CN110511777B - Slurry bed Fischer-Tropsch synthesis reactor catalyst online renewal device and method - Google Patents
Slurry bed Fischer-Tropsch synthesis reactor catalyst online renewal device and method Download PDFInfo
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- CN110511777B CN110511777B CN201810494652.3A CN201810494652A CN110511777B CN 110511777 B CN110511777 B CN 110511777B CN 201810494652 A CN201810494652 A CN 201810494652A CN 110511777 B CN110511777 B CN 110511777B
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- 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
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/342—Apparatus, reactors with moving solid catalysts
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/703—Activation
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Abstract
本发明涉及费托催化剂在线更新领域，公开了浆态床费托合成反应器催化剂在线更新装置及方法。该装置包括：依次连通的流化床活化反应器、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，以及与浆态床费托合成反应器和气液固分离器连通的液固处理单元，其中，流化床活化反应器用于将新鲜费托催化剂与还原性气体接触进行催化剂活化；液固处理单元用于将第一渣蜡和第二渣蜡进行固体废物和废弃催化剂的分离。采用本发明的装置可以降低费托催化剂活化和渣蜡处理的成本，缩短装置开工准备时间，实现浆态床费托合成反应器内催化剂的按天更新，渣蜡处理简便，分离效率高，最大程度保障装置平稳运转。
The invention relates to the field of on-line updating of Fischer-Tropsch catalysts, and discloses a device and method for on-line updating of catalysts in a slurry bed Fischer-Tropsch synthesis reactor. The device comprises: a fluidized bed activation reactor, a cyclone separator, a storage tank, a heater, a slurry bed Fischer-Tropsch synthesis reactor and a gas-liquid-solid separator, and a slurry-bed Fischer-Tropsch synthesis reactor and a gas-liquid The liquid-solid treatment unit communicated with the solid separator, wherein the fluidized bed activation reactor is used for contacting the fresh Fischer-Tropsch catalyst with the reducing gas for catalyst activation; the liquid-solid treatment unit is used for the first slag wax and the second slag wax Separation of solid waste and spent catalyst. The device of the invention can reduce the cost of Fischer-Tropsch catalyst activation and slag wax treatment, shorten the start-up preparation time of the device, realize daily renewal of the catalyst in the slurry bed Fischer-Tropsch synthesis reactor, the slag wax treatment is simple, the separation efficiency is high, and the maximum To ensure the smooth operation of the device.
Description
Technical Field
The invention relates to the field of online updating of catalysts of Fischer-Tropsch synthesis reactors, in particular to an online updating device for catalysts of a Fischer-Tropsch synthesis reactor in a slurry bed and an online updating method for the catalysts of the Fischer-Tropsch synthesis reactor in the slurry bed by using the device.
Background
When the slurry bed Fischer-Tropsch synthesis reactor is adopted to carry out Fischer-Tropsch synthesis reaction, the catalyst has a longer updating period and a high updating proportion, most of the updating periods are 5-7 days, the shorter updating period is 3-4 days, and the proportion of updating the catalyst each time is about 6-20 percent, so that the continuous and stable operation of the Fischer-Tropsch synthesis reaction device is not beneficial in actual start-up operation, and a short-period and flexible updating method is needed.
CN1562484A discloses an in-situ reduction method of a slurry bed Fischer-Tropsch synthesis iron-based catalyst, the catalyst is activated in a Fischer-Tropsch synthesis reactor, and then the air inlet condition is switched to directly carry out Fischer-Tropsch and synthesis reactions. Because the catalyst has a certain service life, the long-period stable operation of the Fischer-Tropsch synthesis device can be ensured only by frequently carrying out online updating, but the patent does not mention how to carry out online updating of the catalyst.
CN102553657A discloses a fischer-tropsch catalyst reduction method, which comprises the steps of firstly desulfurizing a feed gas, mixing the fischer-tropsch catalyst with liquid paraffin to obtain a homogenized catalyst slurry, pressing the catalyst into a reduction reactor by using an activator, inert gas or nitrogen, introducing the desulfurized feed gas and circulating gas into the reduction reactor, controlling the reduction conditions, and carrying out the reduction reaction of the fischer-tropsch catalyst. This patent carries out catalyst activation reduction through the slurry bed, and the activation catalyst is the thick liquid form, and the thick liquid form is difficult for preserving, and the activation cycle is long moreover for the ft synthesis device is worked on preparation time longer, and this just causes the ft synthesis operation in-process catalyst replacement dumb, and the device is difficult to smooth operation in succession. Also, there is no mention of how to perform the catalyst renewal on-line in this patent.
In addition, in the prior art, the wax residues generated in the fischer-tropsch synthesis reaction are usually treated by a multi-stage filtration method, the multi-stage filtration process is complex, the separation efficiency of solid waste and the waste catalyst is not high, secondary pollution is easy to generate, and the catalyst cannot be supplied as required due to the fact that the weight of the waste catalyst cannot be accurately obtained, so that the fischer-tropsch synthesis device cannot stably operate.
