A method of calcining an industrial iron-based fischer-tropsch synthesis powder catalyst

Abstract

The present application belongs to the technical field of the calcination of Fischer-Tropsch synthesis catalyst / catalyst precursor, and particularly relates to a calcination method of industrial iron-based Fischer-Tropsch synthesis powder catalyst, which adopts a two-stage rotary furnace series calcination process to calcine and treat the industrial iron-based Fischer-Tropsch synthesis powder catalyst precursor to be treated, so as to obtain a calcined spherical powder iron-based catalyst; wherein the material output by the material outlet of the first-stage rotary furnace directly enters the second-stage rotary furnace in a continuous manner through the material inlet of the second-stage rotary furnace; the air draft in the second-stage rotary furnace directly reversely enters the first-stage rotary furnace through the material outlet of the first-stage rotary furnace, so that the material in the rotary furnace and the air draft form a convection; the hot air tail gas in the heating chamber of the second-stage rotary furnace is sent to the furnace chamber of the second-stage rotary furnace through the fresh air after heat exchange through the furnace chamber air inlet of the second-stage rotary furnace. The iron-based catalyst obtained by the calcination method has a lower attrition index, and has superior Fischer-Tropsch synthesis reaction performance while maintaining excellent attrition resistance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of calcination of Fischer-Tropsch synthesis catalyst / catalyst precursor, and particularly relates to a calcination method of an industrial iron-based Fischer-Tropsch synthesis powder catalyst. BACKGROUND

[0002] A slurry bubble column reactor and a synthetic oil process matched therewith for synthesizing liquid hydrocarbon / wax hydrocarbon products from synthesis gas (CO, H2) by catalytic reaction under the action of a Fischer-Tropsch synthesis catalyst such as precipitated iron or supported cobalt, are increasingly valued and favored by researchers and developers. The slurry bubble column reactor (i.e., slurry bed reactor) has a high requirement not only on the catalytic activity of the catalyst, but also on the wear resistance strength index of the catalyst, so as to facilitate the efficient separation between the synthesis reaction products (such as waxes and other hydrocarbons) and the catalyst and the stability of the catalytic synthesis reaction operation. Therefore, in the Fischer-Tropsch synthesis reaction, the precipitated iron-based catalyst precursor needs to be subjected to a medium-high temperature calcination treatment before use, so as to enhance the strength and other properties of the catalyst.

[0003] The carrier or catalyst precursor is subjected to heat treatment, i.e., calcination, in air or inert gas flow at a temperature not lower than its use temperature. Existing laboratory researches have shown that the calcination process and conditions of the iron-based catalyst or its precursor have a great influence on its structure and Fischer-Tropsch reaction performance (see: Effect of calcination behaviors on precipitated iron–manganese Fischer–Tropsch synthesis catalyst. Catalysis Letters, (2007) Vol. 117, 130-135.). Within a certain temperature range, as the calcination temperature increases, the wear resistance of the iron-based catalyst will be enhanced, but the Fischer-Tropsch synthesis reaction activity will be negatively affected (see: Influence of calcination temperature on the performance of iron-based catalysts for Fischer-Tropsch synthesis in slurry bubble column reactor. Chinese Journal of Catalysis, (2005), 26(4):340-348.). Especially for the industrial iron-based catalyst for slurry bubble column reactor, large-scale industrial equipment such as tunnel kiln, rotary furnace, belt calcination furnace (mesh belt kiln), roller kiln, etc. are generally used for calcination. The temperature field, air volume control precision, sealing performance, etc. of different equipment cannot be compared with small-scale laboratory experiments, and therefore, it is easy to cause phenomena such as temperature flying, under-firing, over-firing, and uneven calcination.

[0004] Chinese patent document CN1260007C discloses a microspherical Fischer-Tropsch synthesis iron-based catalyst and its preparation and application. The catalyst precursor prepared by spray forming is calcined in a tunnel kiln under air atmosphere at 400-600°C for 2-12 hours, preferably at 450-580°C for 3-6 hours. The catalyst prepared by the invention has high wear resistance index and can be directly used for slurry bed Fischer-Tropsch synthesis. However, the industrial tunnel kiln of the invention is a batch operation and cannot be operated continuously, and the cost of manpower, material resources and energy consumption is high.

[0005] Chinese patent document CN1260006C discloses a calcination method for slurry phase Fischer-Tropsch synthesis industrial iron-based catalyst. The spray-formed spherical iron-based catalyst is laid on the material conveying belt of a convective airflow belt dryer with a thickness of 20-100 mm, and by adjusting the inlet temperature, residence time of the heating section and constant temperature section of the dryer, and the outlet temperature and residence time of the cooling section, a calcined catalyst without screening can be directly used for industrial slurry phase Fischer-Tropsch synthesis. The catalyst calcined by the invention has a wear resistance index of less than 0.5%, and has the characteristics of continuous large-batch drying of materials, easy operation, less failure, and less equipment investment. However, when calcining microspherical catalysts, the thickness of the laid material is limited due to the limitation of heat conduction of the material layer, and the microspherical particles cannot be directly laid on the track, and need to be placed on a tray on the track, resulting in small processing capacity of a single device, and the material cannot be transported in a closed dense phase, the dust emission is too large, the environment is not friendly, the labor intensity of workers is high, and the heat, material and energy consumption are high.

[0006] Patent document WO1999049965A1 discloses a calcination method for slurry phase self-supporting precipitated small particle iron-based catalyst. The diameter of the catalyst particles is less than 45 microns, and the most accessible diameter distribution is 22 microns. A rotary kiln is used as a dryer, and the catalyst particles are in a moving state when they are dried in the rotary kiln dryer. The preferred calcination temperature is 250-500°C, and the residence time at the calcination temperature is at least 0.1 hour. One of the embodiments shows that the length of the device is 2.1 m, the diameter is 0.47 m, the inclination angle is 2°, and the rotation rate is 1 rpm. At a feeding speed of 30 kg / h, the residence time of the catalyst is 1 hour. The patent technology uses a single (stage) rotary kiln to dry and calcine the catalyst, and the residence time of the catalyst in the kiln is relatively short (from the data of the embodiments disclosed, the length / diameter ratio of the rotary furnace is only about 4.47), and the control of the temperature field and residence time of the catalyst in the furnace is not fine enough.

[0007] In summary, in addition to the deficiencies in process control during the roasting process, the existing industrial roasting process and technology also basically adopt the mode of hot air single-pass, tail gas direct discharge, etc., which is not energy-saving. Therefore, it is necessary to further improve the roasting device and process of industrial Fischer-Tropsch synthesis powder catalyst / catalyst precursor, so as to improve the performance of the roasted catalyst and reduce the loss rate, solve the problems of energy and energy waste, and achieve the purpose of energy saving and consumption reduction and carbon emission reduction. SUMMARY

[0008] In view of this, the present application provides a kind of industrial iron-based Fischer-Tropsch synthesis powder catalyst roasting method, the roasting method is simple in operation, energy saving and consumption reduction, the wear and tear of catalyst material during roasting process is low, and the iron-based powder catalyst after roasting treatment is used in slurry bed Fischer-Tropsch synthesis process, which can maintain excellent wear resistance while having superior Fischer-Tropsch synthesis reactivity, low Fe content in liquid / wax phase product filtered / separated from Fischer-Tropsch reactor.

