WO2023092377A1 - 费托合成催化剂连续操作的方法和装置 - Google Patents

费托合成催化剂连续操作的方法和装置 Download PDF

Info

Publication number
WO2023092377A1
WO2023092377A1 PCT/CN2021/133080 CN2021133080W WO2023092377A1 WO 2023092377 A1 WO2023092377 A1 WO 2023092377A1 CN 2021133080 W CN2021133080 W CN 2021133080W WO 2023092377 A1 WO2023092377 A1 WO 2023092377A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
fischer
tropsch synthesis
reactor
activation
Prior art date
Application number
PCT/CN2021/133080
Other languages
English (en)
French (fr)
Inventor
杜冰
卜亿峰
赵用明
佟瑞利
冯留海
门卓武
Original Assignee
国家能源投资集团有限责任公司
北京低碳清洁能源研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国家能源投资集团有限责任公司, 北京低碳清洁能源研究院 filed Critical 国家能源投资集团有限责任公司
Priority to PCT/CN2021/133080 priority Critical patent/WO2023092377A1/zh
Publication of WO2023092377A1 publication Critical patent/WO2023092377A1/zh

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon

Definitions

  • the invention relates to the technical field of Fischer-Tropsch synthesis, in particular to a method and device for continuous operation of a Fischer-Tropsch synthesis catalyst.
  • Fischer-Tropsch synthesis process realizes the conversion of synthesis gas to hydrocarbons under the action of a solid catalyst.
  • Fischer-Tropsch catalysts include iron-based and cobalt-based catalysts.
  • the Fischer-Tropsch process with coal-based syngas as raw material is mostly used in industry with iron-based catalysts.
  • the Fischer-Tropsch catalyst produced by the catalyst factory is in an oxidized state and has no catalytic activity. Before the Fischer-Tropsch synthesis reaction, a reduction activation operation is required to convert the oxidized catalyst into an active reduced phase state.
  • CN1562484A discloses a method for activating a catalyst in situ in a slurry bed reactor.
  • the catalyst activation reaction and the Fischer-Tropsch synthesis reaction are realized by adjusting the process conditions, which can be used as a method for activating the catalyst when the device is started.
  • the catalyst in the Fischer-Tropsch synthesis reactor needs to be replaced during the normal production process. Therefore, it is necessary to add a supporting catalyst activation system to realize the replacement of the catalyst during operation.
  • the current supporting activation method Including gas-liquid-solid three-phase slurry bed activation and gas-solid two-phase fluidized bed activation, among which gas-solid fluidized bed activation has the advantages of simple operation, short activation time and large processing scale.
  • An excellent catalyst activation process can make the performance of the catalyst in Fischer-Tropsch synthesis more sufficient and stable.
  • CN110511777A discloses a catalyst online renewal device and method during the operation of a Fischer-Tropsch synthesis reactor.
  • the method specifies the connection process from the catalyst activation system to the Fischer-Tropsch synthesis system, and connects the fluidized bed activation reactor, cyclone separation device, storage tank, heater, slurry bed Fischer-Tropsch synthesis reactor, gas-liquid-solid separator, and liquid-solid treatment unit.
  • This device stores the activated catalyst in the gas-solid fluidized bed to realize daily catalyst replacement.
  • CN106311361A discloses a catalyst activation and online update system and method, the method divides the whole process into an activation step, a storage step and a mixing and dosing step, the activated catalyst is stored in a storage tank, and then introduced into the dosing tank and added to the dosing tank The synthetic product is added to the catalyst tank and the protective gas is passed through. According to the reaction needs in the synthesis reactor, the mixed slurry is transported to the synthesis reactor to complete the online update of the catalyst.
  • the catalyst activation methods disclosed in CN103551207A, CN111450780A and CN111036153A focus on the introduction of the activation reactor and process.
  • the above methods can achieve a good activation effect of the catalyst without causing a large amount of damage to the catalyst.
  • the disclosed methods can clearly see that The activation process is a batch operation, and there are steps in the activation process, such as raising the temperature of the reactor, raising the pressure, adjusting the atmosphere, lowering the temperature, and lowering the pressure, which is time-consuming and energy-consuming, and the discontinuous operation will also limit the degree of automation of the operation.
  • the catalyst replacement cycle in the Fischer-Tropsch synthesis reactor usually takes as long as 2-5 days, resulting in unstable performance.
  • the purpose of the present invention is to provide a new method and device for continuous operation of Fischer-Tropsch synthesis catalysts in order to overcome the problems of long activation time, complicated operation and high energy consumption in the existing Fischer-Tropsch synthesis catalysts, which can combine intermittent activation operations Converted to continuous operation, realizing the pipeline operation mode of catalyst activation process and online replacement process, reducing the complexity and energy consumption of the operation, and improving the stability of the catalyst in the Fischer-Tropsch synthesis reactor.
  • a first aspect of the present invention provides a method for Fischer-Tropsch synthesis catalyst continuous operation, the method may further comprise the steps:
  • the activated catalyst is first delivered to the slurry tank equipped with liquid paraffin and/or heavy wood, and then the slurry in the slurry tank is forced into the Fischer-Tropsch synthesis reactor;
  • step (3a), (3b) or (3c) is used for supplementing the Fischer-Tropsch synthesizer with the activated catalyst or slurry as supplementary catalyst to complete the online replacement of the discharged catalyst;
  • the fresh catalyst when the discharged catalyst accounts for ⁇ 0.5% by weight of the activated catalyst loaded in the Fischer-Tropsch synthesis reactor in real time, the fresh catalyst is activated;
  • the weight percent of the loaded activated catalyst is less than 0.5%, and the fresh catalyst is not activated;
  • the activated catalyst loaded in real time in the Fischer-Tropsch synthesis reactor the activated catalyst initially loaded in the Fischer-Tropsch synthesis reactor-the exhausted catalyst+the supplemented catalyst.
  • the second aspect of the present invention provides a device for continuous operation of a Fischer-Tropsch synthesis catalyst, the device comprising: a connected activation reactor and at least one Fischer-Tropsch synthesis reactor; Storage/slurry tanks between reactors, and control units;
  • the activation reactor is used for reducing and activating the fresh catalyst and the mixed gas containing reducing gas to obtain recycle gas and activated catalyst;
  • the storage tank is used to store the activated catalyst
  • the slurry tank is used to mix the activated catalyst with liquid paraffin and/or heavy wood to form a slurry
  • the Fischer-Tropsch synthesis reactor is used to carry out the Fischer-Tropsch synthesis reaction with the activated catalyst and synthesis gas in the Fischer-Tropsch synthesis reactor;
  • the control unit is connected to the Fischer-Tropsch synthesis reactor and is used to monitor the state of the activated catalyst in the Fischer-Tropsch synthesis reactor.
  • the activated catalyst When the activated catalyst is deactivated in the process of the Fischer-Tropsch synthesis reaction, it becomes a deactivated catalyst , part of the deactivated catalyst is discharged in the form of slag wax as the discharged catalyst;
  • the control unit is connected to the activated catalyst outlet of the activation reactor, the outlet of the storage tank/slurry tank and the discharge catalyst outlet of the Fischer-Tropsch synthesis reactor, for monitoring the amount of the discharge catalyst, and the activation reactor Or the activated catalyst in the storage tank, or the slurry in the slurry tank as a supplementary catalyst to complete the online replacement of the discharged catalyst;
  • the control unit is also used for monitoring the amount of activated catalyst loaded in real time in the discharged catalyst and the Fischer-Tropsch synthesis reactor; Percentage ⁇ 0.5%, the control unit sets the activation reactor to carry out the reduction activation reaction; when the discharged catalyst accounts for ⁇ 0.5% by weight of the activated catalyst loaded in the Fischer-Tropsch synthesis reactor in real time, the control unit Setting the activation reactor does not carry out the reduction activation reaction;
  • the activated catalyst loaded in real time in the Fischer-Tropsch synthesis reactor the activated catalyst initially loaded in the Fischer-Tropsch synthesis reactor-the exhausted catalyst+the supplemented catalyst.
  • the present invention has the following advantages:
  • the operation method provided by the present invention under the premise of not reducing the activation effect of the Fischer-Tropsch synthesis catalyst, the existing intermittent activation operation of the catalyst is converted into a continuous operation, realizing the Fischer-Tropsch synthesis catalyst activation process and on-line replacement process
  • the continuous operation mode keeps the activation process condition of the activation reactor unchanged, saves the time spent on raising and lowering the temperature of the activation reactor, raising and lowering the pressure, and gas replacement, and reduces the operation complexity and energy consumption;
  • the fresh catalyst and the activated catalyst are used for solid-solid heat exchange, which saves the time for heating and cooling the activation reactor and adjusting the composition of the reaction gas, shortens the activation process and reduces operational complexity and energy consumption;
  • the operating method provided by the present invention reduces the replacement cycle and replacement rate of the deactivated catalyst in the Fischer-Tropsch synthesis reactor, making the overall performance of the catalyst in the Fischer-Tropsch synthesis reactor more stable, thereby effectively reducing the equipment investment of the activation reactor cost;
  • Fig. 1 is a device for continuous activation of a Fischer-Tropsch synthesis catalyst provided by the present invention.
  • a first aspect of the present invention provides a method for continuous activation of a Fischer-Tropsch synthesis catalyst, the method comprising the following steps:
  • the activated catalyst is first delivered to the slurry tank equipped with liquid paraffin and/or heavy wood, and then the slurry in the slurry tank is forced into the Fischer-Tropsch synthesis reactor;
  • step (3a), (3b) or (3c) is used for supplementing the Fischer-Tropsch synthesizer with the activated catalyst or slurry as supplementary catalyst to complete the online replacement of the discharged catalyst;
  • the fresh catalyst when the discharged catalyst accounts for ⁇ 0.5% by weight of the activated catalyst loaded in the Fischer-Tropsch synthesis reactor in real time, the fresh catalyst is activated;
  • the weight percent of the loaded activated catalyst is less than 0.5%, and the fresh catalyst is not activated;
  • the activated catalyst loaded in real time in the Fischer-Tropsch synthesis reactor the activated catalyst initially loaded in the Fischer-Tropsch synthesis reactor-the exhausted catalyst+the supplemented catalyst.
  • the fresh catalyst when the discharged catalyst accounts for ⁇ 0.5% by weight of the activated catalyst loaded in real time in the Fischer-Tropsch synthesis reactor, the fresh catalyst is activated, that is, step (1) is repeated, and the fresh catalyst is activated. Start a new round of activation; when the discharge catalyst accounts for ⁇ 0.5% by weight of the activated catalyst loaded in real time in the Fischer-Tropsch synthesis reactor, the fresh catalyst does not activate, that is, repeat steps (2), ( 3a)/(3b)/(3c), the activated catalyst is replaced online as a supplementary catalyst until the weight ratio of the discharged catalyst to the activated catalyst loaded in real time in the Fischer-Tropsch synthesis reactor is ⁇ 0.5%, and the The fresh catalyst starts a new round of activation.
  • the catalyst is a Fischer-Tropsch synthesis catalyst.
  • the fresh catalyst is a fresh Fischer-Tropsch synthesis catalyst;
  • the activated catalyst is an activated Fischer-Tropsch synthesis catalyst.
  • step (1) the fresh catalyst is completely converted into the activated catalyst; in step (2), the amount of deactivated catalyst in the Fischer-Tropsch synthesis reactor is less than the The amount of the activated catalyst of the initial filling in the Fischer-Tropsch synthesis reactor, the amount of the discharged catalyst is less than the amount of the deactivated catalyst; in steps (3a), (3b), (3c), the amount of the supplemented catalyst Less than the amount of activated catalyst described in step (1).
  • the fresh catalyst in step (1), has a bulk density of 0.5-2 g/cm 3 , for example, 0.5 g/cm 3 , 0.6 g/cm 3 , 0.8 g/cm 3 , 1g/cm 3 , 1.2g/cm 3 , 1.5g/cm 3 , 1.8g/cm 3 , 2g/cm 3 , and any value within the range of any two values, preferably 0.6-1.5g/cm 3.
  • the average particle diameter is 50-120 ⁇ m, for example, 50 ⁇ m, 70 ⁇ m, 90 ⁇ m, 100 ⁇ m, 120 ⁇ m, and any value in the range composed of any two values, preferably 70-100 ⁇ m.