Disclosure of Invention
The invention aims to solve the problems of long updating period, high proportion, large disturbance to a device, complex wax residue treatment, low separation efficiency and no contribution to continuous and stable operation of the device in the prior art, and provides the online updating device and the online updating method for the catalyst of the slurry bed Fischer-Tropsch synthesis reactor.
In order to achieve the above object, the first aspect of the present invention provides an online catalyst renewal apparatus for a slurry bed fischer-tropsch synthesis reactor, comprising: a fluidized bed activation reactor 1, a cyclone separator 2, a storage tank 3, a heater 4, a slurry bed Fischer-Tropsch synthesis reactor 5 and a gas-liquid-solid separator 6 which are communicated in sequence, and a liquid-solid processing unit 8 communicated with the slurry bed Fischer-Tropsch synthesis reactor 5 and the gas-liquid-solid separator 6, wherein,
the fluidized bed activation reactor 1 is used for contacting a fresh Fischer-Tropsch catalyst with reducing gas to carry out catalyst activation;
the cyclone separator 2 is used for separating active catalyst from the product obtained by the catalyst activation;
the storage tank 3 is used for storing the separated active catalyst;
the heater 4 is used for heating the active catalyst to obtain a heated active catalyst;
the slurry bed Fischer-Tropsch synthesis reactor 5 is used for carrying out Fischer-Tropsch synthesis reaction on the active catalyst and reaction gas to obtain gas and first wax residues;
the gas-liquid-solid separator 6 is used for separating the gas to obtain second wax residue and reaction tail gas;
the liquid-solid treatment unit 8 is used for separating the synthetic wax and the solid waste from the first wax residue and the second wax residue.
Preferably, the apparatus further comprises a scale 31 for weighing the total weight of the tank 3 and the active catalyst stored in the tank 3.
Preferably, the device also comprises an oil recovery and tail gas decarbonization unit 7 arranged behind the gas-liquid-solid separator 6 and used for separating gas obtained from the Fischer-Tropsch synthesis reaction to obtain circulating tail gas and CO2Purge gas, light oil, synthetic water and heavy oil.
Preferably, the liquid-solid treatment unit 8 is a magnetic separator.
Preferably, the slurry bed Fischer-Tropsch synthesis reactor 5 further comprises a reaction gas feed inlet 51 for feeding reaction gas to the slurry bed Fischer-Tropsch synthesis reactor 5.
The second aspect of the invention provides a method for carrying out online updating on a catalyst in a Fischer-Tropsch synthesis reactor of a slurry bed by using the device, which comprises the following steps:
(A) adding a fresh Fischer-Tropsch catalyst into a fluidized bed activation reactor 1, and activating the catalyst in the atmosphere of reducing gas;
(B) removing fine particle Fischer-Tropsch catalyst and/or dust and tail gas generated by activation from the activated catalyst through a cyclone separator 2 to obtain an active catalyst, and conveying the active catalyst to a storage tank 3;
(C) introducing part of the active catalyst in the storage tank 3 into a heater 4 for heating to obtain a heated active catalyst, conveying the heated active catalyst to a slurry bed Fischer-Tropsch synthesis reactor 5, and carrying out Fischer-Tropsch synthesis reaction with reaction gas to obtain gas and first wax residues;
(D) and separating the gas in a gas-liquid-solid separator 6 to obtain reaction tail gas and second wax residues, and separating the second wax residues and the first wax residues into synthetic wax and solid waste in a liquid-solid treatment unit 8.
According to the technical scheme, the fluidized bed activation reactor, the cyclone separator, the storage tank, the slurry bed Fischer-Tropsch synthesis reactor, the gas-liquid-solid separator, the liquid-solid treatment unit and the like are combined, so that the activated catalyst is easy to store, the start-up preparation time of the Fischer-Tropsch synthesis reactor is shortened, the activation and wax residue treatment costs of the Fischer-Tropsch catalyst are reduced, the online updating of the catalyst in the slurry bed Fischer-Tropsch synthesis reactor according to the day is realized, and the stable operation of the device is ensured to the greatest extent.
Drawings
FIG. 1 is a schematic diagram of an on-line catalyst rejuvenation apparatus for a slurry Fischer-Tropsch synthesis reactor according to the invention.