[0009] In order to achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0010] A kind of industrial iron-based Fischer-Tropsch synthesis powder catalyst roasting method, comprising: using two-stage rotary furnace series roasting process to roasting treatment of the industrial iron-based Fischer-Tropsch synthesis powder catalyst precursor to be treated, to obtain the spherical powder iron-based catalyst after roasting;

[0011] In the two-stage rotary furnace series roasting process, the roasting device used includes: a first rotary furnace and a second rotary furnace, the first rotary furnace for low-temperature drying and roasting is connected in series with the second rotary furnace for high-temperature roasting to form a two-stage rotary furnace series device;

[0012] Among them,

[0013] The first rotary furnace and the second rotary furnace are both provided with a material outlet and a material inlet (for example, the ends of the first rotary furnace and the second rotary furnace are both provided with a material outlet, and the first ends of the first rotary furnace and the second rotary furnace are both provided with a material inlet); the material outlet of the first rotary furnace is connected with the material inlet of the second rotary furnace, and the material output by the material outlet of the first rotary furnace directly enters the second rotary furnace in a continuous manner through the material inlet of the second rotary furnace; the air volume extracted from the second rotary furnace directly enters the first rotary furnace in a reverse manner through the material outlet of the first rotary furnace, so that the material in the rotary furnace and the air volume form a convection; the hot air tail gas in the heating chamber of the second rotary furnace is used to transport fresh air to the furnace chamber of the second rotary furnace through the furnace chamber air inlet of the second rotary furnace after heat exchange.

[0014] According to the roasting method provided by the present application, in some embodiments, in the two-stage rotary furnace series roasting process,

[0015] The temperature control range of the first rotary furnace is 170-390℃ (for example, 180℃, 200℃, 250℃, 300℃, 350℃, 380℃), and the average residence time of the material is 2-12 hours (for example, 3 hours, 4 hours, 6 hours, 8 hours, 10 hours);

[0016] The temperature control range of the second rotary furnace is 480-720℃ (for example, 490℃, 500℃, 550℃, 600℃, 650℃, 700℃), and the average residence time of the material is 3-12 hours (for example, 4 hours, 5 hours, 6 hours, 8 hours, 10 hours).

[0017] In some embodiments, the structures and / or parameters of the first rotary furnace and the second rotary furnace are the same or different; preferably, the structures and / or parameters of the first rotary furnace and the second rotary furnace are the same.

[0018] In some embodiments, the structures and / or parameters of the first rotary furnace and the second rotary furnace each include:

[0019] The length / diameter ratio of the length L of the heating section of the furnace barrel to the inner diameter Φ of the furnace barrel satisfies L / Φ = 10-35 (for example, 11, 12, 14, 16, 20, 24, 28, 30, 34), preferably 13-25.

[0020] Further, to better illustrate the parameter characteristics of the calcination rotary furnace in the method of the present application, the data of the device in the example given in the patent document WO1999049965A1 are compared, as shown in Table 1. According to the parameters given in Example 1 of the patent document WO1999049965A1, the length / diameter ratio of the rotary furnace is 4.47 (while the length / diameter ratio of the rotary furnace defined in the present application is at least twice as large). According to this length / diameter ratio, the length of the rotary furnace in Example 1 of the patent document WO1999049965A1 should be 4.47 m when the diameter is 1 m. If the average residence time of the material in the furnace is 1 hour as given in the patent document, then the average residence time of the material in the rotary furnace of the present application is longer (for example, about 3.35 hours when L / Φ = 15) under the same conditions (such as the inclination angle, the rotation speed, the feeding amount, etc.). That is, compared with the rotary furnace in the patent document WO1999049965A1, the average residence time of the material in the rotary furnace of the present application can be prolonged by more than three times or more under the same conditions. In other words, when the processing scale of the calcination material is the same, the adjustment range of the residence time of the material in the furnace is too small when the calcination is performed according to the parameters given in the patent document WO1999049965A1, which can easily cause phenomena such as undercooking and overcooking in the calcination process.

[0021] Table 1 Comparison between rotary furnace parameters of the present application and existing patents

[0022]

[0023] furnace barrel rotation rate < 1 rpm (for example, rotation rate is 0.01 rpm, 0.05 rpm, 0.1 rpm, 0.2 rpm, 0.4 rpm, 0.6 rpm, 0.8 rpm, 0.9 rpm);

[0024] furnace body inclination angle < 2° (for example, inclination angle is 0°, 0.05°, 0.1°, 0.5°, 0.8°, 1°, 1.5°, 1.8°), preferably furnace body inclination angle < 1°.

[0025] In some embodiments, a flow guide groove is arranged in the furnace barrel of the primary rotary furnace and the secondary rotary furnace.

[0026] In some embodiments, the height H of the flow guide groove and the diameter / height ratio of the furnace barrel inner diameter Φ satisfy: Φ / H = 4-30 (for example, Φ / H is 5, 6, 8, 10, 12, 14, 18, 20, 25, 28), preferably 5-15.

[0027] A plurality of flow guide grooves can be arranged in the furnace barrel of the primary rotary furnace and the secondary rotary furnace.

[0028] In some embodiments, in the primary rotary furnace, the spacing of the flow guide grooves is set to enable the residence time of each unit mass of catalyst precursor in the furnace barrel heating section to be 2-12 hours (for example, 3 hours, 4 hours, 5 hours, 6 hours, 8 hours, 10 hours).

[0029] In some embodiments, in the secondary rotary furnace, the spacing of the flow guide grooves is set to enable the residence time of each unit mass of catalyst precursor in the furnace barrel heating section to be 3-12 hours (for example, 4 hours, 5 hours, 6 hours, 8 hours, 10 hours).

[0030] In some embodiments, in the primary rotary furnace, the spacing of the flow guide grooves is set to enable the residence time of each unit mass of catalyst precursor in the furnace barrel heating section to be 4-8 hours (for example, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours).

[0031] In some embodiments, in the secondary rotary furnace, the spacing of the flow guide grooves is set to enable the residence time of each unit mass of catalyst precursor in the furnace barrel heating section to be 4-8 hours (for example, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours).

[0032] In some embodiments, the temperature of the material in the furnace bucket of the first rotary furnace and the second rotary furnace is monitored by using a multi-point embedded temperature measurement method or a wireless temperature measurement monitoring method to realize real-time online monitoring of the temperature of the material in the furnace bucket. For example, the temperature of the material in the furnace bucket is monitored by using a four-point transversely uniformly distributed embedded thermocouple or a six-point transversely uniformly distributed embedded thermocouple. The monitoring device involved herein is a conventional device in the art, and the basic structure and monitoring operation thereof will not be described here.