  • Fresh catalysts satisfying the above-mentioned limited conditions are more conducive to the Fischer-Tropsch synthesis reaction in a slurry bed.
  • the average particle diameter represents the arithmetic mean of all particle diameters; the particle diameter represents the actual diameter of the particles.
  • the fresh catalyst is selected from iron-based catalysts and/or cobalt-based catalysts, preferably iron-based catalysts.
  • the type of iron-based catalyst has a wide selection range, and can be selected from at least one of precipitated iron catalyst, supported iron catalyst and molten iron catalyst.
  • the conditions of the reduction activation reaction have a wide selection range, as long as the activation components in the fresh catalyst are converted from oxidized state to elemental state or reduced state.
  • the conditions of the reduction activation reaction include: temperature is 230-300°C, preferably 250-280°C; time is 2-24h, preferably 4-12h; pressure is 3-6MPa, Preferably it is 2.5-3.5MPa; the gas velocity is 0.1-0.9m/s, preferably 0.1-0.6m/s.
  • the gas velocity is the gas velocity obtained by dividing the gas operating condition volume flow at the inlet of the activation reactor by the cross-sectional area of the reactor.
  • the pressures mentioned in the present invention all represent gauge pressure.
  • the volume ratio of hydrogen and carbon monoxide in the reducing gas is 0.01-100:1, for example, 0.01:1, 0.1:1, 0.15:1, 1:1, 5:1 1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, and any value within the range composed of any two values, preferably 0.1-80:1.
  • the recycle gas is returned and mixed into the mixed gas.
  • the mixed gas containing reducing gas consumed by the fresh catalyst activation is reduced; at the same time, avoid most of the H in the recycle gas and CO will be discharged as tail gas, wasting too much big.
  • the activation reactor is a gas-solid fluidized bed reactor.
  • step (2) when the CO conversion rate in the Fischer-Tropsch synthesis reactor ⁇ set value, and the set value is 80-99%, the Fischer-Tropsch synthesis reactor The deactivation of the activated catalyst during the Tropsch synthesis reaction becomes a deactivated catalyst.
  • the activity of the Fischer-Tropsch synthesis catalyst is represented by the conversion rate of CO, and the conversion rate of CO in the Fischer-Tropsch synthesis reactor is controlled within (setting value ⁇ 1%).
  • the CO conversion rate in the Fischer-Tropsch synthesis reactor is less than or equal to the set value, the on-line replacement of the deactivated catalyst is started; when the catalyst is replaced in the Fischer-Tropsch synthesis reactor, the CO conversion rate slightly increases to about the set value. With the prolongation of time, the activity of the catalyst will slowly decrease, which is manifested by a gradual decrease in the conversion rate of CO.
  • the replacement rate of the deactivated catalyst is 0.1-20%, for example, 0.1%, 0.5%, 1%, 3%, 5%, 8%, 10%, 13%, 15%, 20%, and any value in the range of any two numerical values, preferably 0.5-15%;
  • the replacement cycle of the deactivated catalyst is 1-120h, for example, 1h, 3h, 6h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 60h, 70h, 80h, 96h, 100h, 120h, and any value in the range composed of any two values, preferably 3-96h.
  • the replacement rate refers to the weight ratio of the discharged catalyst to the activated catalyst loaded in the Fischer-Tropsch synthesis reactor in real time, wherein, in the Fischer-Tropsch synthesis reactor in real time
  • the loaded activated catalyst the initially loaded activated catalyst in the Fischer-Tropsch synthesis reactor - the discharged catalyst + the supplemented catalyst.
  • the heat of the activated catalyst is absorbed and reused, which saves the time and energy required for the cooling of the activated catalyst and the heating of the fresh catalyst, shortens the time of the activation process and reduces the complexity of operation and energy consumption. Also reduces the corresponding equipment investment.
  • the method further includes: performing solid-solid heat exchange between the fresh catalyst and the activated catalyst before step (3a), (3b) or (3c).
  • the temperature of the fresh catalyst after the solid-solid heat exchange is 100-230°C, preferably 130-190°C; the activation after the solid-solid heat exchange
  • the temperature of the catalyst is 120-230°C, preferably 150-200°C.
  • the weight ratio of the fresh catalyst to the activated catalyst is 0.1-2.5:1, for example, 0.1:1, 0.3:1, 0.5:1, 0.8:1, 1:1, 1.5:1, 2:1, 2.5:1, and any value in the range composed of any two values, preferably 0.3-2:1.
  • the weight ratio of the discharged catalyst to the replenished catalyst is 1:0.1-20, for example, 1:0.1, 1:0.5, 1 :1, 1:2, 1:3, 1:4, 1:5, 1:10, 1:15, 1:20, and any value in the range composed of any two values, preferably 1:0.1- 10, more preferably 1:0.1-4.
  • the weight of the supplementary catalyst is calculated by the weight of the activated catalyst or the activated catalyst in the slurry.
  • the temperature of the Fischer-Tropsch synthesis reactor is controlled It is 230-300°C, for example, 230°C, 240°C, 250°C, 260°C, 285°C, 300°C, and any value in the range composed of any two values, preferably 240-285°C; the pressure is 2- 3.5MPa, for example, 2MPa, 2.5MPa, 3MPa, 3.3MPa, 3.5MPa, and any value in the range composed of any two values, preferably 2.5-3.3MPa.
  • step (3a) when the activated catalyst is directly transported into the Fischer-Tropsch synthesis reactor, the connection between the Fischer-Tropsch synthesis reactor and the activation reactor is controlled.
  • the pressure difference is not more than 1MPa, for example, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.8MPa, 1MPa, and any value in the range composed of any two values, preferably not more than 0.5MPa. In this preferred situation, it can further ensure that the activated catalyst is quickly transported into the Fischer-Tropsch synthesis reactor.
  • part of the deactivated catalyst is set as the discharged catalyst in the form of slag wax Discharge the Fischer-Tropsch synthesis reactor, set the replacement rate of the deactivated catalyst at 0.1-20%, calculate the discharge amount of the discharged catalyst according to the concentration of the deactivated catalyst in the Fischer-Tropsch synthesizer, and use the discharged catalyst in the form of slag wax Discharge; treat that the fresh catalyst is activated, adjust the pressure of the activation reactor, and use the activation catalyst in the activation reactor (preferably after the activation catalyst is solid-solid heat-exchanged with a new round of fresh catalyst) by the pressure difference (not more than 1MPa) as
  • the supplementary catalyst is directly sent to the Fischer-Tropsch synthesis reactor, wherein the weight ratio of the exhausted catalyst to the supplementary catalyst is 1:0.1-20.
  • the present invention by controlling the temperature of the storage tank and controlling the pressure difference between the storage tank and the Fischer-Tropsch synthesis reactor, it can be effectively avoided when the activated catalyst is stored in the discharge tank or the activated catalyst is stored in the discharge tank.
  • the temperature of the storage tank is controlled to be 0 -250°C, for example, 0°C, 20°C, 50, 80, 100°C, 130°C, 150°C, 200°C, 250°C, and any value in the range composed of any two values, preferably 20-150°C .
  • step (3b) when the activated catalyst in the storage tank is delivered to the Fischer-Tropsch synthesis reactor, control the connection between the storage tank and the Fischer-Tropsch synthesis reactor.
  • the pressure difference between the synthesis reactors does not exceed 1MPa, for example, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.8MPa, 1MPa, and any value in the range composed of any two values, preferably not exceeding 0.5MPa.
  • part of the deactivated catalyst is set as the discharged catalyst in the form of slag wax Discharge the Fischer-Tropsch synthesis reactor, set the replacement rate of the deactivated catalyst at 0.1-20%, calculate the discharge amount of the exhausted catalyst according to the concentration of the deactivated catalyst in the Fischer-Tropsch synthesizer, and use the exhausted catalyst in the form of slag wax Discharge; adjust the pressure of the storage tank, and the activated catalyst in the storage tank (preferably after the activated catalyst is solid-solid heat-exchanged with a new round of fresh catalyst) is transported to the Fischer-Tropsch synthesis reactor, wherein, the weight ratio of the discharged catalyst to the replenished catalyst is 1:0.1-20.
  • the delivery method of step (3c) does not need to further add liquid medium in the Fischer-Tropsch synthesis reactor in advance, for example, liquid paraffin and/or heavy wood, which is conducive to simplifying the process flow; while adopting the step ( 3c)
  • This delivery method is also suitable for on-line replacement of catalyst during normal operation. This is because the Fischer-Tropsch heavy wax produced during the low-temperature slurry bed Fischer-Tropsch synthesis reaction is liquid under reaction conditions. If the gas-solid activation The catalyst is directly transferred to the reactor, which belongs to the gas-solid direct transfer to the slurry bed system, and there are certain risks.
  • the added amount of the activated catalyst, liquid paraffin and/or heavy wood makes the solid content of the slurry less than 15wt%, for example, 1wt%, 3wt%, 5wt%, 7wt%, 9wt%, 12wt%, 14wt%, and any value in the range composed of any two numerical values, preferably 3-12wt%.
  • the slurry can smoothly enter the Fischer-Tropsch synthesis reactor through the pressure difference, without causing clogging or deposition due to excessive concentration; Low, affecting the Fischer-Tropsch synthesis efficiency.
  • step (3c) when the slurry in the slurry tank is injected into the Fischer-Tropsch synthesis reactor, control the slurry tank and the Fischer-Tropsch synthesis reactor The temperature difference between them does not exceed 50°C, for example, 0°C, 5°C, 10°C, 15°C, 20°C, 30°C, 40°C, 50°C, and any value in the range composed of any two values, preferably not More than 30°C; control the pressure difference between the slurry tank and the Fischer-Tropsch synthesis reactor to not exceed 1MPa, for example, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.8MPa, 1MPa, and any two Any value within the range of numerical composition, preferably not more than 0.5 MPa.
  • Such setting conditions are more conducive to rapid equilibrium between the temperature of the existing slurry in the Fischer-Tropsch synthesis reactor and the temperature of the newly added slurry.
  • part of the deactivated catalyst is set as the discharged catalyst in the form of slag wax Discharge the Fischer-Tropsch synthesis reactor, set the replacement rate of the deactivated catalyst at 0.1-20%, calculate the discharge amount of the exhausted catalyst according to the concentration of the deactivated catalyst in the Fischer-Tropsch synthesizer, and use the exhausted catalyst in the form of slag wax Discharge; adjust the temperature and pressure of the slurry tank, by temperature difference (not more than 50 °C) and pressure difference (not more than 1MPa) in the slurry tank containing activated catalyst (preferably the activated catalyst and a new round of fresh catalyst After solid-solid heat exchange), the slurry is sent to the Fischer-Tropsch synthesis reactor as a supplementary catalyst, wherein the weight ratio of the discharged catalyst to the supplementary catalyst is 1:0.1-20.
  • the method when carrying out step (3a), or when carrying out step (3b) described activated catalyst is transported in Fischer-Tropsch synthesis reactor, or carrying out step (3c) described slurry pressure is injected into When in the Fischer-Tropsch synthesis reactor, the method also includes: adding liquid paraffin and/or heavy wood to the Fischer-Tropsch synthesis reactor.
  • the invention can effectively avoid the collision wear of the activated catalyst during the feeding process by adding liquid paraffin and/or heavy wood to the Fischer-Tropsch synthesis reactor.
  • the method further includes: collecting and/or treating the discharged catalyst.
  • the method further includes feeding gas into the storage tank, and the present invention has no special limitation on the gas, as long as it does not contain O, S, Cl, etc., so that all The component oxidized or deactivated by the activated catalyst is sufficient, preferably an inert gas such as nitrogen.
  • this gas is used as protective gas on the one hand, avoids the oxidation of air to activated catalyst; Used to transfer the activated catalyst from the holding tank to the slurry tank containing liquid paraffin and/or heavy wood.
  • the method comprises the following steps:
  • the activated catalyst is first delivered to the slurry tank equipped with liquid paraffin and/or heavy wood, and then the slurry in the slurry tank is forced into the Fischer-Tropsch synthesis reactor;
  • step (3a), (3b) or (3c) is used for supplementing the Fischer-Tropsch synthesizer with the activated catalyst or slurry as supplementary catalyst to complete the online replacement of the discharged catalyst;
  • the fresh catalyst when the discharged catalyst accounts for ⁇ 0.5% by weight of the activated catalyst loaded in the Fischer-Tropsch synthesis reactor in real time, the fresh catalyst is activated;
