CN114106877B

CN114106877B - System and method for producing low-sulfur marine fuel oil

Info

Publication number: CN114106877B
Application number: CN202010877416.7A
Authority: CN
Inventors: 邵志才; 韩勇; 胡志海; 陈坦; 李妍; 段涛; 牛传峰; 徐文静; 杨鹤; 张宪迎; 田鹏程; 陶丽; 戴立顺; 李莎莎; 邓中活; 叶巍; 方强
Original assignee: Shanghai Samyo Fluid Technology Co ltd; Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Shanghai Samyo Fluid Technology Co ltd; Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-08-27
Filing date: 2020-08-27
Publication date: 2023-06-09
Anticipated expiration: 2040-08-27
Also published as: CN114106877A

Abstract

The invention relates to a system and a method for producing low-sulfur marine fuel oil, comprising a slurry oil filter unit, an optional slurry oil hydrogenation unit and a low-sulfur marine fuel oil blending unit, wherein a filter of a filter assembly with at least one flexible filter material is arranged in the slurry oil filter unit. And blending the de-solidified oil slurry and/or the hydrogenated oil slurry with blending components in a low-sulfur marine fuel oil blending unit to obtain the low-sulfur marine fuel oil. The invention effectively solves the problems of low efficiency and high cost of removing solid particles during the filtration of the slurry oil. The production cost of the low-sulfur marine fuel oil is effectively reduced by utilizing the full fraction of the slurry oil.

Description

System and method for producing low-sulfur marine fuel oil

Technical Field

The invention relates to the field of heavy oil processing, in particular to a system and a method for producing low-sulfur marine fuel oil by adopting slurry oil.

Background

With the continuous aggravation of global environmental problems, environmental regulations are continuously put out at home and abroad to limit the sulfur content of marine fuel oil (hereinafter referred to as ship combustion). The international maritime organization (english: international Maritime Organization, abbreviated as IMO) requires that the sulfur content of fuel oil for use by a ship traveling in a general area from 1 st 2012 is not higher than 3.5% (4.5% before 2012), and the upper limit of the sulfur content of ship combustion at 1 st 2020 is reduced to 0.5%. The low-sulfur heavy ship fuel can be produced by utilizing low-sulfur residual oil or hydrogenated residual oil, but the production cost is higher, and the low-cost blending component needs to be searched, so that the production cost of the low-sulfur ship fuel oil is reduced.

Catalytic cracking is an important process technology for producing gasoline and diesel oil by lightening heavy oil, is one of the most important and most widely applied technologies in the current oil refining field, but a small part of slurry oil is a byproduct of catalytic cracking, and particularly, the current catalytic cracking mostly adopts hydrogenated residual oil or wax oil doped with residual oil as a raw material, the slurry oil yield is higher, generally about 5%, the yield is high and even reaches 8%, and the slurry oil is a low-value byproduct. However, the slurry oil contains about 1-6 g/L of catalytic cracking catalyst particles, and the content of (Si+Al) in the low-sulfur residue type marine fuel oil is lower than 60 mug/g according to the ISO international standard and GB/T17411-2015, and the untreated slurry oil cannot meet the raw material index requirement for producing marine combustion.

Some slurries have sulfur levels above 0.5 wt.% and cannot be used directly as a blending component for low sulfur marine combustion. In order to increase the value of slurry oil, the solid particulate matter in the slurry oil must be removed first. There are various methods for removing solid particles, such as sedimentation, flocculation, centrifugation, etc., but these methods have too low removal efficiency. Filtration is a better method for removing solid particles in slurry oil, but a multi-stage filtration method is adopted around the improvement of filtration precision. After removing solid particles, the slurry oil with high sulfur content can be used as a blending component of low sulfur marine fuel oil after desulfurization.

CN102002385a discloses a device and a method for separating residues from catalytic cracking slurry oil, which comprises at least two filter groups, wherein each filter group consists of a prefilter and a fine filter, the prefilter is a wedge-shaped metal wound wire filter element, the filtering precision is 2-10 micrometers, and the fine filter is an asymmetric metal powder sintered filter element, and the precision is 0.2-1.0 micrometers. CN103865571a describes a method for heavy oil removal of solid particulate matter, the filtration system comprising at least one prefilter, at least two fine filters, the fine filter cartridge accuracy being better than the prefilter accuracy, the prefilter being in series with the fine filter. The method for reforming the filter cake by the fresh or back-washed fine filter is that the filter cake is formed on the fine filter by the filtered filtrate after the pre-filter filtration, and the filter cake is not formed on the fine filter directly by the original liquid to be filtered. The prior art generally adopts a filter group consisting of a low-precision prefilter and a high-precision fine filter with different precision to filter, and has the defects of complex manufacture and higher fine filter cost.

In the prior art, a fixed bed hydrogenation method is also adopted to remove sulfides in the slurry oil for reuse. CN104119952B provides a hydrotreating process for hydrocarbon oil, in which hydrocarbon oil and hydrogen are contacted with a plurality of hydrogenation catalyst beds in a hydrotreating apparatus; the main and standby hydrotreating reactors may be used alternately. CN103013567B is a process for producing needle coke from catalytic slurry oil, which is provided with a protection zone and a hydrogenation reaction zone, wherein the catalytic slurry oil firstly enters the protection zone to adsorb most of catalytic cracking catalyst powder, then is mixed with hydrogen into a heating furnace, and enters the hydrogenation reaction zone for hydrogenation treatment reaction after heating. However, the above method has the disadvantages of high cost, a large amount of waste catalyst, and the like.

CN102786981a provides a new process for catalytic cracking slurry oil, which is to decompress and fractionate the catalytic slurry oil, the temperature of the distillation mouth is 360-480 ℃, and the light slurry oil and the slurry oil after head pulling are obtained, and the light slurry oil is directly used as marine residue fuel oil or is blended with other components to produce marine fuel oil.

Disclosure of Invention

The invention aims to solve the technical problems of complex oil slurry filtering process, short operation period, high cost of the oil slurry treatment process, low utilization value of heavy oil slurry and the like in the prior art, and provides a system and a method for producing low-sulfur marine fuel oil with low cost.

The invention provides a system for producing low-sulfur marine fuel oil, which comprises an oil slurry filtering unit, an optional oil slurry hydrogenation unit and a low-sulfur marine fuel oil blending unit, wherein the oil slurry filtering unit is provided with an oil slurry inlet, a solid removal oil slurry outlet and a filter residue outlet; the slurry hydrogenation unit is provided with a solid removal slurry inlet, an optional heavy oil raw material inlet and a hydrogenation slurry outlet; the low-sulfur marine fuel oil blending unit is provided with a solid removal slurry inlet and/or a hydrogenation slurry inlet, a blending component inlet and a low-sulfur marine fuel oil outlet;

the solid removing slurry outlet of the slurry filtering unit is communicated with the solid removing slurry inlet of the optional slurry hydrogenation unit or the solid removing slurry inlet of the low-sulfur marine fuel oil blending unit;

The slurry oil filter unit is internally provided with a filter, the filter is internally provided with at least one filter component of a flexible filter material, and the flexible filter material is selected from one or more of polyethylene, nylon, polyphenylene sulfide, polyimide, polytetrafluoroethylene, aramid fiber, polyurethane and glass fiber, or the flexible filter material formed by compounding any two or more of the above materials; the filtering precision of the flexible filter material is 0.1-15 micrometers.