[0033] In the method of the present application, the devices, components or equipment involved, such as the hopper screw feeder, the first rotary furnace, the second rotary furnace, etc., are all conventional devices in the art, and the basic structure and use thereof will not be described here.

[0034] In the present application, the inclination angle of the first rotary furnace and the second rotary furnace is set to be small (especially less than 1° or 0°), which can well prevent irregular positive displacement of the material during heat treatment in the rotary furnace, thereby avoiding the problem of inaccurate real-time material temperature monitoring caused thereby, and ensuring that the desired heat treatment effect can be achieved.

[0035] The first rotary furnace and the second rotary furnace are both provided with a flow guide groove, which can bring the following obvious benefits: ①It can avoid a series of disadvantages caused by using other internal setting methods (such as internal setting of a material lifting plate or a scoop plate), such as large up-and-down rolling amplitude of the catalyst material in the furnace bucket, breakage of spherical particles during calcination caused by impact of the material on the furnace wall, generation of irregularly shaped fine powder, increase in the amount of fine powder with small particle size (such as particle size < 30 μm or less), etc.; ②It can ensure that the catalyst material moves uniformly along the axial direction in the furnace bucket, thereby accurately ensuring the residence time of the material at the target heat treatment temperature in the furnace bucket, and ensuring that the desired heat treatment effect can be achieved.

[0036] By setting the structure and / or parameters of the first rotary furnace and the second rotary furnace, the present application can avoid the phenomena of "local over-temperature" and "under-cooking" of the catalyst material in the furnace body during calcination, improve the wear resistance of the catalyst after calcination and the yield of qualified products, and thereby ensure that the catalyst exhibits excellent reaction performance in the Fischer-Tropsch synthesis reaction.

[0037] In some embodiments, the calcination device further comprises a hopper screw feeder, and the feeding amount of the catalyst precursor is adjusted to be 0.1-1.3 t / h (for example, 0.2 t / h, 0.4 t / h, 0.8 t / h, 1.0 t / h, 1.1 t / h) by adjusting the hopper screw feeder. For example, the catalyst precursor to be treated is continuously input into the rotary furnace series device through the material inlet of the first rotary furnace by the hopper screw feeder.

[0038] In the present application, the roasting device used in the two-stage rotary furnace series roasting process is composed of a series of primary rotary furnace and secondary rotary furnace; wherein the primary rotary furnace is used for low-temperature drying and roasting, and the secondary rotary furnace is used for high-temperature roasting. The series connection mode of the primary rotary furnace and the secondary rotary furnace not only enables the continuous direct conveying of the material in the two-stage rotary furnace, but also enables the convection of the material and the air volume in the furnace body through the design and adjustment of the inlet and outlet modes. The design has the following advantages:

[0039] 1) From the perspective of process engineering: Since the primary rotary furnace and the secondary rotary furnace are two separate rotary furnaces, the process operations such as feeding and discharging, temperature rising and falling can be controlled respectively, ensuring flexible and accurate control of process conditions, and overcoming the defect that the single furnace length is too long to cause deformation during operation to meet the process requirements;

[0040] 2) From the perspective of product performance: By selecting and regulating the temperature control range and the average residence time of the material in the primary rotary furnace and the secondary rotary furnace, the temperature control range and the residence time combined with the two-stage series process and precise temperature control operation can accurately control the material temperature, realize ideal dehydration and crystal transformation of the material during roasting, and greatly strengthen the skeleton strength of the industrial scale production of the catalyst product after roasting;

[0041] 3) From the perspective of energy saving and emission reduction: The exhaust air of the secondary rotary furnace is directly reversed into the primary rotary furnace with residual heat, which can greatly reduce the heating load of the primary rotary furnace, and combined with the recycling of the exhaust heat energy in the heating chamber of the secondary rotary furnace, the energy consumption such as natural gas consumption can be greatly reduced, thereby realizing energy saving and emission reduction.

[0042] The roasting method of the industrial iron-based Fischer-Tropsch synthesis powder catalyst in the present application has the characteristics of low investment, low operating cost, energy saving and environmental friendly, and is suitable for large-scale industrial production of catalyst.

[0043] If the attrition resistance of the iron-based catalyst product after the calcination treatment is poor, a large amount of fine powder (such as particles with a particle size of <30 microns) will be produced due to crushing during the Fischer-Tropsch synthesis reaction, causing serious wall sticking on the filter, and further causing a series of engineering problems such as difficulty in separating the Fischer-Tropsch synthesis wax oil product from the catalyst, filter clogging, and high Fe content in the liquid / wax phase product filtered / separated from the reactor. The method of the present application can ensure that the loss of fine powder due to attrition between particles during calcination is reduced, and the qualified rate of spherical particles with a particle size of >30 microns is >99% when the iron-based Fischer-Tropsch synthesis powder catalyst is calcined. At the same time, the iron-based catalyst has superior Fischer-Tropsch synthesis reaction performance and excellent chemical attrition resistance when used in a Fischer-Tropsch synthesis slurry bed reactor, and the Fe content of the impurities in the obtained Fischer-Tropsch synthesis product is greatly reduced. DETAILED DESCRIPTION

[0044] In order to enable a detailed understanding of the technical features and content of the present application, the preferred embodiments of the present application will be described in more detail below. Although the preferred embodiments of the present application are described in the examples, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments described herein.

[0045] In this paper, the material to be treated before calcination is referred to as "catalyst precursor", and the material obtained after calcination can be referred to as a catalyst (although strictly speaking, the material obtained after calcination does not exhibit Fischer-Tropsch reaction activity until it is reduced, but here it is only used to refer to the material before and after calcination, and is not used to limit its use and function), and the catalyst after the calcination treatment can be directly added to the reduction reactor of the Fischer-Tropsch synthesis process.

[0046] The following examples and comparative examples use the following analysis test methods:

[0047] 1. Attrition index of spherical powder iron-based catalyst: the test sample is tested by using the ASTM D5757-11 air jet cup attrition index determination method.

[0048] 2. Specific surface area and pore volume of spherical powder iron-based catalyst: the test sample is determined by low-temperature nitrogen adsorption method, and the specific surface area is the BET specific surface area.

[0049] 3. Particle size distribution of spherical powder iron-based catalyst: determined by a laser particle size instrument.

[0050] 4. Fe content in the liquid phase product after Fischer-Tropsch synthesis reaction: determined by inductively coupled plasma spectrometer ICP.

[0051] 5. The attrition rate (also known as the running loss rate or chemical attrition value) of the spherical powder iron-based catalyst under Fischer-Tropsch reaction conditions: The technical solution disclosed in patent document CN112414995A (A method for measuring the attrition rate of a catalyst) is referred to for determination.

