CN111068690A

CN111068690A - Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof

Info

Publication number: CN111068690A
Application number: CN201811214350.2A
Authority: CN
Inventors: 陶跃武; 庞颖聪; 李剑锋; 宋卫林; 戴毅敏; 姚全明
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2018-10-18
Filing date: 2018-10-18
Publication date: 2020-04-28

Abstract

The invention relates to a catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof, which mainly solves the problem of low selectivity of the low-carbon olefin in the prior art, the catalyst for directly preparing the low-carbon olefin from the synthesis gas comprises a carrier and an active component, wherein the active component contains a composition with the following chemical formula in atomic ratio: fe₁₀₀Cu_aCo_bD_jO_x(ii) a D comprises at least one selected from alkali metals and alkaline earth metals; the value range of a is 5.0-60.0; the value range of b is 1.0-20.0; the value range of j is 0.01-45.0; x is enough to satisfy catalysisThe total number of oxygen atoms required by the valence of each element in the agent. The technical scheme better solves the problem and can be used for the industrial production of directly preparing the low-carbon olefin from the fluidized bed synthesis gas.

Description

Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof

Technical Field

The invention relates to a catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof.

Background

The method for converting synthesis gas into hydrocarbons by the action of catalyst is invented by FransFischer and Hans Tropsch, German scientists, and is called F-T synthesis for short in 1923, namely the process that CO is subjected to heterogeneous catalytic hydrogenation reaction on a metal catalyst to generate a mixture mainly comprising straight-chain alkane and olefin. Research and development in germany were carried out in the last 20 th century and industrialization was achieved in 1936, after which it was closed because of the inability to compete economically with the petroleum industry; south Africa has abundant coal resources but scarce petroleum resources, so that the development of coal-to-oil industrial technology is continuously dedicated, and 1955, a first coal-based F-T synthetic oil plant (Sasol-1) with the production capacity of 25-40 ten thousand tons of products per year is built.

The two global oil crises in 1973 and 1979 caused the price of crude oil in the world to fall and rise greatly, and the F-T synthesis technology re-aroused interest in industrialized countries based on the consideration of strategic technical reserves. In 1980 and 1982, Sasol company in south Africa built and produced two coal-based synthetic oil plants in succession. However, the great reduction of the oil price in the world in 1986 postpones the large-scale industrialization process of the F-T synthesis technology in other countries.

Since the 90 s of the twentieth century, petroleum resources have been in shortage and deterioration, and the exploratory reserves of coal and natural gas have been increasing, so that F-T synthesis technology has attracted much attention again. At present, the main raw materials of the low-carbon olefins in the world are petroleum hydrocarbons, wherein naphtha accounts for most of the raw materials, and alkane, hydrogenated diesel oil, part of heavy oil and the like are also used. Natural gas or light petroleum fractions are mostly used as raw materials at home and abroad, low-carbon olefin is produced by adopting a steam cracking process in an ethylene combination device, the steam cracking is a high-energy consumption device in petrochemical industry, and the steam cracking completely depends on non-renewable petroleum resources, so that alternative resources are urgently needed to be searched along with the gradual shortage of the petroleum resources. Therefore, the research work of preparing olefin by replacing petroleum with other resources is gradually emphasized, and some famous petroleum companies and scientific research institutes in the world perform the research and obtain good results.

Over the course of decades, fischer-tropsch catalysts have also developed in a great deal, and typically comprise the following components: active metals (transition metals of group VIII), oxide supports or structural assistants (SiO)₂,Al₂O₃Etc.), chemical assistants (alkali metal oxides, transition metals) and noble metal assistants (Ru, Re, etc.). Fe produces a large amount of olefins and oxygen-containing compounds, Ru and Co produce mainly long-chain saturated hydrocarbons, and Ni produces mainly methane. Because of the loss of carbonyl compounds easily formed during Ni pressurization reaction and serious methanation, and the expensive Ru and Rh equivalents, the currently commonly used catalysts are divided into two categories from the aspect of active components: iron-based catalysts and cobalt-based catalysts. The selectivity of the cocatalyst has great influence on the selectivity of the low-carbon olefin, the improvement of the selectivity of the low-carbon olefin is mainly realized by the cocatalyst, and the selection and addition technology of the cocatalyst is one of key technologies for developing excellent catalysts.