  • the weight percent of the loaded activated catalyst is less than 0.5%, and the fresh catalyst is not activated;
  • the activated catalyst loaded in real time in the Fischer-Tropsch synthesis reactor the activated catalyst initially loaded in the Fischer-Tropsch synthesis reactor-the exhaust catalyst+the supplementary catalyst;
  • step (2) when the conversion rate of CO in the Fischer-Tropsch synthesis reactor ⁇ set value, and the set value is 80-99%, the activated catalyst is present in the Fischer-Tropsch synthesis reaction process Deactivation is a deactivated catalyst;
  • step (3a), (3b) or (3c) the weight ratio of the discharged catalyst to the supplemented catalyst is 1:0.1-20.
  • the second aspect of the present invention provides a device for continuous activation of a Fischer-Tropsch synthesis catalyst, the device comprising: a connected activation reactor and at least one Fischer-Tropsch synthesis reactor; Storage/slurry tanks between reactors, and control units;
  • the activation reactor is used for reducing and activating the fresh catalyst and the mixed gas containing reducing gas to obtain recycle gas and activated catalyst;
  • the storage tank is used to store the activated catalyst
  • the slurry tank is used to mix the activated catalyst with liquid paraffin and/or heavy wood to form a slurry
  • the Fischer-Tropsch synthesis reactor is used to carry out the Fischer-Tropsch synthesis reaction with the activated catalyst and synthesis gas in the Fischer-Tropsch synthesis reactor;
  • the control unit is connected to the Fischer-Tropsch synthesis reactor and is used to monitor the state of the activated catalyst in the Fischer-Tropsch synthesis reactor.
  • the activated catalyst When the activated catalyst is deactivated in the process of the Fischer-Tropsch synthesis reaction, it becomes a deactivated catalyst , part of the deactivated catalyst is discharged in the form of slag wax as the discharged catalyst;
  • the control unit is connected to the activated catalyst outlet of the activation reactor, the outlet of the storage tank/slurry tank and the discharge catalyst outlet of the Fischer-Tropsch synthesis reactor, for monitoring the amount of the discharge catalyst, and the activation reactor Or the activated catalyst in the storage tank, or the slurry in the slurry tank as a supplementary catalyst to complete the online replacement of the discharged catalyst;
  • the control unit is also used for monitoring the amount of activated catalyst loaded in real time in the discharged catalyst and the Fischer-Tropsch synthesis reactor; Percentage ⁇ 0.5%, the control unit sets the activation reactor to carry out the reduction activation reaction; when the discharged catalyst accounts for ⁇ 0.5% by weight of the activated catalyst loaded in the Fischer-Tropsch synthesis reactor in real time, the control unit Setting the activation reactor does not carry out the reduction activation reaction;
  • the activated catalyst loaded in real time in the Fischer-Tropsch synthesis reactor the activated catalyst initially loaded in the Fischer-Tropsch synthesis reactor-the exhausted catalyst+the supplemented catalyst.
  • control unit is also used to monitor the CO conversion rate in the Fischer-Tropsch synthesis reactor, when the CO conversion rate in the Fischer-Tropsch synthesis reactor ⁇ set value, and the set value is preferably 80-99%, the control unit is set to deactivate the activated catalyst in the Fischer-Tropsch synthesis reactor.
  • the device further includes: a heat exchanger, the heat exchanger is connected to the activated catalyst outlet of the activation reactor, and is used for solid-solid heat exchange between the activated catalyst and the fresh catalyst to obtain the The activated catalyst after the solid-solid heat exchange and the fresh catalyst after the solid-solid heat exchange.
  • a heat exchanger is connected to the activated catalyst outlet of the activation reactor, and is used for solid-solid heat exchange between the activated catalyst and the fresh catalyst to obtain the The activated catalyst after the solid-solid heat exchange and the fresh catalyst after the solid-solid heat exchange.
  • the activated catalyst after the solid-solid heat exchange of the heat exchanger is connected to the inlet of the Fischer-Tropsch synthesizer and the inlet of the storage tank/slurry tank, and is respectively used to convert the solid-solid heat exchange
  • the activated catalyst is directly transported to the Fischer-Tropsch synthesis reactor, and the activated catalyst after solid-solid heat exchange is first transported to the storage tank/slurry tank.
  • the fresh catalyst after solid-solid heat exchange of the heat exchanger is connected to the inlet of the activation reactor for activating the fresh catalyst after solid-solid heat exchange.
  • the device further includes: a slag wax collection tank connected to the outlet of the discharged catalyst of the Fischer-Tropsch synthesis reactor, for collecting the discharged catalyst.
  • the device further includes: a slag wax treatment unit connected to the outlet of the slag wax collection tank, for treating the discharged catalyst.
  • a device for the continuous activation of a Fischer-Tropsch synthesis catalyst provided by the present invention, as shown in Figure 1, the device includes: a connected activation reactor I and at least one Fischer-Tropsch synthesis reactor II; Storage tank/slurry tank III between I and Fischer-Tropsch reactor II, and control unit VII;
  • the activation reactor I is used for reducing and activating the fresh catalyst 2 and the mixed gas 1 containing reducing gas to obtain the recycle gas 4 and the activated catalyst 3;
  • the storage tank III is used for storing the activated catalyst 3;
  • the slurry tank III is used for The activated catalyst 3 is mixed with liquid paraffin and/or heavy wood to form a slurry;
  • the Fischer-Tropsch synthesis reactor II is used to carry out the Fischer-Tropsch synthesis reaction with the activated catalyst 3 and the synthesis gas 6;
  • the control unit VII is connected to the Fischer-Tropsch synthesis reactor II, with To monitor the state of the activated catalyst, when the activated catalyst is deactivated into a deactivated catalyst during the process of the Fischer-Tropsch synthesis reaction, part of the deactivated catalyst is discharged as the exhausted catalyst 7 in the form of slag wax II; the control unit VII is connected to the activated
  • control unit VII is also used to monitor the conversion rate of CO in the Fischer-Tropsch synthesis reactor II, when the conversion rate of CO in the Fischer-Tropsch synthesis reactor II is ⁇ a set value, and the set value is 80-99%,
  • the control unit VII sets the partially deactivated catalyst in the Fischer-Tropsch synthesis reactor II as the discharged catalyst 7 to be discharged in the form of slag wax;
  • the device also includes: a heat exchanger IV, the heat exchanger IV is connected to the activation catalyst outlet of the activation reactor 1, and is used for solid-solid heat exchange between the activation catalyst 3 and the fresh catalyst 2;
  • the device also includes: a slag wax collection tank V connected to the discharge catalyst outlet of the Fischer-Tropsch synthesis reactor II, for collecting the discharge catalyst 7;
  • the device also includes: a slag wax treatment unit VI connected to the outlet of the slag wax collection tank V for treating the discharged catalyst 7 .
  • the operating temperature of the activation reactor is 260°C
  • the pressure is 3.3MPa
  • the reducing gas is hydrogen and synthesis gas
  • the volume ratio of hydrogen and carbon monoxide in the reducing gas is 0.15:1
  • the inlet air velocity is 0.25m/s
  • the time is 6h
  • the recycle gas passes through the gas compressor, and then returns to the activation reactor.
  • the control unit controls:
  • the weight ratio of discharging catalyst and supplementary catalyst in the Fischer-Tropsch synthesis reactor is set to be 1:1; (2) When the CO conversion rate of Fischer-Tropsch synthesis reaction is 97%, there is activated catalyst deactivation in the Fischer-Tropsch synthesis reaction process
  • the CO conversion rate is basically maintained within the range of 97.5 ⁇ 1%, and the performance is stable.
  • Fischer-Tropsch synthesis reactors with a catalyst loading capacity of 70t (slurry bed reactor, reaction temperature 275°C, pressure 2.9MPa, fresh gas to gas ratio 5000Nm 3 /h/cat, tower gas H 2 / CO is 3.0-4.5%) pilot plant for catalyst replacement renewal, every 4 Fischer-Tropsch synthesis slurry bed reactors share one activation reactor (gas-solid fluidized bed reactor), and batch reduction operation is adopted.
  • Each batch of activated catalysts is supplied to 4 Fischer-Tropsch synthesis reactors at the same time, and the activation time of each batch is 38h (because it is an intermittent operation, the length of time for heating and cooling is increased, and the time spent for each activation is about 38h (wherein the constant temperature Time 12h)), for the 4 Fischer-Tropsch synthesis reactors, the replacement period of the deactivated catalyst in each Fischer-Tropsch synthesizer is 38h, and the deactivated catalyst for each replacement is 12.7t.
  • Table 1 provides a comparison of the equipment scales of the continuous activation reactor provided by Example 1 and the batch activation reactor provided by Comparative Example 1.
  • the total scale of the continuous activation reactor is smaller, that is, the total scale of the reactor will be smaller after catalyst activation using a multi-stage series continuous activation device, saving equipment investment costs.
  • Fischer-Tropsch synthesis reactor with a catalyst loading capacity of 20kg (slurry bed reactor, reaction temperature 265°C, pressure 2.8MPa, fresh gas-to-agent ratio 5000Nm 3 /h/cat, H 2 /CO in the tower gas is 3.0-4.0%) pilot plant for catalyst replacement renewal
  • the Fischer-Tropsch synthesis reactor independently uses an activation reactor (gas-solid fluidized bed reactor), the continuous operation of the activation reactor replacement cycle is 6h, each The replacement rate is 0.8% (about 160g), the inner diameter of a single reactor is 0.1m, and the total height is 6m.
  • the operating temperature of the activation reactor is 260°C
  • the pressure is 3.3MPa
  • the reducing gas is hydrogen and synthesis gas
  • the volume ratio of hydrogen and carbon monoxide in the reducing gas is 0.15:1
  • the inlet air velocity is 0.25m/s
  • the time is 6h
  • the recycle gas passes through the gas compressor, and then returns to the activation reactor.
  • the control unit controls:
  • the CO conversion rate is basically maintained within the range of 97.5 ⁇ 1%, and the performance is stable.
  • the scale of the whole system becomes smaller and the activation time is greatly reduced.
  • Fischer-Tropsch synthesis reactor with a catalyst loading capacity of 20kg (slurry bed reactor, reaction temperature 265°C, pressure 2.8MPa, fresh gas-to-agent ratio 5000Nm 3 /h/cat, H 2 /CO in the tower gas is 3-4%) pilot plant for catalyst replacement update
  • the Fischer-Tropsch synthesis reactor independently uses an activation reactor (gas-solid fluidized bed reactor), the continuous operation of the activation reactor replacement cycle is 6h, each time The replacement rate is 0.8%, about 160g; the inner diameter of the activation reactor is 0.1m, the total height is 6m, the operating temperature of the activation reactor is 260°C, the pressure is 3.3MPa, the reducing gas is hydrogen and synthesis gas, and the reducing gas
  • the volume ratio of hydrogen to carbon monoxide is 0.15:1, the inlet air velocity is 0.25m/s, and the time is 6h.
  • the circulating gas passes through the gas compressor and returns to the activation reactor.
  • the fresh catalyst 25°C was subjected to solid-solid heat exchange with the activated catalyst (260°C) before entering the activation reactor, and the temperature of the fresh catalyst rose from 25°C to 150°C.
  • the reduction time of a single batch of catalyst is about 6 hours, and the energy consumption is about 180kW/h.
  • Fischer-Tropsch synthesis reactor with a catalyst loading capacity of 20kg (slurry bed reactor, reaction temperature 265°C, pressure 2.8MPa, fresh gas-to-agent ratio 5000Nm 3 /h/cat, H 2 /CO in the tower gas is 3-4%) pilot plant for catalyst replacement update
  • the Fischer-Tropsch synthesis reactor independently uses an activation reactor (gas-solid fluidized bed reactor), the continuous operation of the activation reactor replacement cycle is 6h, each replacement
  • the ratio is 0.8%, about 160g, the inner diameter of a single activation reactor is 0.1m, the total height is 6m, the operating temperature of the activation reactor is 260°C, the pressure is 3.3MPa, the reducing gas is hydrogen and synthesis gas, and the reducing gas
  • the volume ratio of hydrogen and carbon monoxide in the medium is 0.15:1, the inlet air velocity is 0.25m/s, and the time is 6h.
  • the tail gas enters the gas compressor, returns and enters the activation reactor.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明涉及费托合成技术领域，具体涉及一种费托合成催化剂连续操作的方法和装置。本发明提供的操作方法，在不降低费托合成催化剂的活化效果的前提下，将现有的催化剂间歇的活化操作转变为连续操作，实现了费托合成催化剂活化过程和在线置换过程的连续操作，尤其是结合新鲜催化剂和活化催化剂的固固换热，使得活化反应器保持活化工艺条件不变，节省了活化反应器升温和降温、升压降压以及气体置换等消耗的时间，降低了操作复杂性和能耗；同时，降低了费托合成反应器中失活催化剂的置换周期和置换率，使得费托合成反应器内催化剂整体性能更加稳定，从而有效降低了活化反应器的设备投资费用。