Description of the reference numerals
1. Fluidized bed activation reactor 2, cyclone
3. Storage tank 31 and weighing scale
32. A first nitrogen inlet 33 and a second nitrogen inlet
4. Heater 41, third nitrogen inlet
5. Slurry bed Fischer-Tropsch synthesis reactor 51, reaction gas feed inlet
6. Gas-liquid-solid separator 7 and oil recovery and tail gas decarburization unit
8. Liquid-solid processing unit
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides an online catalyst renewal apparatus for a slurry bed fischer-tropsch synthesis reactor, as shown in fig. 1, the apparatus comprising: a fluidized bed activation reactor 1, a cyclone separator 2, a storage tank 3, a heater 4, a slurry bed Fischer-Tropsch synthesis reactor 5 and a gas-liquid-solid separator 6 which are communicated in sequence, and a liquid-solid processing unit 8 communicated with the slurry bed Fischer-Tropsch synthesis reactor 5 and the gas-liquid-solid separator 6, wherein,
the fluidized bed activation reactor 1 is used for contacting a fresh Fischer-Tropsch catalyst with reducing gas to carry out catalyst activation;
the cyclone separator 2 is used for separating active catalyst from the product obtained by the catalyst activation;
the storage tank 3 is used for storing the separated active catalyst;
the heater 4 is used for heating the active catalyst to obtain a heated active catalyst;
the slurry bed Fischer-Tropsch synthesis reactor 5 is used for carrying out Fischer-Tropsch synthesis reaction on the active catalyst and reaction gas to obtain gas and first wax residues;
the gas-liquid-solid separator 6 is used for separating the gas to obtain second wax residue and reaction tail gas;
the liquid-solid treatment unit 8 is used for separating the synthetic wax and the solid waste from the first wax residue and the second wax residue.
In the present invention, the product obtained by the catalyst activation contains not only the active catalyst having an appropriate particle size but also fine particles and/or dust having a smaller particle size and the off-gas generated by the activation. The cyclone 2 can separate fine particles and/or dust having a small particle size and off-gas generated by activation from an active catalyst having a suitable particle size.
In the present invention, the particle size range separated by the cyclone is suitable for the Fischer-Tropsch synthesis reaction, for example, the catalyst with the particle size of less than 25 μm is easy to cause the blockage of the Fischer-Tropsch synthesis reactor, so the cyclone can be limited to separate the fine particles with the particle size of less than 25 μm.
In the present invention, the apparatus further comprises a scale 31 for weighing the total weight of the tank 3 and the active catalyst stored in the tank 3, so as to facilitate the metering of the weight of the active catalyst into the slurry bed Fischer-Tropsch synthesis reactor 5.
In the present invention, the tank 3 is provided with a first nitrogen inlet 32 for preventing oxidation of the active catalyst in the tank 3, which acts as a nitrogen seal.
In the present invention, the storage tank 3 is provided with a second nitrogen inlet 33 for blowing the active catalyst in the storage tank 3 into the heater 4.
In the present invention, the heater 4 is used to heat the active catalyst to obtain a heated active catalyst. The heater 4 can prevent the temperature change from being overlarge when the active catalyst is added into the slurry bed Fischer-Tropsch synthesis reactor 5, thereby being beneficial to the stable operation of the device.
In the present invention, the heater 4 is provided with a third nitrogen inlet 41 for the heated active catalyst to be forced into the slurry bed Fischer-Tropsch synthesis reactor 5.
In the invention, the gas-liquid-solid separator 6 separates to obtain the second wax residue and the reaction tail gas, wherein the reaction tail gas can be cooled (air cooling, water cooling and the like) to obtain carbon monoxide, hydrogen and C1～C4Isogaseous products, and C5The above oil products.
In the invention, the device also comprises an oil recovery and tail gas decarbonization unit 7 arranged behind the gas-liquid-solid separator 6 and used for separating gas obtained from Fischer-Tropsch synthesis reaction to obtain circulating tail gas and CO2Purge gas, light oil, synthetic water and heavy oil. Wherein the obtained circulating tail gas mainly contains carbon monoxide, hydrogen and C1～C4The components can be used as reaction gas for the Fischer-Tropsch synthesis reaction of a slurry bed.
In the present invention, the liquid-solid treatment unit 8 may be a magnetic separator. Among them, magnetic separation is a technique of subjecting a substance to magnetic field treatment, and is a conventional technique in the art, and is not described herein again.
In the present invention, the slurry bed Fischer-Tropsch synthesis reactor 5 further comprises a reaction gas feed inlet 51 for feeding reaction gas into the slurry bed Fischer-Tropsch synthesis reactor 5.
The second aspect of the invention provides a method for carrying out online updating on a catalyst in a Fischer-Tropsch synthesis reactor of a slurry bed by using the device, which comprises the following steps:
(A) adding a fresh Fischer-Tropsch catalyst into a fluidized bed activation reactor 1, and activating the catalyst in the atmosphere of reducing gas;
(B) removing fine particle Fischer-Tropsch catalyst and/or dust and tail gas generated by activation from the activated catalyst through a cyclone separator 2 to obtain an active catalyst, and conveying the active catalyst to a storage tank 3;
(C) introducing part of the active catalyst in the storage tank 3 into a heater 4 for heating to obtain a heated active catalyst, conveying the heated active catalyst to a slurry bed Fischer-Tropsch synthesis reactor 5, and carrying out Fischer-Tropsch synthesis reaction with reaction gas to obtain gas and first wax residues;
(D) and separating the gas in a gas-liquid-solid separator 6 to obtain reaction tail gas and second wax residues, and separating the second wax residues and the first wax residues into synthetic wax and solid waste in a liquid-solid treatment unit 8.