The F-T synthesis reactors are further classified into fixed bed reactors, fluidized bed reactors and slurry bed reactors according to the difference in the catalysts used and the difference in the target products. The fixed bed reactor has complex structure, high price, difficult heat removal and lower productivity of the whole device. The slurry bed is characterized by low reaction temperature, easy control, low conversion rate, most of products of high carbon hydrocarbon and difficult liquid-solid separation of slurry in the reactor. The fluidized bed reactor has the characteristics of higher temperature, higher conversion rate, no difficulty of liquid-solid separation and mostly low-carbon hydrocarbon as a product; the lower construction and operating costs, while the lower pressure differential saves a lot of compression costs and facilitates the removal of the heat evolved during the reaction, while the longer run is possible due to the lower gas line speed and less wear problems.

The iron catalyst has many advantages, such as obtaining low-carbon olefin with high selectivity and preparing gasoline with high octane value, and the iron catalyst also has the characteristics of wide operating condition and large product adjustability. The preparation method of the iron catalyst mainly comprisesThere are three types: the precipitation method (precipitation catalyst) comprises the steps of preparing a mixed solution according to a certain proportion by using Fe and auxiliary agents such as Mn, Cu, K and the like, heating to boil, adding a precipitator, stirring, filtering and washing. Adding water into the obtained filter cake for repulping, adding a certain amount of potassium silicate, drying, carrying out extrusion forming, then, grinding and screening; sintering process (sintering catalyst); oxide mixing method (molten iron catalyst) using mill scale or magnetite powder as raw material and adding Al as auxiliary agent₂O₃MgO, MnO, CuO and the like are fed into an electric arc furnace at 1500 ℃ for melting, and the outflow melt is subjected to casting, cooling and multistage crushing.

At present, the iron-based catalyst is used for directly synthesizing low-carbon olefin by F-T in a fixed bed, for example, the patent CN1040397C mentions an iron-based catalyst for Fischer-Tropsch synthesis of low-carbon olefin, and the selectivity of the low-carbon olefin can be as high as 69%. However, the fixed bed reactor has a complex structure, high price, difficult heat removal and low productivity of the whole device. The fluidized bed reactor has the characteristics of higher temperature, higher conversion rate, no difficulty of liquid-solid separation and mostly low-carbon hydrocarbon as a product; the lower construction and operating costs, while the lower pressure differential saves a lot of compression costs and facilitates the removal of the heat evolved during the reaction, while the longer run is possible due to the lower gas line speed and less wear problems. Most of the prior reports on the application of the catalyst to the fluidized bed F-T synthesis are molten iron type catalysts, for example, a molten iron type catalyst for the F-T synthesis is mentioned in patent CN 1704161A; however, the existing fluidized bed F-T synthesis has the problems of insufficiently concentrated products and insufficiently high selectivity of low-carbon olefins.

Disclosure of Invention

One of the technical problems to be solved by the invention is the problem of low selectivity of low-carbon olefin in the prior art, and the invention provides a catalyst for directly preparing low-carbon olefin from synthesis gas, wherein the catalyst has the characteristic of high selectivity of low-carbon olefin.

The second technical problem to be solved by the present invention is the application of the above catalyst.

The third technical problem to be solved by the invention is a preparation method of the catalyst.

In order to solve one of the above technical problems, the technical solution of the present invention is as follows:

the catalyst for directly preparing the low-carbon olefin by the synthesis gas comprises a carrier and an active component, wherein the active component contains a composition with the following chemical formula in atomic ratio:

Fe₁₀₀Cu_aCo_bD_jO_x

d comprises at least one selected from alkali metals and alkaline earth metals;

the value range of a is 5.0-60.0;

the value range of b is 1.0-20.0;

the value range of j is 0.01-45.0;

x is the total number of oxygen atoms required to satisfy the valences of the elements in the catalyst.

In the above technical solution, the support is not particularly limited, and those commonly used in the art may be used, for example, but not limited to, including at least one of alumina, silica and titania.

In the above technical solution, the alkali metal is preferably at least one selected from the group consisting of Li, Na, K, Rb and Cs.

In the above aspect, the alkaline earth metal is preferably at least one selected from the group consisting of Be, Mg, Ca, Sr, and Ba.

In the above technical solution, D further preferably includes alkali metal, alkaline earth metal, noble metal and rare earth metal at the same time, in this case, the active component preferably contains a composition having the following chemical formula in terms of atomic ratio:

Fe₁₀₀Cu_aCo_bMg_cK_dA_fL_eO_x

a is selected from at least one of noble metals;

l is selected from at least one of lanthanide metals;

the value range of a is 5.0-60.0;

the value range of b is 1.0-20.0;

the value range of c is 1.0-20.0;

the value range of d is 0.1-10.0;

the value range of f is 0.01-0.5;

the value range of e is 0.01-10;

In the above technical solution, the noble metal is preferably at least one of the group consisting of Pd, Pt, Ru, and Rh; more preferably, the noble metal comprises at least two of Pd, Pt and Ru simultaneously, and the two elements, such as Pd and Pt, Pd and Ru and Pt and Ru, have synergistic effect on improving the selectivity of the low-carbon olefin. In this case, the atomic ratio between the two elements is not particularly limited, but is not limited to 0.1 to 10, and more specific atomic ratios may be 0.2, 0.4, 0.6, 0.8, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 9.0, and the like.