The flexible filter material preferably has a filtration accuracy of 0.1 to 10 micrometers, more preferably 0.2 to 5 micrometers.

In the present invention, "optional" means optional components. For example, a slurry hydroprocessing unit may be provided with an optional heavy oil feedstock inlet, meaning that the slurry hydroprocessing unit may or may not be provided with a heavy oil feedstock inlet.

In the invention, the heavy oil raw material is one or more mixed oil selected from residual oil, straight-run wax oil, coker wax oil, catalytic cracking heavy cycle oil, catalytic cracking diesel oil and coal tar.

In the present invention, the slurry oil is a liquid hydrocarbon containing particulate matter impurities, and the source thereof is not limited, and may be any liquid hydrocarbon containing particulate matter impurities obtained during any processing. Preferably, the slurry oil is a catalytic cracking slurry oil.

In the existing catalytic cracking production device, a heavy cycle oil side extraction port is arranged at the lower part of a catalytic cracking main fractionating tower, and a heavy cycle oil side extraction port is not arranged at the lower part of the catalytic cracking main fractionating tower, so that the catalytic cracking heavy cycle oil is pressed into the bottom of the tower to be extracted together with slurry oil to be used as catalytic cracking slurry oil. In the invention, the catalytic cracking slurry oil contains optional catalytic cracking heavy cycle oil.

The flexible filter material has the characteristics of excellent chemical stability, good wear resistance and fatigue resistance, strong interception of particulate matters, high filtering precision and good material strength. In addition, the filter assembly adopting the flexible filter material overcomes the defect that the hard filter material is easy to be blocked by fine solid particles, improves the filter efficiency, prolongs the running period of the filter, reduces the abrasion of the filter and effectively prolongs the service life of the filter.

In the present invention, the manner in which the flexible filter material is formed into the filter assembly is not particularly limited as long as filtration can be achieved. In one embodiment of the present invention, the flexible filter material may be formed in a shape of a planar membrane, a hemispherical shape, a bag shape, or the like, thereby being used for a filter assembly. The bag shape is preferable in terms of filtration efficiency, filtration effect, subsequent treatment of the filter residue, regeneration efficiency of the filter, and the like.

In a preferred aspect of the invention, the filter assembly of the flexible filter material is in the form of a pinhole-free filter bag.

In the present invention, the pinhole-free filter bag of the flexible filter material is prepared by a method well known in the art, and in one embodiment, the pinhole-free filter bag of the flexible filter material is prepared by a sewing process, and the sewing pores thereof are sealed with an acidic sealant material. In another embodiment, the pinhole-free filter bag is made from a flexible filter material woven directly into a cylinder.

Preferably, the gram weight of the flexible filter material is 300-1000 g/m ² Preferably 520 to 660g/m ² 。

In a preferred case, the warp breaking strength of the flexible filter material is 850N/5cm to 9000N/5cm, preferably 1000N/5cm to 2400N/5cm; the weft breaking strength is 1000N/5 cm-11000N/5 cm, preferably 1200N/5 cm-2600N/5 cm; the thickness is 0.5-3.4 mm; preferably 0.5 to 3.0mm, more preferably 1.8 to 2.9mm.

In one embodiment of the present invention, the flexible filter medium in the filter of the present invention may be a single layer (single layer) or may be a plurality of layers (two or more layers). In the case of the multilayer form, the multilayer flexible filter material is laminated, and there is no limitation on the number of layers to be laminated and the arrangement of the layers.

In a preferred embodiment of the present invention, the flexible filter material includes at least a releasing layer and a base fabric layer, and the base fabric layer is woven from the above raw materials that can be made into the flexible filter material by using weaving techniques known in the art. The weaving technique is not limited in any way, including but not limited to hydroentanglement, thermal, wet weaving, spunbonding, melt blowing, needle punching, stitch bonding, hot rolling, and the like. The releasing layer is formed on the base cloth layer by a method known in the art such as a hot pressing method, a film coating method, a hot rolling method, or the like, using the above-described raw materials that can be made into a flexible filter material. The releasing layer and the base cloth layer can be prepared independently and sequentially, and can also be prepared integrally. The flexible filter material comprising at least the releasing layer and the base layer of the present invention may be prepared by a method known in the art, or may be commercially available.

In a preferred embodiment of the present invention, the porosity of the releasing layer is 25% to 98%, and the porosity of the base layer is 30% to 40%.

In a preferred embodiment of the present invention, the porosity of the releasing layer is 50% to 98% when the filtration accuracy of the flexible filter material is 2 to 25 μm.

In a preferred embodiment of the present invention, the porosity of the releasing layer is 25% to 70% when the filtration accuracy of the flexible filter material is 0.1 to less than 2 μm.

According to the invention, the solid removing layer is formed on the base cloth layer, so that the filtering effect of the filtering material can be further improved, and the service life of the filter can be prolonged.

In a preferred aspect, the base fabric layer is polytetrafluoroethylene and/or polyphenylene sulfide. Namely, the base cloth layer is made of single polytetrafluoroethylene material or single polyphenylene sulfide material or mixed fiber of the two materials.

In a preferred embodiment of the present invention, the base fabric layer is made of polytetrafluoroethylene filament fibers.

In order to achieve better slurry filtering effect, the stripping layer is preferably made of polytetrafluoroethylene, and further preferably made of polytetrafluoroethylene with a three-dimensional void structure.

In one embodiment of the present invention, the flexible filter material includes at least a releasing layer and a base layer, but is not limited thereto, and may be modified and derived based thereon. For example, other layers may be further included on the basis of the releasing layer and the base fabric layer of the present invention, without adversely affecting the effect of the present invention. In one embodiment of the invention, the debonding layer is disposed adjacent to the base fabric layer. In one embodiment of the invention, the flexible filter material comprises only the debonding layer and the scrim layer.

For the flexible filter material comprising a release layer and a base layer according to the invention, it is preferred that the release layer is a surface layer, i.e. the flexible filter material, when used in a filter, is the slurry oil to be filtered first contacts the release layer.

In one embodiment of the invention, a flexible filter is made from the debonding layer and the base fabric layer described above, and optionally other layers. That is, the flexible filter itself may be divided into a base layer, a release layer, and optionally other layers.

In one embodiment of the present invention, the flexible filter material further includes an inner layer on the basis of the above-described releasing layer and base layer. Namely, the flexible filter material of the invention at least comprises 3 layers, namely a releasing layer, a base cloth layer and an inner layer.

In one embodiment of the present invention, the inner layer is made of fibers having a fineness of 1 to 3D on the base fabric layer on the side opposite to the release layer by a method (for example, needling or hydroentangling) known in the art. In one embodiment of the present invention, the raw material for the fibers used to make the inner layer may be selected from the above-described raw materials that can be made into a flexible filter material. In one embodiment of the present invention, the raw material for making the inner layer is one or more selected from polyethylene, nylon, terylene, polypropylene, polyphenylene sulfide, polyimide, polytetrafluoroethylene, aramid, polyurethane and glass fiber; preferably one or more selected from polyimide, polytetrafluoroethylene, polyphenylene sulfide and glass fiber.

