CN105080547A - Catalyst for CO hydrogenation to produce low-carbon olefins and a method for CO hydrogenation to produce low-carbon olefins - Google Patents

Abstract

The invention provides a catalyst for preparing low-carbon olefin by CO hydrogenation, which comprises the following components: 20-80% by weight of zirconium, 5-60% by weight of iron, 5-40% by weight of silicon and 5-30% by weight of aluminum. The invention provides a method for preparing low-carbon olefin by CO hydrogenation, which comprises the following steps: the raw gas containing CO is contacted with hydrogen-containing gas and a catalyst, wherein the catalyst is the catalyst provided by the invention. Compared with the conventional catalyst, the catalyst provided by the invention has the following advantages: (1) the catalyst has good dispersion performance and simple preparation process; (2) the reaction condition is mild, the catalyst activity is high, the selectivity of the low-carbon olefin is high, and the stability is good.

Description

Catalyst for CO hydrogenation to produce low-carbon olefins and a method for CO hydrogenation to produce low-carbon olefins

technical field

The present invention relates to a kind of catalyst that is used for CO hydrogenation to produce low-carbon olefins, in particular to a kind of Zr-Fe-Si-Al multi-metal catalyst that can convert synthesis gas into low-carbon olefins with high activity and high selectivity and A method for preparing light olefins by CO hydrogenation.

Background technique

As basic organic chemical raw materials, light olefins play a pivotal role in modern petroleum and chemical industries. Especially for ethylene and propylene, with the increasing demand and the continuous expansion of application fields, it is increasingly important to conduct extensive research on their synthesis methods.

The methods for preparing low-carbon olefins can be generally divided into two categories: one is the petroleum route, and the other is the non-petroleum route. So far, the world still mainly adopts the traditional light oil cracking method, that is, the petroleum route to produce low-carbon olefins such as ethylene and propylene. In the case of rising oil prices, it is technically and economically attractive to use natural gas as raw material to directly or indirectly produce low-carbon olefins through synthesis gas. For example, natural gas is used as raw material to produce low-carbon olefins through oxidative coupling and other methods; natural gas or coal is used as raw material to produce synthesis gas, and the synthesis gas is synthesized through Fischer-Tropsch synthesis (direct method) or methanol or dimethyl ether (indirect method) ) technology for producing low carbon olefins, etc. The direct production of light olefins from synthesis gas is a one-step reaction to generate the target product, and its technological process is simpler and more economical than the indirect method.

Catalysts for the directional conversion of syngas to light olefins generally use Fe as the active component, and add some additives at the same time; the carrier of the catalyst is usually various types of molecular sieves and activated carbon. Among them, molecular sieve-supported catalysts have attracted attention in improving the selectivity of low-carbon olefins because they can realize the shape selection of products through the regularly adjustable pore structure of molecular sieve supports.

Exxon's Chinese patent application CN1260823A reported a method for converting syngas into light olefins with modified molecular sieves, which uses Fe ₃ (CO) ₁₂ /ZSM-5 modified molecular sieve catalysts, at 260 ° C, H ₂ / Under the reaction conditions of CO volume ratio of 3 and GHSV of 1000h ^-1 , the total selectivity of ethylene and propylene is 65%. Such an excellent effect, in addition to catalyst factors, also depends on reaction engineering factors.

The Chinese invention patent application (application number: 92109866.9) of the Dalian Institute of Chemical Physics reported that the use of high-silicon molecular sieves to support active components such as Fe-Mn achieved better selectivity for the production of low-carbon olefins from syngas. The disclosed catalyst is an iron-manganese metal oxide-molecular sieve (K-Fe-MnO/Silicalite-2) composite catalyst, the CO conversion rate reaches 70-90%, and the C2-C4 olefin selectivity is 72-74%. However, the pore structure of the molecular sieve will change during the process of loading active components on the molecular sieve, and the active metal on the outer surface is not affected by the pore structure of the carrier, which is unfavorable for obtaining high selectivity, and the role of the carrier cannot be fully exerted.

