CN111187639A - Device and method for separating waste catalyst in Fischer-Tropsch synthesis slag wax - Google Patents
Device and method for separating waste catalyst in Fischer-Tropsch synthesis slag wax Download PDFInfo
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- CN111187639A CN111187639A CN201811362360.0A CN201811362360A CN111187639A CN 111187639 A CN111187639 A CN 111187639A CN 201811362360 A CN201811362360 A CN 201811362360A CN 111187639 A CN111187639 A CN 111187639A
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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
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/10—Magnetic separation acting directly on the substance being separated with cylindrical material carriers
- B03C1/14—Magnetic separation acting directly on the substance being separated with cylindrical material carriers with non-movable magnets
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Abstract
The invention relates to the field of Fischer-Tropsch synthesis slag wax treatment, and discloses a device and a method for separating a waste catalyst in Fischer-Tropsch synthesis slag wax. The device comprises: the device comprises a closed box body, a rotary sealing rotary drum, a magnet and a scraper blade, wherein the closed box body is provided with a wax residue inlet, a synthetic wax outlet, a waste catalyst outlet and a heat insulation structure; the position of the magnet corresponds to the space between the wax residue inlet and the synthetic wax outlet in the box body, and the magnet is used for attracting the waste catalyst in the Fischer-Tropsch synthetic wax residue to be attached to the outer surface of the rotary drum; the scraper is used to remove the spent catalyst on the outer surface of the drum. The device and the method provided by the invention can better realize the recovery of the heavy wax in the Fischer-Tropsch synthesis slag wax.
Description
Technical Field
The invention relates to the field of Fischer-Tropsch synthesis slag wax treatment, in particular to a device for separating a waste catalyst in Fischer-Tropsch synthesis slag wax and a method for separating the catalyst in the Fischer-Tropsch synthesis slag wax.
Background
In the slurry bed Fischer-Tropsch synthesis process adopting the iron-based catalyst, the catalyst is gradually deactivated, but the iron-based catalyst cannot be regenerated, so that the catalyst in the slurry bed Fischer-Tropsch synthesis reactor needs to be periodically added and discharged to keep the overall activity of the catalyst in the reactor to meet the requirement.
The residual wax discharged from the slurry bed reactor is slurry containing 10-20 wt% of catalyst and wax, and needs to be separated and treated to recover wax. The prior art generally adopts a filtration method to realize the separation of the waste catalyst and the wax, but has the problems of incapability of continuous production, low efficiency and high operation cost.
CN104307235A discloses sediment wax filtration equipment to be located vertical cylinder casing (6) inside central authorities central collecting pipe (5) and be the axis, parallel mount has a plurality of horizontal blade (1), and every horizontal blade (1) includes blade body (11) and surface filtration channel layer, its characterized in that at least: and a sealing device (4) is arranged at the joint of the bottom of the central collecting pipe (5) and the discharge pipe (3), and the sealing device (4) is comprehensively sealed by adopting a sealing ring (41) and a friction plate (43).
CN105542855A discloses a wax residue treatment method, which comprises the following steps: 1) heating the slag wax to keep the wax in the slag wax in a molten state; 2) carrying out high-temperature separation on the slag wax subjected to the heating treatment to obtain molten wax and solid residue; 3) and carrying out incineration treatment on the solid residues.
CN101970605A discloses a process for selectively removing fischer-tropsch catalyst, a process for selectively removing fischer-tropsch catalyst from a fischer-tropsch synthesis reactor, comprising: a step of extracting a slurry containing a Fischer-Tropsch synthesis crude oil obtained by a Fischer-Tropsch synthesis reaction and a magnetic Fischer-Tropsch catalyst from a Fischer-Tropsch synthesis reactor, a step of separating a catalyst having a predetermined particle size or more from the slurry by using a first solid-liquid separation device, and a step of separating a catalyst which has not been separated by the first solid-liquid separation device from the slurry after the catalyst having the predetermined particle size or more has been separated by using a second solid-liquid separation device; wherein the catalyst separated from the slurry by the first solid-liquid separation device is returned to the Fischer-Tropsch synthesis reactor and reused, the catalyst separated from the slurry by the second solid-liquid separation device is discharged outside the system, and the average particle diameter of the catalyst discharged outside the system is smaller than the average particle diameter of the catalyst in the slurry at the outlet of the Fischer-Tropsch synthesis reactor.
CN102186593A discloses a system for separating liquids from solids comprising: an immobilization apparatus comprising an immobilization vessel comprising a bed of magnetizable material and a magnet configured to generate a magnetic field within the immobilization vessel, wherein the immobilization vessel further comprises an immobilization vessel outlet and an immobilization vessel inlet for a fluid comprising a liquid and metal-containing particles.
