CN112745879B

CN112745879B - Method for converting carbon monoxide into hydrocarbons

Info

Publication number: CN112745879B
Application number: CN201911049499.4A
Authority: CN
Inventors: 徐润; 侯朝鹏; 顾畅; 夏国富; 牛传峰; 胡志海
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2022-12-09
Anticipated expiration: 2039-10-31
Also published as: CN112745879A

Abstract

The invention discloses a method for converting carbon monoxide into hydrocarbons, which comprises the following steps: the synthesis gas raw material of carbon monoxide and hydrogen is contacted with a catalyst through a laminated structure reactor, and the reaction raw material containing carbon monoxide and hydrogen is converted into hydrocarbon through a hydro-polymerization reaction, wherein the laminated structure reactor comprises a plurality of reaction channel layers containing the catalyst and a plurality of heat conduction channel layers containing heat conduction media, the reaction channel layers consist of a plurality of reaction channels loaded with the catalyst, and the heat conduction channel layers consist of a plurality of fluid channels; the catalyst is a Fe-based raspberry type microsphere cavity catalyst. The invention solves the problems of uneven internal pressure difference and large pressure drop of the existing micro-channel reactor, and obviously improves the whole reaction activity and selectivity.

Description

Method for converting carbon monoxide into hydrocarbons

Technical Field

The present invention relates to a process for converting a feedstock containing carbon monoxide and hydrogen into hydrocarbons using an iron-based catalyst.

Background

The process for the catalytic conversion of carbon monoxide and hydrogen to aliphatic hydrocarbons was discovered in 1923 by the german scientists Frans Fischer and Hans tropch, and the reaction was therefore named Fischer-Tropsch synthesis (Fischer-Tropsch synthesis). The reaction can prepare clean fuel and other high value-added chemicals on a large scale, and opens up a technical route of non-petroleum fuel. Catalysts and associated reactors have been the core technology in fischer-tropsch synthesis technology.

Generally, metals such as Fe, co, ni, ru and the like can be used as main active components of the catalyst, and a slurry bed reactor process and a fixed bed reactor process are the main technologies adopted in the industry at present. The iron-based catalyst has low requirements on the hydrogen-carbon ratio, the impurity content and the like of raw material gas, and the cost of the catalyst is low, so that the iron-based catalyst becomes the first choice catalyst of most technical routes taking coal and biomass as raw materials. Conventional reactors such as a fixed bed reactor and a slurry bed reactor have respective advantages and disadvantages, the fixed bed reactor is simple to operate, the impurity tolerance is high, but the problems of large pressure drop and hot spots exist, and the slurry bed reactor can realize isothermal operation, but the problems of large mass transfer resistance and solid-liquid separation of a catalyst and a product exist. Iron-based catalyst and slurry bed reactor processes from Sasol corporation of south africa and cobalt-based catalyst and fixed bed reactor processes from Shell, the netherlands are the primary representatives of the art in this field.

The microchannel reactor has high mass and heat transfer efficiency, simple reaction operation and isothermal operation, and is a new direction and research hotspot of chemical engineering at present. For example, CN103418321B discloses a stacked microchannel reactor, which comprises an upper cover plate, a first reaction plate, a second reaction plate, and a lower cover plate, wherein the two reaction plates are stacked alternately, and can be provided with multiple groups as required, and a design of one inlet and two outlets is adopted, so that the reactor has the characteristics of high reaction uniformity, high reaction efficiency, and small fluid pressure loss. CN101733056B proposes an impinging stream micro-channel reactor, wherein a strip-shaped longitudinal channel or a micro-pore channel for material collision is carved on a micro-channel flat plate, one or more transverse micro-channels are carved on two sides of the longitudinal channel, and the channel is connected with a fluid inlet and a fluid outlet, so that the problem of non-uniform distribution of a flow field of the micro-channel reactor is solved, and the high uniformity of the reaction is realized. CN100529020C discloses a micro-channel reactor for Fischer-Tropsch synthesis, which is composed of a processing micro-channel with the height or width of 10mm and a heat exchange channel, wherein the Fischer-Tropsch synthesis reaction is carried out in the processing micro-channel containing a cobalt-based catalyst, and H is subjected to a reaction of H and H ₂ And CO to hydrocarbons, wherein the process microchannels and the heat exchange channels form a heat exchange zone, and heat generated by the reaction is absorbed in the heat exchange zone by a medium in the heat exchange channels.