The Chinese invention patent ZL03109585.2 of Beijing University of Chemical Technology discloses a Fe/activated carbon catalyst with activated carbon as a carrier and manganese, copper, zinc, silicon, potassium, etc. When the temperature is 300-400°C, the pressure is 1-2MPa, the space velocity of the synthesis gas is 400-1000h ^-1 and the CO conversion rate can reach 95% under the condition of no feed gas circulation, the content of hydrocarbons in the gas phase products The selectivity of ethylene, propylene, and butene in hydrocarbons can reach more than 68%. However, the catalyst is severely coked during use and cannot be operated for a long time.

Chinese patent application CN10129384A uses a preparation method of vacuum impregnation to highly disperse the main catalyst component Fe and auxiliary agents on the carrier activated carbon, thereby obtaining high catalytic activity and good catalytic effect. Under the process conditions of temperature 300-400°C, pressure 1-2Mpa, and synthesis gas space velocity 400-1000h ^-1 , the conversion rate of CO reaches 95%, and light olefins account for more than 68% of the mass content of hydrocarbons in gas phase products , but it is easy to deactivate by carbon deposition at high temperature.

Chinese patent application CN1065026A discloses a catalyst for producing ethylene from syngas and a preparation method. By adding more than ten chemical elements such as Nb, Ga, Pr, Sc, In, Yh, Ce, La, etc., the selectivity of ethylene can reach more than 90%, but CO The conversion rate is low, and the cycle of syngas will inevitably increase equipment and operating costs.

Chinese patent application CN103157489A adopts the co-current precipitation method to highly disperse Fe and additives on the surface of self-made alkaline carrier. Under the process conditions of 200-500°C, pressure 0-5Mpa, and synthesis gas space velocity 600-2400h ^-1 , CO conversion The rate reaches 75-85%, and the low-carbon olefins account for 50-60% of the mass content of hydrocarbons in the gas phase product. However, the strength of the catalyst is poor, and it cannot be operated in a slurry bed reactor for a long time.

DeJong et al. (Science, 2012, 335, 835) evenly dispersed iron nanoparticles on a weakly interactive α-alumina or carbon nanofiber carrier to convert syngas directly to produce C2-C4 light olefins. At 80%, low-carbon olefins account for 50% of the mass content of hydrocarbon products, and have relatively good anti-coking performance, but the catalyst preparation process is complicated and it is difficult to realize industrial application.

Over the years, some research groups have attempted to develop high-temperature molten iron catalysts for improving the selectivity of Fischer-Tropsch synthesis for direct production of light olefins. Chinese patent application CN101757925A provides a molten iron catalyst composed of iron oxide and cocatalysts such as alumina, calcium oxide, and potassium oxide for the production of low-carbon olefins from synthesis gas. The catalyst has a Fischer-Tropsch synthesis activity and selectivity It is relatively high, with a single-pass conversion rate of over 95%, methane selectivity of less than 10%, and low-carbon olefin content of over 35%. However, the poor mechanical properties of molten iron catalysts at high temperatures may lead to blockage of the catalyst bed in fixed bed operation, or cause fouling of separation equipment in fluidized bed processes, which limits the use of molten iron catalysts in low Fischer-Tropsch synthesis. Application of carbene reaction process.

At present, the catalysts for preparing low-carbon olefins in the prior art encounter different degrees of difficulties in the preparation of repeatable performance and industrial scale-up. Therefore, it is of great significance to design a catalyst with a new structure to obtain high selectivity of light olefins for the industrial application of synthesis gas to light olefins.

Contents of the invention

The purpose of the present invention is mainly to provide an iron-zirconium catalyst with good stability, high activity and good selectivity of low-carbon olefins to directly convert synthesis gas into low-carbon olefins for the above-mentioned shortcomings of the prior art.

To achieve the aforementioned purpose, according to the first aspect of the present invention, the present invention provides a catalyst for CO hydrogenation to produce low-carbon olefins, the catalyst comprising: 20-80% by weight of zirconium, 5-60% by weight of iron , 5-40% by weight of silicon and 5-30% by weight of aluminum.

According to the second aspect of the present invention, the present invention provides a method for preparing light olefins by CO hydrogenation, the method comprising: contacting CO-containing feed gas with hydrogen-containing gas and a catalyst, wherein the catalyst is the catalyst.

Compared with conventional catalysts, the catalyst provided by the invention has the following advantages: (1) the catalyst has good dispersion performance and simple preparation process; (2) the reaction conditions are mild, the catalyst has high activity, high selectivity to low-carbon olefins, and good stability.