According to the method of the invention, in the step (D), the reaction tail gas is introduced into an oil recovery and tail gas decarbonization unit 7 for separation to obtain the circulating tail gas and CO2Purge gas, light oil, synthetic water and heavy oil.
According to the process of the invention, in step (A), the reducing gas, which may be synthesis gas and/or a mixture of hydrogen and carbon monoxide, is aimed at activating the fresh Fischer-Tropsch catalyst.
According to the method of the present invention, in step (C), the total weight of the storage tank 3 and the active catalyst stored in the storage tank 3 is weighed by the weighing scale 31, and the weight of the portion of the active catalyst introduced into the heater 4 is measured.
According to the method of the present invention, in step (C), nitrogen gas introduced through the second nitrogen inlet 33 is used to blow a portion of the active catalyst in the storage tank 3 into the heater 4.
According to the process of the present invention, in step (C), nitrogen is introduced through the third nitrogen inlet 41 for pressurizing the heated active catalyst into the slurry bed Fischer-Tropsch synthesis reactor 5.
According to the process of the invention, in step (C), the reaction gas is aimed at enabling the Fischer-Tropsch synthesis reaction. The reaction gas may be syngas and/or recycled tail gas from the oil recovery and tail gas decarbonization unit 7.
According to the process of the present invention, the fluidized bed activation reactor 1 is operated under conditions that allow the activation of the fischer-tropsch catalyst, including but not limited to: the activation temperature is 250-300 ℃, the activation pressure is 0.1-1MPa, and the activation time is 5-20 h.
In the process according to the invention, the heater 4 is operated under conditions aimed at heating the active catalyst to the reaction temperature of the slurry bed Fischer-Tropsch synthesis reactor, including but not limited to: the heating temperature is 250 ℃ to 300 ℃, and the heating rate is 15-30 ℃/h.
According to the process of the invention, the slurry bed Fischer-Tropsch synthesis reactor 5 is operated under conditions aimed at enabling the Fischer-Tropsch synthesis reaction, including but not limited to: the reaction temperature is 250 ℃ and 300 ℃, and the reaction pressure is 2.5-3.5 MPa.
According to the method of the present invention, the gas-liquid-solid separator 6 is operated under the condition that the reaction tail gas and the second wax residue can be separated, and the operation condition includes but is not limited to: the separation temperature is 250 ℃ and 300 ℃, and the separation pressure is 2.5-3.5 MPa.
According to the process of the present invention, the content of the spent catalyst in the solid waste separated by the liquid-solid treatment unit 8 is greater than 60% by weight.
According to the method of the invention, the liquid-solid treatment unit 8 employs a magnetic separation treatment method. The magnetic separation treatment method is not easy to generate secondary pollution, and has high separation efficiency and good separation effect, thereby accurately obtaining the weight of the waste catalyst.
According to a specific embodiment of the present invention, the weight of the portion of the active catalyst in the storage tank 3 in the step (C) is the same as the weight of the waste catalyst in the solid waste. For example, 2.1t of solid waste containing 1.5t of waste catalyst is weighed by a scale 31, 1.5t of active catalyst in the storage tank is introduced into a heater 4 to be heated to obtain heated active catalyst, and the heated active catalyst is conveyed to a slurry bed Fischer-Tropsch synthesis reactor 5 to be subjected to Fischer-Tropsch synthesis reaction with reaction gas. Therefore, the catalyst in the slurry bed Fischer-Tropsch synthesis reactor is updated on line according to the day, and the stable operation of the device is ensured to the maximum extent by combining the fluidized bed activation reactor, the cyclone separator, the storage tank, the slurry bed Fischer-Tropsch synthesis reactor, the gas-liquid-solid separator, the liquid-solid processing unit and the like.
The present invention will be described in detail below by way of examples.
Example 1
(A) As shown in FIG. 1, 10t of fresh catalyst was charged into the fluidized bed reactor 1, and activation was carried out in the atmosphere of synthesis gas at an activation temperature of 260 ℃ under an activation pressure of 0.2MPa and at a space velocity of 1000Nm for fresh synthesis gas3/t-cat/h，H2The CO is 5.0, the activation time is 12h, and the operation period of the fluidized bed reactor is 2.5 days.
(B) The activated catalyst is separated from the catalyst and/or dust with the particle size of less than 25 mu m and tail gas generated by activation by a cyclone separator 2, and the active catalyst with the particle size of more than 25 mu m is obtained. And the active catalyst is transferred to a storage tank 3 for storage, the storage tank being provided with a scale 31, a first nitrogen inlet 32 and a second nitrogen inlet 33. The scale 31 is used for weighing the total weight of the storage tank 3 and the active catalyst stored in the storage tank 3, and is convenient for metering the weight of the catalyst added into the slurry bed Fischer-Tropsch synthesis reactor; the first nitrogen inlet 32 is connected to a nitrogen line, functioning as a nitrogen seal, for preventing oxidation of the active catalyst; the second nitrogen inlet 33 is connected to a nitrogen line for blowing the active catalyst in the storage tank 3 into the heater 4.