However, the catalyst adopted by the microchannel reactor in the prior art is a common microsphere catalyst, and the problems of uneven pressure difference in a reaction channel, large pressure drop of the reactor, low reaction performance and the like exist.

Disclosure of Invention

The invention aims to provide a method for converting carbon monoxide into hydrocarbons, which solves the problems of uneven internal pressure difference of reaction channels, large pressure drop of a reactor, low reaction performance and the like in the prior art.

The invention provides a method for converting carbon monoxide into hydrocarbons, which comprises the following steps: a synthesis gas raw material of carbon monoxide and hydrogen is contacted with a catalyst through a laminated structure reactor, and the reaction raw material containing the carbon monoxide and the hydrogen is converted into hydrocarbons through a hydrogenation polymerization reaction, wherein the laminated structure reactor comprises a plurality of reaction channel layers containing the catalyst and a plurality of heat conduction channel layers containing a heat conduction medium, the reaction channel layers are composed of a plurality of reaction channels loaded with the catalyst, and the heat conduction channel layers are composed of a plurality of fluid channels; the catalyst is a Fe-based raspberry type microsphere cavity catalyst.

In a preferred case, the layered structure reactor is repeatedly formed by a layered structure, the layered structure is formed by a reaction channel layer containing a catalyst and a heat conduction channel layer containing a heat conduction medium, n reaction channels form a single reaction channel layer, m fluid channels form a single heat conduction channel layer, x reaction channel layers and y heat conduction channel layers form the layered structure reactor, wherein n is 5-10000, m is 5-10000, x is 1-10000, and y is 2-10000; the reaction channels and the fluid channels have a minimum side length of 10 to 1000 microns, preferably 100 to 800 microns.

In the present invention, the heat conducting channel layer provides heat required by the reaction channel layer, or conducts heat generated by the reaction channel layer.

In the present invention, the minimum side length refers to the smallest height or width on a single channel cross section.

In a preferred aspect, the perpendicular distance between the central axes of the adjacent reaction channels and heat conducting channels is 10 to 10000 microns, and more preferably 100 to 8000 microns.

In the present invention, it is preferable that the reaction channel layer and the heat conduction channel layer are combined in a staggered, interlaced, or parallel manner.

In the present invention, it is preferable that the reaction channels and the fluid channels are combined in an interlaced, or side-by-side manner.

In a preferred case, the layered structure reactor is made of one or more of a metal material, a ceramic material and a polymer material. Wherein, the metal material can be steel, aluminum, nickel, titanium, copper and metal alloy; the ceramic material may be glass, quartz, silicon carbide. And a composite material composed of the above materials.

Preferably, the layered structure is stacked from a planar structure; or cast using 3D manufacturing techniques. The layered structure reactor may be fabricated by any known technique, such as machining, laser machining, electrochemical machining, etching, etc., by forming channels and holes in a substrate sheet, and assembling the substrate sheets by diffusion welding, laser welding, brazing, and the like. The layered structure reactor has the characteristics of simple design, easy processing and modular structure.

In the invention, the preferable Fe-based raspberry type microsphere cavity catalyst is a hollow microsphere with a large pore on the surface, a hollow structure is arranged in the hollow microsphere, and the large pore and the hollow structure are communicated to form a cavity with an opening at one end; the particle size of the microspheres is 60-600 μm, preferably 80-500 μm, and the diameter of the hollow structure is 10-200 μm, preferably 20-150 μm.