[0052] 6. The slurry phase Fischer-Tropsch synthesis reaction performance of the calcined spherical powder iron-based catalyst:

[0053] The Fischer-Tropsch synthesis reaction performance of the sample to be tested is evaluated on a 2L stirred tank slurry bed device in the laboratory; the number of moles of CO in the feed is determined and analyzed at the feed inlet of the Fischer-Tropsch synthesis reactor, and the number of moles of CO in the outfeed is determined and analyzed at the reactor outlet, and the following formula is used for calculation:

[0054] CO conversion rate % = (number of moles of CO in the feed - number of moles of CO in the outfeed) / (number of moles of CO in the feed) x 100%;

[0055] The sources of the raw materials used in the following examples and comparative examples are as follows:

[0056] The industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is prepared by the currently more typical traditional parallel flow continuous co-precipitation method combined with spray drying molding technology. The specific preparation process can be referred to the literature including but not limited to: Quan Lin et al, Development of an Iron-Based Fischer-Tropsch Catalyst with High Attrition Resistance and Stability for Industrial Application. Catalysts, 2021, 11, 908. and Changhai et al, Influence of Process Parameters of Binder Introduction on the Performance of Precipitated Iron-Based Fischer-Tropsch Synthesis Catalyst [J]. Journal of Coal, 2021, 46(10): 3350-3356.

[0057] Example 1

[0058] The calcination method is as follows: the industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is transported to a calcination device, and a two-stage rotary furnace series calcination process is used for calcination treatment.

[0059] The used calcination device comprises: a hopper screw feeder, a first rotary furnace, and a second rotary furnace, the first rotary furnace for low-temperature drying and calcination is connected in series with the second rotary furnace for high-temperature calcination, and a device of two-stage rotary furnace series connection is formed. The two rotary furnaces are connected in series as follows: the end of the first rotary furnace and the end of the second rotary furnace are both provided with a material outlet, and the first end of the first rotary furnace and the first end of the second rotary furnace are both provided with a material inlet; the material outlet of the first rotary furnace is connected with the material inlet of the second rotary furnace, and the material output by the material outlet of the first rotary furnace directly enters the second rotary furnace in a continuous manner through the material inlet of the second rotary furnace; the air volume of the air extraction in the second rotary furnace directly enters the first rotary furnace in a reverse manner through the material outlet of the first rotary furnace, so that the material in the rotary furnace and the air volume form a convection; the hot air tail gas in the heating chamber of the second rotary furnace is sent to the furnace chamber of the second rotary furnace through the air inlet of the furnace chamber of the second rotary furnace after heat exchange, so as to realize heat recycling. The hopper screw feeder is used to continuously convey the industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated to the material inlet of the first rotary furnace.

[0060] The structural parameters of the first rotary furnace and the second rotary furnace are basically the same, and the structural parameters are as follows:

[0061] The length L of the furnace barrel heating section is 15 m, and the inner diameter Φ of the furnace barrel is 1 m.

[0062] The rotation rate of the furnace barrel is 0.5 rpm.

[0063] The inclination angle of the furnace body is 0.0°.

[0064] A flow guide groove is arranged in the furnace barrel, and the height H of the flow guide groove is 0.08 m.

[0065] The temperature of the material in the furnace barrel is measured by using four-point transverse uniform distribution embedded thermocouples.

[0066] The hopper screw feeder is adjusted to control the feeding amount of the catalyst precursor to be 0.4 t / h.

[0067] In the two-stage rotary furnace series calcination process, the average temperature of the dried and calcined material in the first rotary furnace is controlled to be 205℃, and the time for the material to be fed from the furnace inlet to the furnace outlet is 7 hours; the material outlet of the first rotary furnace is directly connected with the material inlet of the second rotary furnace through a heat preservation pipeline, so that the material output by the first rotary furnace is directly heat preserved and enters the second rotary furnace; the average temperature of the material in the calcination furnace of the second rotary furnace is controlled to be 575℃, and the time for the material to be fed from the furnace inlet to the furnace outlet is 4.5 hours by adjusting the rotation rate.

[0068] After the material is roasted, it is directly dropped into a receiving tank through a pipeline after a two-stage rotary furnace cooling section, to obtain a roasted iron-based spherical catalyst which can be directly used in an industrial slurry-phase Fischer-Tropsch synthesis reactor without screening, and is numbered as FTC-A.

[0069] The structure and performance indicators of the obtained FTC-A material after roasting are shown in Tables 2 and 3. The Fischer-Tropsch synthesis reaction performance evaluation results are shown in Table 4.

[0070] Example 2

[0071] The roasting method is as follows: the industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is conveyed to a roasting device, and a two-stage rotary furnace series roasting process is used for roasting treatment.

[0072] The roasting device used includes a hopper screw feeder, a first-stage rotary furnace and a second-stage rotary furnace. The first-stage rotary furnace for low-temperature drying and roasting and the second-stage rotary furnace for high-temperature roasting are connected in series to form a two-stage rotary furnace series device. In the two-stage rotary furnace series connection mode, the ends of the first-stage rotary furnace and the second-stage rotary furnace are each provided with a material outlet, and the first ends of the first-stage rotary furnace and the second-stage rotary furnace are each provided with a material inlet. The material outlet of the first-stage rotary furnace is connected to the material inlet of the second-stage rotary furnace, and the material output from the material outlet of the first-stage rotary furnace directly enters the second-stage rotary furnace through the material inlet of the second-stage rotary furnace in a continuous manner. The air volume drawn from the second-stage rotary furnace directly enters the first-stage rotary furnace in a reverse direction through the material outlet of the first-stage rotary furnace, so that the material in the rotary furnace and the air volume form a convection. The hot air tail gas in the heating chamber of the second-stage rotary furnace is used to convey fresh air to the furnace chamber of the second-stage rotary furnace through the furnace inlet of the second-stage rotary furnace after heat exchange, to realize the recycling of heat energy. The industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is continuously conveyed to the material inlet of the first-stage rotary furnace by the hopper screw feeder.

[0073] The structural parameters of the first-stage rotary furnace and the second-stage rotary furnace are basically the same, and the structural parameters are as follows:

[0074] The length L of the furnace barrel heating section is 18 m, and the inner diameter Φ of the furnace barrel is 1 m.

[0075] The rotation rate of the furnace barrel is 0.3 rpm.

[0076] The inclination angle of the furnace body is 0.5°.

[0077] A flow guide groove is arranged in the furnace barrel, and the height H of the flow guide groove is 0.12 m.

[0078] The inner material temperature of the furnace barrel is measured by four-point transverse uniform distribution embedded thermocouples.

[0079] The feeding amount of the catalyst precursor is controlled to be 0.6 t / h by adjusting the hopper screw feeder.

