Catalyst for synthesis of hydrocarbons from co and h2 (fisher- tropsch process)
FIELD: chemical industry; conversion of synthesis gas into alcohols and hydrocarbons.
SUBSTANCE: proposed catalyst contains the following constituents, mass-%: active component in terms of CO; promoter-fluorine, 0.1-1.0; the remainder being carrier-aluminum oxide.
EFFECT: enhanced conversion of CO.
1 dwg, 2 tbl, 6 ex
The invention relates to the chemical industry, in particular to the composition of the catalysts, and can be used for the conversion of synthesis gas to alcohols and hydrocarbons.
Known catalytic composition consisting of cobalt in the amount of 1-50 wt.% tantalum in an amount of 0.05-5 wt.% and supplements inert carrier up to 100%consisting of silicon dioxide, aluminum oxide, titanium dioxide and related compounds .
Closest to the invention to the technical essence and the achieved effect is the catalyst for the conversion of synthesis gas to hydrocarbons but the Fischer-Tropsch synthesis, representing the cobalt 12-40 wt.%; megall platinum group: platinum, iridium, rhodium or a mixture of 0.1 to 1.9 wt.%; else γ-alumina. When the catalyst contains 0.25-4,75% platinum group metal content of cobalt and 1% promoters of a mixture of oxides of rare earth elements .
The disadvantages are considered catalysts should be attributed to the low degree of conversion of CO to alcohols and hydrocarbons. Using the prototype of platinum-group metals has a number of significant drawbacks. In addition to the high cost of such catalytic systems have serious limitations but the composition of the synthesis gas, but rather on the content of sulfur compounds, which is the catalytic poison for such promoters.
To use the drop-mentioned disadvantages of the proposed catalyst, consisting of the active component, promoter F and carrier of aluminum oxide at the following content, wt.%:
|Active ingredient (in terms of Soo)||10-20|
It was found that the addition of fluorine in a concentration of from 0.1 to 1 wt.% the catalyst leads to a substantial increase in CO conversion. Fluorine may be added at the time of receipt of the original media, and directly in the preparation of the catalytic composition.
The temperature of the reaction may range from 150 to 300°as for conventional catalysts for Fischer-Tropsch synthesis, a pressure of from 1 to 100 ATM and a flow rate and synthesis gas from 100 to 2000 h-1.
The proposed catalytic composition may be prepared as the method of mixing (examples 1-5)and impregnation (example 6).
Testing of the obtained catalysts was carried out in a flow type reactor at P=10 ATM, T-175°V catalyst 25 cm3, the volumetric rate of the synthesis gas was 100 h-1. The composition of the synthesis gas was responsible hydrogen concentration 67% and concentration FROM 33%vol.
Catalytic composition containing 15 wt.% cobalt (in recalculation is on Soo), deposited on alumina without fluorine. The rest is aluminum oxide.
Catalytic composition containing 15 wt.% cobalt (in terms of COO) and 0.27 wt.% fluorine. The rest is aluminum oxide.
Catalytic composition containing 15 wt.% cobalt in terms of COO and 1.0 wt.% fluorine. The rest is aluminum oxide.
Catalytic composition containing 15 wt.% cobalt in terms of COO and 1.8 wt.% fluorine. The rest is aluminum oxide.
Catalytic composition containing 10 wt.% cobalt in terms of COO and 1 wt.% fluorine. The rest is aluminum oxide.
Catalytic composition containing 20 wt.% cobalt in terms of COO and 1 wt.% fluorine. The rest is aluminum oxide.
In table 1 presents the results of the effects of fluoride on the conversion of CO in the synthesis gas obtained under the same conditions (T, °and linear velocities). As can be seen from comparison of example 1 and example 2 (table 1), the fluorine is a promoter for cobalt catalysts for Fischer-Tropsch synthesis, since its introduction has a significant impact on increasing CO conversion.
The influence of fluorine on the conversion of CO in the synthesis gas
|# example||The binder content, wt.%||The content of the fluorine, wt.%||Conversion, %|
Comparative data for the conversion FROM the known and the proposed catalytic composition
|Known catalyst||The proposed catalyst|
|Composition, wt.%||Conversion,%||Composition, wt.%||Conversion, %|
|Co - 20 Pt - 0,17||40||Co - 15F - 0,27||71,6|
|Co - 20 Rh - 0,33||53||Co - 15 F - 1||61,7|
|Co - 20 Ir - 0,33||53||Co - 20 F - 1||65|
Comparative data for the conversion FROM the known and the proposed catalytic compositions are presented in table 2. As can be seen from comparing the data of example 1 and the prototype, the introduction of the kata is eticheskoi composition of fluoride significantly increases the conversion of synthesis gas (table 2) SFT. From the data presented in table 1, it is seen that the increase in the fluoride content of 1 to 1.8 wt.% leads to loss of catalytic activity. As shown by our study, the optimum ratio of 0.1 to 1.0 wt.% fluorine. The influence of fluoride concentration in the catalytic compositions for the conversion of synthesis gas, as clearly illustrated in the drawing.
