A 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, especially waste vegetable oils, animal fats, algal oils and lipid fractions of ligno-cellulose waste, carried out in two steps in a coupled flow system in the presence of heterophase catalysts, wherein in the first step, the oil and/or waste oil is/are heated at temperatures in the range 100-500 C., at pressures in the range 0.1-5 MPa 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 at temperatures in the range 100-500 C., at pressures in the range 0.1-5 MPa, 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, ZiO.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 thereof with a selected metal oxide or oxides.

3. The method as claimed in claim 1, wherein the mixture of hydrogen and carbon monoxide used in both steps of the process is a mixture obtained by the 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 using atmospheric pressure.

Description

EXAMPLE 1

[0022] 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.

[0023] 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

[0024] 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.

[0025] 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

[0026] 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 1) 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.

[0027] 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

[0028] 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.

[0029] 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 C12-C17 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

[0030] 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 11 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 1) 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.

[0031] 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

[0032] 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.

[0033] 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

[0034] 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 dm3/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.

[0035] 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.

[0036] For comparison:

[0037] 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] C6-Cis 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.