CN103846160A discloses a separation method of slurry bed fischer-tropsch synthesis heavy product and catalyst, comprising: degassing slurry of Fischer-Tropsch synthesis heavy products from a slurry bed reactor and magnetic Fischer-Tropsch synthesis catalyst particles, and then feeding the slurry into a separator; in the settling zone of the lower middle part of the separator, the large particles of the catalyst are settled by gravity and are primarily separated from the heavy Fischer-Tropsch synthesis product; wherein the dilute slurry enters a magnetic separation area at the middle upper part of the separator, and the thick slurry rich in catalyst particles at the lower part of the separator automatically circulates back to the slurry bed reactor; the middle upper part of the separator is provided with a magnetic separation area close to the wall of the separator, the magnetic separation area consists of a magnet arranged outside the separator, a fluid flow channel in the separator and a catalyst guide pipe, and is provided with n layers of magnetic separation devices; the slurry after the preliminary separation enters a magnetic separation area along the fluid flow channel, a first layer of magnetic separation device from bottom to top of the magnetic separation area firstly adsorbs catalyst particles, when the adsorbed catalyst particles reach a set amount, the magnetic field of the device is removed, the catalyst particles without magnetic adsorption sink to the catalyst guide pipe by gravity, flow to the bottom of the separator along the catalyst guide pipe and circulate back to the slurry bed reactor, meanwhile, a second layer of magnetic separation device from bottom to top of the magnetic separation area is started to adsorb the catalyst particles flowing upwards along with the liquid, then the magnetic field is removed, and the catalyst particles without magnetic adsorption sink to the catalyst guide pipe by gravity; until the nth magnetic separation device starts the magnetic field and removes the magnetic field operation, make more catalyst particles separate and circulate back to the slurry bed reactor in the magnetic separation zone, after the nth magnetic separation device is processed, only contain the heavy product of Fischer-Tropsch synthesis of a small amount of catalyst particles and enter the filtering zone on the upper portion of the separator along the said fluid flow path; one or more groups of filter elements are arranged in the filter area, and the Fischer-Tropsch synthesis heavy product containing a small amount of catalyst particles after magnetic separation is discharged out of the separator after the catalyst particles are further separated by the filter elements; periodically back washing the filter element to make the filtered catalyst particles flow to the bottom of the separator along the guide pipe by means of gravity and circulate back to the slurry bed reactor.
But the practical application of the prior art still has the problems of poor continuous operability, complex process and low recovery rate of the wax residue.
Disclosure of Invention
The invention aims to solve the problems of poor operation continuity, complex process and low recovery rate of heavy wax in the separation of waste catalysts from Fischer-Tropsch synthesis residue wax in the prior art, and provides a device and a method for separating the waste catalysts from the Fischer-Tropsch synthesis residue wax.
In order to achieve the above object, the first aspect of the present invention provides an apparatus for separating a spent catalyst from fischer-tropsch synthesis residue wax, comprising:
the device comprises a closed box body, a rotary sealing rotary drum, a magnet and a scraper blade, wherein the closed box body is provided with a wax residue inlet, a synthetic wax outlet, a waste catalyst outlet and a heating and heat-insulating structure;
the position of the magnet corresponds to the space between the wax residue inlet and the synthetic wax outlet in the box body, and the magnet is used for attracting the waste catalyst in the Fischer-Tropsch synthetic wax residue to be attached to the outer surface of the rotary drum; the scraper is used to remove the spent catalyst on the outer surface of the drum.
Preferably, the box body is arranged at a distance from the rotary drum to form a space for flowing the Fischer-Tropsch synthesis wax slag or moving the waste catalyst.
Preferably, the drum is spaced from the magnets, which occupy 1/4-2/3 of the inner circumference of the drum.
Preferably, the apparatus further comprises drive means for driving the drum to rotate in a direction opposite to the direction of flow of the Fischer-Tropsch wax in the housing.
The second aspect of the invention provides a method for separating a waste catalyst in Fischer-Tropsch synthesis slag wax, which comprises the following steps:
(a) carrying out flash evaporation and cooling on the Fischer-Tropsch synthesis product to obtain Fischer-Tropsch synthesis residue wax from which synthesis gas and light hydrocarbon are removed;
(b) introducing the wax residue into the device, and performing magnetic separation under heating and inert atmosphere to obtain synthetic wax and a waste catalyst;
(c) and introducing the synthetic wax into a precoating filter for precoating filtration to obtain heavy wax and waste clay.
Preferably, in step (a), the flash pressure is 0.3-1MPa, and the temperature reached by the temperature reduction is 120-230 ℃.
Preferably, in step (b), the slag wax flows downward by gravity, and the rotating direction of the rotating drum in the device is opposite to the flowing direction of the slag wax.
Preferably, the surface linear velocity of the drum rotation is 0.01 to 1.5 m/s.
Preferably, in step (b), the heating temperature is 120-230 ℃; the working pressure of the device is 0.1-0.8 MPa.
Preferably, in the step (b), the magnetic induction intensity of the magnetic separation is 100-15000 gauss.
Through the technical scheme, the magnetic separation device with the rotary drum can more effectively separate the waste catalyst in the Fischer-Tropsch synthesis slag wax, the rotary drum and the slag wax in the device rotate and flow in opposite directions under the protection of heating and inert atmosphere, the fixed magnet arranged in the rotary drum can attract the waste catalyst in the slag wax to be attached to the surface of the rotary drum, and the continuous removal of the waste catalyst in the slag wax can be realized along with the rotation of the rotary drum. The device is simple and convenient to operate, can continuously operate and effectively realizes the separation of the waste catalyst in the wax residue. By utilizing the device, the method for separating the waste catalyst in the Fischer-Tropsch synthesis slag wax can better realize the recovery of the heavy wax in the Fischer-Tropsch synthesis slag wax.
Drawings
FIG. 1 is a schematic cross-sectional view of an apparatus for separating spent catalyst from Fischer-Tropsch wax according to the present invention;
FIG. 2 is a schematic flow diagram of the process of the present invention for separating spent catalyst from Fischer-Tropsch wax.