Preferably, the macropores have a pore size of 5 to 100. Mu.m.

In a preferable case, the shell thickness of the Fe-based raspberry type microsphere cavity catalyst is 1-100 μm.

In a preferred aspect, the sphericity of the Fe-based raspberry-type microsphere cavity catalyst is from 0.50 to 0.99.

In the invention, the preferable Fe-based raspberry type microsphere cavity catalyst comprises an active metal component Fe, a structural auxiliary agent and optional other auxiliary agents, wherein the composition of each component in terms of corresponding oxide satisfies W _Fe ：W _b ：W _c ＝(5～85)：(10 to 80): (0 to 15); wherein b is a structural auxiliary agent selected from one or more of alumina, silica, titania and zirconia; c is other auxiliary agents selected from one or more of IA, IIA, IB, IIB, VIIB and VIII elements.

The Fe-based raspberry type microsphere cavity catalyst provided by the invention has better mass transfer and heat transfer characteristics, and the strength is obviously higher than that of a microsphere catalyst in the prior art. When the catalyst is applied to the reactor with the layered structure, the stability is high, and the pressure drop of the reactor is small.

The preparation method of the Fe-based raspberry type microsphere cavity catalyst is not limited in the invention, and any preparation method capable of obtaining the structure is applicable.

In one preferred embodiment of the invention, the Fe-based raspberry-type microsphere cavity catalyst can be prepared by the following preparation method:

(1) Uniformly dispersing soluble salts or colloidal particles of active components, structural auxiliary agents and optional other auxiliary agents into a dispersing agent, precipitating by using a precipitator, and then separating and washing materials after precipitation reaction to obtain a catalyst precursor;

(2) Mixing the catalyst precursor obtained in the step (1) with nitrate, a pore-forming agent and/or an explosive agent to prepare slurry, so as to obtain dispersed slurry; aging the dispersed slurry;

(3) And (3) carrying out spray drying and forming on the slurry obtained in the step (2) to obtain a precursor of the Fe-based raspberry type microsphere cavity catalyst, and roasting to obtain the Fe-based raspberry type microsphere cavity catalyst.

Preferably, the dispersant is selected from one or more of water, alcohols, ketones and acids.

Preferably, the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate and yttrium nitrate.

In a preferred case, the pore former is selected from one or more of starch, synthetic cellulose, polymeric alcohol and surfactant.

In a preferred aspect, the blasting agent is selected from one or more of picric acid, trinitrotoluene, digested glycerol, nitrocotton, danesel explosives, hexogen, and C4 plastic explosives.

Preferably, in the step (3), the aged dispersion slurry is sent to a drying device, and the temperature of the air is 400-1200 ℃, preferably 450-700 ℃; the air outlet temperature is 100-300 ℃, preferably 120-200 ℃, and the drying and forming are carried out.

In the invention, the reaction channel is filled with the Fe-based raspberry type microsphere cavity catalyst, and under the preferable condition, the ratio of the grain size of the Fe-based raspberry type microsphere cavity catalyst to the minimum side length of the reaction channel is 1/10-1/2. In the present invention, the catalyst particle diameter means the maximum value of the distance between any two points on the cross section of the catalyst.

In a preferred case, the heat conducting medium in the fluid channel is selected from one or more of heat conducting oil, water, steam, hydrogen and nitrogen.

In a preferred aspect, the reaction conditions in the layered structure reactor are: the operation pressure is 1.0-5.0MPa, the reaction temperature is 150-300 ℃, the volume ratio of the synthesis gas raw material to the catalyst is 1000-60000 ₂ The molar ratio of/CO fed is between 0.5 and 3.0. The synthesis gas feedstock produces aliphatic hydrocarbons containing at least one carbon, preferably at least 2 carbons or more, and more preferably 5 carbons or more.