[0080] In the two-stage rotary furnace series roasting process, the average temperature of the dry roasting material in the first-stage rotary furnace is controlled to be 285℃, and the material is fed from the furnace mouth to the furnace tail in 5 hours; the material outlet of the first-stage rotary furnace is directly connected to the material inlet of the second-stage rotary furnace through an insulation pipeline, so that the material output from the first-stage rotary furnace is directly insulated and enters the second-stage rotary furnace; the average temperature of the roasting material in the second-stage rotary furnace is controlled to be 535℃, and the feeding time of the material from the furnace mouth to the furnace tail is controlled to be 6.5 hours by adjusting the rotation rate.

[0081] After the material is roasted, it directly falls into the receiving tank through the conveying pipeline of the cooling section of the second-stage rotary furnace, and the roasted iron-based spherical catalyst without screening can be directly used in the industrial slurry-phase Fischer-Tropsch synthesis reactor, which is numbered as FTC-B.

[0082] The structure and performance indicators of the FTC-B material after roasting are shown in Tables 2 and 3. The Fischer-Tropsch synthesis reaction performance evaluation results are shown in Table 4.

[0083] Example 3

[0084] The roasting method is as follows: the industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is conveyed to a roasting device, and a two-stage rotary furnace series roasting process is used for roasting treatment.

[0085] The roasting device used includes a hopper screw feeder, a first-stage rotary furnace, and a second-stage rotary furnace. The first-stage rotary furnace for low-temperature drying and roasting is connected in series with the second-stage rotary furnace for high-temperature roasting to form a two-stage rotary furnace series device. The two-stage rotary furnace series device has the following structure: the ends of the first-stage rotary furnace and the second-stage rotary furnace are both provided with material outlets, and the first ends of the first-stage rotary furnace and the second-stage rotary furnace are both provided with material inlets; the material outlet of the first-stage rotary furnace is connected to the material inlet of the second-stage rotary furnace, and the material output from the material outlet of the first-stage rotary furnace directly enters the second-stage rotary furnace through the material inlet of the second-stage rotary furnace in a continuous manner; the air volume drawn from the second-stage rotary furnace directly enters the first-stage rotary furnace in a reverse direction through the material outlet of the first-stage rotary furnace, so that the material in the rotary furnace and the air volume form a convection; the hot air tail gas in the heating chamber of the second-stage rotary furnace is heat-exchanged to convey fresh air to the furnace chamber of the second-stage rotary furnace through the air inlet of the furnace chamber of the second-stage rotary furnace, thereby realizing the recycling of heat energy. The industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is continuously conveyed to the material inlet of the first-stage rotary furnace through the hopper screw feeder.

[0086] The structure parameters of the first-stage rotary furnace and the second-stage rotary furnace are basically the same, and the structure parameters are as follows:

[0087] Length of heating section of furnace shell L: 15 m, inner diameter of furnace shell Φ: 1 m;

[0088] Rotary speed of furnace shell: 0.5 rpm;

[0089] Inclination angle of furnace body: 0.0°;

[0090] A flow guide groove is arranged in the furnace shell, and the height H of the flow guide groove is 0.08 m;

[0091] The temperature of the material in the furnace shell is measured by using four point transversely uniformly distributed embedded thermocouples.

[0092] The feeding amount of the catalyst precursor is controlled to be 0.25 t / h by adjusting the screw feeder of the hopper.

[0093] In the two-stage rotary furnace series roasting process, the average temperature of the dry roasting material in the first-stage rotary furnace is controlled to be 185℃, and the time for the material to be fed from the furnace mouth to be discharged from the furnace tail is 10 hours; the material outlet of the first-stage rotary furnace is directly connected to the material inlet of the second-stage rotary furnace by using a heat preservation pipeline, so that the material output from the first-stage rotary furnace is directly heat preserved and enters the second-stage rotary furnace; the average temperature of the roasting material in the second-stage rotary furnace is controlled to be 485℃, and the time for the material to be fed from the furnace mouth to be discharged from the furnace tail is 8 hours by adjusting the rotary speed.

[0094] After the material is roasted, it is directly dropped into a receiving tank after passing through the conveying pipeline of the cooling section of the second-stage rotary furnace, and an iron-based spherical catalyst after roasting, which can be directly used in an industrial slurry-phase Fischer-Tropsch synthesis reactor without screening, is obtained, and the number of the catalyst is FTC-C.

[0095] The structure and performance indexes of the obtained FTC-C material after roasting are shown in Tables 2 and 3, and the Fischer-Tropsch synthesis reaction performance evaluation results are shown in Table 4.

[0096] Example 4

[0097] The roasting method is as follows: the industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is conveyed to a roasting device, and a two-stage rotary furnace series roasting process is used for roasting treatment.

[0098] The roasting device used comprises: a hopper screw feeder, a first rotary furnace, and a second rotary furnace, the first rotary furnace for low-temperature drying and roasting is connected in series with the second rotary furnace for high-temperature roasting to form a device with two rotary furnaces connected in series. The two rotary furnaces are connected in series as follows: the ends of the first rotary furnace and the second rotary furnace are both provided with material outlets, and the first ends of the first rotary furnace and the second rotary furnace are both provided with material inlets; the material outlet of the first rotary furnace is connected with the material inlet of the second rotary furnace, and the material output by the material outlet of the first rotary furnace directly enters the second rotary furnace in a continuous manner through the material inlet of the second rotary furnace; the air volume drawn from the second rotary furnace directly enters the first rotary furnace in a reverse manner through the material outlet of the first rotary furnace, so that the material in the rotary furnace and the air volume form a convection; the hot air tail gas in the heating chamber of the second rotary furnace is used to transport fresh air to the furnace chamber of the second rotary furnace through the air inlet of the furnace chamber of the second rotary furnace after heat exchange, so as to realize the recycling of heat energy. The hopper screw feeder is used to continuously transport the industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated to the material inlet of the first rotary furnace.

[0099] The structural parameters of the first rotary furnace and the second rotary furnace are basically the same, and the structural parameters are as follows:

[0100] The length L of the furnace barrel heating section is 18 m, and the inner diameter Φ of the furnace barrel is 1 m.

[0101] The rotation rate of the furnace barrel is 0.3 rpm.

[0102] The inclination angle of the furnace body is 0.5°.

[0103] A flow guide groove is arranged in the furnace barrel, and the height H of the flow guide groove is 0.12 m.

[0104] The temperature of the material in the furnace barrel is measured by using four point transverse uniform distribution embedded thermocouples.

[0105] The hopper screw feeder is adjusted to control the feeding amount of the catalyst precursor to be 0.8 t / h.

[0106] In the two-stage rotary furnace series roasting process, the average temperature of the dry roasting material in the first rotary furnace is controlled to be 315℃, and the time for the material to be fed from the furnace inlet to the furnace outlet is 5 hours; the material outlet of the first rotary furnace is directly connected with the material inlet of the second rotary furnace through a heat preservation pipeline, so that the material output by the first rotary furnace is directly heat preserved and enters the second rotary furnace; the average temperature of the material in the roasting furnace of the second rotary furnace is controlled to be 675℃, and the time for the material to be fed from the furnace inlet to the furnace outlet is 3 hours by adjusting the rotation rate.