Other features and advantages of the present invention will be described in detail in the following detailed description.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

As mentioned above, the present invention provides a catalyst for CO hydrogenation to produce low-carbon olefins, wherein the catalyst includes: 20-80% by weight of zirconium, 5-60% by weight of iron, 5-40% by weight Silicon and 5-30% by weight of aluminum.

In the present invention, low-carbon olefins refer to C2-C4 olefins.

The catalyst of the present invention has higher activity and low-carbon olefin selectivity. For the present invention, it is further preferred that the catalyst includes: 35-38% by weight of zirconium, 24-39% by weight of iron, and 11-24% by weight of silicon and 9-14% by weight aluminum.

According to the catalyst of the present invention, preferably, the catalyst further includes one of Group VIII metals other than iron, Group VIIB metals, Group IVB metals other than zirconium, Group VIB metals, Group IB metals, Group IIB metals and rare earth metals or multiple metals, such as one or more of manganese, cobalt, cerium, titanium, platinum, molybdenum, ruthenium and palladium. A more preferred content is 0.5 to 15% by weight.

According to a preferred embodiment of the present invention, it is preferred that the catalyst further includes one or more metals of Group VIII metals, Group VIIB metals and rare earth metals other than iron, preferably selected from manganese, cobalt, cerium and One or more of ruthenium.

According to a preferred embodiment of the present invention, the catalyst further includes one or more of manganese, cobalt, cerium and ruthenium, and the content is 2-13% by weight.

According to a more preferred embodiment of the present invention, preferably, the catalyst further includes at least two of manganese, cobalt, cerium and ruthenium.

According to the catalyst of the present invention, the catalyst is an alloy catalyst, more preferably the catalyst is an amorphous alloy catalyst.

The present invention has no special requirements on the preparation method of the catalyst, as long as it meets the above composition. For example, when the catalyst described in the present invention is an alloy catalyst, it only needs to be formulated according to the composition of the catalyst of the present invention to prepare an alloy catalyst.

As another example, when the catalyst needs to be prepared as an amorphous alloy catalyst, its preparation method can also be a conventional preparation method in the field, and any existing method for preparing an amorphous alloy catalyst can be used. For the present invention, preferably said amorphous alloy catalyst can be prepared according to the following steps:

Zirconium, iron, silicon, aluminum and or not with one of Group VIII metals other than iron, Group VIIB metals, Group IVB metals other than zirconium, Group VIB metals, Group IB metals, Group IIB metals and rare earth metals Or a variety of metals are heated to melt and then cooled to form an alloy, which is obtained by extracting the solidified alloy with an alkaline solution to extract part of the aluminum. More preferably, it is composed of zirconium, iron, silicon, aluminum and or not with metals of Group VIII other than iron, metals of Group VIIB, metals of Group IVB other than zirconium, metals of Group VIB, metals of Group IB, metals of Group IIB and rare earth metals The melt of an alloy composed of one or more metals solidifies rapidly at a cooling rate greater than 1000°C/S, and the solidified product is added to the lye heated to an extraction temperature of 10-100°C under stirring to make the alloy The aluminum in the mixture fully reacts with the alkali, then the liquid is filtered off, the solid sample is washed with distilled water until the pH is 7 to obtain the catalyst, the concentration of the alkali solution is 2-40% by weight, and the weight ratio of the alloy to the alkali is 1:1-10.

In the preparation method provided by the invention, the molten metal can be cooled by rapidly rotating single roller or double roller, and the metal can also be rapidly cooled by spraying and spraying at a temperature above 1300°C.

In the preparation method provided by the present invention, the alkali extraction process is as follows: the rapidly solidified quenched alloy is added into the alkali solution heated to the extraction temperature under stirring, so that the aluminum in the alloy fully reacts with the alkali solution to obtain black Solid catalyst, the extraction temperature is preferably 40-90°C, the alkali concentration is preferably 10-20% by weight, the extraction time is 5-600min, preferably 30-120min, and the alloy particle size is 8-400 mesh, preferably 80-200 Therefore, the weight ratio of the alloy to the base is preferably 1:1.5-4. After alkali extraction, the catalyst sample is washed with distilled water until neutral, and it is best stored under the protection of inert gas or hydrogen.