In the technical scheme, the preferable range of the value of a is 10.0-50.0. Such as, but not limited to, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, and the like.

In the above technical solution, the preferable range of the value of b is 5.0-45.0, such as but not limited to 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, and the like.

In the above technical solution, the preferable range of the value of c is 5.0 to 15.0, such as but not limited to 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, and the like.

In the above technical solution, the preferable range of d is 1.0-8.0, such as but not limited to 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, and the like.

In the above technical solution, the preferable range of the value of e is 1.0-8.0, such as but not limited to 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, and the like.

In the above technical solution, the preferable range of f is 0.01 to 0.4, for example, but not limited to, 0.05, 0.1, 0.15, 0.2, 0.25, 0.30, 0.35, and the like.

In the above technical solution, the lanthanide includes Ce.

In the above technical scheme, the amount of the carrier is not particularly limited, and can be reasonably selected by a person skilled in the art without creative efforts. For example, but not limited to, the amount of the carrier is 20 to 80% by weight of the catalyst, and within this range, for example, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, etc., and more preferably 30 to 70%, as non-limiting examples of the amount of the catalyst.

The catalyst of the invention can be reduced or not reduced before being used for the reaction of producing the low-carbon olefin by the synthesis gas one-step method, but is preferably reduced. When reducing, the reducing conditions are not particularly limited and can be reasonably selected by the person skilled in the art, for example but not limited to the reducing conditions of the catalyst prepared according to the invention: the pressure is 0.05 to 5MPa, preferably

0.1-4 MPa; the reducing gas can be hydrogen, carbon monoxide or synthesis gas, and when the reducing gas is synthesis gas, H thereof₂The mol ratio of/CO is 0.1-6.0, preferably 0.2-6.0; the load of reducing gas is 100-8000 mL/h^-1·g^-1Preferably 500 to 6000mL · h^-1·g^-1(ii) a The reduction temperature is 200-600 ℃, preferably 220-500 ℃; the reduction time is 1 to 100 hours, preferably 6 to 72 hours.

For comparison, the reduction conditions used for the catalyst prepared in the embodiment of the present invention are:

the temperature is 400 DEG C

Pressure 3.0MPa

Catalyst loading 100g

Catalyst load 4000mL h^-1·g^-1

Reducing gas (molar ratio) H₂/CO＝2/1

The reduction time was 24 hours.

To solve the second technical problem, the technical solution of the present invention is as follows:

the application of the catalyst in the technical scheme of one of the technical problems in the reaction for directly preparing the low-carbon olefin from the synthesis gas.

The technical key of the present invention is the choice of catalyst, which can be reasonably selected by those skilled in the art for the process conditions of a specific application without inventive effort, such as but not limited to:

in the presence of the catalyst in any of the technical schemes of the technical problems, the synthesis gas reacts to generate the low-carbon olefin.

As known to those skilled in the art, lower olefins are C2-C4 olefins, more specifically ethylene, propylene and butylene or mixtures thereof. The butene includes butene-1, butene-2, isobutene and butadiene.

The reaction temperature can be 200-600 ℃, preferably 220-500 ℃;

the pressure of the reaction can be 0.5-10 MPa, preferably 1-8 MPa; (ii) a

H in synthesis gas₂The mol ratio of/CO can be 0.1-5.0, preferably 0.5-3.0;

the volume space velocity of the synthetic gas can be 100-8000 mL/h based on the amount of the catalyst before reduction^-1·g^-1Preferably 500 to 6000mL · h^-1·g^-1More preferably 2000 to 6000mL · h^-1·g^-1。

For the sake of comparability, the evaluation conditions of the catalyst used in the embodiment of the present invention were as follows:

phi 38 mm fluidized bed reactor

The reaction temperature is 330 DEG C

The reaction pressure is 2.0MPa

The catalyst loading corresponded to 100g of catalyst before reduction

Catalyst loading 3000 mL. h based on the amount of catalyst before reduction^-1·g^-1

Raw material ratio (mol) H₂/CO＝2/1。

In order to solve the third technical problem of the invention, the technical scheme of the invention is as follows:

the preparation method of the catalyst in any one of the technical schemes of the technical problems comprises the following process steps:

obtaining slurry comprising a catalyst carrier and active component elements, wherein the pH value of the slurry is 1-6;

feeding the slurry into a spray dryer for spray forming;

and (4) roasting.