In one embodiment of the present invention, the inner layer of the present invention is preferably made of high strength fibers, thereby further improving the strength of the flexible filter material and reducing the risk of plastic deformation of the flexible filter material under continuous loading for a long period of time, extending the operational cycle of the slurry filter, and extending the service life of the filter.

In one embodiment of the present invention, when the flexible filter material includes at least a release layer, a base layer, and an inner layer, the release layer and the base layer are consistent with the description of the invention above with respect to the release layer and the base layer.

In one embodiment of the present invention, the flexible filter material may further include other layers on the basis of the releasing layer, the base layer and the inner layer without adversely affecting the effect of the present invention. In one embodiment of the invention, the flexible filter material comprises only the debonding layer, the scrim layer, and the inner layer.

In one embodiment of the invention, a flexible filter is made from the above-described debonding layer, base and inner layers, and optionally other layers. That is, the flexible filter itself may be divided into a base fabric layer, and an inner layer, and optionally other layers.

For the flexible filter material comprising a release layer, a base cloth layer and an inner layer according to the present invention, it is preferred that the release layer is a surface layer, i.e. the flexible filter material, when used in a slurry filter, the slurry to be filtered first contacts the release layer.

The flexible filter material comprising at least the releasing layer, the base cloth layer and the inner layer of the present invention may be prepared by a method known in the art or may be commercially available.

In one embodiment of the present invention, the flexible filter material of the present invention further comprises an accuracy layer and an inner layer on the basis of the above-described releasing layer and base layer. Namely, the flexible filter material of the invention at least comprises 4 layers, namely a releasing layer, an accuracy layer, a base cloth layer and an inner layer.

In one embodiment of the present invention, the precision layer is made of ultra fine fibers having fineness of 0.2 to 0.3D on the base fabric layer between the releasing layer and the base fabric layer by a method well known in the art (e.g., a needle punching method or a water punching method, etc.). In one embodiment of the present invention, the raw material of the ultrafine fibers used to make the precision layer may be selected from the above-described raw materials that can be made into a flexible filter material. In one embodiment of the invention, the superfine fiber used for preparing the precision layer is one or more selected from polyethylene, nylon, terylene, polypropylene, polyphenylene sulfide, polyimide, polytetrafluoroethylene, aramid, polyurethane and glass fiber; preferably one or more selected from polyimide, polytetrafluoroethylene, polyphenylene sulfide and glass fiber.

In one embodiment of the invention, the precision layer is made of ultrafine fibers having a fineness smaller than that of the inner layer. Without being bound by any theory, the inventors of the present invention believe that the filtration efficiency and filtration accuracy of the flexible filter material can be further improved by forming a three-dimensional structure due to the interaction between these ultrafine fibers. On the other hand, by using the superfine fiber with smaller fineness, the surface contact area and the surface tension can be enlarged, so that the combination between the solid removing layer and the precision layer and the combination between the solid removing layer and the base cloth layer are firmer, the falling off is avoided, and the service cycle of the flexible filter material is further prolonged.

In one embodiment of the present invention, when the flexible filter material includes at least a release layer, an accuracy layer, a base layer, and an inner layer, the release layer, the base layer, and the inner layer are consistent with the description of the release layer, the base layer, and the inner layer described above with respect to the present invention.

For the flexible filter material comprising a releasing layer, an accuracy layer, a base cloth layer and an inner layer according to the present invention, it is preferable that the releasing layer is a surface layer, i.e. when the flexible filter material is used in a slurry filter, the slurry to be filtered first contacts the releasing layer.

In one embodiment of the present invention, a flexible filter material is made from the above-described debonding layer, accuracy layer, base layer, and inner layer. That is, the flexible filter itself may be divided into a releasing layer, an accuracy layer, a base cloth layer, and an inner layer.

In one embodiment of the present invention, the flexible filter material of the present invention may further optionally include other layers on the basis of the above-described releasing layer, precision layer, base layer and back layer without adversely affecting the effect of the present invention. In one embodiment of the invention, the flexible filter material comprises only the debonding layer, the polishing layer, the scrim layer, and the backing layer.

The flexible filter material comprising at least the releasing layer, the precision layer, the base cloth layer and the inner layer of the present invention may be prepared by a method known in the art or may be commercially available.

In one embodiment of the invention, a filter assembly includes a cake layer formed of a filter aid disposed on the filter assembly; the filter aid is one or a mixture of a plurality of diatomite, cellulose, perlite, talcum powder, activated clay, filter residues obtained by a filter and waste catalytic cracking catalyst; the thickness of the filter cake layer formed by the filter aid is 0.1-10 mm.

In one embodiment of the present invention, when a cake layer formed of a filter aid is provided on a flexible filter material, the flexible filter material has a filtration accuracy of 3 to 25 μm. In one embodiment of the present invention, in the case where a cake layer formed of a filter aid is provided on a flexible filter material, the flexible filter material has a grammage of 300 to 1000g/m ² . In one embodiment of the present invention, in the case where a cake layer formed of a filter aid is provided on a flexible filter material, the thickness of the flexible filter material is 0.5 to 3.0mm. In one embodiment of the present invention, when a filter cake layer formed of a filter aid is provided on a flexible filter material, the flexible filter material has a warp breaking strength of 1000N/5cm to 9000N/5cm and a weft breaking strength of 1000N/5cm to 11000N/5cm.

In one embodiment of the present invention, after a cake layer formed of a filter aid is provided on the filter assembly, the pressure difference of the filter assembly is 0.01 to 0.07MPa. When the differential pressure is lower than 0.01MPa, an effective filter aid filter cake layer cannot be formed on the filter material, so that an excellent filtering effect cannot be achieved or the service life of the filter cannot be prolonged, and when the differential pressure is higher than 0.07MPa, the reserved differential pressure rising space for the use differential pressure of the filter is reduced, so that the effective time of slurry oil filtration is shortened.

In one embodiment of the present invention, the filter assembly of the present invention includes a filter cake layer formed of a filter aid disposed on the flexible filter material including at least a solids removal layer and a base fabric layer.

In one embodiment of the invention, the filter is an upflow filter or a downflow filter, and is provided with a slurry inlet, a de-solidified slurry outlet, a filter residue outlet and a regeneration medium inlet.

In one embodiment of the invention, the lower part of the filter is provided with a slurry inlet, the upper part of the filter is provided with a solid removal slurry outlet, and the bottom of the filter is provided with a filter residue outlet.

In one embodiment of the invention, the slurry filter unit is provided with a regeneration medium buffer tank and a regeneration medium inlet line in communication with each filter, respectively.

In the present invention, the regeneration medium includes a rinse oil and a purge medium. The leaching oil is one or more selected from slurry oil, de-solidified slurry oil, catalytic cracking diesel oil and catalytic cracking heavy cycle oil; the purging medium is inactive gas and/or flushing oil; the flushing oil is one or more selected from solid removal slurry oil, catalytic cracking diesel oil and catalytic cracking heavy cycle oil.

In one embodiment of the invention, a shower oil inlet and a shower are provided in the upper part of the filter.

In one embodiment of the invention, the filter is provided with a purge medium inlet. Preferably, a purge medium inlet is provided at the top of the filter and/or at the upper part of the filter.