In the method provided by the invention, the base is a soluble strong base, such as alkali metal and alkaline earth metal hydroxide, which can be NaOH, KOH and Ba(OH) ₂ , preferably NaOH or KOH.

As mentioned above, the present invention provides a method for preparing light olefins by CO hydrogenation, the method comprising: contacting CO-containing feed gas with hydrogen-containing gas and a catalyst, the catalyst being the catalyst described in the present invention.

In the present invention, the hydrogen-containing gas may be a hydrogen-containing gas or other hydrogen-containing gas. For the present invention, preferably, the hydrogen-containing gas is hydrogen.

According to the method of the present invention, the preferred contacting conditions include: a temperature of 200-500° C., more preferably 280-320° C., and a temperature of 300° C. is used as an illustration in the embodiment of the present invention.

According to the method of the present invention, the raw material gas can be various gases containing carbon monoxide, pure carbon monoxide, or mixed gas, such as synthesis gas.

According to the method of the present invention, the preferred contact conditions include: a pressure of 0.1-15 MPa.

According to the method of the present invention, the preferred contacting conditions further include: the molar ratio of H ₂ to CO is 0.5-10:1.

According to the method of the present invention, the contact can be carried out in various reactors, for example, it can be carried out in a slurry bed reactor and a fixed bed reactor. For the present invention, when the contact is carried out in a fixed bed reactor , the contact conditions include: the space velocity is 500-100000h ^-1 . In the present invention, the space velocity refers to the gas space velocity.

The present invention will be further described below by embodiment, but content of the present invention is not limited thereby.

In the examples, the content of each component in the catalyst is measured by plasma emission spectrometry (ICP).

Example 1

Add 1.5kg of zirconium, 1.0kg of iron, 0.5kg of cobalt, 0.5kg of silicon and 2.5kg of aluminum into a graphite crucible, heat it in a high-frequency furnace until it melts, and then spray the melt from the nozzle of the crucible to a speed of On the 800 rpm copper roller, cooling water is passed through the copper roller, the alloy liquid is rapidly cooled at a cooling rate greater than 1000°C/s, and then thrown out along the tangent of the copper roller to form scale-like strips, which are ground to The particle diameter is below 50 microns, resulting in a master alloy. Slowly add 50 g of the master alloy into a three-necked flask filled with 500 g of 20% by weight potassium hydroxide aqueous solution, control its temperature to 60°C and stir at a constant temperature for 1 hour, stop heating and stirring, and filter off the liquid; use a 100°C Wash with distilled water to pH 7. The prepared catalyst is numbered Catalyst-1, and the composition of Catalyst-1 is shown in Table 1.

Example 2

Add 1.5kg of zirconium, 1.0kg of iron, 1.0kg of silicon and 2.5kg of aluminum into a graphite crucible, heat it in a high-frequency furnace until it melts, and then spray the molten liquid from the nozzle of the crucible to a rotating speed of 800 rpm On the copper roller, cooling water is passed through the copper roller, and the alloy liquid is rapidly cooled at a cooling rate greater than 1000°C/s and then thrown out along the tangent of the copper roller to form scale-like strips, which are ground to a particle diameter of 50 Below microns, a master alloy is obtained. Slowly add 50 g of the master alloy into a three-necked flask containing 500 g of 20% by weight potassium hydroxide aqueous solution, control its temperature to 60°C and stir at a constant temperature for 1 hour, stop heating and stirring, and filter off the liquid; use a 100°C Wash with distilled water to pH 7. The prepared catalyst is numbered Catalyst-2, and the composition of Catalyst-2 is shown in Table 1.

Example 3

Add 1.5kg of zirconium, 1.5kg of iron, 0.2kg of manganese, 0.5kg of silicon and 2.5kg of aluminum into the graphite crucible, heat it in a high-frequency furnace until it melts, and then spray the melt from the nozzle of the crucible to a speed of On the 800 rpm copper roller, cooling water is passed through the copper roller, the alloy liquid is rapidly cooled at a cooling rate greater than 1000°C/s, and then thrown out along the tangent of the copper roller to form scale-like strips, which are ground to The particle diameter is below 50 microns, resulting in a master alloy. Slowly add 50 g of the master alloy into a three-necked flask containing 500 g of 20% by weight potassium hydroxide aqueous solution, control its temperature to 60°C and stir at a constant temperature for 1 hour, stop heating and stirring, and filter off the liquid; use a 100°C Wash with distilled water to pH 7. The prepared catalyst is numbered Catalyst-3, and the composition of Catalyst-3 is shown in Table 1.