(C) 1.5t of active catalyst in the storage tank 3 is heated to 260 ℃ at a heating rate of 20 ℃/h through the heater 4 every day, and nitrogen introduced through a third nitrogen inlet 41 of the heater 4 is pressed into the slurry bed Fischer-Tropsch synthesis reactor 5. In a slurry bed Fischer-Tropsch synthesis reactor 5, carrying out Fischer-Tropsch synthesis reaction on an active catalyst and synthesis gas, wherein the reaction temperature of the slurry bed Fischer-Tropsch synthesis reactor is 265 ℃, the reaction pressure is 3MPa, the catalyst inventory is 70t, and synthetic wax, gas and first slag wax are obtained after the Fischer-Tropsch synthesis reaction. And introducing the gas into a gas-liquid-solid separator 6 for separation, wherein the separation temperature is 250 ℃, and the pressure is 2.5MPa, so as to obtain second wax residue and reaction tail gas. WhereinIntroducing reaction tail gas into an oil recovery and tail gas decarbonization unit 7 for separation to obtain circulating tail gas and CO2The purge gas, the light oil, the synthetic water and the heavy oil, and the circulating tail gas can be recycled.
(D) 0.5t of second wax residue containing solid waste and waste catalyst is separated from the bottom of the gas-liquid-solid separator 6 every day; the first wax residue containing solid waste and spent catalyst was discharged from the bottom of the slurry Fischer-Tropsch reactor 5 at 9.7t per day. And the liquid-solid treatment unit 8 performs magnetic separation on the synthetic wax and the solid waste from the second wax residue and the first wax residue by adopting a magnetic separation method to obtain 2.1t of solid waste, wherein the solid waste contains 1.5t of waste catalyst.
And calculating to obtain: the catalyst of the slurry bed Fischer-Tropsch synthesis reactor is updated by 2.1 percent every day (the calculation formula is 1.5t/70t multiplied by 100 percent), the disturbance to the device is small, and the continuous and stable operation of the device is realized. The content of the waste catalyst in the solid waste was 71.4 wt% (the calculation formula was 1.5t/2.1t × 100%), and the separation efficiency was high.
Example 2
(A) As shown in FIG. 1, 10t of fresh catalyst was charged into the fluidized bed reactor 1, and activation was carried out in the atmosphere of synthesis gas at an activation temperature of 250 ℃ and an activation pressure of 0.1MPa at a space velocity of 1000Nm for fresh synthesis gas3/t-cat/h，H2The CO is 5.0, the activation time is 20h, and the operation period of the fluidized bed reactor is 2.5 days.
(B) The activated catalyst is separated from the catalyst and/or dust with the particle size of less than 25 mu m and tail gas generated by activation by a cyclone separator 2, and the active catalyst with the particle size of more than 25 mu m is obtained. And the active catalyst is transferred to a storage tank 3 for storage, the storage tank being provided with a scale 31, a first nitrogen inlet 32 and a second nitrogen inlet 33. The scale 31 is used for weighing the total weight of the storage tank 3 and the active catalyst stored in the storage tank 3, and is convenient for metering the weight of the catalyst added into the slurry bed Fischer-Tropsch synthesis reactor; the first nitrogen inlet 32 is connected to a nitrogen line, functioning as a nitrogen seal, for preventing oxidation of the active catalyst; the second nitrogen inlet 33 is connected to a nitrogen line for blowing the active catalyst in the storage tank 3 into the heater 4.
(C) 1.5t of active catalyst in the storage tank 3 is heated to 250 ℃ at a heating rate of 15 ℃/h through the heater 4 every day, and nitrogen introduced through a third nitrogen inlet 41 of the heater 4 is pressed into the slurry bed Fischer-Tropsch synthesis reactor 5. In a slurry bed Fischer-Tropsch synthesis reactor 5, carrying out Fischer-Tropsch synthesis reaction on an active catalyst and synthesis gas, wherein the reaction temperature of the slurry bed Fischer-Tropsch synthesis reactor is 250 ℃, the reaction pressure is 3.5MPa, the catalyst inventory is 70t, and synthetic wax, gas and first slag wax are obtained after the Fischer-Tropsch synthesis reaction. And introducing the gas into a gas-liquid-solid separator 6 for separation, wherein the separation temperature is 250 ℃, and the pressure is 3.5MPa, so as to obtain second wax residue and reaction tail gas. Wherein, the reaction tail gas is led into an oil recovery and tail gas decarbonization unit 7 for separation to obtain the circulating tail gas and CO2The purge gas, the light oil, the synthetic water and the heavy oil, and the circulating tail gas can be recycled.
