Storing method of activated catalysts for Fischer-Tropsch synthesis

Abstract

The present invention relates to a method for producing the activated catalyst for Fischer-Tropsch synthesis comprising: a first step of reducing a catalyst for Fischer-Tropsch synthesis; a second step of preparing liquid hydrocarbon in which a part or all of molecular oxygen is eliminated; and a third step of introducing the reduced catalyst prepared in the first step into the liquid hydrocarbon prepared in the second step while blocking its contact with air. Since the reduced catalyst used for Fischer-Tropsch synthesis is introduced into liquid hydrocarbon from which molecular oxygen is removed or coated by liquid hydrocarbon, the catalyst for Fischer-Tropsch synthesis activated based on the present invention maintains a high activity even if exposed to the air for a long time, thereby easily facilitating the long-term storage and long-distance transfer of the reduced catalyst.

Claims

1. A method for producing an activated catalyst for Fischer-Tropsch synthesis comprising: a first step of reducing a catalyst for Fischer-Tropsch synthesis using hydrogen or carbon monoxide-containing reduced gas; a second step of eliminating molecular oxygen by bubbling an inert gas in liquid hydrocarbon for more than 12 hours to prepare liquid hydrocarbon in which a part or all of molecular oxygen is eliminated, wherein the liquid hydrocarbon is a saturated or unsaturated hydrocarbon having 5 or more carbons, and the liquid hydrocarbon is a liquid at room temperature; a third step of introducing the reduced catalyst prepared in the first step into the liquid hydrocarbon prepared in the second step without contacting the catalyst with air to prepare a coated catalyst particle with the liquid hydrocarbon; and a fourth step of isolating the coated catalyst particle prepared in the third step from the liquid hydrocarbon.

2. The method for producing the activated catalyst according to claim 1, wherein the first step is carried out at a temperature ranging from 300 to 500° C.

3. The method for producing the activated catalyst according to claim 1, wherein the inert gas is inert to the reduced catalyst.

4. The method for producing the activated catalyst according to claim 1, wherein the inert gas is selected from the group consisting of nitrogen, neon, helium, argon, krypton, xeon, radon, and a mixture thereof.

5. The method for producing the activated catalyst according to claim 1, wherein the liquid hydrocarbon is squalane.

6. The method for producing the activated catalyst according to claim 1, wherein the inert gas is bubbled for more than 24 hours to eliminate molecular oxygen in the liquid hydrocarbon.

7. The method for producing the activated catalyst according to claim 1, wherein the catalyst comprises cobalt or iron as an active ingredient.

8. The method for producing the activated catalyst according to claim 1, wherein the catalyst is supported by any one support selected from the group consisting of silica, alumina, titania, zeolite, a mesopore carbon structure, a carbon nanotube, mesopore silica, a silica/alumina mixture, a titania/silica mixture and an alumina/titania mixture.

9. The method for producing the activated catalyst according to claim 7, wherein the catalyst containing the metal further comprises one or more co-catalyst metals selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru) and rhenium (Re).

10. A method for preparing liquid or solid hydrocarbon using a Fischer-Tropsch synthesis reaction comprising: step a) activating a catalyst for Fischer-Tropsch synthesis according to claim 1 to generate an activated catalyst; step b) applying the activated catalyst to a Fischer-Tropsch synthesis reactor; and step c) carrying out the Fischer Tropsch synthesis reaction using the activated catalyst.

11. The method of claim 10, wherein the Fischer-Tropsch synthesis reaction is carried out at a temperature ranging from 200 to 300° C.

12. The method of claim 10, wherein the Fischer-Tropsch synthesis reactor is a tube type fixed-bed reactor.

13. The method of claim 10 further comprising a step of collecting and storing the activated catalyst after step a).

14. The method of claim 10, wherein the catalyst is activated by reducing at a temperature ranging from 300 to 500° C.

Description

BEST MODE FOR CARRYING OUT THE INVENTION

(1) Hereinafter, the present invention will be described in details with reference to the following examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

(2) An excellence of the present invention is proven by a comparison and review between the present invention and the preservation method using molecular oxygen in the Examples below.

Example 1: A Preservation Method for the Reduced Catalyst Using Liquid Hydrocarbon

(3) A catalyst having a composition of 0.05Pt-24Co/1.5Si/alumina (numbers in front of the elements represent the mass ratios of the corresponding elements included in the catalyst particles) was prepared by impregnation, and subsequently, the catalyst was dried for 12 hours at 110° C. and calcinated for 5 hours at 400° C. Next, 0.3 g of the calcinated catalyst was filled in the reactor, and reduced under atmospheric pressure for 5 hours at 400° C. using 80 sscm of hydrogen-containing gas (5% H.sub.2/He).

(4) Squalane (C.sub.30H.sub.62), a type of liquid hydrocarbon, was bubbled with Argon for 24 hours while eliminating molecular oxygen in the liquid. When pouring the reduced catalyst particles into a container of squalane, the catalyst should not be in contact with air upon its introduction by pushing air in the upper container after blowing a sufficient amount of the inert gas into the container. Next, the container of squalane remained open in air at room temperature for 1 week for air to move in and out of the container.