The process provided herein produces at least 0.6 grams of liquid hydrocarbon compound per gram of catalyst per hour; the selectivity to methane is less than 10%.

The invention has the characteristics that:

the reactor with the layered structure can strengthen heat and mass transfer, and has the characteristics of simple design, easy processing and modular structure. In particular, the Fe-based raspberry type microsphere cavity catalyst is adopted in the layered structure reactor, and has the characteristics of high activity, good selectivity and strong stability. The invention solves the problems of uneven internal pressure difference and large pressure drop of the existing micro-channel reactor, and obviously improves the whole reaction activity and selectivity.

Drawings

FIG. 1 is a schematic view of one embodiment of a layered structure reactor in the process of the present invention.

FIG. 2 is a schematic view of one embodiment of a layered structure reactor in the process of the present invention.

FIG. 3 is a schematic diagram of one embodiment of a layered structure reactor in the method of the present invention.

FIG. 4 is an SEM photograph of the Fe-based raspberry-type microsphere cavity catalyst C1 prepared in example 4.

Detailed Description

The method provided by the present invention will be further described with reference to the accompanying drawings, but the present invention is not limited thereto, and the attached facilities for maintaining the pressure of the reactor, such as connecting pipes, valves, flanges, sealing rings or sealing strips, and catalyst supports, etc. included in the reactor, which are well known to those skilled in the art, are omitted.

Fig. 1 is a three-dimensional perspective view of one of the reactors of the layered structure in the method of the present invention, which includes a reaction channel plate 1, a flow channel plate 2, a reaction channel 3, and a flow channel 4. The superposition of the channel plates forms a reactor with a laminated structure. And filling a Fe-based raspberry type microsphere cavity catalyst in the reaction channel.

Fig. 2 is a three-dimensional perspective view of one of the layered structure reactors in the method of the present invention, which includes a reaction and flow channel plate 1, a reaction channel 3, a flow channel 4, and a partition plate 5. The superposition of the channel plates forms a reactor with a laminated structure. And filling a Fe-based raspberry type microsphere cavity catalyst in the reaction channel.

Fig. 3 is a three-dimensional perspective view of one of the layered structure reactors in the method of the present invention, which includes a reaction and flow channel plate 1, a reaction channel 3, and a flow channel hole 4. The superposition of the channel plates forms a reactor with a laminated structure. And filling a Fe-based raspberry type microsphere cavity catalyst in the reaction channel.

The process of the present invention is further illustrated by the following examples, which are not intended to limit the invention thereto.

Example 1

As shown in FIG. 1, a reactor with a laminated structure is provided, plates of the reactor adopt chemical etching channels, and brazing is adopted between the plates for processing. And respectively processing a reaction channel laminate and a heat conduction channel laminate by adopting chemical etching. The reaction channel is a linear channel, the length of which is 100mm, the width of which is 10mm, the depth of which is 1mm, and the left channel and the right channel are separated by 5mm. The fluid channel is 100mm long, 10mm wide and 1mm deep. The reaction channel direction and the fluid channel direction are arranged crosswise at an angle of 90 degrees. 1 piece of upper cover plate, 10 pieces of reaction channel laminate, 11 pieces of fluid channel laminate and 1 piece of lower cover plate are welded together by high-temperature brazing, and the brazing filler metal adopts alloy Al-20Cu-10Si-2Ni. Specific surface area per unit of reactor 1100m ² /m ³ The ratio of the flow channel area to the reaction channel area was 1.4.

Example 2

A layered structure reactor is shown in fig. 2. The reactor plates are mechanically punched by stainless steel plates to form channels, and the plates are processed by a brazing method. And respectively processing a channel layer plate and a partition plate. The reaction channel direction and the fluid channel are arranged in parallel at intervals. The reaction channel is linear, and has a length of 100mm, a width of 10mm, a depth of 1mm, and a left-right interval of 5mm. The fluid channel is 100mm long, 5mm wide and 1mm deep. The 10 channel laminates and the 11 partition plates are alternately combined to form a reaction channel layer and a fluid channel layer, and are welded together by high-temperature brazing, and the brazing filler metal is made of alloy Al-20Cu-10Si-2Ni. Specific surface area per unit of reactor 1200m ² /m ³ The ratio of the flow channel area to the reaction channel area was 1.2.