Description of the reference numerals
1 bracket 2 case 3 magnet
4 slag wax inlet 5 shell 6 rotary drum
7 shaft 8 waste catalyst outlet 9 scraper
10 outlet for synthetic wax
E2 slag wax flash tank E3 magnetic separation device of E1 slurry bed reactor
E5 waste catalyst receiving tank E6 precoating filter of E4 synthetic wax intermediate tank
E7 heavy wax tank E8 waste clay receiving tank E9 incinerator
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 apparatus for separating a waste catalyst from fischer-tropsch wax residue, as shown in fig. 1, including:
a closed box body 2 provided with a wax residue inlet 4, a synthetic wax outlet 10, a waste catalyst outlet 8 and a heating and heat-preserving structure, a rotatable sealed rotary drum 6 arranged in the box body 2, a magnet 3 fixed in the rotary drum 6, and a scraper 9 arranged at the waste catalyst outlet 8 and contacted with the outer surface of the rotary drum 6;
the position of the magnet 3 corresponds to the space between the wax residue inlet 4 and the synthetic wax outlet 10 in the box body 2, and is used for attracting the waste catalyst in the Fischer-Tropsch synthetic wax residue to be attached to the outer surface of the rotary drum 6; the scraper 9 is used to remove the spent catalyst on the outer surface of the drum 6.
The device provided by the invention can be shown in figure 1, and can be horizontally placed, and the whole box body 2 is horizontally placed on the bracket 1. The box 2 may be a horizontally placed long cylinder with the central axis of the cylinder parallel to the ground. The drum 6 is disposed coaxially with the casing 2. The diameter of the rotary drum 6 is smaller than that of the box body 2, and preferably, the box body 2 is arranged at a distance from the rotary drum 6 to form a space for flowing Fischer-Tropsch synthesis slag wax or moving waste catalyst. The space formed between the drum 6 and the housing 2 can accommodate Fischer-Tropsch wax or spent catalyst. The magnet 3 is fixedly arranged inside the drum 6 and does not rotate with the drum 6. In the present invention, it is preferable that the drum 6 is disposed at a distance from the magnets 3, and the magnets 3 occupy 1/4-2/3 of the inner circumference of the drum 6. The magnet 3 is arranged to form a magnetic area and a non-magnetic area inside the box body 2. The magnetized zone may correspond to the space between the wax inlet 4 and the synthetic wax outlet 10 through which the Fischer-Tropsch synthetic wax passes. The rest space in the box body 2 is the nonmagnetic zone and comprises a waste catalyst outlet 8, and the Fischer-Tropsch synthesis slag wax does not pass through the nonmagnetic zone. While the Fischer-Tropsch wax is in the magnetized zone, the contained spent catalyst may be attracted to the surface of the rotating drum 6. When the rotating drum 6 rotates to a non-magnetic area, the attracted waste catalyst can fall off. The magnet 3 can be a cylindrical body with the bottom surface and the top surface in the same fan shape, the cylindrical body and the rotary drum 6 are coaxially arranged, the central angle of the fan shape can be 90-240 degrees, and only the requirement of providing a magnetic field for attracting the waste catalyst in the slag wax is met.
According to the invention, the apparatus preferably further comprises drive means for driving the drum 6 in rotation in a direction opposite to the direction of flow of the Fischer-Tropsch wax in the tank 2. Thus, when the rotary drum 6 rotates to pass through the magnetic zone, the waste catalyst in the Fischer-Tropsch synthesis slag wax passing through the magnetic zone is attracted in a contact or non-contact mode; the rotary drum 6 then carries the attracted waste catalyst to rotate into the nonmagnetic zone and does not contact with the Fischer-Tropsch synthesis wax residue, and the waste catalyst can be separated from the rotary drum 6 in the nonmagnetic zone. The drum 6 from which the spent catalyst is removed can continue to rotate to reenter the magnetized zone, repeating the operation of attracting the spent catalyst.
In the invention, preferably, as shown in figure 1, the Fischer-Tropsch synthesis wax slag can enter the device from a wax slag inlet 4 and flows into a space between the box body 2 and the rotary drum 6 in a counter-clockwise direction under the action of gravity, and a space through which the magnet 3 flows corresponding to the wax slag is a magnetic area which provides a magnetic field to attract the waste catalyst in the wax slag; the waste catalyst is attached to the surface of the rotary drum 6, and the wax residue after catalyst removal continuously flows into the bottom of the device anticlockwise and is discharged from a synthetic wax outlet 10; the rotary drum 6 with the waste catalyst continuously rotates along the clockwise direction, does not contact with the Fischer-Tropsch synthesis slag wax, and then rotates to a nonmagnetic area, so that the waste catalyst is not attracted by a magnetic field any more, can be separated from the rotary drum 6 through the scraper 9, and is discharged from the waste catalyst outlet 8.
According to the present invention, it is preferable that the synthetic wax outlet 10 is provided at the bottom of the tank 2 and is opened downward, the wax residue inlet 4 is provided above one side of the tank 2 and is opened upward, and the spent catalyst outlet 8 is provided below a different side of the tank 2 from the wax residue inlet 4 and is opened downward. As shown in fig. 1, the wax residue inlet 4 and the synthetic wax outlet 10 are located in the magnetic region, and the spent catalyst outlet 8 is located in the non-magnetic region.
In the invention, the size of the device can be determined according to the treatment requirement of the wax residue, and the treatment capacity of the wax residue can be met. The diameters of the magnet 3, the drum 6 and the case 2 may be increased in this order.
According to the present invention, preferably, sealing structures are provided at the wax residue inlet 4, the synthetic wax outlet 10 and the spent catalyst outlet 8, respectively, to seal the case 2. For ensuring that the spent catalyst does not come into contact with air in order to avoid danger. Meanwhile, the rotary drum 6 is also arranged to seal the magnet 3 inside and is not in direct contact with the Fischer-Tropsch synthesis slag wax, the waste catalyst and the synthetic wax.