In one embodiment of the invention, the filters are provided with filter aid inlets, the slurry oil filtration unit is provided with filter aid buffer tanks, and the filter aid buffer tanks are respectively communicated with the filter aid inlets of each filter; the filter aid is one or a mixture of a plurality of diatomite, cellulose, perlite, talcum powder, activated clay, filter residues obtained by a filter and waste catalytic cracking catalyst;

Preferably, the filter aid buffer tank is filled with filter aid and a mixing medium, wherein the mixing medium is liquid hydrocarbon.

In the present invention, one filter may be provided in the slurry filtering unit, or two or more filters may be provided. When a plurality of filters are provided, the present invention is not limited to any connection means. The filters may be arranged in parallel or in series, or may be switched between parallel and series, or may be used in both parallel and series. When a plurality of filters are provided, a plurality of filters having uniform filtration accuracy may be used, or a plurality of filters having non-uniform filtration accuracy may be used.

In one embodiment of the invention, the filter unit is provided with at least one filter group, each filter group is provided with at least two filters, and each filter is provided with a slurry inlet, a de-solidified slurry outlet, a regeneration medium inlet and a filter residue outlet, and pipelines respectively communicated with the respective inlets and outlets; in the same filter group, a communication pipeline is arranged between the solid-removing slurry outlet of each filter and the slurry inlet of each filter in the same group, and a communication valve is arranged on the communication pipeline. The order of the filtration accuracy of the plurality of filters included in each filter group is uniform.

In one embodiment of the invention, a slurry filtration unit includes a control system including an on-line differential pressure monitoring module, a filter control module, and a regeneration control module. The online pressure difference monitoring module is used for monitoring the pressure difference of the online filter. The filter control module is used to control individual filters to switch into and out of the filtration system. The regeneration control module is used for controlling the regeneration process of the filter, and when the pressure difference of the filter reaches a set pressure difference, the regeneration process is to remove filter cake particles on the pinhole-free filter bag by adopting a reverse purging and/or leaching oil spraying mode.

According to the slurry oil filter unit, the filter assembly of the flexible filter material is adopted in the filter, one implementation mode is a pinhole-free filter bag, and the preferable flexible filter material has the characteristics of strong interception to particulate matters, high filter precision and good material strength. Due to the adoption of the flexible filter material, the defects that asphaltene and colloid in the slurry oil are easily adsorbed on the flexible filter material and adhere, coke and block are overcome, the filtering efficiency is improved, and the operation period of the slurry oil filtering unit is prolonged. In addition, the slurry oil filter unit provided by the invention has the characteristics of convenience in slag unloading and good regeneration performance.

In one embodiment of the invention, the slurry hydrogenation unit comprises a hydrogenation reaction zone and a gas-liquid separation zone, and a solid removal slurry outlet is communicated with an inlet of the hydrogenation reaction zone; the hydrogenation reaction zone is provided with one or more reactors selected from a fixed bed reactor, a slurry bed reactor and a boiling bed reactor, and an outlet of the hydrogenation reaction zone is communicated with an inlet of the gas-liquid separation zone; the gas-liquid separation zone is provided with a gas outlet and a hydrogenated slurry oil outlet.

The de-solidified oil slurry from the oil slurry filtering unit and optional heavy oil raw material enter a hydrogenation reaction zone of the oil slurry hydrogenation unit, and are contacted with a hydrogenation catalyst to react in the presence of hydrogen-containing gas, so that most of sulfur compounds in the oil slurry are removed, aromatic hydrocarbon is partially saturated, asphaltene and colloid are simultaneously subjected to hydroconversion, and a reaction effluent enters a gas-liquid separation zone to carry out gas-liquid separation, so that a gas stream and hydrogenated oil slurry are obtained. The resulting hydrogenated slurry preferably has a sulfur content of 0.5 wt.% or less.

In one embodiment of the invention, the hydrogenation reaction zone is internally provided with a hydrogenation protective agent, a hydrodemetallization agent and/or a hydrotreating agent in a graded manner in sequence.

In one embodiment of the invention, the fixed bed reactor of the hydrogenation reaction zone is sequentially filled with a hydrogenation protecting agent, a hydrodemetallation agent or a hydrotreating agent, the filling volume fraction of the hydrogenation protecting agent is 5-90% and the filling volume fraction of the hydrodemetallation agent or the hydrotreating agent is 5-90% based on the whole catalyst in the fixed bed reactor.

In one embodiment of the invention, the fixed bed reactor of the hydrogenation reaction zone is sequentially filled with a hydrogenation protecting agent, a hydrodemetallization agent and a hydrotreating agent, wherein the filling volume fraction of the hydrogenation protecting agent is 10% -70%, the filling volume fraction of the hydrodemetallization agent is 10% -60% and the filling volume fraction of the hydrotreating agent is 20% -80% based on the whole catalyst in the fixed bed reactor.

The hydrogenation protecting catalyst, the hydrogenation demetallizing agent and the hydrotreating agent are respectively filled with one or more. In the present invention, the grading of the hydrogenation protecting agent, hydrodemetallization agent and/or hydrotreating agent may be optimized according to the pore structure, activity, raw material properties, operation conditions, etc. of the catalyst. In the present invention, the hydrogenation protecting agent, hydrodemetallation agent and hydrotreatment agent may employ hydrogenation protecting agents, hydrodemetallation agents and hydrotreatment agents which are common in the art. For example, the active component of the hydroprotectant, hydrodemetallating agent and hydrotreating agent may be a non-noble metal selected from group VIB and/or group VIII, preferably a combination of nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum; the carrier is selected from oxygen One or more of aluminum oxide, silicon oxide or titanium oxide. The carrier can be modified by adding elements such as phosphorus, boron or fluorine. The catalyst is in the shape of extrudate or sphere with diameter of 0.5-50.0 mm and bulk density of 0.3-1.2 g/cm ³ A specific surface area of 50 to 300m ² And/g. For example, the hydrogenation protecting agent, the hydrogenation demetallizing agent and the hydrotreating agent can respectively adopt RG series, RUF series, RDM series, RMS series and RCS series commercial catalysts developed by China petrochemical and petrochemical science institute.

In one embodiment of the invention, a low sulfur marine fuel oil blending unit is provided with a blending component pipeline and a blending product tank; the blending component pipeline is selected from pipelines for transporting one or more of normal pressure residual oil, vacuum residual oil, catalytic diesel oil, straight-run wax oil, hydrogenated wax oil and hydrogenated residual oil. The invention is not limited to the specific parameters of the blending component lines and blending product tanks in the low sulfur marine fuel oil blending unit. So long as the low sulfur marine fuel oil meeting the low sulfur marine fuel oil standard can be obtained by blending.

In one embodiment of the present invention, the low sulfur marine fuel oil blending unit is provided with an inlet for the additive, and there is no particular limitation on the additive itself, as long as it is capable of blending to obtain a low sulfur marine fuel oil that meets the low sulfur marine fuel oil standard.