(D) 0.5t of second wax residue containing solid waste and waste catalyst is separated from the bottom of the gas-liquid-solid separator 6 every day; the first wax residue containing solid waste and spent catalyst was discharged from the bottom of the slurry Fischer-Tropsch reactor 5 every two days for 9.7 t. And the liquid-solid treatment unit 8 performs magnetic separation on the synthetic wax and the solid waste from the second wax residue and the first wax residue by adopting a magnetic separation method to obtain 2.1t of solid waste, wherein the solid waste contains 1.5t of waste catalyst.
And calculating to obtain: the catalyst of the slurry bed Fischer-Tropsch synthesis reactor is updated by 2.1 percent every day (the calculation formula is 1.5t/70t multiplied by 100 percent), the disturbance to the device is small, and the continuous and stable operation of the device is realized. The content of the waste catalyst in the solid waste was 71.4 wt% (the calculation formula was 1.5t/2.1t × 100%), and the separation efficiency was high.
Example 3
(A) As shown in FIG. 1, 10t of fresh catalyst was charged into a fluidized bed reactor 1, and activation was carried out in the atmosphere of synthesis gas at an activation temperature of 300 ℃ and an activation pressure of 1MPa at a space velocity of 1000Nm for fresh synthesis gas3/t-cat/h，H2the/CO is 5.0, the activation time is 5h, and the operation period of the fluidized bed reactor is 2 days.
(B) The activated catalyst is separated from the catalyst and/or dust with the particle size of less than 25 mu m and tail gas generated by activation by a cyclone separator 2, and the active catalyst with the particle size of more than 25 mu m is obtained. And the active catalyst is transferred to a storage tank 3 for storage, the storage tank being provided with a scale 31, a first nitrogen inlet 32 and a second nitrogen inlet 33. The scale 31 is used for weighing the total weight of the storage tank 3 and the active catalyst stored in the storage tank 3, and is convenient for metering the weight of the catalyst added into the slurry bed Fischer-Tropsch synthesis reactor; the first nitrogen inlet 32 is connected to a nitrogen line, functioning as a nitrogen seal, for preventing oxidation of the active catalyst; the second nitrogen inlet 33 is connected to a nitrogen line for blowing the active catalyst in the storage tank 3 into the heater 4.
(C) 1.5t of active catalyst in the storage tank 3 is heated to 300 ℃ at the heating rate of 30 ℃/h through the heater 4 every day, and nitrogen introduced through a third nitrogen inlet 41 of the heater 4 is pressed into the slurry bed Fischer-Tropsch synthesis reactor 5. In a slurry bed Fischer-Tropsch synthesis reactor 5, carrying out Fischer-Tropsch synthesis reaction on an active catalyst and synthesis gas, wherein the reaction temperature of the slurry bed Fischer-Tropsch synthesis reactor is 300 ℃, the reaction pressure is 2.5MPa, the catalyst inventory is 70t, and synthetic wax, gas and first slag wax are obtained after the Fischer-Tropsch synthesis reaction. And introducing the gas into a gas-liquid-solid separator 6 for separation, wherein the separation temperature is 300 ℃, and the pressure is 2.5MPa, so as to obtain second wax residue and reaction tail gas. Wherein, the reaction tail gas is led into an oil recovery and tail gas decarbonization unit 7 for separation to obtain the circulating tail gas and CO2The purge gas, the light oil, the synthetic water and the heavy oil, and the circulating tail gas can be recycled.
(D) 0.5t of second wax residue containing solid waste and waste catalyst is separated from the bottom of the gas-liquid-solid separator 6 every day; the first wax residue containing solid waste and spent catalyst was discharged from the bottom of the slurry Fischer-Tropsch reactor 5 at 9.7t per day. And the liquid-solid treatment unit 8 performs magnetic separation on the synthetic wax and the solid waste from the second wax residue and the first wax residue by adopting a magnetic separation method to obtain 2.1t of solid waste, wherein the solid waste contains 1.5t of waste catalyst.
And calculating to obtain: the catalyst of the slurry bed Fischer-Tropsch synthesis reactor is updated by 2.1 percent every day (the calculation formula is 1.5t/70t multiplied by 100 percent), the disturbance to the device is small, and the continuous and stable operation of the device is realized. The content of the waste catalyst in the solid waste was 71.4 wt% (the calculation formula was 1.5t/2.1t × 100%), and the separation efficiency was high.
Comparative example 1
(A) Adding 10t of fresh catalyst into a slurry bed reactor, and activating in the atmosphere of synthesis gas at the activation temperature of 260 ℃, the activation pressure of 2.9MPa and the airspeed of the fresh synthesis gas of 1000Nm3/t-cat/h，H2the/CO was 5.0, the activation time was 24h and the operating cycle of the slurry reactor was 3 days.
(B) Every 7 days, 10t of active catalyst was pressed into the slurry bed Fischer-Tropsch reactor. In a slurry bed Fischer-Tropsch synthesis reactor, carrying out Fischer-Tropsch synthesis reaction on an active catalyst and synthesis gas, wherein the reaction temperature of the slurry bed Fischer-Tropsch synthesis reactor is 265 ℃, the reaction pressure is 3MPa, the catalyst inventory is 70t, and synthetic wax, gas and residue wax are obtained after the Fischer-Tropsch synthesis reaction.