With reference to fig. 1, the device for magnetically separating the waste catalyst in the Fischer-Tropsch synthesis slag wax comprises: the device comprises a rotating shaft 7, a magnet 3 (fixed), a rotary drum 6 (rotatable), a box body 2 (a shell 5 is provided with a steam coil pipe or an electric tracing wire with a heat insulation structure), a wax residue feeding hole 4, a scraping plate 9, a synthetic wax outlet 10, a waste catalyst outlet 8 and a support 1. The Fischer-Tropsch synthesis slag wax flows into the device from the slag wax feed inlet 4, flows to the bottom of the box body 2 anticlockwise under the action of gravity, passes through a magnetic area with a magnetic field generated by the magnet 3, and is attracted and attached to the outer surface of the rotary drum 6 by the waste catalyst in the Fischer-Tropsch synthesis slag wax; the rotary drum 6 rotates clockwise under the drive of the motor, the waste catalyst rotates to a non-magnetic area along with the rotary drum 6, and the waste catalyst falls off from the rotary drum 6 under the action of the scraper 9, and then leaves the device from a waste catalyst outlet 8. The Fischer-Tropsch synthesis residue wax flowing to the bottom of the box body 2 is separated to obtain the waste catalyst, the synthetic wax containing a small amount of non-magnetic catalyst fine powder is obtained, and the waste catalyst flows out of the device from a synthetic wax outlet 10 below the device.
In the present invention, the scraper 9 is preferably disposed perpendicular to the surface of the drum 6. To more effectively remove the spent catalyst from the surface of the bowl 6.
In a second aspect, the present invention provides a method for separating a waste catalyst from fischer-tropsch wax residue, as shown in fig. 2, including:
(a) carrying out flash evaporation and cooling on the Fischer-Tropsch synthesis product to obtain Fischer-Tropsch synthesis residue wax from which synthesis gas and light hydrocarbon are removed;
(b) introducing the wax residue into the device for separating the waste catalyst in the Fischer-Tropsch synthesis wax residue, and performing magnetic separation under heating and inert atmosphere to obtain the synthetic wax and the waste catalyst;
(c) and introducing the synthetic wax into a precoating filter for precoating filtration to obtain heavy wax and waste clay.
The invention provides a method for separating waste catalysts in Fischer-Tropsch synthesis slag wax by using the device for separating the waste catalysts in the Fischer-Tropsch synthesis slag wax. The Fischer-Tropsch synthesis product can be slurry containing the waste catalyst and heavy wax, which is obtained by carrying out Fischer-Tropsch synthesis reaction on synthesis gas in a slurry bed reactor E1 in the presence of a Fischer-Tropsch synthesis catalyst. The pressure in the Fischer-Tropsch synthesis reaction process can be 2-3MPa, and the temperature can be 250-270 ℃. The solid content of the spent catalyst in the fischer-tropsch synthesis product may be in the range 10 to 20 wt%.
According to the present invention, step (a) may be carried out in the slag wax flash drum E2. The pressure in the slag wax flash tank E2 is reduced, and the synthesis gas and the low-carbon hydrocarbon dissolved in the Fischer-Tropsch synthesis product can be volatilized and removed. Preferably, in step (a), the flash pressure is from 0.3 to 1 MPa. Meanwhile, the Fischer-Tropsch synthesis product can be cooled to reach a temperature of 120-230 ℃, preferably 150-200 ℃.
According to the invention, Fischer-Tropsch synthesis slag wax (slag wax for short, wherein the solid content of the waste catalyst can be 10-20 wt%) is subjected to magnetic separation in the device provided by the invention at a certain temperature and under an inert atmosphere. Preferably, in step (b), the slag wax flows downward by gravity, and the rotating direction of the rotating drum in the device is opposite to the flowing direction of the slag wax.
According to the device for separating the waste catalyst from the Fischer-Tropsch synthesis wax, the heating and heat-insulating structure can provide temperature to ensure that the wax is in a flowing state. Preferably, in step (b), the heating temperature is 120-. The heating mode can be that the heat preservation structure used outside the box body in the device for separating the waste catalyst in the Fischer-Tropsch synthesis slag wax provided by the invention is steam or electric tracing, and preferably steam tracing. The inert atmosphere can be nitrogen to ensure the safety of the magnetic separation process and prevent the catalyst carried by the wax residue from being oxidized. The inert atmosphere is introduced to ensure that the working pressure of the device is 0.1-0.8MPa, preferably 0.1-0.3 MPa.
According to the invention, the rotation of the rotary drum 6 can separate the waste catalyst attracted and adhered in the magnetic area from the wax slag, and the waste catalyst can be separated and recovered by rotating the rotary drum to the non-magnetic area. Preferably, the drum 6 rotates at a surface linear velocity of 0.01 to 1.5m/s, preferably 0.03 to 0.8 m/s. And sufficient meeting time between the rotary drum 6 and the wax residue is ensured, and the effect of separating the waste catalyst is ensured.
In the invention, the magnet can be selected from a permanent magnet and/or an electromagnetic magnet, and is preferably a permanent magnet. Preferably, in the step (b), the magnetic induction intensity of the magnetic field formed by the magnetic separation magnet on the surface of the drum is 100-15000 gauss, preferably 300-5000 gauss, and more preferably 500-2000 gauss. In the present invention, the magnetic induction of the magnetic separation means the magnetic induction of the magnetic field formed by the magnet 3 on the surface of the drum 2.