[0107] After the material is roasted, it is directly dropped into a receiving tank through a pipeline after a two-stage rotary furnace cooling section, to obtain a roasted iron-based spherical catalyst which can be directly used in an industrial slurry-phase Fischer-Tropsch synthesis reactor without screening, and is numbered as FTC-D.

[0108] The structure and performance indicators of the obtained FTC-D material after roasting are shown in Tables 2 and 3. The Fischer-Tropsch synthesis reaction performance evaluation results are shown in Table 4.

[0109] Example 5

[0110] The roasting method is as follows: the industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is conveyed to a roasting device, and a two-stage rotary furnace series roasting process is used for roasting treatment.

[0111] The roasting device used includes a hopper screw feeder, a first-stage rotary furnace and a second-stage rotary furnace. The first-stage rotary furnace for low-temperature drying and roasting and the second-stage rotary furnace for high-temperature roasting are connected in series to form a two-stage rotary furnace series device. In the two-stage rotary furnace series connection mode, the ends of the first-stage rotary furnace and the second-stage rotary furnace are each provided with a material outlet, and the first ends of the first-stage rotary furnace and the second-stage rotary furnace are each provided with a material inlet. The material outlet of the first-stage rotary furnace is connected to the material inlet of the second-stage rotary furnace, and the material output from the material outlet of the first-stage rotary furnace directly enters the second-stage rotary furnace in a continuous manner through the material inlet of the second-stage rotary furnace. The air volume drawn from the second-stage rotary furnace directly enters the first-stage rotary furnace in a reverse manner through the material outlet of the first-stage rotary furnace, so that the material in the rotary furnace and the air volume form a convection. The hot air tail gas in the heating chamber of the second-stage rotary furnace is used to convey fresh air to the furnace chamber of the second-stage rotary furnace through the furnace inlet of the second-stage rotary furnace after heat exchange, to realize the recycling of heat energy. The industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is continuously conveyed to the material inlet of the first-stage rotary furnace by the hopper screw feeder.

[0112] The structural parameters of the first-stage rotary furnace and the second-stage rotary furnace are basically the same, and the structural parameters are as follows:

[0113] The length L of the furnace barrel heating section is 20 m, and the inner diameter Φ of the furnace barrel is 1.5 m.

[0114] The rotation rate of the furnace barrel is 0.5 rpm.

[0115] The inclination angle of the furnace body is 0.0°.

[0116] A flow guide groove is arranged in the furnace barrel, and the height H of the flow guide groove is 0.12 m.

[0117] The internal temperature of the furnace barrel is measured by using six horizontally distributed embedded thermocouples.

[0118] The feeding amount of the catalyst precursor is controlled to be 0.55 t / h by adjusting the hopper screw feeder.

[0119] In the two-stage rotary furnace series roasting process, the average temperature of the dry roasting material in the first-stage rotary furnace is controlled to be 275°C, and the time for the material to be fed from the furnace mouth to be discharged from the furnace tail is 11 hours; the material outlet of the first-stage rotary furnace is directly connected to the material inlet of the second-stage rotary furnace through an insulation pipeline, so that the material output from the first-stage rotary furnace is directly insulated and enters the second-stage rotary furnace; the average temperature of the roasting material in the second-stage rotary furnace is controlled to be 585°C, and the time for the material to be fed from the furnace mouth to be discharged from the furnace tail is controlled to be 3.5 hours by adjusting the rotation rate.

[0120] After the material is roasted, it directly falls into a receiving tank through the conveying pipeline of the cooling section of the second-stage rotary furnace, and an iron-based spherical catalyst after roasting, which can be directly used in an industrial slurry-phase Fischer-Tropsch synthesis reactor without screening, is obtained, and is numbered as FTC-E.

[0121] The structure and performance indexes of the FTC-E material after roasting are shown in Tables 2 and 3. The Fischer-Tropsch synthesis reaction performance evaluation results are shown in Table 4.

[0122] Example 6

[0123] The roasting method is as follows: the industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is conveyed to a roasting device, and a two-stage rotary furnace series roasting process is used for roasting treatment.

[0124] The roasting device used includes a hopper screw feeder, a first-stage rotary furnace and a second-stage rotary furnace, the first-stage rotary furnace for low-temperature drying and roasting is connected in series with the second-stage rotary furnace for high-temperature roasting to form a two-stage rotary furnace series device. In the two-stage rotary furnace series device, the ends of the first-stage rotary furnace and the second-stage rotary furnace are both provided with material outlets, and the first ends of the first-stage rotary furnace and the second-stage rotary furnace are both provided with material inlets; the material outlet of the first-stage rotary furnace is connected to the material inlet of the second-stage rotary furnace, and the material output from the material outlet of the first-stage rotary furnace directly enters the second-stage rotary furnace through the material inlet of the second-stage rotary furnace in a continuous manner; the air volume drawn from the second-stage rotary furnace directly enters the first-stage rotary furnace in a reverse direction through the material outlet of the first-stage rotary furnace, so that the material in the rotary furnace and the air volume form a convection; the hot air tail gas in the heating chamber of the second-stage rotary furnace is used to convey fresh air to the furnace chamber of the second-stage rotary furnace through the air inlet of the furnace chamber of the second-stage rotary furnace after heat exchange, so as to realize heat recycling. The industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is continuously conveyed to the material inlet of the first-stage rotary furnace through the hopper screw feeder.

[0125] The structural parameters of the first-stage rotary furnace and the second-stage rotary furnace are basically the same, and the structural parameters are as follows:

[0126] Length of heating section of furnace L: 15m, inner diameter of furnace Φ: 1m;

[0127] Rotary speed of furnace: 0.5rpm;

[0128] Inclination angle of furnace: 0.5°;

[0129] A guide groove is arranged in the furnace, and the height of the guide groove H: 0.08m;

[0130] The temperature of the material in the furnace is measured by four point transversely distributed embedded thermocouples.

[0131] The feeding amount of the catalyst precursor is controlled to be 0.4t / h by adjusting the screw feeder of the hopper.

[0132] In the two-stage rotary furnace series roasting process, the average temperature of the dry roasting material in the first-stage rotary furnace is controlled to be 205℃, and the time for the material to be fed from the furnace mouth to the furnace tail is 7 hours; the material outlet of the first-stage rotary furnace is directly connected to the material inlet of the second-stage rotary furnace through a heat preservation pipeline, so that the material output from the first-stage rotary furnace is directly heat preserved and enters the second-stage rotary furnace; the average temperature of the material in the roasting furnace of the second-stage rotary furnace is controlled to be 645℃, and the time for the material to be fed from the furnace mouth to the furnace tail is controlled to be 3.5 hours by adjusting the rotary speed.