A method of producing a low sulfur marine fuel oil employing any of the above systems comprising:

(1) The slurry oil enters a slurry oil filtering unit, and is filtered by a filtering component of at least one flexible filtering material in a filter to obtain de-solidified slurry oil and filter residues;

if the sulfur content of the de-solidified oil slurry is more than or equal to 0.5 weight percent, the de-solidified oil slurry enters the step (2) for treatment;

if the sulfur content of the de-solidified oil slurry is less than 0.5 weight percent, the de-solidified oil slurry enters the step (3) for blending;

(2) The de-solidified slurry oil and optional heavy oil raw materials enter a slurry oil hydrogenation unit together, contact with a hydrogenation catalyst for reaction under the action of hydrogen, and the reaction effluent is separated to obtain hydrogenated slurry oil;

(3) Blending the solid-removed slurry oil obtained in the step (1) and/or the hydrogenated slurry oil obtained in the step (2) with blending components in a low-sulfur marine fuel oil blending unit to obtain low-sulfur marine fuel oil;

the sulfur content of the blending component is less than 0.5 wt% and is one or more selected from atmospheric residuum, vacuum residuum, catalytic diesel oil, straight-run wax oil, hydrogenated wax oil and hydrogenated residuum.

In the invention, the slurry oil is liquid hydrocarbon with particulate impurities, preferably a catalytic cracking slurry oil obtained by any catalytic cracking unit; the catalytic cracking slurry oil contains optional catalytic cracking heavy cycle oil.

In the invention, the heavy oil raw material entering the slurry hydrogenation unit is one or more mixed oil selected from residual oil, straight-run wax oil, coker wax oil, catalytic cracking heavy cycle oil, catalytic cracking diesel oil and coal tar.

In one embodiment of the invention, when the sulfur content in the slurry is less than 0.5 wt.%, the de-solidified slurry may be blended directly with the blending components to produce a low sulfur marine fuel oil product.

In one embodiment of the invention, the filtration temperature in the filter of the slurry filtration unit is 30 to 250 ℃, preferably 50 to 240 ℃, more preferably 60 to 180 ℃.

In one embodiment of the invention, the pressure differential in use of the filter of the slurry filter unit is between 0.01 and 0.5MPa.

In one embodiment of the invention, the method of regenerating the filter after use is to spray the rinse oil on the surface of the flexible filter material forming the filter cake and/or reverse-sweep with a sweep medium.

The leaching oil is one or more selected from slurry oil, de-solidified slurry oil, catalytic cracking heavy cycle oil and catalytic cracking diesel oil;

the purging medium is inactive gas and/or flushing oil.

The inactive gas is a gas which does not react with slurry oil and particulate matters in the filtering system, and is preferably nitrogen. In some cases, fuel gas may also be selected. Preferably, the flushing oil is one or more selected from solid removal slurry oil, catalytic cracking heavy cycle oil and catalytic cracking diesel oil.

In one embodiment of the invention, when the slurry filter unit is filtering, the method comprises the following steps:

(1) And (3) filtering: passing the slurry into at least one filter;

(2) The control step: the online pressure difference monitoring module monitors the pressure difference of the online filter, the filter control module controls the filter to cut in and cut out of the filter system, and the regeneration control module controls the regeneration process of the filter; and

(3) And a regeneration step: spraying the surface of the filter cake formed by the flexible filter material by adopting the leaching oil and/or reversely blowing by adopting a blowing medium;

when the online pressure difference monitoring module monitors that the pressure difference of the online filter reaches a set value I, the filter control module cuts the non-online filter into the filtering system to carry out the filtering step, cuts the online filter with the pressure difference reaching the set value I out of the filtering system, wherein the set value I is in the range of 0.01-0.5 MPa,

and discharging slag and reversely purging the filter of the cut-out filtering system by using the leaching oil and/or the purging medium through the regeneration control module.

In one embodiment of the invention, there is (1-1) a cake layer forming step prior to (1) the filtration step in the slurry filtration unit: introducing a filter aid into a filter to form a filter cake layer of the filter aid on a filter element of the filter; the filter aid is one or a mixture of a plurality of diatomite, cellulose, perlite, talcum powder, activated clay, filter residues obtained by a filter and waste catalytic cracking catalyst;

When the online pressure difference monitoring module monitors that the pressure difference of the filter in the filter cake layer forming step reaches a set value II, the filter formed with the filter cake layer is cut into a filtering system through the filter control module to carry out the filtering step (1), and the set value II is in the range of 0.01-0.07 MPa.

When a single filter is provided in the slurry filtration unit, it is preferable to operate in such a manner that the filtration mode and the regeneration mode are alternately performed.

When the slurry filtration unit is provided with a plurality of filters, it is preferable to operate in such a manner that the in-line filter and the spare filter are alternately switched. When the pressure difference of the online filter reaches or exceeds the pressure difference set value, the standby filter can be cut into the filtering system, and the online filter is cut out of the filtering system to regenerate and discharge slag. The filter residue discharged from the liquid mixture has good fluidity and can be discharged out of the filtering system; the waste water can also be directly returned to the process for repeated use according to the process requirement; the filter cake can also be stabilized, dried in the filter and directly discharged out of the filter system as a completely solidified filter residue.

The invention adopts the repeated and alternate online filter operation mode, can effectively and continuously operate the whole filter system, and ensures the long-term stable operation period of the whole filter system. In addition, under the condition that a combined mode of a front coarse precision filter and a rear higher precision filter in the prior art is not adopted, the invention can also carry out high-precision filtration, and effectively reduces the filtration cost.

In one embodiment of the present invention, if the sulfur content of the de-solidified slurry is 0.5 wt% or more, the de-solidified slurry is fed to the slurry hydrogenation unit of step (2) for hydrotreating. The de-solidified oil slurry from the oil slurry filtering unit and optional heavy oil raw material enter a hydrogenation reaction zone of the oil slurry hydrogenation unit, and are contacted with a hydrogenation catalyst to react in the presence of hydrogen-containing gas, so that most of sulfur compounds in the oil slurry are removed, aromatic hydrocarbon is partially saturated, asphaltene and colloid are simultaneously subjected to hydroconversion, and a reaction effluent enters a gas-liquid separation zone to carry out gas-liquid separation, so that a gas stream and hydrogenated oil slurry are obtained. The resulting hydrogenated slurry preferably has a sulfur content of 0.5 wt.% or less.

In one embodiment of the invention, the reaction conditions of the slurry hydrogenation unit are: the reaction temperature is 100-400 ℃, the reaction pressure is 1.0-20.0 MPa, the volume ratio of hydrogen to oil is 10-1000, and the liquid hourly space velocity is 0.10-10.0 h ^-1 The method comprises the steps of carrying out a first treatment on the surface of the Preferred reaction conditions are: the reaction temperature is 200-380 DEG CThe pressure is 2.0-16.0 MPa, the hydrogen-oil volume ratio is 50-500, and the liquid hourly space velocity is 0.2-5.0 h ^-1 。

In the present invention, the separation conditions of the gas-liquid separation zone are well known to those skilled in the art, and the separation pressure in the gas-liquid separation zone is the system pressure, i.e., the pressure in the separation zone is the same as the pressure in the hydrogenation reaction zone.

In one embodiment of the invention, the hydrogen content of the hydrogen-containing gas entering the slurry hydrogenation unit hydrogenation reaction zone is 20-100% by volume. Preferably, the hydrogen-containing gas entering the hydrogenation reaction zone is selected from one or more of catalytic cracking dry gas, coking dry gas, hydrogenation device low-pressure gas and hydrogen.

And (3) blending the solid-removed slurry oil obtained in the step (1) and/or the hydrogenated slurry oil obtained in the step (2) with blending components in a low-sulfur marine fuel oil blending unit to obtain the low-sulfur marine fuel oil.

