ZrO.sub.2//Al.sub.2O.sub.3 in the amount of 0.5 kg, in step II10% Pd/(Al.sub.2O.sub.3+P.sub.2O.sub.5) in the amount of 0.25 kg, after their activation at high temperatures. Temperature in the reactors in step I and step II was then lowered to 100 C. and the reactor in step I were fed with a mixture of hydrogen and carbon monoxide in a molar ratio of 1:2, respectively, at a rate of 4 dm.sup.3/h and with Feedstock II at a rate of 0.2 dm.sup.3/h. At the same time, the mixture of hydrogen and carbon monoxide was continued to be introduced at the same molar ratio in a continuous manner in Step II. Temperature was then increased successively to 420 C. (step I) and 300 C. (step II) and, as soon as the reaction conditions stabilized (approx. 1 h), the final product was collected. A pressure of 0.1 MPa was applied in the both steps.

(8) At a 100% conversion of the acids, the content of saturated C.sub.6-C.sub.19 n- and iso-paraffins in the product was 87% by weight, of which C.sub.12-C.sub.17 constituted 82% by weight, and unsaturated C.sub.6-C.sub.19 in the amount of 5% by weight, of which C.sub.12-C.sub.17 constituted 2% by weight, and aromatics in the amount of 8% by weight, including 5% of hexamethylbenzene. The product after step I was found to have a content of 30% by weight of the spatial isomers of C.sub.16-C.sub.17.

Example 5

(9) The process was carried out in a flow-type catalytic system. The process was carried out using the following catalysts: in step I10% ZrO.sub.2//Al.sub.2O.sub.3 in the amount of 0.5 kg g, in step II10% Pd/ZrO.sub.2 in the amount of 0.3 kg, after their activation at high temperatures. Temperature in the reactors in step I and step II was then lowered to 100 C. and the reactor in step I were fed with a mixture of hydrogen and carbon monoxide in a molar ratio of 1 and 2, respectively, at a rate of 4 dm.sup.3/h and with Feedstock II at a rate of 0.2 dm.sup.3/h. At the same time, the mixture of hydrogen and carbon monoxide was continued to be introduced at the same molar ratio in a continuous manner in Step II. Temperature was then increased successively to 420 C. (step I) and 300 C. (step II) and, as soon as the reaction conditions stabilized (approx. 1 h), the final product was collected. A pressure of 0.1 MPa was applied in the both steps.

(10) At a 100% conversion of the acids, the content of saturated C.sub.6-C.sub.19 n- and iso-paraffins in the product was 86% by weight, of which C.sub.12-C.sub.17 constituted 81% by weight, and unsaturated C.sub.6-C.sub.19 in the amount of 8% by weight, of which C.sub.12-C.sub.17 constituted 3% by weight, and aromatics in the amount of 6% by weight, including 3% of hexamethylbenzene. The product after step I was found to have a content of 20% by weight of the spatial isomers of C.sub.16-C.sub.17.

Example 6

(11) The process was carried out in a flow-type catalytic system. The process was carried out using the following catalysts: in step I15% ZrO.sub.2//SiO.sub.2 in the amount of 0.5 kg, in step II5% Pt/(Al.sub.2O.sub.3+SiO.sub.2+P.sub.2O.sub.5) in the amount of 0.25 kg, after their activation at high temperatures. Temperature in the reactors in step I and step II was then lowered to 100 C. and the reactor in step I were fed with a mixture of hydrogen and carbon monoxide in a molar ratio of 1:2, respectively, at a rate of 4 dm.sup.3/h and with Feedstock II at a rate of 0.2 dm.sup.3/h. At the same time, the mixture of hydrogen and carbon monoxide was continued to be introduced at the same molar ratio of 1 and 2 in a continuous manner in Step II. Temperature was then increased successively to 420 C. (step I) and 300 C. (step II) and, as soon as the reaction conditions stabilized (approx. 1 h), the final product was collected. A pressure of 2 MPa was applied in the both steps.

(12) At a 100% conversion of the acids, the content of saturated C.sub.6-C.sub.19 n- and iso-paraffins in the product was 88% by weight, of which C.sub.12-C.sub.17 constituted 83% by weight, and unsaturated C.sub.6-C.sub.19 in the amount of 7% by weight, of which C.sub.12-C.sub.17 constituted 5% by weight, and aromatics in the amount of 5% by weight, including 3% of hexamethylbenzene. The product after step I was found to have a content of 25% by weight of the spatial isomers of C.sub.16-C.sub.17.

Example 7

(13) The process was carried out in a flow-type catalytic system. The process was carried out using the following catalysts: in step I5% MoO/10% CoO/SiO.sub.2 in the amount of 0.5 kg, in step II10% Pd/Al.sub.2O.sub.3 in the amount of 0.25 kg after their activation at high temperatures. Temperature in the reactors in step I and step II was then lowered to 100 C. and the reactor in step I were fed with a mixture of hydrogen and carbon monoxide in a molar ratio of 1:2, respectively, at a rate of 4 dm.sup.3/h and with Feedstock I after heating it to a temperature of 60 C. at a rate of 0.2 dm.sup.3/h. At the same time, hydrogen gas was continued to be introduced in a continuous manner in Step II. Temperature was then increased successively to 420 C. (step I) and 300 C. (step II) and, as soon as the reaction conditions stabilized (approx. 1 h), the final product was collected. A pressure of 0.1 MPa was applied in the both steps.

(14) At a 100% conversion of the acids, the content of saturated C.sub.6-C.sub.19 n- and iso-paraffins in the product was 86% by weight, of which C.sub.12-C.sub.17 constituted 82% by weight, and unsaturated C.sub.6-C.sub.19 in the amount of 9% by weight, of which C.sub.12-C.sub.17 constituted 6% by weight, and aromatics in the amount of 5% by weight, including 2% of hexamethylbenzene. The product after step I was found to have a content of 20% by weight of the spatial isomers of C.sub.16-C.sub.17.

(15) For comparison:

(16) The product obtained according to the method described in the Polish patent application P.401772 (Example XII) has a content of saturated C.sub.6-C.sub.18 hydrocarbons in the amount of 85% by weight, of which C.sub.12-C.sub.17 constitutes 66% by weight, unsaturated [hydrocarbons] C.sub.6-C.sub.18 in the amount of 7.2% by weight, of which C.sub.12-C.sub.17 constitutes 6% by weight, and 7.8% by weight of other products, mainly esters and alcohols. No spatial isomers were found after step I. Moreover, the formation of hexamethylbenzene was not observed.