Description

费托合成催化剂连续操作的方法和装置 技术领域
本发明涉及费托合成技术领域，具体涉及一种费托合成催化剂连续操作的方法和装置。
背景技术
基于我国富煤、贫油、少气的能源结构禀赋以及日益严苛的油品环保性能要求，大力发展以费托合成为核心的煤炭间接液化技术具有重要意义。相比传统石油炼制过程，煤炭间接液化的产品更加清洁、产品方案更加灵活，同时面对国际局势和原油价格不稳定的复杂情况，发展煤炭间接液化具有一定的经济优势，也是一种战略储备。
费托合成过程在固体催化剂的作用下实现合成气向烃类的转化。目前费托催化剂括铁基和钴基这两种，以煤基合成气为原料的费托过程在工业上多采用铁基催化剂。催化剂厂生产的费托催化剂为氧化状态，不具有催化活性，在进行费托合成反应之前，需要还原活化操作将氧化态的催化剂转化为具有活性的还原相态。
CN1562484A公开了一种浆态床反应器原位活化催化剂的方法，通过调整工艺条件实现催化剂活化反应和费托合成反应，可以作为装置开工催化剂的活化方法。但是由于铁基催化剂易失活，正常生产过程中还需要对费托合成反应器内的催化剂进行置换，因此，需要增加配套的催化剂活化系统来实现运转过程中催化剂的置换，目前配套的活化方法包括气液固三相浆态床活化和气固两相流化床活化两种，其中气固流化床活化具有操作简单、活化耗时短、处理规模大等优点。优良的催化剂活化工艺方法可以使催化剂在费托合成中的性能表现更加充分、稳定。
CN110511777A公开了一种费托合成反应器运转过程中的催化剂在线更新装置及方法，该方法指定了从催化剂活化系统到费托合成系统的连接流程，依次连通了流化床活化反应器、旋风分离器、储罐、加热器、浆态床费托合成反应器和气液固分离器以及液固处理单元，该装置降气固流化床活化的催化剂储存起来，实现催化剂的按天置换。
CN106311361A公开了一种催化剂活化与在线更新系统及方法，该方法将整个过程分为了活化步骤、存储步骤和调浆加剂步骤，活化的催化剂储存在储罐中，之后导入加剂罐并向加剂罐中添加合成产品并通入保护气体，根据合成反应器中的反应需要，将混合浆液输送至合成反应器，完成催化剂的在线更新。
CN110511777A和CN106311361A公开的方法中，在费托催化剂活化后均会先转移至储罐再转移至费托反应器中，催化剂活化工艺没有重点介绍，但可以看出均为间歇操作。
同时，CN103551207A、CN111450780A和CN111036153A公开的催化剂活化方法侧重在活化反应器和工艺的介绍，上述方法均可以实现催化剂的良好活化效果，同时也不会造成催化剂的大量破损，公开的方法可以明确看出活化过程均为间歇操作，活化过程存在反应器升温、升压、调整气氛、降温、降压的步骤，耗时且耗能，非连续化的操作也会限制操作的自动化程度。同时由于间歇活化过程的耗时，通常费托合成反应器内的催化剂置换周期要长达2-5天，造成性能的不稳定。
因此，亟需一种新的费托合成催化剂连续操作的方法和装置。
发明内容
本发明的目的是为了克服现有费托合成催化剂存在活化时间长、操作复杂、能耗高等问题，提供一种新的费托合成催化剂连续操作的方法和装置，该方法可以将间歇的活化操作转变为连续操作，实现了催化剂活化过程与在线置换过程的流水线操作方式，降低了操作的复杂性和能耗，提高了费托合成反应器中催化剂的稳定性。
为了实现上述目的，本发明第一方面提供一种费托合成催化剂连续操作的方法，该方法包括以下步骤：
(1)将新鲜催化剂与含还原气体的混合气引入活化反应器进行还原活化反应，得到循环气和活化催化剂；
(2)将所述活化催化剂与合成气在费托合成反应器中进行费托合成反应，当所述费托合成反应的过程中有所述活化催化剂失活为失活催化剂时，将部分所述失活催化剂作为排出催化剂以渣蜡的形式排出；
(3a)将所述活化催化剂直接输送到费托合成反应器中；或者
(3b)将所述活化催化剂先输送到储料罐中，再将所述储料罐中的所述活化催化剂输送到费托合成反应器中；或者
(3c)将所述活化催化剂先输送到装有液体石蜡和/或重柴的浆液罐中，再将所述浆液罐中的浆液压入费托合成反应器中；
其中，步骤(3a)、(3b)或(3c)用于将所述活化催化剂或浆液作为补充催化剂补充到费托合成器中以完成对所述排出催化剂的在线置换；
其中，当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数≥0.5％，所述新鲜催化剂进行活化；当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数＜0.5％，所述新鲜催化剂不进行活化；
其中，所述费托合成反应器中实时装填的活化催化剂＝所述费托合成反应器中初始装填的活化催化剂-所述排出催化剂+所述补充催化剂。
本发明第二方面提供一种费托合成催化剂连续操作的装置，该装置包括：连通的活化反应器和至少一个费托合成反应器；该装置还包括设置于所述活化反应器和费托合成反应器之间的储料罐/浆液罐，以及控制单元；
所述活化反应器用于将新鲜催化剂与含还原气体的混合气进行还原活化反应，得到循环气和活化催化剂；
所述储料罐用于将所述活化催化剂进行储存；
所述浆液罐用于将所述活化催化剂与液体石蜡和/或重柴混合形成浆液；
所述费托合成反应器用于将所述活化催化剂与合成气在费托合成反应器中进行费托合成反应；
所述控制单元连接所述费托合成反应器，用于监控所述费托合成反应器中活化催化剂的状态，当所述费托合成反应的过程中有所述活化催化剂失活为失活催化剂时，将部分所述失活催化剂作为排出催化剂以渣蜡的形式排出；
所述控制单元连接所述活化反应器的活化催化剂出口、储料罐/浆液罐的出口和费托合成反应器的排出催化剂出口，用于监控所述排出催化剂的用量，将所述活化反应器或所述储料罐中的活化催化剂、或者所述浆液罐中的浆液作为补充催化剂以完成对所述排出催化剂的在线置换；
所述控制单元还用于监控所述排出催化剂和所述费托合成反应器中实时装填的活化催化剂的用量；当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数≥0.5％，所述控制单元设置所述活化反应器进行还原活化反应；当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数＜0.5％，所述控制单元设置所述活化反应器不进行还原活化反应；
其中，所述费托合成反应器中实时装填的活化催化剂＝所述费托合成反应器中初始装填的活化催化剂-所述排出催化剂+所述补充催化剂。
相比现有技术，本发明具有以下优势：
(1)本发明提供的操作方法，在不降低费托合成催化剂的活化效果的前提下，将现有的催化剂间歇的活化操作转变为连续操作，实现了费托合成催化剂活化过程和在线置换过程的连续操作方式，使得活化反应器保持活化工艺条件不变，节省了活化反应器升温和降温、升压降压以及气体置换等消耗的时间，降低了操作复杂性和能耗；
尤其是，本发明提供的方法中采用新鲜催化剂与活化催化剂进行固固换热的方式，节省了活化反应器升温和降温以及调整反应气体组成的时间，缩短了活化过程并降低了操作复杂性及能耗；
(2)本发明提供的操作方法，降低了费托合成反应器中失活催化剂置换周期和置换率，使得费托合成反应器内催化剂整体性能更加稳定，从而有效降低了活化反应器的设备投资费用；
(3)本发明提供的方法中，由于每次费托合成反应器置换的催化剂质量为传统间歇活化置换的0.05-0.5倍，因此，本发明限定的活化反应器的规模也相应降低到传统间歇置换(活化反应器)的0.05-0.5倍，也相应降低了配套的管道等规模，极大地降低了催化剂活化装置的投资和运转费用。
附图说明
图1是本发明提供的一种费托合成催化剂连续活化的装置。
附图标记说明
I、活化反应器          II、费托合成反应器  III、储料罐/浆液罐
IV、换热器             V、渣蜡收集罐       VI、渣蜡处理单元
VII、控制单元
1、含还原气体的混合气  2、新鲜催化剂       3、活化催化剂
4、循环气              5、补充催化剂       6、合成气
7、排出催化剂
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种费托合成催化剂连续活化的方法，该方法包括以下步骤：
(1)将新鲜催化剂与含还原气体的混合气引入活化反应器进行还原活化反 应，得到循环气和活化催化剂；
(2)将所述活化催化剂与合成气在费托合成反应器中进行费托合成反应，当所述费托合成反应的过程中有所述活化催化剂失活为失活催化剂时，将部分所述失活催化剂作为排出催化剂以渣蜡的形式排出；
(3a)将所述活化催化剂直接输送到费托合成反应器中；或者
(3b)将所述活化催化剂先输送到储料罐中，再将所述储料罐中的所述活化催化剂输送到费托合成反应器中；或者
(3c)将所述活化催化剂先输送到装有液体石蜡和/或重柴的浆液罐中，再将所述浆液罐中的浆液压入费托合成反应器中；
其中，步骤(3a)、(3b)或(3c)用于将所述活化催化剂或浆液作为补充催化剂补充到费托合成器中以完成对所述排出催化剂的在线置换；
其中，当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数≥0.5％，所述新鲜催化剂进行活化；当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数＜0.5％，所述新鲜催化剂不进行活化；
其中，所述费托合成反应器中实时装填的活化催化剂＝所述费托合成反应器中初始装填的活化催化剂-所述排出催化剂+所述补充催化剂。
在本发明中，当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数≥0.5％，所述新鲜催化剂进行活化，即，重复步骤(1)，所述新鲜催化剂开始新一轮的活化；当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数＜0.5％，所述新鲜催化剂不进行活化，即，重复步骤(2)、(3a)/(3b)/(3c)，所述活化催化剂作为补充催化剂进行在线置换，直至所述排出催化剂与所述费托合成反应器中实时装填的活化催化剂的重量比≥0.5％，所述新鲜催化剂又开始新一轮的活化。
在本发明中，没有特殊情况说明下，所述催化剂为费托合成催化剂。例如，所述新鲜催化剂为新鲜的费托合成催化剂；所述活化催化剂为活化的费托合成催化剂。
在本发明中，没有特殊情况说明下，步骤(1)中，所述新鲜催化剂完全转化为所述活化催化剂；步骤(2)中，所述费托合成反应器中失活催化剂的量小于所述费托合成反应器中初始装填的活化催化剂的量，所述排出催化剂的量小于所述失活催化剂的量；步骤(3a)、(3b)、(3c)中，所述补充催化剂的量小于步骤(1)中所述活化催化剂的量。
在本发明的一些实施方式中，步骤(1)中，所述新鲜催化剂的堆积密度为0.5-2g/cm 3，例如，0.5g/cm 3、0.6g/cm 3、0.8g/cm 3、1g/cm 3、1.2g/cm 3、1.5g/cm 3、1.8g/cm 3、2g/cm 3，以及任意两个数值组成的范围内中的任意值，优选为0.6-1.5g/cm 3；颗粒平均直径为50-120μm，例如，50μm、70μm、90μm、100μm、120μm，以及任意两个数值组成的范围内中的任意值，优选为70-100μm。满足上述限定条件的新鲜催化剂更有利于浆态床的费托合成反应。
在本发明中，没有特殊情况说明下，所述颗粒平均直径表示所有颗粒直径的算术平均值；所述颗粒直径表示颗粒的实际直径。
在本发明的一些实施方式中，优选地，所述新鲜催化剂选自铁基催化剂和/或钴基催化剂，优选为铁基催化剂。在本发明中，对铁基催化剂的种类具有较宽的选择范围，可以选自沉淀铁催化剂、负载铁催化剂和熔铁催化剂中的至少一种。
在本发明中，对所述还原活化反应的条件具有较宽的选择范围，只要将新鲜 催化剂中的活化组分由氧化态转化为单质态或还原态即可。优选地，步骤(1)中，所述还原活化反应的条件包括：温度为230-300℃，优选为250-280℃；时间为2-24h，优选为4-12h；压力为3-6MPa，优选为2.5-3.5MPa；气速为0.1-0.9m/s，优选为0.1-0.6m/s。在本发明中，所述气速为活化反应器入口的气体工况体积流量，除以反应器截面积得到的气速。