When the active component contains both lanthanide and alkali metal elements, the preparation method of the catalyst preferably comprises the following process steps:

obtaining an aqueous solution comprising metallic elements other than alkali metals in the composition;

adding sol of a carrier with required amount into the aqueous solution, adding an alkali metal hydroxide solution, and adjusting the pH value to 1-6 by using an acid-base regulator to obtain slurry;

feeding the slurry into a spray dryer for spray forming;

and (4) roasting.

In the technical scheme, the roasting temperature is preferably 400-1000 ℃, and more preferably 450-800 ℃.

In the above technical scheme, the roasting time is preferably 0.15 to 10 hours, and more preferably 0.5 to 8 hours.

The process conditions for spray drying and shaping are not particularly limited and can be appropriately selected by those skilled in the art and can achieve comparable technical effects. For example, but not limited to, the inlet temperature of the spray can be 200-380 ℃, the outlet temperature can be 100-230 ℃, the spray drying is carried out to form microspheres, and finally the microspheres are roasted to prepare the catalyst.

In order to facilitate comparison, the spray drying conditions adopted by the specific embodiment of the invention are as follows:

the inlet temperature is 300 ℃,

the exit temperature was 200 ℃.

In the above technical scheme, the soluble ferric salt can be ferric nitrate or ferric sulfate.

In the above technical scheme, the soluble compounds of Cu, Co, Mg and lanthanoid can be nitrates and salts decomposable into oxides.

In the above technical solution, the soluble compound of K may be a nitrate, a chloride or a hydroxide.

In the above technical scheme, the soluble compound of the noble metal can be nitrate, chloride and noble metal complex acid.

In the above-mentioned embodiment, although the atmosphere for firing is not particularly limited, an oxidizing atmosphere or an inert atmosphere is preferable, and an air atmosphere is more preferable from the economical viewpoint.

In the present invention, unless otherwise specified, the pressure including the reaction pressure means a gauge pressure.

The catalyst is used, and the reaction temperature is 200-600 ℃, the reaction pressure is 0.5-10 MPa, and the catalyst load is 100-8000 mL/h^-1·g^-1Raw material ratio (mol) H₂The F-T synthesis reaction is carried out under the condition that the ratio of/CO (0.1-5.0): 1, the CO conversion rate can reach 91.6%, the selectivity of low-carbon olefin in a reaction product can reach 71.4%, and a better technical effect is achieved.

The invention is further illustrated by the following examples.

Detailed Description

[ example 1 ]

1. Catalyst preparation

445.2 g of ferric nitrate (Fe (NO)₃)₃·9H₂O), dissolving in 800g of water to obtain a material I, and taking 14.20 g of cerium nitrate (Ce (NO)₃)₃·6H₂O) is dissolved in 50g of water under heating to obtain a material II, and 65.88 g of copper nitrate (Cu (NO) is taken₃)₂·3H₂O), 22.40 g magnesium nitrate (Mg (NO)₃)₂·6H₂O) and 25.40 g of cobalt nitrate (Co (NO)₃)₂·6H₂O) in the same container, adding 500g of water, stirring and dissolving to obtain a material III.

Mixing the materials I, II and III, adding 312.5 g of 40 wt% of alumina sol material under stirring, then adding 50g of solution containing 2.95 g of KOH, adjusting the pH value of the slurry to 6.0 by using ammonia water, fully stirring, carrying out microspherical molding on the prepared slurry in a spray dryer according to a conventional method, and finally roasting at 500 ℃ for 2.0 hours in a rotary roasting furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 x 1700 mm), wherein the prepared catalyst comprises the following components:

50% by weight Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0O_x+ 50% by weight of Al₂O₃

2. Reduction and evaluation of the catalyst

The prepared catalyst is carried out under the reduction conditions:

the temperature is 400 DEG C

Pressure 3.0MPa

Catalyst loading 100g

Catalyst load 4000mL h^-1·g^-1

Reducing gas H₂/CO＝2/1

Reduction time 24 hours

Reduction was carried out and then the Fischer-Tropsch synthesis reaction was carried out under the following conditions:

phi 38 mm fluidized bed reactor

The reaction temperature is 330 DEG C

The reaction pressure is 2.0MPa

The catalyst loading corresponded to 100g of catalyst before reduction

Raw material ratio (mol) H₂/CO＝2/1。

The experimental results of the synthesis reaction are shown in table 1.