(C) 66.7t of residual wax containing solid waste and spent catalyst were discharged every 7 days from the bottom of the slurry bed Fischer-Tropsch reactor. And separating the synthetic wax from the solid waste by virtue of multistage filtration separation to obtain 20t of solid waste, wherein 9.9t of waste catalyst is contained.
And calculating to obtain: the updating proportion of the catalyst in the slurry bed Fischer-Tropsch synthesis reactor is 14.2 percent (the calculation formula is 10t/70t multiplied by 100 percent) every time (7 days), the disturbance to the device is large, and the continuous and stable operation of the device is not facilitated. The content of the waste catalyst in the solid waste was 49.5% by weight (calculated as 9.9t/20t × 100%), and the separation efficiency was low.
Comparative example 2
(A) Adding 4.3t of fresh catalyst into a slurry bed reactor, and activating in the atmosphere of synthesis gas at the activation temperature of 260 ℃, the activation pressure of 2.9MPa and the airspeed of the fresh synthesis gas of 1000Nm3/t-cat/h，H2the/CO was 5.0, the activation time was 24h and the operating cycle of the slurry reactor was 3 days.
(B) Every 3 days, 4.3t of active catalyst was pressed into the slurry bed Fischer-Tropsch reactor. In a slurry bed Fischer-Tropsch synthesis reactor, carrying out Fischer-Tropsch synthesis reaction on an active catalyst and synthesis gas, wherein the reaction temperature of the slurry bed Fischer-Tropsch synthesis reactor is 265 ℃, the reaction pressure is 3MPa, the catalyst inventory is 70t, and synthetic wax, gas and residue wax are obtained after the Fischer-Tropsch synthesis reaction.
(C) The bottom of the slurry Fischer-Tropsch reactor was drained every 3 days for 28.6t of wax residue containing solid waste and spent catalyst. And separating the synthetic wax from the solid waste by virtue of multistage filtration separation to obtain 8.6t of solid waste, wherein the waste catalyst is contained in the waste wax for 4.2 t.
And calculating to obtain: the catalyst updating proportion of the slurry bed Fischer-Tropsch synthesis reactor is 6.1 percent (the calculation formula is 4.3t/70t multiplied by 100 percent) every time (3 days), the disturbance to the device is large, and the continuous and stable operation of the device is not facilitated. The content of the waste catalyst in the solid waste was 49.0% by weight (calculated as 4.2t/8.6t × 100%), and the separation efficiency was low.
It can be seen from the results of the examples and the comparative examples that, by adopting the online renewing device of the catalyst of the slurry bed Fischer-Tropsch synthesis reactor, the wax residue treatment of the device is simple and convenient, and the separation efficiency is high, specifically, the content of the waste catalyst in the solid waste of the invention can reach 71.4%, while the content of the waste catalyst in the solid waste of the comparative examples 1 and 2 is only about 49.0 wt%. Compared with the catalyst activated by a slurry bed, the catalyst activated by the method is easy to store, and can not occupy the start-up preparation time, so that the start-up preparation time of the Fischer-Tropsch synthesis device is shortened. In addition, the invention realizes the online update of the catalyst in the slurry bed Fischer-Tropsch synthesis reactor according to the day, the update proportion per day is only about 2 percent, and the update proportion per time without adopting the method of the invention is more than 6.1 percent, even reaches 14.2 percent, thereby showing that the device adopting the invention can shorten the Fischer-Tropsch catalyst update period, has small update proportion per time, has small disturbance to the device and can ensure the stable operation of the device to the maximum extent.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (9)
1. An online renewing device of a slurry bed Fischer-Tropsch synthesis reactor catalyst, which comprises: a fluidized bed activation reactor (1), a cyclone separator (2), a storage tank (3), a heater (4), a slurry bed Fischer-Tropsch synthesis reactor (5), a gas-liquid-solid separator (6), an oil recovery and tail gas decarburization unit (7) and a liquid-solid treatment unit (8) which are communicated with the slurry bed Fischer-Tropsch synthesis reactor (5) and the gas-liquid-solid separator (6) in sequence, wherein,
the fluidized bed activation reactor (1) is used for contacting a fresh Fischer-Tropsch catalyst with reducing gas to carry out catalyst activation;
a cyclone (2) for separating the active catalyst from the product resulting from the catalyst activation;
the storage tank (3) is used for storing the separated active catalyst; the storage tank (3) is provided with a scale (31) for weighing the total weight of the storage tank (3) and the active catalyst stored in the storage tank (3);
the heater (4) is used for heating the active catalyst to obtain a heated active catalyst;
the slurry bed Fischer-Tropsch synthesis reactor (5) is used for carrying out Fischer-Tropsch synthesis reaction on the active catalyst and reaction gas to obtain gas and first wax residues;
the gas-liquid-solid separator (6) is used for separating the gas to obtain second wax residue and reaction tail gas;
the oil recovery and tail gas decarbonization unit (7) is used for separating gas obtained by Fischer-Tropsch synthesis reaction to obtain circulating tail gas and CO2Purge gas, light oil, synthetic water and heavy oil;
the liquid-solid treatment unit (8) adopts a magnetic separation treatment mode and is used for separating the synthetic wax from the solid waste from the first wax residue and the second wax residue.