In one embodiment of the invention, the weight percentage of the de-solidified slurry oil and/or the hydrogenated slurry oil is 5-40%, preferably 15-35% based on the low-sulfur marine fuel oil.

Compared with the prior art, the system and the method for producing the low-sulfur marine fuel oil can be used as the blending component of the low-sulfur marine fuel oil after the heavy slurry oil with sulfur content is treated, namely the invention can utilize the whole fraction of the slurry oil, and effectively reduce the production cost of the low-sulfur marine fuel oil. In addition, the invention effectively solves the problems of low efficiency and high cost of removing solid particles during oil slurry filtration. The filtering efficiency is improved, and the running period of the slurry filtering unit and the running period of the whole processing system are prolonged.

Drawings

FIG. 1 is a schematic diagram of one embodiment of a system for producing low sulfur marine fuel oil that does not include a slurry hydrogenation unit provided by the present invention.

FIG. 2 is a schematic diagram of one embodiment of a system for producing low sulfur marine fuel oil that does not include a slurry hydrogenation unit provided by the present invention.

FIG. 3 is a schematic diagram of one embodiment of a system for producing low sulfur marine fuel oil including a slurry hydrogenation unit provided by the present invention.

FIG. 4 is a schematic diagram of one embodiment of a system for producing low sulfur marine fuel oil including a slurry hydrogenation unit provided by the present invention.

Detailed Description

The invention will be further described with reference to the accompanying drawings, without thereby limiting the invention.

FIG. 1 is a schematic diagram of one embodiment of a system for producing low sulfur marine fuel oil that does not include a slurry hydrogenation unit provided by the present invention. As shown in fig. 1, a filter 1 is disposed in the slurry filtering unit, a slurry inlet and a slurry inlet pipeline 3 communicating with the filter 1 are disposed at the lower part of the filter 1, a solid-removing slurry outlet and a communicated solid-removing slurry outlet pipeline 4 are disposed at the upper part of the filter 1, and a residue outlet and a residue discharge pipeline 5 are disposed at the bottom of the filter 1. A filter assembly 2 of flexible filter material is arranged in the filter 1; the flexible filter material is selected from one or more of polyethylene, nylon, polyphenylene sulfide, polyimide, polytetrafluoroethylene, aramid fiber, polyurethane and glass fiber, or a flexible filter material formed by compounding any two or more of the above materials; the filtering precision of the flexible filter material is 0.1-15 micrometers. Regeneration medium inlets are provided at the top and upper part of the filter 1 and communicate with a regeneration medium inlet line 6. The oil slurry removing inlet of the low-sulfur marine fuel oil blending unit 7 is communicated with the oil slurry removing outlet pipeline 4 of the oil slurry filtering unit, the blending component inlet is communicated with the blending component inlet pipeline 8, and the low-sulfur marine fuel oil outlet is communicated with the low-sulfur marine fuel oil outlet pipeline 9.

FIG. 2 is a schematic illustration of one embodiment of a low sulfur marine fuel oil production system provided in accordance with the present invention that does not include a slurry hydrogenation unit, wherein two filters are provided in the slurry filtration unit. As shown in fig. 2, a filter 1, a filter 3, a slurry inlet line 5, a de-solidified slurry outlet line 7 and a residue discharge line 9 are arranged in the slurry filtering unit, and are communicated with the filter 1; a slurry inlet line 6, a de-solidified slurry outlet line 8, and a residue discharge line 10 in communication with the filter 3. A pinhole-free filter bag 2 of a flexible filter material is arranged in the filter 1; the filter 3 is provided with a pinhole-free filter bag 4 of flexible filter material. A regeneration medium inlet is arranged at the top of the filter 1 and is communicated with a regeneration medium inlet pipeline 11; the upper part of the filter 1 is provided with a regeneration medium inlet and communicates with a regeneration medium inlet line 13. A regeneration medium inlet is arranged at the top of the filter 3 and is communicated with a regeneration medium inlet pipeline 12; the upper part of the filter 3 is provided with a regeneration medium inlet and communicates with a regeneration medium inlet line 14. A communication line 15 is provided between the de-solidified slurry outlet of the filter 1 and the oil inlet to be filtered of the filter 3.

The unsecured oil slurry outlet pipelines 7 and 8 are communicated with an unsecured oil slurry inlet of the low-sulfur marine fuel oil blending unit 16, a blending component inlet is communicated with a blending component inlet pipeline 17, and a low-sulfur marine fuel oil outlet is communicated with a low-sulfur marine fuel oil outlet pipeline 18.

When the slurry filter unit shown in fig. 2 is used for filtering, the filter 1 and the filter 3 may be used in parallel, may be used in series, or may be used in a switching manner. When the filter 1 is used in a switching manner, the filter 3 is regenerated or is in a standby state at the same time when the filter is used for online filtration; or when the filter 3 is in-line filtering, the filter 1 is simultaneously regenerated or in a standby state.

As shown in fig. 3, a filter 1 is disposed in the slurry filtering unit, a slurry inlet and a slurry inlet line 3 communicating with the filter 1 are disposed at the lower portion of the filter 1, a solid-removing slurry outlet and a communicating solid-removing slurry outlet line 4 are disposed at the upper portion of the filter 1, and a residue outlet and a residue discharge line 5 are disposed at the bottom of the filter 1. A filter assembly 2 of flexible filter material is arranged in the filter 1. Regeneration medium inlets are provided at the top and upper part of the filter 1 and communicate with a regeneration medium inlet line 6. The solid removal slurry oil outlet pipeline 4 is communicated with the inlet of the hydrogenation reaction zone 7 of the slurry oil hydrogenation unit, the hydrogen-containing gas pipeline 12 is communicated with the inlet of the hydrogenation reaction zone 7 of the slurry oil hydrogenation unit, the outlet pipeline 8 of the hydrogenation reaction zone 7 is communicated with the inlet of the separation unit 9, and the separation unit is provided with a gas-phase logistics outlet and outlet pipeline 10 and a hydrogenated slurry oil outlet and outlet pipeline 11.

The hydrogenation slurry inlet of the low-sulfur marine fuel oil blending unit 13 is communicated with the hydrogenation slurry outlet pipeline 11 of the slurry hydrogenation unit, the blending component inlet is communicated with the blending component inlet pipeline 14, and the low-sulfur marine fuel oil outlet is communicated with the low-sulfur marine fuel oil outlet pipeline 15.

FIG. 4 is a schematic diagram of one embodiment of a system for producing low sulfur marine fuel oil including a slurry hydrogenation unit provided with two filters in a slurry filtration unit. As shown in fig. 4, a filter 1, a filter 3, a slurry inlet line 5, a de-solidified slurry outlet line 7 and a residue discharge line 9 are arranged in the slurry filtering unit, and are communicated with the filter 1; a slurry inlet line 6, a de-solidified slurry outlet line 8, and a residue discharge line 10 in communication with the filter 3. A pinhole-free filter bag 2 of a flexible filter material is arranged in the filter 1; the filter 3 is provided with a pinhole-free filter bag 4 of flexible filter material. A regeneration medium inlet is arranged at the top of the filter 1 and is communicated with a regeneration medium inlet pipeline 11; the upper part of the filter 1 is provided with a regeneration medium inlet and communicates with a regeneration medium inlet line 13. A regeneration medium inlet is arranged at the top of the filter 3 and is communicated with a regeneration medium inlet pipeline 12; the upper part of the filter 3 is provided with a regeneration medium inlet and communicates with a regeneration medium inlet line 14. A communication line 15 is provided between the de-solidified slurry outlet of the filter 1 and the oil inlet to be filtered of the filter 3.