Example 3

A layered structure reactor is shown in fig. 3. The reactor plates form a channel structure by adopting a chemical etching and machining method, and the plates are processed by adopting a high-temperature vacuum diffusion welding method. The stainless steel plate is firstly machined to form a plurality of rectangular holes, and linear pits are formed on the surface of the stainless steel plate by etching. The linear type gallery forms a reaction channel after being packaged, and the reaction channel is 100mm long, 10mm wide, 1mm deep and 5mm left and right apart. The fluid channel is formed by overlapping rectangular holes of a plurality of plates, and the length of the channel is 20mm, the width is 5mm and the depth is 5mm after 10 channel plates are overlapped1mm. The reaction channel direction and the fluid channel direction are arranged crosswise at an angle of 90 degrees. The 10 channel laminates were welded together using high temperature brazing. The specific surface area per unit of the reactor is 1500m ² /m ³ The ratio of the flow channel area to the reaction channel area was 1.2.

Example 4

The preparation process of the Fe-based raspberry type microsphere cavity catalyst C1 comprises the following steps:

(1) Preparation of catalyst precursor

Dissolving 3.28kg of ferric nitrate nonahydrate, 1.53kg of aluminum nitrate nonahydrate, 235g of copper nitrate and 110g of zinc nitrate hexahydrate in 5L of deionized water, dissolving 4.3kg of ammonium carbonate in 5L of deionized water completely, adding ammonium carbonate into the ferric nitrate aluminum nitrate solution continuously until the pH value of the solution is 9.0-9.1, standing at room temperature after complete precipitation, aging for 12h, filtering, and washing twice with 8L of deionized water;

(2) Pulping

Dispersing the filter cake into 10L of deionized water, stirring vigorously for pulping, adding 1.2kg of PEG4000, 0.65kg of ammonium nitrate and 120g of potassium nitrate in sequence, and stirring at 30 ℃ for pulping for 2h.

(3) Spray drying and forming

The slurry was shaped by passing it through a Niro Bowen non Nozzle Tower model spray dryer at a spray drying pressure of 6.5 to 9.0MPa, an inlet temperature of 500 ℃ or less and an outlet temperature of about 150 ℃. And calcined in air at 500 ℃ for 4h.

The Fe-based raspberry type microsphere cavity catalyst C1 is obtained, the average particle size is 150 mu m, the average diameter of the hollow structure is 45 mu m, and the pore diameter of the macropore is 20 mu m. The content of the active component iron calculated by oxide is 65 wt%, the content of the alumina is 22 wt%, and the content of other auxiliary agents is 13 wt%.

The SEM photograph of the Fe-based raspberry type microsphere hollow catalyst C1 is shown in FIG. 4.

Example 5

The procedure of example 4 was followed except that 3.28kg of iron nitrate nonahydrate, 118g of copper nitrate and 120g of manganese nitrate tetrahydrate were dissolved in 5L of deionized water in step (1), and 4.7kg of sodium carbonate and 508g of sodium silicate were completely dissolved in 5L of deionized water.

The Fe-based raspberry type microsphere cavity catalyst C2 is obtained, the average particle size is 150 mu m, the average diameter of the hollow structure is 45 mu m, and the pore size of the macropore is 20 mu m. The content of the active component iron calculated by oxide is 65 wt%, the content of silicon oxide is 25 wt%, and the content of other auxiliary agents is 10 wt%.