2. The device according to claim 1, wherein the tank (3) is provided with a first nitrogen inlet (32) for preventing oxidation of the active catalyst inside the tank (3);
and/or the storage tank (3) is provided with a second nitrogen inlet (33) for blowing the active catalyst in the storage tank (3) into the heater (4).
3. An apparatus according to claim 1, wherein the heater (4) is provided with a third nitrogen inlet (41) for pressing heated active catalyst into the slurry bed fischer-tropsch synthesis reactor (5).
4. The apparatus according to claim 1, wherein the liquid-solid treatment unit (8) is a magnetic separator;
and/or the slurry bed Fischer-Tropsch synthesis reactor (5) also comprises a reaction gas feeding hole (51) for feeding reaction gas into the slurry bed Fischer-Tropsch synthesis reactor (5).
5. A method for on-line catalyst renewal of a slurry Fischer-Tropsch synthesis reactor by the apparatus of any one of claims 1 to 4, comprising the steps of:
(A) adding a fresh Fischer-Tropsch catalyst into a fluidized bed activation reactor (1), and activating the catalyst in the atmosphere of reducing gas;
(B) removing fine particle Fischer-Tropsch catalyst and/or dust and tail gas generated by activation from the activated catalyst through a cyclone separator (2) to obtain an active catalyst, and conveying the active catalyst to a storage tank (3);
(C) introducing part of the active catalyst in the storage tank (3) into a heater (4) for heating to obtain a heated active catalyst, conveying the heated active catalyst to a slurry bed Fischer-Tropsch synthesis reactor (5), and carrying out Fischer-Tropsch synthesis reaction with reaction gas to obtain gas and first slag wax;
(D) and separating the gas in a gas-liquid-solid separator (6) to obtain reaction tail gas and second wax residues, and separating the second wax residues and the first wax residues into synthetic wax and solid waste in a liquid-solid treatment unit (8).
6. The method according to claim 5, wherein step (D) further comprises passing the reaction off-gas to an oil recovery and off-gas decarbonization unit (7) for separationSeparating to obtain circulating tail gas and CO2Purge gas, light oil, synthetic water and heavy oil.
7. The process of claim 5, wherein, in step (A), the reducing gas is syngas and/or a mixture of hydrogen and carbon monoxide;
and/or, in step (C), weighing the total weight of the storage tank (3) and the active catalyst stored in the storage tank (3) by a weighing scale (31) and weighing the part of the active catalyst passing into the heater (4);
and/or, in step (C), nitrogen introduced through the second nitrogen inlet (33) is used to blow part of the active catalyst in the storage tank (3) into the heater (4);
and/or, in step (C), nitrogen is introduced through the third nitrogen inlet (41) for pressurising the heated active catalyst into the slurry bed Fischer-Tropsch synthesis reactor (5);
and/or, in step (C), the reaction gas is synthesis gas and/or recycled tail gas from an oil recovery and tail gas decarbonization unit (7).
8. The method according to claim 6, wherein the operating conditions of the fluidized bed activation reactor (1) comprise: the activation temperature is 250-300 ℃, the activation pressure is 0.1-1MPa, and the activation time is 5-20 h;
and/or the operating conditions of the heater (4) comprise: the heating temperature is 250-300 ℃, and the heating rate is 15-30 ℃/h;
and/or the operating conditions of the slurry bed Fischer-Tropsch synthesis reactor (5) comprise: the reaction temperature is 250 ℃ and 300 ℃, and the reaction pressure is 2.5-3.5 MPa;
and/or the operating conditions of the gas-liquid-solid separator (6) comprise: the separation temperature is 250 ℃ and 300 ℃, and the separation pressure is 2.5-3.5 MPa.
9. A process according to claim 5, wherein the solid waste separated by the liquid-solid treatment unit (8) has a spent catalyst content of more than 60% by weight.
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| CN103551207A (en) * | 2013-11-01 | 2014-02-05 | 神华集团有限责任公司 | Fixed fluidized bed or gas-solid bubbling bed Fischer-Tropsch catalyst reduction activation system and technique |
| CN106311361A (en) * | 2015-06-24 | 2017-01-11 | 神华集团有限责任公司 | System and method for activation and online renewing of catalyst |
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| CN103551207A (en) * | 2013-11-01 | 2014-02-05 | 神华集团有限责任公司 | Fixed fluidized bed or gas-solid bubbling bed Fischer-Tropsch catalyst reduction activation system and technique |
| CN106311361A (en) * | 2015-06-24 | 2017-01-11 | 神华集团有限责任公司 | System and method for activation and online renewing of catalyst |
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