[ example 2 ]

1. Catalyst preparation

444.2 g of ferric nitrate (Fe (NO)₃)₃·9H₂O), dissolving in 800g of water to obtain a material I, and taking 14.20 g of cerium nitrate (Ce (NO)₃)₃·6H₂O) is dissolved in 50g of water under heating to obtain a material II, and 65.74 g of copper nitrate (Cu (NO) is taken₃)₂·3H₂O), 22.30 g magnesium nitrate (Mg (NO)₃)₂·6H₂O) and 25.30 g of cobalt nitrate (Co (NO)₃)₂·6H₂O) in the same container, adding 500g of water, stirring and dissolving to obtain a material III.

Mixing the materials I, II and III,312.5 g of a 40% by weight aluminum sol mass were added with stirring, followed by 2.95 g of KOH and 0.64 g of PdCl₂50g of the solution (b) was adjusted to a pH of 6.0 with aqueous ammonia, and after sufficiently stirring, the resulting slurry was formed into microspheres in a spray dryer according to a conventional method, and finally calcined at 500 ℃ for 2.0 hours in a rotary calciner having an inner diameter of 89 mm and a length of 1700 mm (phi 89 x 1700 mm), to obtain a catalyst having a composition:

50% by weight Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Pd_0.2O_x+ 50% by weight of Al₂O₃

2. Reduction and evaluation of the catalyst

The prepared catalyst is carried out under the reduction conditions:

the temperature is 400 DEG C

Pressure 3.0MPa

Catalyst loading 100g

Catalyst load 4000mL h^-1·g^-1

Reducing gas H₂/CO＝2/1

Reduction time 24 hours

phi 38 mm fluidized bed reactor

The reaction temperature is 330 DEG C

The reaction pressure is 2.0MPa

The catalyst loading corresponded to 100g of catalyst before reduction

Raw material ratio (mol) H₂/CO＝2/1。

The experimental results of the synthesis reaction are shown in table 1.

[ example 3 ]

1. Catalyst preparation

443.4 g of ferric nitrate (Fe (NO)₃)₃·9H₂O), dissolving in 800g of water to obtain a material I, and taking 14.20 g of cerium nitrate (Ce (NO)₃)₃·6H₂O) is dissolved in 50g of water under heating to obtain a material II, 65.62 g of copper nitrate (Cu (NO) is taken₃)₂·3H₂O), 22.30 g magnesium nitrate (Mg (NO)₃)₂·6H₂O) and 25.30 g of cobalt nitrate (Co (NO)₃)₂·6H₂O) in the same container, adding 500g of water, stirring and dissolving to obtain a material III.

The materials I, II and III were mixed, 312.5 g of a 40% by weight aluminum sol material were added with stirring, and 2.94 g of KOH and 2.97 g of H were added₂PtCl₆·6H₂50g of O solution, adjusting the pH value of the slurry to 6.0 by ammonia water, fully stirring, carrying out microspherical molding on the prepared slurry in a spray dryer according to a conventional method, and finally roasting at 500 ℃ for 2.0 hours in a rotary roasting furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 x 1700 mm), wherein the prepared catalyst comprises the following components:

50% by weight Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Pt_0.2O_x+ 50% by weight of Al₂O₃

2. Reduction and evaluation of the catalyst

The prepared catalyst is carried out under the reduction conditions:

the temperature is 400 DEG C

Pressure 3.0MPa

Catalyst loading 100g

Catalyst load 4000mL h^-1·g^-1

Reducing gas H₂/CO＝2/1

Reduction time 24 hours

phi 38 mm fluidized bed reactor

The reaction temperature is 330 DEG C

The reaction pressure is 2.0MPa

The catalyst loading corresponded to 100g of catalyst before reduction

Raw material ratio (mol) H₂/CO＝2/1。

The experimental results of the synthesis reaction are shown in table 1.

[ example 4 ]

1. Catalyst preparation

444.1 g of ferric nitrate (Fe (NO)₃)₃·9H₂O), dissolving in 800g of water to obtain a material I, and taking 14.20 g of cerium nitrate (Ce (NO)₃)₃·6H₂O) is dissolved in 50g of water under heating to obtain a material II, and 65.73 g of copper nitrate (Cu (NO) is taken₃)₂·3H₂O), 22.30 g magnesium nitrate (Mg (NO)₃)₂·6H₂O) and 25.30 g of cobalt nitrate (Co (NO)₃)₂·6H₂O) in the same container, adding 500g of water, stirring and dissolving to obtain a material III.