在本发明中，没有特别说明的情况下，本发明所述的压力均表示表压。
在本发明的一些实施方式中，优选地，所述还原气体中氢气和一氧化碳的体积比为0.01-100：1，例如，0.01:1、0.1:1、0.15:1、1:1、5:1、10:1、15:1、20:1、25:1、30:1、35:1、40:1、50:1、60:1、70:1、80:1、90:1、100:1，以及任意两个数值组成的范围内中的任意值，优选为0.1-80：1。
在本发明的一些实施方式中，优选地，将所述循环气返回并混入所述混合气。当所述循环气返回活化反应器时，所述新鲜催化剂活化消耗的含还原气体的混合气降低；同时，避免所述循环气中绝大部分的H 2和CO将作为尾气排放出去，浪费太大。
在本发明的一些实施方式中，优选地，步骤(1)中，所述活化反应器为气固流化床反应器。
在本发明的一些实施方式中，优选地，步骤(2)中，当所述费托合成反应器中CO转化率≤设定值，且所述设定值为80-99％，所述费托合成反应过程中有所述活化催化剂失活为失活催化剂。
在本发明中，没有特殊情况说明下，费托合成催化剂的活性以CO转化率来表示，在费托合成反应器中CO转化率控制在(设定值±1％)以内。当费托合成反应器中CO转化率≤设定值，开启失活催化剂的在线置换；当费托合成反应器内置换催化剂后，CO转化率为略微升高至设定值左右，随着反应时间的延长，催化剂的活性会缓慢下降，表现为CO转化率逐渐下降。
根据本发明，优选地，所述失活催化剂的置换率为0.1-20％，例如，0.1％、0.5％、1％、3％、5％、8％、10％、13％、15％、20％，以及任意两个数值组成的范围中的任意值，优选为0.5-15％；所述失活催化剂的置换周期为1-120h，例如，1h、3h、6h、10h、15h、20h、25h、30h、35h、40h、45h、50h、60h、70h、80h、96h、100h、120h，以及任意两个数值组成的范围中的任意值，优选为3-96h。
在本发明中，没有特殊情况说明下，所述置换率是指所述排出催化剂与所述费托合成反应器中实时装填的活化催化剂的重量比，其中，所述费托合成反应器中实时装填的活化催化剂＝所述费托合成反应器中初始装填的活化催化剂-所述排出催化剂+所述补充催化剂。
在本发明中，将所述活化催化剂的热量进行吸收再利用，节省了活化催化剂降温和新鲜催化剂升温所需要的时间和能量，缩短了活化过程的时间并降低了操作复杂性和能耗，同时也减少了相应的设备投资。
在本发明的一些实施方式中，优选地，该方法还包括：在步骤(3a)、(3b)或(3c)之前，将所述新鲜催化剂与活化催化剂进行固固换热。
在本发明的一些实施方式中，优选地，步骤(1)中，所述固固换热后新鲜催化剂的温度为100-230℃，优选为130-190℃；所述固固换热后活化催化剂的温度为120-230℃，优选为150-200℃。
在本发明的一些实施方式中，优选地，在所述固固热换的过程中，所述新鲜催化剂与活化催化剂的重量比为0.1-2.5：1，例如，0.1:1、0.3:1、0.5:1、0.8:1、1:1、1.5:1、2:1、2.5:1，以及任意两个数值组成的范围中的任意值，优选为0.3-2： 1。
根据本发明，优选地，步骤(3a)、(3b)或(3c)，所述排出催化剂与所述补充催化剂的重量比为1：0.1-20，例如，1:0.1、1:0.5、1:1、1:2、1:3、1:4、1:5、1:10、1:15、1:20，以及任意两个数值组成的范围中的任意值，优选为1：0.1-10，更优选为1：0.1-4。其中，所述补充催化剂的重量以活化催化剂或浆液中活化催化剂的重量计。
在本发明的一些实施方式中，优选地，在将所述活化催化剂通过步骤(3a)、(3b)或(3c)输送到费托合成反应器之前，控制所述费托合成反应器的温度为230-300℃，例如，230℃、240℃、250℃、260℃、285℃、300℃，以及任意两个数值组成的范围中的任意值，优选为240-285℃；压力为2-3.5MPa，例如，2MPa、2.5MPa、3MPa、3.3MPa、3.5MPa，以及任意两个数值组成的范围中的任意值，优选为2.5-3.3MPa。
在本发明的一些实施方式中，优选地，步骤(3a)中，当所述活化催化剂直接输送到所述费托合成反应器中时，控制所述费托合成反应器与活化反应器之间的压差不超过1MPa，例如，0.1MPa、0.2MPa、0.3MPa、0.4MPa、0.5MPa、0.8MPa、1MPa，以及任意两个数值组成的范围中的任意值，优选不超过0.5MPa。在该种优选情况下，能够进一步确保所述活化催化剂快速输送到费托合成反应器内。
在本发明的一种具体实施方式中，当所述费托合成反应器中CO转化率为设定值(例如，97％)时，设置部分所述失活催化剂作为排出催化剂以渣蜡的形式排出费托合成反应器，设置失活催化剂的置换率为0.1-20％，根据费托合成器内失活催化剂的浓度计算所述排出催化剂的排除量，并将所述排出催化剂以渣蜡形式排出；待新鲜催化剂活化完毕，调整活化反应器的压力，通过压差(不超过1MPa)将活化反应器中的活化催化剂(优选将活化催化剂与新一轮的新鲜催化剂固固换热后)作为补充催化剂直接输送到费托合成反应器中，其中，所述排出催化剂与补充催化剂的重量比为1：0.1-20。
在本发明中，通过控制所述储料罐的温度并控制所述储料罐与费托合成反应器之间的压差，能够有效避免当活化催化剂在出料罐中储存时或者将活化催化剂从储料罐输送到费托合成反应器的过程中水对活化催化剂的影响，从而进一步保证活化催化剂的活性和性能。
在本发明的一些实施方式中，优选地，步骤(3b)中，在将所述储料罐中的活化催化剂输送到所述费托合成反应器之前，控制所述储料罐的温度为0-250℃，例如，0℃、20℃、50、80、100℃、130℃、150℃、200℃、250℃，以及任意两个数值组成的范围中的任意值，优选为20-150℃。
在本发明的一些实施方式中，优选地，步骤(3b)中，当将所述储料罐中的活化催化剂输送到所述费托合成反应器中时，控制所述储料罐与费托合成反应器之间的压差不超过1MPa，例如，0.1MPa、0.2MPa、0.3MPa、0.4MPa、0.5MPa、0.8MPa、1MPa，以及任意两个数值组成的范围中的任意值，优选不超过0.5MPa。
在本发明的一种具体实施方式中，当所述费托合成反应器中CO转化率为设定值(例如，97％)时，设置部分所述失活催化剂作为排出催化剂以渣蜡的形式排出费托合成反应器，设置失活催化剂的置换率为0.1-20％，根据费托合成器内失活催化剂的浓度计算所述排出催化剂的排出量，并将所述排出催化剂以渣蜡形式排出；调整储料罐的压力，通过压差(不超过1MPa)将所述储料罐中的活化催化剂(优选将活化催化剂与新一轮的新鲜催化剂固固换热后)作为补充催化剂输送到费托合成反应器，其中，所述排出催化剂与补充催化剂的重量比为1： 0.1-20。
在本发明中，采用步骤(3c)这种输送方式不需要再进一步在费托合成反应器中提前加入液体介质，例如，液体石蜡和/或重柴，有利于简化工艺流程；同时采用步骤(3c)这种输送方式也适合于正常运转时催化剂的在线置换，这是由于低温浆态床费托合成反应过程中生产的费托重质蜡在反应工况下是液态，如果气固活化后催化剂直接转移到反应器，属于气固直接输送到浆态床体系，存在一定的风险。
在本发明的一些实施方式中，优选地，步骤(3c)中，所述活化催化剂、液体石蜡和/或重柴的加入量，使得所述浆液的固含量小于15wt％，例如，1wt％、3wt％、5wt％、7wt％、9wt％、12wt％、14wt％，以及任意两个数值组成的范围中的任意值，优选为3-12wt％。在本发明中，通过限定所述浆液的固含量，使得所述浆液能够顺利通过压差进入费托合成反应器中，既不会因为浓度过高，造成堵塞或沉积；也不会因为浓度过低，影响费托合成效率。
在本发明的一些实施方式中，优选地，步骤(3c)中，当将所述浆液罐中的浆液压入所述费托合成反应器中时，控制所述浆液罐与费托合成反应器之间的温差不超过50℃，例如，0℃、5℃、10℃、15℃、20℃、30℃、40℃、50℃，以及任意两个数值组成的范围中的任意值，优选不超过30℃；控制所述浆液罐与费托合成反应器之间的压差不超过1MPa，例如，0.1MPa、0.2MPa、0.3MPa、0.4MPa、0.5MPa、0.8MPa、1MPa，以及任意两个数值组成的范围中的任意值，优选不超过0.5MPa。这样的设置条件更有利于费托合成反应器内已有浆液的温度和新加入浆液的温度达到快速平衡。
在本发明的一种具体实施方式中，当所述费托合成反应器中CO转化率为设定值(例如，97％)时，设置部分所述失活催化剂作为排出催化剂以渣蜡的形式排出费托合成反应器，设置失活催化剂的置换率为0.1-20％，根据费托合成器内失活催化剂的浓度计算所述排出催化剂的排出量，并将所述排出催化剂以渣蜡形式排出；调整所述浆液罐的温度和压力，通过温差(不超过50℃)和压差(不超过1MPa)将所述浆液罐中的含活化催化剂(优选将活化催化剂与新一轮的新鲜催化剂固固换热后)的浆液作为补充催化剂输送到费托合成反应器中，其中，所述排出催化剂与补充催化剂的重量比为1：0.1-20。
在本发明中，在进行步骤(3a)时，或者在进行步骤(3b)中将所述活化催化剂输送到费托合成反应器中时，或者在进行步骤(3c)中将所述浆液压入费托合成反应器中时，该方法还包括：向费托合成反应器中加入液体石蜡和/或重柴。本发明通过向费托合成反应器中加入液体石蜡和/或重柴，能够有效避免活化催化剂在加料过程中的碰撞磨损。
根据本发明，优选地，该方法还包括：将所述排出催化剂进行收集/或处理。
在本发明的一些实施方式中，优选地，该方法还包括向所述储料罐中通入气体，本发明对所述气体没有特别的限定，只要不含有O、S、Cl等能使所述活化催化剂氧化或失活的组分即可，优选为惰性气体例如氮气。在本发明中，该气体一方面作为保护气，避免空气对活化催化剂的氧化；另一方面起到输送的作用，用于将储料罐中的活化催化剂输送到费托合成反应器中或者用于将储料罐中的活化催化剂输送到装有液体石蜡和/或重柴的浆液罐中。
根据本发明一种特别优选的实施方式，该方法包括以下步骤：
(1)将新鲜催化剂与含还原气体的混合气引入活化反应器进行还原活化反应，得到循环气和活化催化剂；
(2)将所述活化催化剂与合成气在费托合成反应器中进行费托合成反应，当所述费托合成反应的过程中有所述活化催化剂失活为失活催化剂时，将部分所述失活催化剂作为排出催化剂以渣蜡的形式排出；
(3a)将所述活化催化剂直接输送到费托合成反应器中；或者
(3b)将所述活化催化剂先输送到储料罐中，再将所述储料罐中的所述活化催化剂输送到费托合成反应器中；或者
(3c)将所述活化催化剂先输送到装有液体石蜡和/或重柴的浆液罐中，再将所述浆液罐中的浆液压入费托合成反应器中；
其中，步骤(3a)、(3b)或(3c)用于将所述活化催化剂或浆液作为补充催化剂补充到费托合成器中以完成对所述排出催化剂的在线置换；
其中，当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数≥0.5％，所述新鲜催化剂进行活化；当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数＜0.5％，所述新鲜催化剂不进行活化；
其中，所述费托合成反应器中实时装填的活化催化剂＝所述费托合成反应器中初始装填的活化催化剂-所述排出催化剂+所述补充催化剂；
其中，步骤(2)中，当所述费托合成反应器中CO转化率≤设定值，且所述设定值为80-99％，所述费托合成反应过程中有所述活化催化剂失活为失活催化剂；
其中，步骤(3a)、(3b)或(3c)中，所述排出催化剂与补充催化剂的重量比为1：0.1-20。