The solid removal slurry oil outlet pipelines 7 and 8 are communicated with the inlet of the hydrogenation reaction zone 16 of the slurry oil hydrogenation unit, the hydrogen-containing gas pipeline 21 is communicated with the inlet of the hydrogenation reaction zone 16 of the slurry oil hydrogenation unit, the outlet pipeline 17 of the hydrogenation reaction zone 16 is communicated with the inlet of the separation unit 18, the separation unit is provided with a gas phase material flow outlet and outlet pipeline 19, and the hydrogenated slurry oil outlet and outlet pipeline 20.

The hydrogenated slurry inlet of the low-sulfur marine fuel oil blending unit 22 is communicated with the hydrogenated slurry outlet pipeline 20 of the slurry hydrogenation unit, the blending component inlet is communicated with the blending component inlet pipeline 23, and the low-sulfur marine fuel oil outlet is communicated with the low-sulfur marine fuel oil outlet pipeline 24.

When the slurry filter unit shown in fig. 4 is used for filtering, the filter 1 and the filter 3 may be used in parallel, may be used in series, or may be used in a switching manner. When the filter 1 is used in a switching manner, the filter 3 is regenerated or is in a standby state at the same time when the filter is used for online filtration; or when the filter 3 is in-line filtering, the filter 1 is simultaneously regenerated or in a standby state.

The invention is further illustrated by the following examples, which are not intended to limit the invention in any way.

Examples 1 to 3

With the system for producing low sulfur marine fuel oil shown in fig. 1, a single filter is provided in the slurry filter unit, and a pinhole-free filter bag of flexible filter material is provided in the filter. The flexible filter material is provided with a solid removing layer and a base cloth layer, and specific property parameters are shown in table 1.

TABLE 1

Slurry a was filtered by passing it through a slurry inlet line in communication with the filter into the filter described in example 1, and the de-solidified slurry 1 was withdrawn from the de-solidified slurry outlet line. The filter temperature of the filter was 100℃and the filtration was set to a differential pressure of 0.12MPa for regeneration. Collecting the de-solidified oil slurry 1 when the pressure difference of the filter is 0.04MPa, stopping feeding when the pressure difference reaches 0.12MPa, stopping collecting the de-solidified oil slurry, spraying a filter cake by using the de-solidified oil slurry 1, and simultaneously carrying out back flushing by using nitrogen at 100 ℃.

Slurry a was filtered by passing it through a slurry inlet line in communication with the filter into the filter described in example 2 and the de-solidified slurry was withdrawn from a de-solidified slurry outlet line. The filter temperature of the filter is 180 ℃, and the filter is set to the pressure difference of 0.30MPa for regeneration. Collecting the de-solidified oil slurry 2 when the pressure difference of the filter is 0.04MPa, stopping feeding when the pressure difference reaches 0.30MPa, stopping collecting the de-solidified oil slurry, spraying a filter cake by using the oil slurry A, and simultaneously carrying out back blowing by using nitrogen at 180 ℃.

Slurry a was filtered by passing it through a slurry inlet line in communication with the filter into the filter described in example 3, and the de-solidified slurry was withdrawn from a de-solidified slurry outlet line. The filtration temperature of the filter was 250℃and the filtration was set to a differential pressure of 0.45MPa for regeneration. Collecting the de-solidified oil slurry 3 when the pressure difference of the filter is 0.05MPa, stopping feeding when the pressure difference reaches 0.45MPa, stopping collecting the de-solidified oil slurry, spraying a filter cake by using the oil slurry A, and simultaneously carrying out back flushing by using nitrogen at the temperature of 250 ℃.

Analytical data for slurry a and the collected de-solidified slurry are shown in table 2.

TABLE 2

Blending the solid removing slurry oil 1, the solid removing slurry oil 2 and the solid removing slurry oil 3 with blending components such as low-sulfur residual oil, hydrogenated residual oil and low-sulfur diesel oil respectively. The properties of the low-sulfur residual oil 1, the hydrogenated residual oil 1 and the low-sulfur diesel oil 1 are shown in table 3, the main properties of different blending schemes and blending products are shown in table 4, and the indexes of the low-sulfur residual oil 1, the hydrogenated residual oil 1 and the low-sulfur diesel oil meet the standard requirements of low-sulfur marine fuel oil GB/T17411-2015.

TABLE 3 Table 3

Project	Low sulfur residuum 1	Hydrogenated residuum 1	Low sulfur diesel 1
				Density (20 ℃ C.) (g/cm) ³ )	0.920	0.921	0.958
Viscosity at 100 ℃ (mm) ² /s)		28.7
				Viscosity (mm) at 50 DEG C ² /s)	142	220	2.77
Sulfur, wt%	0.49	0.23	0.45
				Solid particulate matter content (μg/g)	0	0	0
Metal content, μg/g
				Si	0	0	0
Al	0	0	0

TABLE 4 Table 4

Examples 4 to 6

With the system for producing low sulfur marine fuel oil shown in fig. 2, two filters are provided in the slurry filter unit, and pinhole-free filter bags of flexible filter materials are provided in the filters. Specific property parameters of the flexible filter materials are shown in tables 5, 6 and 7.

TABLE 5

	Example 4
		Material of material	Polytetrafluoroethylene
Porosity of the porous material	38％
		Gram weight	550±5％g/m ²
Strength of warp direction breaking	2100N/5cm
		Weft breaking strength	2300N/5cm
Thickness of (L)	2.5±10％mm
		Filtration accuracy	1μm

TABLE 6

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TABLE 7

Slurry B was filtered by passing it through a slurry inlet line in communication with the filter into the filter described in example 4. The filter temperature of the filter was 130℃and the filtration was set to a differential pressure of 0.25MPa for regeneration. Collecting the de-solidified oil slurry 4 when the pressure difference of the filter is 0.05MPa, switching the online filter when the pressure difference reaches 0.25MPa, and back blowing the filter of the cut-out filter system by utilizing 130 ℃ nitrogen.

Slurry B was filtered by passing it through a slurry inlet line in communication with the filter into the filter described in example 5. The filtration temperature of the filter was 150℃and the filtration was set to a differential pressure of 0.18MPa for regeneration. Collecting the de-solidified oil slurry 5 when the pressure difference of the filter is 0.04MPa, switching on-line filter when the pressure difference reaches 0.18MPa, and spraying the filter cake surface by the de-solidified oil slurry 5 while back blowing by using nitrogen at 150 ℃ by the filter of the cut-out filter system.

Slurry B was filtered by passing it through a slurry inlet line in communication with the filter into the filter described in example 6. The filtering temperature of the filter is 180 ℃, and the filtering is set to the pressure difference of 0.40MPa for back flushing. Collecting the de-solidified oil slurry 6 when the pressure difference of the filter is 0.04MPa, switching the online filter when the pressure difference reaches 0.40MPa, and back blowing the filter of the cut-out filter system by utilizing nitrogen at 150 ℃.

Analytical data for slurry B and the collected de-solidified slurry are shown in table 8.