In the present invention, the precoating filter E6 can contact the obtained synthetic wax with the precoating material to perform precoating separation, and further remove the fine powder of the waste catalyst contained in the synthetic wax, thereby providing a heavy wax having a higher purity. Specific processes for precoat separation using precoat filter E6 may include: the heavy wax, the argil and the diatomite are uniformly stirred to prepare the precoating raw material. The weight ratio of the white clay to the diatomite is 10-13 parts by weight and 1.3-2.6 parts by weight, respectively, compared with 100 parts by weight of the heavy wax. The precoating raw material is firstly fed into the precoating filter E6 for precoating circulation to form a layer of filter cake in the precoating filter E6, and then the synthetic wax is fed into the precoating filter E6 for precoating separation.
With reference to FIG. 2, the synthesis gas is subjected to Fischer-Tropsch synthesis in a slurry bed Fischer-Tropsch synthesis reactor E1. When the catalyst is replaced, discharging a product (slurry containing the waste catalyst and heavy wax) in a slurry bed Fischer-Tropsch synthesis reactor (with the pressure of 2-3MPa) E1 into a slag wax flash tank E2 with a stirrer, wherein the pressure of the slag wax flash tank E2 is 0.3-1MPa, the pressure of the product is reduced, the synthesis gas and the low-carbon hydrocarbons dissolved in the product volatilize out, and the cooled Fischer-Tropsch synthesis slag wax is obtained at the outlet of the slag wax flash tank E2; the slag wax is introduced into a magnetic separation device E3, continuous magnetic separation of the waste catalyst and the slag wax is realized under the rotation of a rotary drum 6 and the action of a magnet 3, the separated synthetic wax containing a trace amount of catalyst fine particles enters a synthetic wax intermediate tank E4, and the separated waste catalyst (which is discharged from a waste catalyst outlet 8, can be mixed in a small amount of wax and has high solid content) enters a waste catalyst receiving tank E5; the synthetic wax in the synthetic wax intermediate tank E4 is sent into a precoating filter E6 for further precoating and filtering, catalyst fine powder is separated, the obtained qualified heavy wax enters a filtering wax tank E7, and the obtained waste clay containing the catalyst fine powder is discharged into a waste clay receiving tank E8; the waste catalyst and the waste clay can be finally sent to an incinerator E9 for incineration treatment.
The present invention will be described in detail below by way of examples.
Example 1
The synthesis gas uses an iron-based catalyst to carry out Fischer-Tropsch synthesis reaction in a slurry bed Fischer-Tropsch synthesis reactor (the pressure is 3.0MPa and the temperature is 260 ℃) E1, the obtained slurry containing the catalyst and heavy wax is discharged into a slag wax flash tank E2 with a stirrer, and the pressure of the slag wax flash tank E2 is 0.5 MPa. And (4) volatilizing the synthesis gas and the low-carbon hydrocarbons dissolved in the slurry due to the reduction of the pressure to obtain the Fischer-Tropsch synthesis slag wax. The temperature of the slag wax flash tank E2 is 200 ℃, and the mass fraction of the waste catalyst in the slag wax is 16%.
The slag wax in the slag wax flash tank E2 is introduced into the feed inlet of a magnetic separation device E3, and the feeding amount is 300 kg/h. In the magnetic separation device E3, the box body 2 is a cylinder with the diameter of 700mm and the length of 800 mm; a rotary drum 6 with the diameter of 600mm and the length of 700mm is arranged in the box body 2; the magnet 3 is a permanent magnet and a fan-shaped cylindrical body, the central angle of the fan shape is 90 degrees, and the box body 2, the rotary drum 6 and the magnet 3 are coaxially arranged. The magnetic field generated by the magnet 3 makes the magnetic induction intensity of the surface of the rotary drum 6 be 1500 gauss when the rotary drum 6 has the magnetic area.
The surface linear velocity of the drum 6 was 0.10 m/s. The slag wax flows anticlockwise in a gap between the inner wall of the box body 2 and the outer surface of the rotary drum 6, and the rotary drum 6 rotates clockwise; the shell of the magnetic separation device E3 is heated by steam, the temperature in the magnetic separation device E3 is 180 ℃, and the pressure is 0.1 MPa. After passing through a magnetic separation device E3, synthetic wax with the solid content of the waste catalyst of 180 mug/g is obtained at a synthetic wax outlet 10, and the waste catalyst with the solid content of 62 weight percent is obtained at a waste catalyst outlet 8.
The synthetic wax is further sent into a precoating filter E6 for precoating separation, catalyst fine powder is separated, and the solid content of the waste catalyst in the obtained filtered heavy wax is lower than 20 mu g/g.
The waste catalyst separated by the magnetic separation device E3 and the waste clay discharged by the precoating filter E6 are sent to an incinerator E9 and are incinerated for 4 hours at 1000 ℃, and no organic matters are detected in the solid waste.
Example 2
The synthesis gas uses an iron-based catalyst to carry out Fischer-Tropsch synthesis reaction in a slurry bed Fischer-Tropsch synthesis reactor (the pressure is 2.0MPa and the temperature is 270 ℃) E1, the obtained slurry containing the catalyst and heavy wax is discharged into a slag wax flash tank E2 with a stirrer, and the pressure of the slag wax flash tank E2 is 0.3 MPa. And (4) volatilizing the synthesis gas and the low-carbon hydrocarbons dissolved in the slurry due to the reduction of the pressure to obtain the Fischer-Tropsch synthesis slag wax. The temperature of the slag wax flash tank E2 is 180 ℃, and the mass fraction of the waste catalyst in the slag wax is 10%.