本发明第二方面提供一种费托合成催化剂连续活化的装置，该装置包括：连通的活化反应器和至少一个费托合成反应器；该装置还包括设置于所述活化反应器和费托合成反应器之间的储料罐/浆液罐，以及控制单元；
所述活化反应器用于将新鲜催化剂与含还原气体的混合气进行还原活化反应，得到循环气和活化催化剂；
所述储料罐用于将所述活化催化剂进行储存；
所述浆液罐用于将所述活化催化剂与液体石蜡和/或重柴混合形成浆液；
所述费托合成反应器用于将所述活化催化剂与合成气在费托合成反应器中进行费托合成反应；
所述控制单元连接所述费托合成反应器，用于监控所述费托合成反应器中活化催化剂的状态，当所述费托合成反应的过程中有所述活化催化剂失活为失活催化剂时，将部分所述失活催化剂作为排出催化剂以渣蜡的形式排出；
所述控制单元连接所述活化反应器的活化催化剂出口、储料罐/浆液罐的出口和费托合成反应器的排出催化剂出口，用于监控所述排出催化剂的用量，将所述活化反应器或所述储料罐中的活化催化剂、或者所述浆液罐中的浆液作为补充催化剂以完成对所述排出催化剂的在线置换；
所述控制单元还用于监控所述排出催化剂和所述费托合成反应器中实时装填的活化催化剂的用量；当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数≥0.5％，所述控制单元设置所述活化反应器进行还原活化反应；当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数＜0.5％，所述控制单元设置所述活化反应器不进行还原活化反应；
其中，所述费托合成反应器中实时装填的活化催化剂＝所述费托合成反应器中初始装填的活化催化剂-所述排出催化剂+所述补充催化剂。
根据本发明，优选地，所述控制单元还用于监控所述费托合成反应器中CO转化率，当所述费托合成反应器中CO转化率≤设定值，且设定值优选为80-99％，所述控制单元设置所述控制单元设置所述费托合成反应器中有所述活化催化剂失活为失活催化剂。
根据本发明，优选地，该装置还包括：换热器，所述换热器连接所述活化反应器的活化催化剂出口，用于将所述活化催化剂与新鲜催化剂进行固固换热，得到所述固固换热后活化催化剂和所述固固换热后新鲜催化剂。
根据本发明，优选地，所述换热器的固固换热后活化催化剂连接所述费托合成器的入口、储料罐/浆液罐的入口，分别用于将所述固固换热后活化催化剂直接输送到所述费托合成反应器中，将所述固固换热后活化催化剂先输送到所述储料罐/浆液罐中。
根据本发明，优选地，所述换热器的固固换热后新鲜催化剂连接所述活化反应器的入口，用于将所述固固换热后新鲜催化剂进行活化。
根据本发明，优选地，该装置还包括：与所述费托合成反应器的排出催化剂出口连接的渣蜡收集罐，用于收集所述排出催化剂。
根据本发明，优选地，该装置还包括：与所述渣蜡收集罐的出口连接的渣蜡处理单元，用于处理所述排出催化剂。
本发明提供的一种费托合成催化剂连续活化的装置，如图1所示，该装置包括：连通的活化反应器I和至少一个费托合成反应器II；该装置还包括设置于活化反应器I和费托合成反应器II之间的储料罐/浆液罐III，以及控制单元VII；
活化反应器I用于将新鲜催化剂2与含还原气体的混合气1进行还原活化反应，得到循环气4和活化催化剂3；储料罐III用于将活化催化剂3进行储存；浆液罐III用于将活化催化剂3与液体石蜡和/或重柴混合形成浆液；费托合成反应器II用于将活化催化剂3与合成气6进行费托合成反应；控制单元VII连接费托合成反应器II，用于监控活化催化剂的状态，当费托合成反应的过程中有所述活化催化剂失活为失活催化剂时，将部分失活催化剂作为排出催化剂7以渣蜡的形式排出II；控制单元VII连接活化反应器I的活化催化剂出口、储料罐/浆液罐III的出口和费托合成反应器II的出口，用于监控排出催化剂7的用量，将活化反应器I或储料罐III中的活化催化剂、或者浆液罐III中的浆液作为补充催化剂5以完成对排出催化剂7的在线置换；控制单元VII还用于监控排出催化剂7和费托合成反应器II中实时装填的活化催化剂的用量；当排出催化剂7占费托合成反应器中实时装填的活化催化剂的重量百分数≥0.5％，控制单元VII设置活化反应器I进行还原活化反应；当排出催化剂7占费托合成反应器中实时装填的活化催化剂的重量百分数＜0.5％，控制单元VII设置活化反应器I不进行还原活化反应；
其中，控制单元VII还用于监控所述费托合成反应器II中CO转化率，当费托合成反应器II中CO转化率≤设定值，且所述设定值为80-99％，控制单元VII设置费托合成反应器II中部分失活催化剂作为排出催化剂7以渣蜡的形式排出；
该装置还包括：换热器IV，换热器IV连接活化反应器I的活化催化剂出口，用于将活化催化剂3与新鲜催化剂2进行固固换热；
该装置还包括：与费托合成反应器II的排出催化剂出口连接的渣蜡收集罐V，用于收集排出催化剂7；
该装置还包括：与渣蜡收集罐V的出口连接的渣蜡处理单元VI，用于处理排出催化剂7。
以下将通过实施例对本发明进行详细描述。
实施例1
按照图1所示的费托合成催化剂连续操作的装置示意图，不同的是，费托合成反应器的数量为4个。
为某催化剂装填量为70t规模的4个费托合成反应器(浆态床反应器，反应温度275℃，压力2.9MPa，新鲜气气剂比5000Nm 3/h/cat，入塔气H 2/CO为2-4.5％)中试装置进行催化剂置换更新，每4个费托合成反应器共用1个活化反应器(气固流化床反应器)，且每一批次活化催化剂供应1个费托合成反应器。其中，每一批次活化耗时为6h，对于4个费托合成反应器来说，每个费托合成器中失活催化剂的置换周期为24h，每次置换的失活催化剂为2t，活化反应器的底部内径为0.8m，总高为12m。
活化反应器的操作温度为260℃，压力为3.3MPa，还原气体为氢气与合成气，且还原气体中氢气和一氧化碳的体积比为0.15:1，入口进气速度为0.25m/s，时间为6h，循环气经气体压缩机，再返回所述活化反应器。
控制单元控制：
(1)设置费托合成反应器中排出催化剂与补充催化剂的重量比为1:1；(2)当费托合成反应的CO转化率为97％，费托合成反应过程中有活化催化剂失活为失活催化剂，将部分失活催化剂作为排出催化剂以渣蜡的形式排出；(3)当排出催化剂占费托合成反应器中实时装填的活化催化剂的重量百分数≥0.5％，费托合成催化剂进行活化，在上述条件下进行活化；(4)当排出催化剂占费托合成反应器中实时装填的活化催化剂的重量百分数＜0.5％，费托合成反应器定量排放所述排出催化剂；(5)将活化催化剂作为补充催化剂直接输送至费托合成反应器中，完成失活催化剂的在线置换；(6)重复上述步骤，实现催化剂活化和在线置换的连续操作。
本次催化剂活化和在线置换的连续操作，CO转化率基本保持在97.5±1％范围内，性能稳定。
传统的催化剂活化间歇操作的流程中，4个费托合成反应器需要2个活化反应器(气固流化床反应器)，活化时间需要30h左右。本发明中4个费托合成反应器只需要1个活化反应器(气固流化床反应器)，催化剂活化时间只有6h。即整个还原系统的规模变小，活化时间大为降低。
对比例1
为某催化剂装填量为70t规模的4个费托合成反应器(浆态床反应器，反应温度275℃，压力2.9MPa，新鲜气气剂比5000Nm 3/h/cat，入塔气H 2/CO为3.0-4.5％)中试装置进行催化剂置换更新，每4个费托合成浆态床反应器共用1个活化反应器(气固流化床反应器)，采用间歇还原操作。每一批次活化催化剂同时供应4个费托合成反应器，每一批次活化耗时为38h(因为是间歇操作，增加了升温降温的时长，每次活化的耗时是38h左右(其中恒温时间12h))，对于4个费托合成反应器来说，每个费托合成器中失活催化剂的置换周期为38h，每次置换的失活催化剂为12.7t。
本次催化剂活化和置换的间歇操作，CO转化率保持在97.5±1.5％范围内，性能波动较大。
为便于明确本发明提供的费托合成催化剂连续操作的装置的建设投资是否 过大，表1为实施例1提供的连续活化反应器和对比例1提供的间歇活化反应器的设备规模对比。
表1
  连续活化反应器 单个间歇活化反应器
活化耗时，h 6 38
置换间隔，h 24 38
单批处理量，t 2 12.8
反应器尺寸 内径0.8m，高12m 内径2.2m，高16m
反应器总体积，m 3 6 70
反应器总表面积，m 2 30 130
由表1数据可知，相比单个间歇操作活化反应器，连续活化反应器的总规模较小，即，采用多级串联的连续活化装置进行催化剂活化后反应器的总规模也会更小，节省了设备投资费用。
实施例2
按照图1所示的费托合成催化剂连续操作的装置示意图。
为某催化剂装填量为20kg规模的费托合成反应器(浆态床反应器，反应温度265℃，压力2.8MPa，新鲜气气剂比5000Nm 3/h/cat，入塔气H 2/CO为3.0-4.0％)中试装置进行催化剂置换更新，该费托合成反应器独立应用1个活化反应器(气固流化床反应器)，活化反应器的连续化操作置换周期为6h，每次置换率为0.8％(约160g)，单个反应器的内径为0.1m，总高为6m。
活化反应器的操作温度为260℃，压力为3.3MPa，还原气体为氢气与合成气，且还原气体中氢气和一氧化碳的体积比为0.15:1，入口进气速度为0.25m/s，时间为6h，循环气经气体压缩机，再返回所述活化反应器。
控制单元控制：
(1)设置费托合成反应器中排出催化剂与补充催化剂的重量比为1:1；(2)当费托合成反应的CO转化率为97％，费托合成反应过程中有活化催化剂失活为失活催化剂，将部分所述失活催化剂作为排出催化剂以渣蜡的形式排出；(3)当排出的所述失活催化剂占费托合成反应器中实时装填的活化催化剂的重量百分数≥0.5％，费托合成催化剂进行活化，在上述条件下进行活化；(4)当排出催化剂占费托合成反应器中实时装填的活化催化剂的重量百分数＜0.5％，费托合成反应器定量排放排出催化剂；(5)将活化催化剂作为补充催化剂直接输送至费托合成反应器中，完成失活催化剂的在线置换；(6)重复上述步骤，实现催化剂活化和在线置换的连续操作。
本次催化剂活化和在线置换的连续操作，CO转化率基本保持在97.5±1％范围内，性能稳定。同时相对于催化剂活化和在线置换的连续操作来说，整个系统的规模变小，活化时间大为降低。
实施例3
为某催化剂装填量为20kg规模的费托合成反应器(浆态床反应器，反应温度265℃，压力2.8MPa，新鲜气气剂比5000Nm 3/h/cat，入塔气H 2/CO为3-4％)中试装置进行催化剂置换更新，该费托合成反应器独立应用1个活化反应器(气固流化床反应器)，活化反应器的连续化操作置换周期为6h，每次置换率为0.8％， 约160g；活化反应器的内径为0.1m，总高为6m，活化反应器的操作温度为260℃，压力为3.3MPa，还原气体为氢气与合成气，且还原气体中氢气和一氧化碳的体积比为0.15:1，入口进气速度为0.25m/s，时间为6h，循环气经气体压缩机，再返回所述活化反应器。
催化剂活化过程中，将新鲜催化剂(25℃)在进入到活化反应器前与活化催化剂(260℃)进行固固换热，新鲜催化剂的温度从25℃升到了150℃。单批催化剂还原时间约为6h，能量消耗约180kW/h。
实施例4
为某催化剂装填量为20kg规模的费托合成反应器(浆态床反应器，反应温度265℃，压力2.8MPa，新鲜气气剂比5000Nm 3/h/cat，入塔气H 2/CO为3-4％)中试装置进行催化剂置换更新，该费托合成反应器独立应用一个活化反应器(气固流化床反应器)，活化反应器的连续化操作置换周期为6h，每次置换的比例为0.8％，约160g，单个活化反应器的内径为0.1m，总高为6m，活化反应器的操作温度为260℃，压力为3.3MPa，还原气体为氢气与合成气，且还原气体中氢气和一氧化碳的体积比为0.15:1，入口进气速度为0.25m/s，时间为6h。尾气进入气体压缩机，再返回并进入活化反应器。
催化剂活化过程中，将新鲜催化剂(25℃)直接进入到活化反应器。单批催化剂还原时间约为6h，能量消耗约210kW/h。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (11)