[0133] After the material is roasted, it is directly dropped into a receiving tank through the conveying pipeline of the cooling section of the second-stage rotary furnace, and an iron-based spherical catalyst after roasting, which is numbered as FTC-F, is obtained, which can be directly used in an industrial slurry phase Fischer-Tropsch synthesis reactor without screening.

[0134] The structure and performance indexes of the FTC-F material after roasting are shown in Tables 2 and 3, and the Fischer-Tropsch synthesis reaction performance evaluation results are shown in Table 4.

[0135] Comparative Example 1

[0136] The roasting method is as follows: the industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is conveyed to a roasting device for roasting treatment.

[0137] The roasting device used includes a hopper screw feeder, a low-temperature rotary furnace, and a high-temperature rotary furnace.

[0138] The industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is continuously fed into the material inlet of the low-temperature rotary furnace by a hopper screw feeder. The average temperature of the dry roasting atmosphere in the low-temperature rotary furnace is controlled at 225°C, and the material is fed from the furnace inlet to the furnace outlet in 6 hours. After the material is dried, it is directly dropped into a receiving tank through the cooling section conveying pipeline of the low-temperature rotary furnace. Then, the material in the receiving tank is transferred into the feeding machine of another high-temperature rotary furnace and fed into the material inlet of the high-temperature rotary furnace by a hopper screw feeder. The average temperature of the roasting furnace atmosphere in the high-temperature rotary furnace is controlled at 605°C, and the material is fed from the furnace inlet to the furnace outlet in 4 hours by adjusting the rotation rate. The hot air exhaust gas from the heating chamber of the two rotary furnaces is respectively discharged after being treated in the exhaust gas treatment system.

[0139] After the material is roasted, it is directly dropped into the receiving tank of the high-temperature rotary furnace through the cooling section conveying pipeline of the high-temperature rotary furnace, and then sieved by a screening machine to obtain the roasted industrial slurry-phase Fischer-Tropsch synthesis reactor iron-based spherical catalyst, numbered as DFT-A.

[0140] The structural parameters of the low-temperature rotary furnace and the high-temperature rotary furnace are basically the same, and the structural parameters are as follows:

[0141] The length L of the heating section of the furnace barrel is 12 m, and the inner diameter Φ of the furnace barrel is 1 m;

[0142] The rotation rate of the furnace barrel is 2 rpm;

[0143] The inclination angle of the furnace body is 3°;

[0144] A lifting baffle is arranged in the furnace barrel, and the height H of the baffle is 0.04 m;

[0145] A thermocouple is arranged in the furnace barrel to measure the atmosphere temperature in the furnace barrel.

[0146] The feeding amount of the catalyst precursor is controlled at 0.4 t / h by adjusting the hopper screw feeder.

[0147] The structure and performance indicators of the obtained DFT-A material after roasting are shown in Tables 2 and 3. The Fischer-Tropsch synthesis reaction performance evaluation results are shown in Table 4.

[0148] Comparative Example 2

[0149] The roasting method is as follows: the industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is fed into a roasting device.

[0150] The roasting device used includes a hopper screw feeder, a low-temperature rotary furnace, and a high-temperature rotary furnace.

[0151] The industrial spherical powder Fe / Cu / K / SiO2 catalyst precursor to be treated is continuously fed into the material inlet of the low-temperature rotary furnace by a hopper screw feeder. The average temperature of the dry roasting atmosphere in the low-temperature rotary furnace is controlled at 285℃, and the material is fed from the furnace inlet to the furnace outlet in 3 hours. After the material is dried, it is directly dropped into a receiving tank through the low-temperature rotary furnace cooling section conveying pipeline. Then, the material in the receiving tank is transferred into the feeding machine of another high-temperature rotary furnace and is fed into the material inlet of the high-temperature rotary furnace by a hopper screw feeder. The average temperature of the roasting atmosphere in the high-temperature rotary furnace is controlled at 575℃, and the material is fed from the furnace inlet to the furnace outlet in 7 hours by adjusting the rotation rate. The hot air exhaust gas of the natural gas combustion in the heating chamber of the two rotary furnaces is respectively discharged after entering the exhaust gas treatment system.

[0152] After the material is roasted, it is directly dropped into the receiving tank of the high-temperature rotary furnace through the high-temperature rotary furnace cooling section conveying pipeline, and then is sieved by a screening machine to obtain the roasted industrial slurry-phase Fischer-Tropsch synthesis reactor iron-based spherical catalyst, numbered as DFT-B.

[0153] The structural parameters of the low-temperature rotary furnace and the high-temperature rotary furnace are basically the same, and the structural parameters of the low-temperature rotary furnace and the high-temperature rotary furnace are as follows:

[0154] The length L of the furnace barrel heating section is 12m, and the inner diameter Φ of the furnace barrel is 1m;

[0155] The rotation rate of the furnace barrel is 2rpm;

[0156] The inclination angle of the furnace body is 3°;

[0157] A lifting baffle is arranged in the furnace barrel, and the height H of the baffle is 0.04m;

[0158] A thermocouple is arranged in the furnace barrel to measure the atmosphere temperature in the furnace barrel.

[0159] The feeding amount of the catalyst precursor is controlled at 0.6t / h by adjusting the hopper screw feeder.

[0160] The structure and performance indicators of the obtained DFT-B material after roasting are shown in Table 2 and Table 3. The Fischer-Tropsch synthesis reaction performance evaluation results are shown in Table 4.

[0161] Table 2: Performance data of the catalyst after roasting obtained in each example and comparative example

[0162]

[0163]

[0164] Table 3: Particle size and qualified product yield of the catalyst after roasting obtained in each example and comparative example

[0165]

[0166] The calcined iron-based spherical catalysts obtained in each of the above examples and comparative examples were used in Fischer-Tropsch synthesis reaction. The Fischer-Tropsch synthesis reaction process and its operating conditions are as follows:

[0167] The evaluation device was a laboratory 2L slurry bed continuous stirred tank reactor;

[0168] The evaluation conditions were: 270°C, 2.5 MPa;

[0169] The space velocity of the synthesis gas in the reactor was 8000 mL / g-cat. / h, and the hydrogen-carbon ratio was 2.5.

[0170] Catalyst loading and test: 20 g of the calcined iron-based spherical catalyst was placed in 750 g of commercial liquid paraffin, and then the mixture was loaded into the slurry bed reactor; then, the catalyst was pre-reduced in the reactor with synthesis gas (H2 / CO = 5.0) at 270°C under normal pressure for 24 hours; then, the temperature and pressure were lowered and raised to the above reaction conditions, respectively, and the evaluation test was started, and the evaluation operation time was 700 hours each time.

[0171] Treatment and analysis of the liquid phase product obtained after the evaluation reaction: after the evaluation reaction was completed each time, the reactor system was cooled to 140°C, the pressure was reduced to normal pressure, and after the stirring was stopped, the reactor vessel containing the slurry was quickly placed in a dry box at 140°C.