The slag wax in the slag wax flash tank E2 is introduced into the feed inlet of a magnetic separation device E3, and the feeding amount is 500 kg/h. In the magnetic separation device E3, the box body 2 is a cylinder with the diameter of 700mm and the length of 800 mm; a rotary drum 6 with the diameter of 600mm and the length of 700mm is arranged in the box body 2; the magnet 3 is a permanent magnet and a fan-shaped cylindrical body, the central angle of the fan shape is 240 degrees, and the box body 2, the rotary drum 6 and the magnet 3 are coaxially arranged. The magnetic field generated by the magnet 3 causes the magnetic induction intensity of the surface of the rotating drum 6 to be 500 gauss when the rotating drum 6 has the magnetic area.
The surface linear velocity of the drum 6 was 0.8 m/s. The liquid heavy wax flows anticlockwise in a gap between the inner wall of the box body 2 and the outer surface of the rotary drum 6, and the rotary drum 6 rotates clockwise; the shell of the magnetic separation device E3 is heated by steam, the temperature in the magnetic separation device E3 is 150 ℃, and the pressure is 0.3 MPa. After passing through a magnetic separation device E3, synthetic wax with the solid content of the waste catalyst of 515 mug/g is obtained at a synthetic wax outlet 10, and the waste catalyst with the solid content of 58 weight percent is obtained at a waste catalyst outlet 8.
The synthetic wax is further sent into a precoating filter E6 for precoating separation, catalyst fine powder is separated, and the solid content of the waste catalyst in the obtained filtered heavy wax is lower than 20 mu g/g.
The waste catalyst separated by the magnetic separation device E3 and the waste clay discharged by the precoating filter E6 are sent to an incinerator E9 and are incinerated for 4 hours at 1000 ℃, and no organic matters are detected in the solid waste.
Example 3
The synthesis gas uses an iron-based catalyst to carry out Fischer-Tropsch synthesis reaction in a slurry bed Fischer-Tropsch synthesis reactor (the pressure is 2.5MPa, the temperature is 250 ℃) E1, the obtained slurry containing the catalyst and heavy wax is discharged into a slag wax flash tank E2 with a stirrer, and the pressure of the slag wax flash tank E2 is 1.0 MPa. And (4) volatilizing the synthesis gas and the low-carbon hydrocarbons dissolved in the slurry due to the reduction of the pressure to obtain the Fischer-Tropsch synthesis slag wax. The temperature of the slag wax flash tank E2 is 150 ℃, and the mass fraction of the waste catalyst in the slag wax is 20%.
The slag wax in the slag wax flash tank E2 is introduced into the feed inlet of a magnetic separation device E3, and the feeding amount is 300 kg/h. In the magnetic separation device E3, the box body 2 is a cylinder with the diameter of 700mm and the length of 800 mm; a rotary drum 6 with the diameter of 600mm and the length of 700mm is arranged in the box body 2; the magnet 3 is a permanent magnet and a fan-shaped cylindrical body, the central angle of the fan shape is 190 degrees, and the box body 2, the rotary drum 6 and the magnet 3 are coaxially arranged. The magnetic field generated by the magnet 3 causes the magnetic induction intensity of the surface of the rotating drum 6 to be 2000 gauss when the rotating drum 6 has the magnetic area.
The surface linear velocity of the drum 6 was 0.03 m/s. The liquid heavy wax flows anticlockwise in a gap between the inner wall of the box body 2 and the outer surface of the rotary drum 6, and the rotary drum 6 rotates clockwise; the shell of the magnetic separation device E3 is heated by steam, the temperature in the magnetic separation device E3 is 200 ℃, and the pressure is 0.2 MPa. After passing through a magnetic separation device E3, synthetic wax with the solid content of the waste catalyst of 150 mug/g is obtained at a synthetic wax outlet 10, and the waste catalyst with the solid content of 65 weight percent is obtained at a waste catalyst outlet 8.
The synthetic wax is further sent into a precoating filter E6 for precoating separation, catalyst fine powder is separated, and the solid content of the waste catalyst in the obtained filtered heavy wax is lower than 20 mu g/g.
The waste catalyst separated by the magnetic separation device E3 and the waste clay discharged by the precoating filter E6 are sent to an incinerator E9 and are incinerated for 4 hours at 1000 ℃, and no organic matters are detected in the solid waste.
Example 4
The synthesis gas uses an iron-based catalyst to carry out Fischer-Tropsch synthesis reaction in a slurry bed Fischer-Tropsch synthesis reactor (the pressure is 3.0MPa and the temperature is 260 ℃) E1, the obtained slurry containing the catalyst and heavy wax is discharged into a slag wax flash tank E2 with a stirrer, and the pressure of the slag wax flash tank E2 is 0.5 MPa. And (4) volatilizing the synthesis gas and the low-carbon hydrocarbons dissolved in the slurry due to the reduction of the pressure to obtain the Fischer-Tropsch synthesis slag wax. The temperature of the slag wax flash tank E2 is 230 ℃, and the mass fraction of the waste catalyst in the slag wax is 15%.
The slag wax in the slag wax flash tank E2 is introduced into the feed inlet of a magnetic separation device E3, and the feeding amount is 700 kg/h. In the magnetic separation device E3, the box body 2 is a cylinder with the diameter of 700mm and the length of 800 mm; a rotary drum 6 with the diameter of 600mm and the length of 700mm is arranged in the box body 2; the magnet 3 is a permanent magnet and a fan-shaped cylindrical body, the central angle of the fan shape is 220 degrees, and the box body 2, the rotary drum 6 and the magnet 3 are coaxially arranged. The magnetic field generated by the magnet 3 makes the magnetic induction intensity of the surface of the rotating drum 6 be 5000 gauss when the rotating drum 6 has a magnetic area.