Comparative Example 1: A Preservation Method for the Catalyst by the Passivation Method Using Molecular Oxygen

Comparative Example 1-1: Passivation Method Using 1 Volume % Oxygen (The Rest of Nitrogen)

(5) As shown in Example 1, the reduced catalyst was cooled down to room temperature and passivated by flowing 1 volume % oxygen-containing liquid mixture (the rest of nitrogen) for 1 hour. Next, the catalysts was taken out of the reactor and placed in air at room temperature for 1 week.

Comparative Example 1-2: Passivation Method Using 5 Volume % Oxygen (The Rest of Nitrogen)

(6) Except for the fact that the oxygen content is 5 volume %, the process was carried out in the same manner as Comparative Example 1-1.

Comparative Example 1-3: Passivation Process Using 10 Volume % Oxygen (The Rest of Nitrogen)

(7) Except for the fact that the oxygen content is 10 volume %, the process was carried out in the same manner as Comparative Example 1-1.

Experimental Example 1: Fischer-Tropsch Synthesis Reaction

(8) Conversion ratios and selectivity were confirmed by carrying out the Fischer-Tropsch synthesis reaction, wherein the activated catalyst prepared in the Examples and the Comparative Examples were introduced into the Fischer-Tropsch synthesis reactor.

(9) The reactor used in the experiments was a tube type fixed-bed reactor, wherein the pipe has a diameter of 9.525 mm and a catalyst amount of 0.3 g, the ratio of the catalyst and a diluent was 1:5 (weight ratio), the size of the catalyst ranged from 50 to 150 μm, and the diluent (α-alumina) having a similar size to the catalyst was used. A reaction temperature ranged from 220 to 230° C., a reaction pressure was 2.0 MPa, and a space velocity was 4,000 mL syngas/g-cat/h, and a syngas composition of H.sub.2/CO/CO.sub.2/Ar=57.3/28.4/9.3/5 was used.

1) Result of the Fischer-Tropsch Synthesis Reaction of the Activated Catalyst in Example 1

(10) The activated catalyst preserved in squalane for 1 week based on Example 1, was isolated from squalane using the Büchner funnel, filter paper, and aspirators. The Fischer-Tropsche synthesis reaction was carried out by introducing the tube type micro-fixed-bed reactor. The results are shown in Table 1 below.

(11) TABLE-US-00001 TABLE 1 Conversion Total Conv Hydrocarbon selectivity T (° C.) SV (ml/g-cat/h) (CO) C.sub.1 C.sub.2-C.sub.4 C.sub.5+ 220 4000 74.40 4.79 6.23 88.98 230 4000 88.98 5.74 6.66 87.59

2) Result of the Fischer-Tropsch Synthesis Reaction of the Activated Catalyst in Comparative Example 1-1

(12) The Fischer-Tropsch synthesis reaction was carried out using the activated catalyst, which was preserved for 1 week based on Example 1-1. The results are shown in Table 2 below.

(13) TABLE-US-00002 TABLE 2 Conversion Total Conv Hydrocarbon selectivity T (° C.) SV (ml/g-cat/h) (CO) C.sub.1 C.sub.2-C.sub.4 C.sub.5+ 220 4000 61.10 4.95 5.48 89.57 230 4000 77.23 5.20 5.66 89.13

3) Result of the Fischer-Tropsch Synthesis Reaction of the Activated Catalyst in Comparative Example 1-2

(14) The Fischer-Tropsch synthesis reaction was carried out using the activated catalyst, which was preserved for 1 week based on Example 1-2. The results are shown in Table 3 below.

(15) TABLE-US-00003 TABLE 3 Conversion Total Conv Hydrocarbon selectivity T (° C.) SV (ml/g-cat/h) (CO) C.sub.1 C.sub.2-C.sub.4 C.sub.5+ 220 4000 60.92 6.12 6.96 86.92 230 4000 79.14 6.44 7.04 86.52

4) Result of the Fischer-Tropsch Synthesis Reaction of the Activated Catalyst in Comparative Example 1-3

(16) Fischer-Tropsch synthesis reaction was carried out using the activated catalyst, which was preserved for 1 week based on Example 1-3. The results are shown in Table 4 below.

(17) TABLE-US-00004 TABLE 4 Conversion Total Conv Hydrocarbon selectivity T (° C.) SV (ml/g-cat/h) (CO) C.sub.1 C.sub.2-C.sub.4 C.sub.5+ 220 4000 62.85 6.02 6.93 87.05 230 4000 81.03 6.41 7.19 86.40

(18) The activated catalysts based on Example 1, even after being exposed to air for 1 week, the conversion ratio was 11.55 to 13.48% higher at a temperature of 220° C. and the ratio was 7.95 to 11.75% higher at a temperature of 230° C. during the Fischer-Tropsch synthesis reaction. Therefore, it was confirmed that the activity of the reduced metal catalyst preserved based on the present invention was much higher compared to the activity of the catalyst preserved based on the passivation method using molecular oxygen. In both cases, the selectivity on hydrocarbon did not show a significant difference.