Example 6

The procedure of example 4 was followed except that 2.52kg of iron nitrate nonahydrate, 698g of cobalt nitrate nonahydrate and 47g of copper nitrate were dissolved in 5L of deionized water in step (1), and 4.7kg of sodium carbonate and 610g of sodium silicate were completely dissolved in 5L of deionized water.

The Fe-based raspberry type microsphere cavity catalyst C3 is obtained, the average particle size is 150 mu m, the average diameter of the hollow structure is 45 mu m, and the pore diameter of the macropore is 20 mu m. The content of the active component iron calculated by oxide is 65 wt%, the content of silicon oxide is 22 wt%, and the content of other auxiliary agents is 13 wt%.

Comparative example 1

3.28kg of ferric nitrate nonahydrate, 1.53kg of aluminum nitrate nonahydrate, 235g of copper nitrate and 110g of zinc nitrate hexahydrate are dissolved in 5L of deionized water, 4.3kg of ammonium carbonate is dissolved in 5L of deionized water completely, ammonium carbonate is added into the ferric nitrate aluminum nitrate solution continuously until the pH value of the solution is between 9.0 and 9.1, the solution is settled completely and then stands at room temperature for aging for 12h, then the solution is filtered, and the solution is washed twice by 8L of deionized water. A spherical catalyst having an average particle diameter of about 140 μm obtained by direct spray-drying molding was designated as DB1. The content of the active component iron calculated by oxide is 65 wt%, the content of the alumina is 22 wt%, and the content of other auxiliary agents is 13 wt%.

Examples 7 to 11, comparative examples 2 to 3

The catalysts obtained in examples 4 to 6 and comparative example 1 were charged in the layered structure reactors of examples 1 to 3, respectively, at a GHSV of 5000 ml/(g) at 0.5MPa _{Catalyst and process for preparing same} H), hydrogen reduction at 400 ℃ for 4 hours. At 2.5MPa and GHSV of 20000 ml/(g) _{Catalyst and process for preparing same} H) feed gas H ₂ The reaction mixture was subjected to a CO conversion reaction at a temperature of 220 ℃ and a CO of 2.0. The reaction results are shown in Table 1.

In comparative example 3, the comparative catalyst was charged in a conventional slurry bed reactor at a GHSV of 5000 ml/(g) at 0.5MPa _{Catalyst and process for producing the same} H) at 400 ℃ for 4 hours at 2.5MPa and a GHSV of 3000 ml/(g) _{Catalyst and process for preparing same} H) feed gas H ₂ The reaction temperature is 230 ℃ and the CO is 2.0. The reaction results are shown in Table 1.

In the present invention, the activity factor is the conversion of Fe per unit mass on the catalyst to hydrocarbons per unit time (minus CO) ₂ ) The amount of CO species of (a).

As can be seen from Table 1, the activity coefficients of the method provided by the invention all exceed 0.04mmol _CO /(g _Fe S) significantly higher than the activity coefficient of comparative example 2 (0.024 mmolCO/(gFe. S)), and at the same time, the methane selectivity in the enhanced process of the invention is also significantly lower than that of the comparative example.

In addition, the pressure drop of the reactor in the method provided by the invention is lower than 0.20MPa and is also obviously lower than that of the reactor in the comparative example 2 (0.42 MPa). The invention solves the problems of uneven internal pressure difference and large pressure drop of the existing micro-channel reactor, and obviously improves the whole reaction activity and selectivity.