The surface linear velocity of the drum 6 was 1.5 m/s. The liquid heavy wax flows anticlockwise in a gap between the inner wall of the box body 2 and the outer surface of the rotary drum 6, and the rotary drum 6 rotates clockwise; the shell of the magnetic separation device E3 is heated by steam, the temperature in the magnetic separation device E3 is 120 ℃, and the pressure is 0.8 MPa. After passing through a magnetic separation device E3, synthetic wax with the solid content of the waste catalyst of 135 mug/g is obtained at a synthetic wax outlet 10, and the waste catalyst with the solid content of 55 weight percent is obtained at a waste catalyst outlet 8.
The synthetic wax is further sent into a precoating filter E6 for precoating separation, catalyst fine powder is separated, and the solid content of the waste catalyst in the obtained filtered heavy wax is lower than 20 mu g/g.
The waste catalyst separated by the magnetic separation device E3 and the waste clay discharged by the precoating filter E6 are sent to an incinerator E9 and are incinerated for 4 hours at 1000 ℃, and no organic matters are detected in the solid waste.
Example 5
The synthesis gas uses an iron-based catalyst to carry out Fischer-Tropsch synthesis reaction in a slurry bed Fischer-Tropsch synthesis reactor (the pressure is 2.5MPa, the temperature is 250 ℃) E1, the obtained slurry containing the catalyst and heavy wax is discharged into a slag wax flash tank E2 with a stirrer, and the pressure of the slag wax flash tank E2 is 1.0 MPa. And (4) volatilizing the synthesis gas and the low-carbon hydrocarbons dissolved in the slurry due to the reduction of the pressure to obtain the Fischer-Tropsch synthesis slag wax. The temperature of the slag wax flash tank E2 is 120 ℃, and the mass fraction of the waste catalyst in the slag wax is 18%.
The slag wax in the slag wax flash tank E2 is introduced into the feed inlet of a magnetic separation device E3, and the feeding amount is 300 kg/h. In the magnetic separation device E3, the box body 2 is a cylinder with the diameter of 700mm and the length of 800 mm; a rotary drum 6 with the diameter of 600mm and the length of 700mm is arranged in the box body 2; the magnet 3 is a permanent magnet and a fan-shaped cylindrical body, the central angle of the fan shape is 120 degrees, and the box body 2, the rotary drum 6 and the magnet 3 are coaxially arranged. The magnetic field generated by the magnet 3 makes the magnetic induction intensity of the surface of the rotating drum 6 be 1000 gauss when the rotating drum 6 has a magnetic area.
The surface linear velocity of the drum 6 was 0.01 m/s. The liquid heavy wax flows anticlockwise in a gap between the inner wall of the box body 2 and the outer surface of the rotary drum 6, and the rotary drum 6 rotates clockwise; the shell of the magnetic separation device E3 is heated by steam, the temperature in the magnetic separation device E3 is 230 ℃, and the pressure is 0.2 MPa. After passing through a magnetic separation device E3, synthetic wax with a solid content of 335 mug/g of waste catalyst is obtained at a synthetic wax outlet 10, and waste catalyst with a solid content of 63 wt% is obtained at a waste catalyst outlet 8.
The synthetic wax is further sent into a precoating filter E6 for precoating separation, catalyst fine powder is separated, and the solid content of the waste catalyst in the obtained filtered heavy wax is lower than 20 mu g/g.
The waste catalyst separated by the magnetic separation device E3 and the waste clay discharged by the precoating filter E6 are sent to an incinerator E9 and are incinerated for 4 hours at 1000 ℃, and no organic matters are detected in the solid waste.
The embodiment of the device and the method provided by the invention has better effect of separating the waste catalyst in the wax residue, can separate the waste catalyst with high solid content after the first-stage magnetic separation and the pre-coating separation are carried out on the wax residue with the waste catalyst content of 10-20 wt%, and can obtain qualified heavy wax products, wherein the solid content of the waste catalyst is below 20 mug/g. The device provided by the invention can realize the accumulated recovery of heavy wax products from the wax residue through continuous long-period operation, and the recovery rate of the heavy wax products can reach more than 70%.
The preferred embodiments of the present invention have been described above in detail, 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 (10)
1. An apparatus for separating a spent catalyst from Fischer-Tropsch synthesis wax residue, comprising:
the device comprises a closed box body, a rotary sealing rotary drum, a magnet and a scraper blade, wherein the closed box body is provided with a wax residue inlet, a synthetic wax outlet, a waste catalyst outlet and a heating and heat-insulating structure;
the position of the magnet corresponds to the space between the wax residue inlet and the synthetic wax outlet in the box body, and the magnet is used for attracting the waste catalyst in the Fischer-Tropsch synthetic wax residue to be attached to the outer surface of the rotary drum; the scraper is used to remove the spent catalyst on the outer surface of the drum.
2. The apparatus of claim 1, wherein the housing is spaced apart from the drum to define a space for the Fischer-Tropsch wax or spent catalyst to flow through;
preferably, the drum is spaced from the magnets, which occupy 1/4-2/3 of the inner circumference of the drum.
3. An apparatus according to claim 1 or claim 2, further comprising drive means for driving the drum in rotation in a direction opposite to the direction of flow of the Fischer-Tropsch wax in the tank.