[0172] 1) After constant temperature standing and settling for 1.0 hour, about 10 g of the liquid phase sample was taken from the upper layer, and the Fe content therein was analyzed by inductively coupled plasma spectrometer (ICP);

[0173] 2) The remaining entire slurry was filtered using a filter membrane with a filter hole aperture of 20 μm to obtain a solid phase, and the obtained solid phase was dried; the weight of the powder equal to or greater than 20 μm in the dried product was measured, and the weight of the powder less than 20 μm was obtained by subtracting the weight of the powder equal to or greater than 20 μm from half of the total weight of the used catalyst.

[0174] The reaction performance data of the Fischer-Tropsch synthesis reaction are shown in Table 4.

[0175] Table 4 Evaluation results of the slurry bed Fischer-Tropsch synthesis reaction of each calcined catalyst

[0176]

[0177]

[0178] From the data of each of the above examples, comparative examples, and Tables 2, 3 and 4, it can be seen that:

[0179] Compared with Comparative Example 1-2, the structure of the catalyst obtained by the calcination method of the present application is more reasonable, for example, the pore volume does not decrease. The pore volume of the catalyst calcined in the comparative example decreases more seriously, which will greatly affect the performance of the Fischer-Tropsch synthesis reaction.

[0180] Under the same abrasion test conditions, the catalysts obtained by the calcination method of the present application (Examples 1-6) have a significantly lower abrasion index, indicating that the catalyst has a higher physical abrasion resistance. At the same time, it also has superior chemical abrasion resistance, which can ensure that the content of the lost catalyst component Fe in the Fischer-Tropsch synthesis product is very low when the catalyst is used for Fischer-Tropsch synthesis reaction. The obtained catalyst has a very strong chemical abrasion resistance, and the effect is particularly obvious after testing according to the actual slurry state bed reactor method which is harsh in abrasion conditions. This is because, in the actual slurry state bed reactor, due to the influence of the heat effect of the catalytic reaction, chemical abrasion will occur to the catalyst, and the degree of chemical abrasion of the slurry state bed Fischer-Tropsch synthesis catalyst is more harsh.

[0181] Under the same slurry phase Fischer-Tropsch synthesis reaction evaluation process conditions, after the same long period of Fischer-Tropsch synthesis reaction process, the catalysts obtained by the present application (Examples 1-6) have higher activity. In addition, under the same evaluation test conditions, the content of impurity Fe in the liquid phase product obtained after the Fischer-Tropsch synthesis reaction of the catalysts obtained by the present application is significantly lower than that of the catalysts obtained by the comparative examples.

[0182] Therefore, it is shown that the catalyst treated by the calcination method provided by the present application has better abrasion resistance, higher synthesis reaction activity, and the obtained Fischer-Tropsch synthesis target product has higher purity.

[0183] The above has described various embodiments of the present application, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the spirit of the present application.

Claims

1. A method of calcination of an industrial iron-based Fischer-Tropsch synthesis powder catalyst precursor, characterized in that, The application relates to a two-stage rotary furnace series roasting process for roasting an industrial iron-based Fischer-Tropsch synthesis powder catalyst precursor. In the two-stage rotary furnace series roasting process, the roasting device comprises a first-stage rotary furnace and a second-stage rotary furnace, the first-stage rotary furnace for low-temperature drying and roasting is connected in series with the second-stage rotary furnace for high-temperature roasting to form a two-stage rotary furnace series device. The first-stage rotary furnace and the second-stage rotary furnace are both provided with a material outlet and a material inlet; the material outlet of the first-stage rotary furnace is connected with the material inlet of the second-stage rotary furnace, and the material output from the material outlet of the first-stage rotary furnace directly enters the second-stage rotary furnace in a continuous manner through the material inlet of the second-stage rotary furnace; the air volume of the air extraction in the second-stage rotary furnace directly enters the first-stage rotary furnace in a reverse manner through the material outlet of the first-stage rotary furnace, so that the material in the rotary furnace and the air volume form a convection; the hot air tail gas in the heating chamber of the second-stage rotary furnace is used to transport fresh air to the furnace chamber of the second-stage rotary furnace through the air inlet of the furnace chamber of the second-stage rotary furnace after heat exchange. The structure and parameters of the first-stage rotary furnace and the second-stage rotary furnace both comprise: The length / diameter ratio of the length L of the furnace barrel heating section to the inner diameter Phi of the furnace barrel satisfies L / Phi=10~35; The rotary rotation rate of the furnace barrel is less than 1 rpm; The inclination angle of the furnace body is less than 2 degrees; The height H of the guide groove and the diameter / high ratio of the inner diameter Phi of the furnace barrel satisfy Phi / H=4~30. In the two-stage rotary furnace series roasting process, The material temperature control range of the first-stage rotary furnace is 170~390 DEG C, and the average material residence time is 2~12 hours; The material temperature control range of the second-stage rotary furnace is 480~720 DEG C, and the average material residence time is 3~12 hours. The structure and parameters of the first-stage rotary furnace and the second-stage rotary furnace are the same or different. The structure and parameters of the first-stage rotary furnace and the second-stage rotary furnace both comprise:

2. The firing method according to claim 1, characterized in that, The length / diameter ratio of the length L of the furnace barrel heating section to the inner diameter Phi of the furnace barrel satisfies L / Phi=13~25; 3. The firing method according to claim 1, characterized in that, The rotary rotation rate of the furnace barrel is less than 1 rpm; The inclination angle of the furnace body is less than 1 degree. The diameter / high ratio of the height H of the guide groove to the inner diameter Phi of the furnace barrel satisfies Phi / H=5~15. In the first-stage rotary furnace, the spacing of the guide grooves is set to enable the residence time of each unit mass of catalyst precursor in the furnace barrel heating section to be 2~12 hours; and / or 4. The firing method according to claim 1, characterized in that, In the second-stage rotary furnace, the spacing of the guide grooves is set to enable the residence time of each unit mass of catalyst precursor in the furnace barrel heating section to be 3~12 hours.

5. The firing method according to claim 1, characterized in that, In the first-stage rotary furnace, the spacing of the guide grooves is set to enable the residence time of each unit mass of catalyst precursor in the furnace barrel heating section to be 4~8 hours; and / or In the second-stage rotary furnace, the spacing of the guide grooves is set to enable the residence time of each unit mass of catalyst precursor in the furnace barrel heating section to be 4~8 hours.

6. The firing method according to claim 5, characterized in that, ​ ​ 7. The firing method according to claim 1, characterized in that, The temperature of the material in the furnace bucket of the primary rotary furnace and the secondary rotary furnace is monitored by using a multi-point embedded temperature measurement method or a wireless temperature measurement monitoring method to realize real-time online monitoring of the temperature of the material in the furnace bucket.

8. The firing method according to claim 1, characterized in that, The calcining device further comprises a hopper screw feeder, and the feeding amount of the catalyst precursor is controlled to be 0.1-1.3 t / h by adjusting the hopper screw feeder.

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