  1. 一种费托合成催化剂连续操作的方法，其特征在于，该方法包括以下步骤：
    (1)将新鲜催化剂与含还原气体的混合气引入活化反应器进行还原活化反应，得到循环气和活化催化剂；
    (2)将所述活化催化剂与合成气在费托合成反应器中进行费托合成反应，当所述费托合成反应的过程中有所述活化催化剂失活为失活催化剂时，将部分所述失活催化剂作为排出催化剂以渣蜡的形式排出；
    (3a)将所述活化催化剂直接输送到费托合成反应器中；或者
    (3b)将所述活化催化剂先输送到储料罐中，再将所述储料罐中的所述活化催化剂输送到费托合成反应器中；或者
    (3c)将所述活化催化剂先输送到装有液体石蜡和/或重柴的浆液罐中，再将所述浆液罐中的浆液压入费托合成反应器中；
    其中，步骤(3a)、(3b)或(3c)用于将所述活化催化剂或浆液作为补充催化剂补充到费托合成器中以完成对所述排出催化剂的在线置换；
    其中，当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数≥0.5％，所述新鲜催化剂进行活化；当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数＜0.5％，所述新鲜催化剂不进行活化；
    其中，所述费托合成反应器中实时装填的活化催化剂＝所述费托合成反应器中初始装填的活化催化剂-所述排出催化剂+所述补充催化剂。
  2. 根据权利要求1所述的方法，其中，步骤(1)中，所述新鲜催化剂的堆积密度为0.5-2g/cm 3，优选为0.6-1.5g/cm 3；颗粒平均直径为50-120μm，优选为70-100μm；
    和/或，所述新鲜催化剂选自铁基催化剂和/或钴基催化剂。
  3. 根据权利要求1或2所述的方法，其中，步骤(1)中，所述还原活化反应的条件包括：温度为230-300℃，优选为250-280℃；时间为2-24h，优选为4-12h；压力为3-6MPa，优选为2.5-3.5MPa；气速为0.1-0.9m/s，优选为0.1-0.6m/s；
    和/或，所述还原气体中氢气和一氧化碳的体积比为0.01-100：1，优选为0.1-80：1。
  4. 根据权利要求1-3中任意一项所述的方法，其中，步骤(2)中，当所述费托合成反应器中CO转化率≤设定值，且所述设定值为80-99％，所述费托合成反应过程中有所述活化催化剂失活为失活催化剂；
    和/或，所述失活催化剂的置换率为0.1-20％，优选为0.5-15％；所述失活催化剂的置换周期为1-120h，优选为3-96h。
  5. 根据权利要求1-4中任意一项所述的方法，其中，该方法还包括：在步骤(3a)、(3b)或(3c)之前，将所述新鲜催化剂与活化催化剂进行固固换热；
    和/或，所述固固换热的过程中，所述新鲜催化剂与活化催化剂的重量比为0.1-2.5：1，优选为0.3-2：1。
  6. 根据权利要求1-5中任意一项所述的方法，其中，步骤(3a)、(3b)或(3c)中，所述排出催化剂与补充催化剂的重量比为1：0.1-20，优选为1：0.1-4；
    和/或，在将所述活化催化剂通过步骤(3a)、(3b)或(3c)输送到所述费托合成反应器之前，控制所述费托合成反应器的温度为230-300℃，优选为240-285℃；压力为2-3.5MPa，优选为2.5-3.3MPa。
  7. 根据权利要求6所述的方法，其中，步骤(3a)中，当所述活化催化剂直接输送到所述费托合成反应器中时，控制所述费托合成反应器与活化反应器之间的压差不超过1MPa，优选不超过0.5MPa。
  8. 根据权利要求6所述的方法，其中，步骤(3b)中，在将所述储料罐中的活化催化剂输送到所述费托合成反应器之前，控制所述储料罐的温度为0-250℃，优选为20-150℃；
    和/或，步骤(3b)中，当将所述储料罐中的活化催化剂输送到所述费托合成反应器中时，控制所述储料罐与费托合成反应器之间的压差不超过1MPa，优 选不超过0.5MPa。
  9. 根据权利要求6所述的方法，其中，步骤(3c)中，所述活化催化剂、液体石蜡和/或重柴的加入量，使得所述浆液的固含量小于15wt％，优选为3-12wt％；
    和/或，步骤(3c)中，当将所述浆液罐中的浆液压入所述费托合成反应器中时，控制所述浆液罐与费托合成反应器之间的温差不超过50℃，优选不超过30℃；控制所述浆液罐与费托合成反应器之间的压差不超过1MPa，优选不超过0.5MPa；
    和/或，该方法还包括：将所述排出催化剂进行收集/或处理。
  10. 一种费托合成催化剂连续操作的装置，其特征在于，该装置包括：连通的活化反应器和至少一个费托合成反应器；该装置还包括设置于所述活化反应器和费托合成反应器之间的储料罐/浆液罐，以及控制单元；
    所述活化反应器用于将新鲜催化剂与含还原气体的混合气进行还原活化反应，得到循环气和活化催化剂；
    所述储料罐用于将所述活化催化剂进行储存；
    所述浆液罐用于将所述活化催化剂与液体石蜡和/或重柴混合形成浆液；
    所述费托合成反应器用于将所述活化催化剂与合成气在费托合成反应器中进行费托合成反应；
    所述控制单元连接所述费托合成反应器，用于监控所述活化催化剂的状态，当所述费托合成反应的过程中有所述活化催化剂失活为失活催化剂时，将部分所述失活催化剂作为排出催化剂以渣蜡的形式排出；
    所述控制单元连接所述活化反应器的活化催化剂出口、储料罐/浆液罐的出口和费托合成反应器的出口，用于监控所述排出催化剂的用量，将所述活化反应器或所述储料罐中的活化催化剂、或者所述浆液罐中的浆液作为补充催化剂以完成对所述排出催化剂的在线置换；
    所述控制单元还用于监控所述排出催化剂和所述费托合成反应器中实时装填的活化催化剂的用量；当所述排出催化剂占所述费托合成反应器中实时装填的 活化催化剂的重量百分数≥0.5％，所述控制单元设置所述活化反应器进行还原活化反应；当所述排出催化剂占所述费托合成反应器中实时装填的活化催化剂的重量百分数＜0.5％，所述控制单元设置所述活化反应器不进行还原活化反应；
    其中，所述费托合成反应器中实时装填的活化催化剂＝所述费托合成反应器中初始装填的活化催化剂-所述排出催化剂+所述补充催化剂。
  11. 根据权利要求10所述的装置，其中，所述控制单元还用于监控所述费托合成反应器中CO转化率，当所述费托合成反应器中CO转化率≤设定值，且所述设定值为80-99％，所述控制单元设置所述费托合成反应器中有所述活化催化剂失活为失活催化剂；
    和/或，该装置还包括：换热器，所述换热器连接所述活化反应器的活化催化剂出口，用于将所述活化催化剂与新鲜催化剂进行固固换热；
    和/或，该装置还包括：与所述费托合成反应器的排出催化剂出口连接的渣蜡收集罐，用于收集所述排出催化剂；
    和/或，该装置还包括：与所述渣蜡收集罐的出口连接的渣蜡处理单元，用于处理所述排出催化剂。
PCT/CN2021/133080 2021-11-25 2021-11-25 费托合成催化剂连续操作的方法和装置 WO2023092377A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/133080 WO2023092377A1 (zh) 2021-11-25 2021-11-25 费托合成催化剂连续操作的方法和装置