4. The apparatus of claim 1, wherein the synthetic wax outlet is disposed at a bottom of the tank and opens downwardly, the wax residue inlet is disposed above one side of the tank and opens upwardly, and the spent catalyst outlet is disposed below a different side of the tank from the wax residue inlet and opens downwardly.
5. The apparatus as set forth in any one of claims 1 to 4, wherein sealing structures are provided at the wax residue inlet, the synthetic wax outlet and the spent catalyst outlet, respectively, to seal the case.
6. A method for separating a waste catalyst in Fischer-Tropsch synthesis residue wax comprises the following steps:
(a) carrying out flash evaporation and cooling on the Fischer-Tropsch synthesis product to obtain Fischer-Tropsch synthesis residue wax from which synthesis gas and light hydrocarbon are removed;
(b) introducing the wax residue into the device of any one of claims 1 to 5, and performing magnetic separation under heating and inert atmosphere to obtain synthetic wax and a waste catalyst;
(c) and introducing the synthetic wax into a precoating filter for precoating filtration to obtain heavy wax and waste clay.
7. The process as claimed in claim 6, wherein in step (a), the flash pressure is 0.3-1MPa, and the temperature is reduced to 120-230 ℃, preferably 150-200 ℃.
8. The method of claim 6, wherein in step (b), the wax residue flows downward by gravity, and the rotating drum of the apparatus rotates in a direction opposite to the direction of the flow of the wax residue; preferably, the surface linear velocity of the drum rotation is 0.01 to 1.5m/s, preferably 0.03 to 0.8 m/s.
9. The method as claimed in claim 6, wherein, in the step (b), the heating temperature is 120-230 ℃, preferably 150-200 ℃; the working pressure of the device is 0.1-0.8MPa, preferably 0.1-0.3 MPa.
10. The method as claimed in claim 6, wherein in step (b), the magnetic induction of the magnetic separation is 100-15000 gauss, preferably 300-5000 gauss, and more preferably 500-2000 gauss.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB188814A (en) * | 1921-08-25 | 1922-11-23 | James Stanley Atkinson | Improvements in or in connection with magnetic separators |
| US4051023A (en) * | 1975-04-11 | 1977-09-27 | Eriez Magnetics | Combination electromagnet and permanent magnet separator |
| CN101970605A (en) * | 2008-03-14 | 2011-02-09 | 日本石油天然气·金属矿物资源机构 | Method for selectively removing catalyst from Fischer-Tropsch crude oil and method for recycling removed catalyst |
| CN102319625A (en) * | 2011-08-30 | 2012-01-18 | 北京矿冶研究总院 | High-efficiency down-flow type magnetic separator with groove body |
| CN102703712A (en) * | 2012-06-29 | 2012-10-03 | 阳光凯迪新能源集团有限公司 | Combined filtration process for recovering noble metal catalyst from fischer-tropsch synthesis products |
| CN103846160A (en) * | 2012-11-30 | 2014-06-11 | 中国石油化工股份有限公司 | Separation method for slurry bed fischer-tropsch synthesis heavy product and catalyst |
| CN104972401A (en) * | 2014-04-03 | 2015-10-14 | 宁波神丰汽车部件有限公司 | Cutting fluid recovering device for grinding machine |
| CN108102716A (en) * | 2017-12-28 | 2018-06-01 | 神华集团有限责任公司 | The filtration system and method for Fischer-Tropsch wax in a kind of Fischer-Tropsch synthesis |
-
2018
- 2018-11-15 CN CN201811362360.0A patent/CN111187639A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB188814A (en) * | 1921-08-25 | 1922-11-23 | James Stanley Atkinson | Improvements in or in connection with magnetic separators |
| US4051023A (en) * | 1975-04-11 | 1977-09-27 | Eriez Magnetics | Combination electromagnet and permanent magnet separator |
| CN101970605A (en) * | 2008-03-14 | 2011-02-09 | 日本石油天然气·金属矿物资源机构 | Method for selectively removing catalyst from Fischer-Tropsch crude oil and method for recycling removed catalyst |
| CN102319625A (en) * | 2011-08-30 | 2012-01-18 | 北京矿冶研究总院 | High-efficiency down-flow type magnetic separator with groove body |
| CN102703712A (en) * | 2012-06-29 | 2012-10-03 | 阳光凯迪新能源集团有限公司 | Combined filtration process for recovering noble metal catalyst from fischer-tropsch synthesis products |
| CN103846160A (en) * | 2012-11-30 | 2014-06-11 | 中国石油化工股份有限公司 | Separation method for slurry bed fischer-tropsch synthesis heavy product and catalyst |
| CN104972401A (en) * | 2014-04-03 | 2015-10-14 | 宁波神丰汽车部件有限公司 | Cutting fluid recovering device for grinding machine |
| CN108102716A (en) * | 2017-12-28 | 2018-06-01 | 神华集团有限责任公司 | The filtration system and method for Fischer-Tropsch wax in a kind of Fischer-Tropsch synthesis |
Non-Patent Citations (4)
| Title |
|---|
| B.A.威尔斯 等著，印万忠 等译: "《矿物加工技术》", 28 February 2011, 冶金工业出版社 * |
| 丁启圣 等编著: "《新型实用过滤技术》", 31 December 2017, 冶金工业出版社 * |
| 中国煤炭教育协会职业教育教材编审委员会: "《重力选煤》", 31 March 2013 * |
| 徐志新，卜亿峰: "《浆态床反应器生产费托合成蜡的脱铁精制工业应用》", 《广州化工》 * |
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