Example 4

Add 1.5kg of zirconium, 1.5kg of iron, 0.2kg of cerium, 0.5kg of silicon and 2.5kg of aluminum into the graphite crucible, heat it in a high-frequency furnace until it melts, and then spray the melt from the nozzle of the crucible to a rotating speed of On the 800 rpm copper roller, cooling water is passed through the copper roller, the alloy liquid is rapidly cooled at a cooling rate greater than 1000°C/s, and then thrown out along the tangent of the copper roller to form scale-like strips, which are ground to The particle diameter is below 50 microns, resulting in a master alloy. Slowly add 50 g of the master alloy into a three-necked flask containing 500 g of 20% by weight potassium hydroxide aqueous solution, control its temperature to 60°C and stir at a constant temperature for 1 hour, stop heating and stirring, and filter off the liquid; use a 100°C Wash with distilled water to pH 7. The prepared catalyst is numbered Catalyst-4, and the composition of Catalyst-4 is shown in Table 1.

Example 5

Add 1.5kg of zirconium, 1.5kg of iron, 0.1kg of ruthenium, 0.5kg of silicon and 2.5kg of aluminum into the graphite crucible, heat it in a high-frequency furnace until it melts, and then spray the molten solution from the nozzle of the crucible to a rotating speed of On the 800 rpm copper roller, cooling water is passed through the copper roller, the alloy liquid is rapidly cooled at a cooling rate greater than 1000°C/s, and then thrown out along the tangent of the copper roller to form scale-like strips, which are ground to The particle diameter is below 50 microns, resulting in a master alloy. Slowly add 50 g of the master alloy into a three-necked flask containing 500 g of 20% by weight potassium hydroxide aqueous solution, control its temperature to 60°C and stir at a constant temperature for 1 hour, stop heating and stirring, and filter off the liquid; use a 100°C Wash with distilled water to pH 7. The prepared catalyst is numbered Catalyst-5, and the composition of Catalyst-5 is shown in Table 1.

Example 6

Add 1.5kg of zirconium, 1.6kg of iron, 0.052kg of ruthenium, 0.3kg of silicon and 2.0kg of aluminum into the graphite crucible, heat it in a high-frequency furnace until it melts, and then spray the molten solution from the nozzle of the crucible to a rotating speed of On the 800 rpm copper roller, cooling water is passed through the copper roller, the alloy liquid is rapidly cooled at a cooling rate greater than 1000°C/s, and then thrown out along the tangent of the copper roller to form scale-like strips, which are ground to The particle diameter is below 50 microns, resulting in a master alloy. Slowly add 50 g of the master alloy into a three-necked flask containing 500 g of 20% by weight potassium hydroxide aqueous solution, control its temperature to 90°C and stir at a constant temperature for 1 hour, stop heating and stirring, and filter off the liquid; use a 100°C Wash with distilled water to pH 7. The prepared catalyst is numbered Catalyst-6, and the composition of Catalyst-6 is shown in Table 1.

Example 7

Add 1.5kg of zirconium, 1.5kg of iron, 0.1kg of palladium, 0.5kg of silicon and 2.5kg of aluminum into a graphite crucible, heat it in a high-frequency furnace until it melts, and then spray the melt from the nozzle of the crucible to a rotating speed of On the 800 rpm copper roller, cooling water is passed through the copper roller, the alloy liquid is rapidly cooled at a cooling rate greater than 1000°C/s, and then thrown out along the tangent of the copper roller to form scale-like strips, which are ground to The particle diameter is below 50 microns, resulting in a master alloy. Slowly add 50 g of the master alloy into a three-necked flask filled with 500 g of 20% by weight potassium hydroxide aqueous solution, control its temperature to 60°C and stir at a constant temperature for 1 hour, stop heating and stirring, and filter off the liquid; use a 100°C Wash with distilled water to pH 7. The prepared catalyst is numbered Catalyst-7, and the composition of Catalyst-7 is shown in Table 1.