Sources of information
1. RF application EN 99107576.
2. Patent RU 2027297, IPC601 J 23/89, C 07 C 1/04.
Catalyst for synthesis of hydrocarbons from CO and H2consisting of the active component CO., promoter and media - alumina, characterized in that as a promoter it contains fluorine at the following content, wt.%:
|The active component in terms of COO||10-20|
FIELD: petrochemical processes.
SUBSTANCE: hydrocarbons are produced via contacting synthesis gas with catalytic composition consisting of mixture of iron-containing Fischer-Tropsch synthesis catalyst and acid component at elevated pressures and temperatures and specified iron-containing catalyst reduction conditions. Specifically, said iron component is a mixture of neodymium and cerium silicates at weight ratio between 1:9 and 9:1 and weight ratio of acid component to iron-containing catalyst ranges from 1:1 to 6:1.
EFFECT: increased selectivity and productivity of catalyst and reduced level of aromatic hydrocarbons in product.
3 cl, 1 tbl, 15 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for preparing mainly C5+-hydrocarbons. Method involves contacting carbon monoxide with hydrogen at temperature 180-270°C and under increased pressure in the presence of catalytic composition comprising as measure for the total mass of catalytic composition from 5 to 30 wt.-% of cobalt, from 0.01 to 5 wt.-% of manganese and at least from 0.01 to 0.9 wt.-% of rhenium and/or ruthenium on a carried made of titanium dioxide. Invention provides reducing amount of carbon dioxide evolved in the process of hydrocarbons synthesis by Fisher-Tropsh to the level 2% vol./vol., not above, but preferably to 1% vol./vol., not above, and without reducing C5+-selectivity.
EFFECT: improved preparing method.
7 cl, 2 tbl, 4 ex
FIELD: cobalt-based catalysts used in Fisher-Tropsh reaction in reactors with gas-liquid-solid agent fluidized bed.
SUBSTANCE: diameter of particles of cobalt-based catalyst applied to carrier is measured by means of Coulter LS230 in interval of from 70 to 250 mcm, area of surface exceeds 175 m2/g and volume of pores exceeds 0.35 cm3/g as measured by BET method. Specification contains also description of Fisher-Tropsh method in reactor with gas-liquid-solid agent fluidized bed. This method includes chemical interaction of CO with H2 for obtaining C5+ hydrocarbons in presence of said catalyst.
EFFECT: enhanced activity of catalyst; facilitated procedure.
8 cl, 3 dwg, 10 tbl, 6 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: cobalt-based catalyst precursor is prepared by impregnation of porous catalyst carrier particles with cobalt salt followed by partial drying and subsequent calcination of impregnated carrier, after which calcined product is partially reduced, impregnated with cobalt salt, partially dried and finally calcined. Preparation of Fischer-Tropsch catalyst comprises similar preparation of precursor thereof and reduction of the latter.
EFFECT: increased catalytic activity.
12 cl, 3 dwg, 1 tbl, 2 ex
FIELD: petrochemical processes catalysts.
SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on granulated halumine may further contain promoters selected from oxides ZrO2 and HfO2 and metals Ru, Pd, and Pt.
EFFECT: increased selectivity and productivity.
2 cl, 3 tbl, 2 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on aluminum metal may additionally contain promoters selected from oxides ZrO2, La2O3, K2O and metals Re, Ru, Pd, and Pt.
EFFECT: increased heat conductivity and selectivity.
2 cl, 2 tbl, 2 ex
FIELD: hydrocarbon manufacturing.
SUBSTANCE: natural gas is brought into reaction with vapor and oxygen-containing gas in at least one reforming zone to produce syngas mainly containing hydrogen and carbon monoxide and some amount of carbon dioxide. Said gas is fed in Fisher-Tropsh synthesis reactor to obtain crude synthesis stream containing low hydrocarbons, high hydrocarbons, water, and unconverted syngas. Then said crude synthesis stream is separated in drawing zone onto crude product stream containing as main component high hydrocarbons, water stream, and exhaust gas stream, comprising mainly remained components. Further at least part of exhaust gas stream is vapor reformed in separated vapor reforming apparatus, and reformed exhaust gas is charged into gas stream before its introducing in Fisher-Tropsh synthesis reactor.
EFFECT: increased hydrocarbon yield with slight releasing of carbon dioxide.
7 cl, 3 dwg, 1 tbl, 5 ex