The materials I, II and III were mixed, 312.5 g of a 40% by weight alumina sol material were added with stirring, followed by 2.95 g of KOH containing 0.91 g of RuCl₃Adjusting the acidity of the slurry with ammonia water to make the pH value of the mixed slurry equal to 6.0, fully stirring to obtain slurry, carrying out microspherical molding on the prepared slurry in a spray dryer, and finally roasting to prepare the catalyst, wherein the catalyst comprises the following components:

50% by weight Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Ru_0.2O_x+ 50% by weight of Al₂O₃

2. Reduction and evaluation of the catalyst

The prepared catalyst is carried out under the reduction conditions:

the temperature is 400 DEG C

Pressure 3.0MPa

Catalyst loading 100g

Catalyst load 4000mL h^-1·g^-1

Reducing gas H₂/CO＝2/1

Reduction time 24 hours

phi 38 mm fluidized bed reactor

The reaction temperature is 330 DEG C

The reaction pressure is 2.0MPa

The catalyst loading corresponded to 100g of catalyst before reduction

Raw material ratio (mol) H₂/CO＝2/1。

The experimental results of the synthesis reaction are shown in table 1.

[ example 5 ]

1. Catalyst preparation

443.8 g of ferric nitrate (Fe (NO)₃)₃·9H₂O), dissolving in 800g of water to obtain a material I, and taking 14.20 g of cerium nitrate (Ce (NO)₃)₃·6H₂O) is dissolved in 50g of water under heating to obtain a material II, 65.68 g of copper nitrate (Cu (NO) is taken₃)₂·3H₂O), 22.30 g magnesium nitrate (Mg (NO)₃)₂·6H₂O) and 25.30 g of cobalt nitrate (Co (NO)₃)₂·6H₂O) in the same container, adding 500g of water, stirring and dissolving to obtain a material III.

The materials I, II and III were mixed, 312.5 g of a 40% by weight aluminum sol material were added with stirring, 2.95 g of KOH, 0.32 g of PdCl₂1.49 g of H₂PtCl₆·6H₂50g of O solution, adjusting the acidity of the slurry by ammonia water to ensure that the pH value of the mixed slurry is 6.0, fully stirring to obtain slurry, carrying out microspherical molding on the prepared slurry in a spray dryer, and finally roasting to prepare the catalyst, wherein the catalyst comprises the following components:

50% by weight Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Pd_0.1Pt_0.1O_x+ 50% by weight of Al₂O₃

2. Reduction and evaluation of the catalyst

The prepared catalyst is carried out under the reduction conditions:

the temperature is 400 DEG C

Pressure 3.0MPa

Catalyst loading 100g

Catalyst load 4000mL h^-1·g^-1

Reducing gas H₂/CO＝2/1

Reduction time 24 hours

phi 38 mm fluidized bed reactor

The reaction temperature is 330 DEG C

The reaction pressure is 2.0MPa

The catalyst loading corresponded to 100g of catalyst before reduction

Raw material ratio (mol) H₂/CO＝2/1。

The experimental results of the synthesis reaction are shown in table 1.

[ example 6 ]

1. Catalyst preparation

444.2 g of ferric nitrate (Fe (NO)₃)₃·9H₂O), dissolving in 800g of water to obtain a material I, and taking 14.20 g of cerium nitrate (Ce (NO)₃)₃·6H₂O) is dissolved in 50g of water under heating to obtain a material II, and 65.73 g of copper nitrate (Cu (NO) is taken₃)₂·3H₂O), 22.30 g magnesium nitrate (Mg (NO)₃)₂·6H₂O) and 25.30 g of cobalt nitrate (Co (NO)₃)₂·6H₂O) in the same container, adding 500g of water, stirring and dissolving to obtain a material III.

Mixing the materials I, II and III, adding 312.5 g of 40% by weight of an aluminium sol material under stirring, and then adding2.95 g of KOH, containing 0.32 g of PdCl₂046 g RuCl₃Adjusting the acidity of the slurry with ammonia water to make the pH value of the mixed slurry equal to 6.0, fully stirring to obtain slurry, carrying out microspherical molding on the prepared slurry in a spray dryer, and finally roasting to prepare the catalyst, wherein the catalyst comprises the following components:

50% by weight Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Pd_0.1Ru_0.1O_x+ 50% by weight of Al₂O₃

2. Reduction and evaluation of the catalyst

The prepared catalyst is carried out under the reduction conditions:

the temperature is 400 DEG C

Pressure 3.0MPa

Catalyst loading 100g

Catalyst load 4000mL h^-1·g^-1

Reducing gas H₂/CO＝2/1

Reduction time 24 hours

phi 38 mm fluidized bed reactor

The reaction temperature is 330 DEG C

The reaction pressure is 2.0MPa

The catalyst loading corresponded to 100g of catalyst before reduction

Raw material ratio (mol) H₂/CO＝2/1。

The experimental results of the synthesis reaction are shown in table 1.