TABLE 1

* Pressure drop of distributor of reactor mainly in slurry bed

Claims

1. A process for converting carbon monoxide to hydrocarbons comprising: a synthesis gas raw material of carbon monoxide and hydrogen is contacted with a catalyst through a laminated structure reactor, and the reaction raw material containing the carbon monoxide and the hydrogen is converted into hydrocarbons through a hydrogenation polymerization reaction, wherein the laminated structure reactor comprises a plurality of reaction channel layers containing the catalyst and a plurality of heat conduction channel layers containing a heat conduction medium, the reaction channel layers are composed of a plurality of reaction channels loaded with the catalyst, and the heat conduction channel layers are composed of a plurality of fluid channels; the catalyst is a Fe-based raspberry type microsphere cavity catalyst, the Fe-based raspberry type microsphere cavity catalyst is a hollow microsphere with a large pore on the surface, a hollow structure is arranged in the hollow microsphere, and the large pore is communicated with the hollow structure to form a cavity with an opening at one end; the particle size of the microsphere is 60-600 μm, the diameter of the hollow structure is 10-200 μm, and the pore diameter of the macropores is 5-100 μm;

the layered structure reactor is repeatedly formed by a layered structure, the layered structure consists of a reaction channel layer containing a catalyst and a heat conduction channel layer containing a heat conduction medium, n reaction channels form a single reaction channel layer, m fluid channels form a single heat conduction channel layer, and x reaction channel layers and y heat conduction channel layers form the layered structure reactor, wherein n is 5-10000, m is 5-10000, x is 1-10000, and y is 2-10000; the minimum side length of the reaction channel and the fluid channel is 10-1000 microns.

2. The method of claim 1, wherein the reaction channel and the fluid channel have a minimum side length of 100 to 800 microns.

3. The method of claim 1 or 2, wherein the vertical distance between the central axes of adjacent reaction channels and flow channels is 10 to 10000 μm.

4. A method according to claim 3, wherein the vertical distance between the central axes of adjacent reaction channels and fluid channels is in the range of 100 to 8000 μm.

5. The method of claim 1 or 2, wherein the reaction channel layer and the heat conducting channel layer are combined in a staggered, side-by-side manner; the reaction channels and the fluid channels are combined in a staggered and parallel manner.

6. The method of claim 1 or 2, wherein the reaction channel layer and the heat conducting channel layer are combined in an interlaced form; the reaction channels and the fluid channels are combined in an interlaced fashion.

7. The method according to claim 1 or 2, wherein the laminated structure reactor is made of one or more of a metal material, a ceramic material and a polymer material.

8. The method of claim 7, wherein said layered structure is built up from planar structures; or cast using 3D manufacturing techniques.

9. The method of claim 1, wherein the microspheres have a particle size of 80 to 500 μm and the hollow structures have a diameter of 20 to 150 μm.

10. The method of claim 1, wherein the shell thickness of the Fe-based raspberry-type microsphere cavity catalyst is 1 to 100 μm.

11. The method of claim 1, wherein the Fe-based raspberry-type microsphere cavity catalyst has a sphericity of 0.50 to 0.99.

12. A process according to claim 1, characterized in that the Fe-based raspberry-type microspherical hollow catalyst comprises the active metal component Fe, a structural auxiliary and optionally further auxiliary agents, the composition of each component, calculated as the corresponding oxide, satisfying W _Fe ：W _b ：W _c = (5 to 85): (10-80): (0 to 15); wherein b is a structural auxiliary agent selected from one or more of alumina, silica, titania and zirconia; c is other auxiliary agents selected from one or more of IA, IIA, IB, IIB, VIIB and VIII elements.

13. The method as claimed in claim 1, wherein the reaction channel is filled with a Fe-based raspberry type microsphere cavity catalyst, and the ratio of the particle size of the Fe-based raspberry type microsphere cavity catalyst to the minimum side length of the reaction channel is 1/10 to 1/2.

14. The method according to claim 1, wherein the heat transfer medium in the fluid channel is one or more selected from the group consisting of heat transfer oil, water, steam, hydrogen and nitrogen.

15. The process of claim 1, wherein the reaction conditions in the layered reactor are: the operation pressure is 1.0-5.0MPa, the reaction temperature is 150-300 ℃, the volume ratio of the synthesis gas raw material to the catalyst is 1000-60000 ₂ The molar ratio of the/CO feed is 0.5-3.0.