Example 8

Add 1.5kg of zirconium, 1.5kg of iron, 0.05kg of ruthenium, 0.05kg of manganese, 0.5kg of silicon and 2.5kg of aluminum into the graphite crucible, heat it in a high-frequency furnace until it melts, and then spray the molten liquid from the nozzle of the crucible On a copper roller with a rotating speed of 800 rpm, cooling water is passed through the copper roller, and the alloy liquid is rapidly cooled at a cooling rate greater than 1000°C/s and then thrown out along the tangent of the copper roller to form scale-like strips, scale-like strips The ribbon is ground to a particle diameter of less than 50 microns to obtain a master alloy. Slowly add 50 g of the master alloy into a three-necked flask filled with 500 g of 20% by weight potassium hydroxide aqueous solution, control its temperature to 60°C and stir at a constant temperature for 1 hour, stop heating and stirring, and filter off the liquid; use a 100°C Wash with distilled water to pH 7. The prepared catalyst is numbered Catalyst-8, and the composition of Catalyst-8 is shown in Table 1.

Example 9

Add 1.5kg of zirconium, 1.5kg of iron, 0.013kg of cobalt, 0.09kg of cerium, 0.5kg of silicon and 2.5kg of aluminum into the graphite crucible, heat it in a high-frequency furnace until it melts, and then spray the molten liquid from the nozzle of the crucible On a copper roller with a rotating speed of 800 rpm, cooling water is passed through the copper roller, and the alloy liquid is rapidly cooled at a cooling rate greater than 1000°C/s and then thrown out along the tangent of the copper roller to form scale-like strips, scale-like strips The ribbon is ground to a particle diameter of less than 50 microns to obtain a master alloy. Slowly add 50 g of the master alloy into a three-necked flask filled with 500 g of 20% by weight potassium hydroxide aqueous solution, control its temperature to 60°C and stir at a constant temperature for 1 hour, stop heating and stirring, and filter off the liquid; use a 100°C Wash with distilled water to pH 7. The prepared catalyst is numbered Catalyst-9, and the composition of Catalyst-9 is shown in Table 1.

Example 10

Add 1.5kg of zirconium, 1.5kg of iron, 0.075kg of ruthenium, 0.03kg of cerium, 0.5kg of silicon and 2.5kg of aluminum into the graphite crucible, heat it in a high-frequency furnace until it melts, and then spray the molten liquid from the nozzle of the crucible On a copper roller with a rotating speed of 800 rpm, cooling water is passed through the copper roller, and the alloy liquid is rapidly cooled at a cooling rate greater than 1000°C/s and then thrown out along the tangent of the copper roller to form scale-like strips, scale-like strips The ribbon is ground to a particle diameter of less than 50 microns to obtain a master alloy. Slowly add 50 g of the master alloy into a three-necked flask filled with 500 g of 20% by weight potassium hydroxide aqueous solution, control its temperature to 60°C and stir at a constant temperature for 1 hour, stop heating and stirring, and filter off the liquid; use a 100°C Wash with distilled water to pH 7. The prepared catalyst is numbered Catalyst-10, and the composition of Catalyst-10 is shown in Table 1.

Comparative example 1-4

The catalyst was prepared according to the method of Example 5, except that the composition of the prepared catalyst was shown in Table 1.

Table 1

Example Catalyst number Catalyst composition 1 Catalyst-1 Zr _36.6 Fe _24.4 Co _12.1 Si _12.2 Al _14.7 2 Catalyst-2 Zr _37.5 Fe _25.0 Si _23.7 Al _13.8 3 Catalyst-3 Zr _35.7 Fe _38.1 Mn _4.8 Si _11.9 Al _9.5 4 Catalyst-4 Zr _36.1 Fe _35.9 Ce _4.3 Si _12.5 Al _11.2 5 Catalyst-5 Zr _35.8 Fe _36.4 Ru _2.4 Si _11.7 Al _13.7 6 Catalyst-6 Zr _40.0 Fe _42.2 Ru _1.4 Si _7.7 Al _8.7 7 Catalyst-7 Zr _35.8 Fe _36.4 Pd _2.4 Si _11.7 Al _13.7 8 Catalyst-8 Zr _35.8 Fe _36.4 Mn _1.2 Ru _1.2 Si _11.7 Al _13.7 9 Catalyst-9 Zr _35.8 Fe _36.4 Co _0.3 Ce _2.1 Si _11.7 Al _13.7 10 Catalyst-10 Zr _35.8 Fe _36.4 Ru _1.8 Ce _0.6 Si _11.7 Al _13.7 Comparative example 1 D1 Zr _45.8 Fe _40.4 Al _13.8 Comparative example 2 D2 Zr _43.2 Fe _44.0 Si _12.8 Comparative example 3 D3 Zr _49.5 Fe _50.5 Comparative example 4 D4 Zr _55.0 Fe _45.0

*The subscript indicates the weight percentage of the metal.