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/133080 WO2023092377A1 (zh) 2021-11-25 2021-11-25 费托合成催化剂连续操作的方法和装置

Publications (1)

Publication Number Publication Date
WO2023092377A1 true WO2023092377A1 (zh) 2023-06-01

Family

ID=86538496

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/133080 WO2023092377A1 (zh) 2021-11-25 2021-11-25 费托合成催化剂连续操作的方法和装置

Country Status (1)

Country Link
WO (1) WO2023092377A1 (zh)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1814350A (zh) * 2005-06-21 2006-08-09 上海兖矿能源科技研发有限公司 颗粒状铁基费托合成催化剂的工业还原方法
WO2011090819A2 (en) * 2010-01-19 2011-07-28 Rentech, Inc. Protected fischer-tropsch catalyst and method of providing same to a fischer-tropsch process
US20120298551A1 (en) * 2011-05-27 2012-11-29 GI - Gasification International, S.A. Fischer-tropsch catalyst activation procedure
US20130018114A1 (en) * 2010-03-30 2013-01-17 Kazuhiko Tasaka Process for producing activated catalyst for fischer-tropsch synthesis reaction, process for producing catalyst slurry, and process for supplying catalyst slurry to fischer-tropsch synthesis reactor
WO2014115932A1 (ko) * 2013-01-24 2014-07-31 한국에너지기술연구원 피셔-트롭쉬 합성반응을 이용한 탄화수소 화합물의 제조 시스템
CN106311361A (zh) * 2015-06-24 2017-01-11 神华集团有限责任公司 催化剂活化与在线更新系统及方法
CN110511777A (zh) * 2018-05-22 2019-11-29 国家能源投资集团有限责任公司 浆态床费托合成反应器催化剂在线更新装置及方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1814350A (zh) * 2005-06-21 2006-08-09 上海兖矿能源科技研发有限公司 颗粒状铁基费托合成催化剂的工业还原方法
WO2011090819A2 (en) * 2010-01-19 2011-07-28 Rentech, Inc. Protected fischer-tropsch catalyst and method of providing same to a fischer-tropsch process
US20130018114A1 (en) * 2010-03-30 2013-01-17 Kazuhiko Tasaka Process for producing activated catalyst for fischer-tropsch synthesis reaction, process for producing catalyst slurry, and process for supplying catalyst slurry to fischer-tropsch synthesis reactor
US20120298551A1 (en) * 2011-05-27 2012-11-29 GI - Gasification International, S.A. Fischer-tropsch catalyst activation procedure
WO2014115932A1 (ko) * 2013-01-24 2014-07-31 한국에너지기술연구원 피셔-트롭쉬 합성반응을 이용한 탄화수소 화합물의 제조 시스템
CN106311361A (zh) * 2015-06-24 2017-01-11 神华集团有限责任公司 催化剂活化与在线更新系统及方法
CN110511777A (zh) * 2018-05-22 2019-11-29 国家能源投资集团有限责任公司 浆态床费托合成反应器催化剂在线更新装置及方法

Similar Documents

Publication Publication Date Title
CN112827495B (zh) 一种储热/催化一体化材料的制备方法
WO2023092377A1 (zh) 费托合成催化剂连续操作的方法和装置
CN114736714A (zh) 费托合成系统及其开工方法和费托合成催化剂的在线置换方法
CN105540551A (zh) 一种双氧水生产中的高效氢化工艺
CN110511777B (zh) 浆态床费托合成反应器催化剂在线更新装置及方法
CN202700501U (zh) 适于kpta生产的无搅拌氧化和深度氧化反应系统
CN100404137C (zh) 颗粒状铁基费托合成催化剂的工业还原方法
CN101979475A (zh) 一种焦炉煤气进行甲烷化合成天然气的工艺
CN102675090B (zh) 聚合级对苯二甲酸生产中的深度氧化方法及深度氧化装置
CN104178234B (zh) 焦炉煤气与发生炉煤气制备天然气及余热利用方法和系统
CN103934044B (zh) 利用费托合成反应器一次还原15t以上催化剂的方法
CN113351225B (zh) 费托合成铁基催化剂的活化方法和费托合成催化剂活化系统
CN210683692U (zh) 一种防止催化剂沉降的浆态床反应装置
CN108285809B (zh) 双系列费托反应装置的开车方法
CN210560262U (zh) 提高工业费托合成投料开车效率的费托合成装置
CN208098032U (zh) 一种f-t合成浆态床反应器的移热装置
CN111036153B (zh) 费托催化剂在气固流化床中的活化方法及产品和应用
CN113292390A (zh) 一种采用无汞催化剂的氯乙烯合成生产工艺
CN115430434B (zh) 费托合成催化剂的还原方法和还原态费托合成催化剂以及费托合成方法
CN111606805B (zh) 煤制乙二醇装置联产碳酸二甲酯的生产工艺及装置
CN115430434A (zh) 费托合成催化剂的还原方法和还原态费托合成催化剂以及费托合成方法
CN109999732A (zh) 一种f-t合成浆态床反应器的移热装置
CN103977843B (zh) 一种甲醇触媒升温还原的方法
CN218609308U (zh) 一种新型1,4-丁炔二醇反应器
CN214781568U (zh) 一种乙二醇液相加氢尾气中氢气回收利用装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21965113

Country of ref document: EP

Kind code of ref document: A1