[ example 7 ]

1. Catalyst preparation

443.8 g of ferric nitrate (Fe (NO)₃)₃·9H₂O), dissolving in 800g of water to obtain a material I, and taking 14.20 g of cerium nitrate (Ce (NO)₃)₃·6H₂O) is dissolved in 50g of water under heating to obtain a material II, and 65.67 g of copper nitrate (Cu (NO) is taken₃)₂·3H₂O), 22.30 g magnesium nitrate (Mg (NO)₃)₂·6H₂O) and 25.30 g of cobalt nitrate (Co (NO)₃)₂·6H₂O) in the same container, adding 500g of water, stirring and dissolving to obtain a material III.

The materials I, II and III were mixed, 312.5 g of a 40% by weight aluminum sol material were added with stirring, followed by 2.95 g of KOH, 1.49 g of H₂PtCl₆·6H₂O, containing.046 g RuCl₃Adjusting the acidity of the slurry with ammonia water to make the pH value of the mixed slurry equal to 6.0, fully stirring to obtain slurry, carrying out microspherical molding on the prepared slurry in a spray dryer, and finally roasting to prepare the catalyst, wherein the catalyst comprises the following components:

50% by weight Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Pt_0.1Ru_0.1O_x+ 50% by weight of Al₂O₃

2. Reduction and evaluation of the catalyst

The prepared catalyst is carried out under the reduction conditions:

the temperature is 400 DEG C

Pressure 3.0MPa

Catalyst loading 100g

Catalyst load 4000mL h^-1·g^-1

Reducing gas H₂/CO＝2/1

Reduction time 24 hours

phi 38 mm fluidized bed reactor

The reaction temperature is 330 DEG C

The reaction pressure is 2.0MPa

The catalyst loading corresponded to 100g of catalyst before reduction

Catalyst loading based on the amount of catalyst before reduction, 3000mL·h^-1·g^-1

Raw material ratio (mol) H₂/CO＝2/1。

The experimental results of the synthesis reaction are shown in table 1.

[ example 8 ]

1. Catalyst preparation

625.8 g of ferric nitrate (Fe (NO)₃)₃·9H₂O), dissolving in 1000g of water to obtain a material I, and taking 53.30 g of cerium nitrate (Ce (NO)₃)₃·6H₂O) is dissolved in 200g of water under heating to obtain a material II, 37.04 g of copper nitrate (Cu (NO)₃)₂·3H₂O), 19.70 g magnesium nitrate (Mg (NO)₃)₂·6H₂O) and 66.90 g of cobalt nitrate (Co (NO)₃)₂·6H₂O) in the same container, adding 200g of water, stirring and dissolving to obtain a material III.

The materials I, II and III were mixed, 187.5 g of a 40% by weight aluminum sol material were added with stirring, followed by 1.04 g of KOH, 1.81 g of PdCl₂And 0.64 g RuCl₃The acidity of the slurry was adjusted with ammonia water to make the pH of the mixed slurry 6.0, and the slurry was stirred sufficiently, and the resulting slurry was spray-dried to form microspheres, and finally calcined to obtain a catalyst composition:

70% by weight Fe₁₀₀Cu_10.0Co_15.0Mg_5.0K_1.0Ce_8.0Ru_0.01Pd_0.4O_x+ 30% by weight of Al₂O₃

2. Reduction and evaluation of the catalyst

The prepared catalyst is carried out under the reduction conditions:

the temperature is 400 DEG C

Pressure 3.0MPa

Catalyst loading 100g

Catalyst load 4000mL h^-1·g^-1

Reducing gas H₂/CO＝2/1

Reduction time 24 hours

phi 38 mm fluidized bed reactor

The reaction temperature is 330 DEG C

The reaction pressure is 2.0MPa

The catalyst loading corresponded to 100g of catalyst before reduction

Raw material ratio (mol) H₂/CO＝2/1。

The experimental results of the synthesis reaction are shown in table 1.