Test case 1-10

This test example illustrates the use of the catalyst provided by the invention to carry out CO hydrogenation reaction in a fixed-bed reactor.

The catalyst was loaded with 0.5g, the reaction temperature was 300°C, the reaction pressure was 0.5MPa, the reaction time was 100h, _H2 /CO=2, and the space velocity was 6000h ^-1 . The reaction results are shown in Table 2 or Table 3.

Test case 11

This test example illustrates the use of the catalyst provided by the invention to carry out CO hydrogenation reaction in a fixed-bed reactor.

According to the method of Test Example 1-10, the difference is that the temperature is 330° C., and the reaction results are shown in Table 3.

Table 2

table 3

It can be seen from the results in Table 2 and Table 3 that the catalyst of the present invention is used for the hydrogenation of carbon monoxide to prepare light olefins, and has high activity and good selectivity.

Test case 12-13

This test example illustrates the use of the catalyst provided by the invention to carry out CO hydrogenation reaction in a fixed-bed reactor.

The catalyst was loaded with 0.5g, the reaction temperature was 300°C, the reaction pressure was 0.5MPa, H ₂ /CO=2, and the space velocity was 6000h ^-1 . The reaction results are shown in Table 4.

As can be seen from the data in Table 4, the catalyst of the present invention has higher activity when used in the CO hydrogenation reaction, and after a long time of reaction, the activity does not decline, so it can be seen that the stability of the catalyst of the present invention is also better.

Table 4

Test comparative examples 1-4

The CO hydrogenation reaction was carried out in a fixed-bed reactor according to the method of Test Example 1-10, except that the catalysts used were D1-D4, and the reaction results are shown in Table 5.

table 5

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific implementation manners may be combined in any suitable manner if there is no contradiction.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (11)

1. for a catalyst for CO Hydrogenation low-carbon alkene, it is characterized in that, this catalyst comprises: the zirconium of 20-80 % by weight, the iron of 5-60 % by weight, the silicon of 5-40 % by weight and the aluminium of 5-30 % by weight.

2. catalyst according to claim 1, wherein, described catalyst comprises: the zirconium of 35-38 % by weight, the iron of 24-39 % by weight, the silicon of 11-24 % by weight and the aluminium of 9-14 % by weight.

3. catalyst according to claim 2, wherein, described catalyst also comprises one or more metals in VIII race's metal beyond deironing, VII B race metal, IV B race metal, VI B race metal, I B race metal, II B race metal and rare earth metal except zirconium, and content is 0.5-15 % by weight.

4. catalyst according to claim 3, wherein, described catalyst also comprises one or more metals in manganese, cobalt, cerium and ruthenium, and content is 2-13 % by weight.

5. catalyst according to claim 3, wherein, described catalyst also comprises at least two kinds of metals in manganese, cobalt, cerium and ruthenium.

6. according to the catalyst in claim 1-5 described in any one, wherein, described catalyst is alloy catalyst.

7. catalyst according to claim 6, wherein, described catalyst is amorphous alloy catalyst.

8. CO Hydrogenation is for a method for low-carbon alkene, and the method comprises: by containing the unstripped gas of CO and hydrogen-containing gas and catalyst exposure, and it is characterized in that, described catalyst is the catalyst in claim 1-7 described in any one.

9. method according to claim 8, wherein, the condition of contact comprises: temperature is 200-500 DEG C.

10. method according to claim 9, wherein, described unstripped gas is synthesis gas, and the condition of contact comprises: temperature is 280-320 DEG C, and pressure is 0.1-15MPa, H ₂be 0.5-10:1 with the mol ratio of CO.

11. methods according to Claim 8 in-10 described in any one, wherein, described contact is carried out in fixed bed reactors, and the condition of contact comprises: air speed is 500-100000h ^-1.