[ example 9 ]

1. Catalyst preparation

228.4 g of ferric nitrate (Fe (NO)₃)₃·9H₂O), dissolving with 600g of water to obtain a material I, and taking 2.40 g of cerium nitrate (Ce (NO)₃)₃·6H₂O) is dissolved in 50g of water under heating to obtain a material II, and 67.60 g of copper nitrate (Cu (NO) is taken₃)₂·3H₂O), 21.50 g magnesium nitrate (Mg (NO)₃)₂·6H₂O) and 8.10 g of cobalt nitrate (Co (NO)₃)₂·6H₂O) in the same container, adding 200g of water, stirring and dissolving to obtain a material III.

The materials I, II and III were mixed, 437.5 g of a 40% by weight aluminum sol material were added with stirring, 3.03 g of KOH, 0.02 g of PdCl₂And 0.94 g RuCl₃Adjusting the acidity of the slurry to make the pH of the mixed slurry equal to 6.0 by using ammonia water, fully stirring to obtain slurry, carrying out microspherical molding on the prepared slurry in a spray dryer, and finally roasting to prepare the catalyst, wherein the catalyst comprises the following components:

30% by weight of Fe₁₀₀Cu_50.0Co_5.0Mg_15.0K_8.0Ce_1.0Ru_0.4Pd_0.01O_x+ 70% by weight of Al₂O₃

2. Reduction and evaluation of the catalyst

The prepared catalyst is carried out under the reduction conditions:

the temperature is 400 DEG C

Pressure 3.0MPa

Catalyst loading 100g

Catalyst load 4000mL h^-1·g^-1

Reducing gas H₂/CO＝2/1

Reduction time 24 hours

phi 38 mm fluidized bed reactor

The reaction temperature is 330 DEG C

The reaction pressure is 2.0MPa

The catalyst loading corresponded to 100g of catalyst before reduction

Raw material ratio (mol) H₂/CO＝2/1。

The experimental results of the synthesis reaction are shown in table 1.

Table 1 (wait for)

	Active ingredient/weight%	Carrier/weight%
			Example 1	Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0O_xPer 50% by weight	Al₂O₃Per 50% by weight
Example 2	Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Pd_0.2O_xPer 50% by weight	Al₂O₃Per 50% by weight
			Example 3	Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Pt_0.2O_xPer 50% by weight	Al₂O₃Per 50% by weight
Example 4	Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Ru_0.2O_xPer 50% by weight	Al₂O₃Per 50% by weight
			Example 5	Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Pd_0.1Pt_0.1O_xPer 50% by weight	Al₂O₃Per 50% by weight
Example 6	Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Pd_0.1Ru_0.1O_xPer 50% by weight	Al₂O₃Per 50% by weight
			Example 7	Fe₁₀₀Cu_25.0Co_8.0Mg_8.0K_4.0Ce_3.0Pt_0.1Ru_0.1O_xPer 50% by weight	Al₂O₃Per 50% by weight
Example 8	Fe₁₀₀Cu_10.0Co_15.0Mg_5.0K_1.0Ce_8.0Ru_0.01Pd_0.4O_x70% by weight	Al₂O₃30% by weight
			Example 9	Fe₁₀₀Cu_50.0Co_5.0Mg_15.0K_8.0Ce_1.0Ru_0.4Pd_0.1O_x30% by weight	Al₂O₃70% by weight

TABLE 1 (continuation)

Claims

1. The catalyst for directly preparing the low-carbon olefin by the synthesis gas comprises a carrier and an active component, wherein the active component contains a composition with the following chemical formula in atomic ratio:

Fe₁₀₀Cu_aCo_bD_jO_x

d comprises at least one selected from alkali metals and alkaline earth metals;

the value range of a is 5.0-60.0;

the value range of b is 1.0-20.0;

the value range of j is 0.01-45.0;

2. The catalyst according to claim 1, wherein the carrier comprises at least one selected from the group consisting of silica, alumina and titania.

3. The catalyst of claim 1, wherein the alkali metal is at least one selected from the group consisting of Li, Na, K, Rb and Cs.

4. The catalyst according to claim 1, wherein the alkaline earth metal is at least one selected from the group consisting of Be, Mg, Ca, Sr, and Ba.

5. The catalyst of claim 1, wherein a is in the range of 10.0 to 50.0.

6. The catalyst of claim 1, wherein b is in the range of 5.0 to 15.0.

7. The catalyst of claim 1, wherein the amount of the carrier is 20 to 80% by weight based on the weight of the catalyst.

8. The catalyst of claim 1, wherein the catalyst is reduced before being used in the reaction of directly preparing the low-carbon olefin from the synthesis gas.

9. The application of the catalyst of any one of claims 1 to 8 in the reaction of directly preparing low-carbon olefins from synthesis gas.

10. A process for preparing the catalyst of claim 1, comprising the process steps of:

feeding the slurry into a spray dryer for spray forming;

and (4) roasting.