TABLE 8

Blending the solid removing slurry oil 4, the solid removing slurry oil 5 and the solid removing slurry oil 6 with blending components such as low-sulfur residual oil, hydrogenated residual oil and low-sulfur diesel oil respectively. The properties of the low-sulfur residual oil 2, the hydrogenated residual oil 2 and the low-sulfur diesel oil 2 are shown in Table 9, the main properties of different blending schemes and blending products are shown in Table 10, and the indexes of the low-sulfur residual oil, the hydrogenated residual oil 2 and the low-sulfur diesel oil meet the standard requirements of low-sulfur marine fuel oil GB/T17411-2015.

TABLE 9

Table 10

Examples 7 to 9

The system for producing low sulfur marine fuel oil shown in fig. 3 is adopted, wherein a single filter is arranged in a filtering unit of a slurry oil treatment system, and a pinhole-free filter bag of a flexible filter material is arranged in the filter. Specific property parameters of the flexible filter material are shown in table 11.

In the embodiment, the slurry hydrogenation unit is carried out on a double-tube reactor pilot plant, and the commercial brands of the hydrogenation protecting agent, the hydrodemetallization catalyst and the hydrodesulphurization agent are RG-30A, RG-30B, RDM-35, RMS-30 and RCS-30 respectively, which are all produced by Kaolin catalyst factories of China petrochemical catalyst division.

The hydrogenation reaction zone of the slurry hydrogenation unit is filled with a hydrogenation protective agent, a hydrodemetallization agent and/or a hydrodesulphurisation agent in sequence, and the specific filling scheme is shown in table 12.

The slurry oil enters a slurry oil filtering unit for filtering, the solid-removed slurry oil obtained by filtering and hydrogen-containing gas are mixed and enter a slurry oil hydrogenation unit, and the hydrogenated slurry oil is obtained after hydrotreatment and gas-liquid separation.

In example 7, slurry C was treated, and the filtration temperature of the filter was 100℃and the back flushing was performed with 100℃nitrogen gas when the filtration pressure was set to 0.12 MPa.

In example 8, slurry C was treated, and the filtration temperature of the filter was 180℃and the back flushing was performed with nitrogen at 180℃when the filtration was set to a pressure difference of 0.30 MPa.

In example 9, slurry D was treated at a filter temperature of 250℃and back-flushing was performed with nitrogen at 250℃when the pressure difference was set to 0.45 MPa.

The properties of the slurries treated in the examples are shown in Table 13. The hydrogenation unit reaction conditions are shown in table 14. The properties of the de-solidified slurry and the hydrogenated slurry are shown in Table 15.

As can be seen from the data in table 15, the slurry filter unit removes most of the solid particulates from the slurry, the slurry hydrogenation unit removes most of the sulfur from the stripped slurry, and the remaining solid particulates are removed, and the resulting hydrogenated slurry can be used as a blending component for low sulfur marine fuel oil. In addition, the slurry oil filter unit provided by the invention has the advantages of long operation period, low cost and good environmental protection.

TABLE 11

Table 12

	Example 7	Example 8	Example 9
				RG-30A/ml	20	20	20
RG-30B/ml	50	30	20
				RDM-35/ml	30	50	30
RMS-30/ml	/	/	10
				RCS-30/ml	/	/	20
Total/ml	100	100	100

TABLE 13

	Slurry oil C	Slurry oil D
			Density (g/cm) ³ )	1.093	1.138
Viscosity at 100 ℃ (mm) ² /s)	32	59
			Viscosity (mm) at 50 DEG C ² /s)	2100	5680
Sulfur, wt%	0.78	1.27
			Solid particulate matter content (μg/g)	3650	9700
Metal content, μg/g
			Si	425	1230
Al	482	1350

TABLE 14

Process conditions	Example 7	Example 8	Example 9
				Reaction temperature, DEG C	360	320	350
Total pressure, MPa	3.0	4.0	8.0
				Hydrogen partial pressure, MPa	1.5	4.0	6.4
Hydrogen to oil ratio (volume)	50	150	300
				Liquid hourly space velocity, hr ^-1	1.5	1.0	0.5

TABLE 15

The hydrogenated slurry oil 7, the hydrogenated slurry oil 8 and the hydrogenated slurry oil 9 are respectively blended with blending components such as low-sulfur residual oil, hydrogenated residual oil, low-sulfur diesel oil and the like. The properties of the low-sulfur residual oil 3, the hydrogenated residual oil 3 and the low-sulfur diesel oil 3 are shown in Table 16, the main properties of different blending schemes and blending products are shown in Table 17, and the other indexes all meet the standard requirements of low-sulfur marine fuel oil GB/T17411-2015.

Table 16

Project	Low sulfur residuum 3	Hydrogenated residuum 3	Low sulfur diesel 3
				Density (20 ℃ C.) (g/cm) ³ )	0.920	0.921	0.958
Viscosity at 100 ℃ (mm) ² /s)		28.7
				Viscosity (mm) at 50 DEG C ² /s)	142	220	2.77
Sulfur, wt%	0.49	0.23	0.45
				Solid particulate matter content (μg/g)	0	0	0
Metal content, μg/g
				Si	0	0	0
Al	0	0	0

TABLE 17

Examples 10 to 11

The system for producing the low-sulfur marine fuel oil is shown in fig. 4, wherein two filters are arranged in a filtering unit of the slurry treatment system, and pinhole-free filter bags of flexible filter materials are arranged in the two filters. The property parameters of the flexible filter are shown in table 18.

The hydrogenation unit reaction zone is filled with hydrogenation protective agent, hydrodemetallization agent and/or hydrodesulphurisation agent in sequence, and the specific filling scheme is shown in table 19.

The coal tar raw material enters a filtering unit for filtering, filtered oil obtained by filtering and hydrogen-containing gas are mixed and enter a hydrogenation unit, and after hydrotreating and gas-liquid separation, hydrogenated liquid phase material flow (hydrogenated coal tar) is obtained.

In example 10, coal tar a was treated, and when the filtration temperature of the filter was 50 ℃ and the filtration pressure was set to 0.30MPa, the filter was switched, and the filter cut out from the filtration system was back-blown with nitrogen at room temperature.

In example 11, coal tar B was treated, and when the filtration temperature of the filter was 80℃and the filtration pressure was set to 0.35MPa, the filter was switched, and the filter was cut out from the filtration system and back-blown with nitrogen gas at 80 ℃.

The properties of the coal tar treated in the examples are shown in table 20. The hydrogenation unit reaction conditions are shown in table 21. The properties of the oil after filtration and hydrogenation are shown in Table 22.

As can be seen from the data in table 22, the slurry filtration unit removes most of the solid particulates from the coal tar, and the hydrogenation unit removes most of the sulfur from the filtered oil, while removing the remaining solid particulates, which can be used as a blending component for low sulfur marine combustion. In addition, the filter unit provided by the invention has the advantages of long operation period, low cost and good environmental protection.

Blending the hydrogenated coal tar 1 and the hydrogenated coal tar 2 with low-sulfur residual oil, hydrogenated residual oil, low-sulfur diesel oil and other blending components respectively. The properties of the low-sulfur residual oil 4, the hydrogenated residual oil 4 and the low-sulfur diesel oil 4 are shown in table 23, the main properties of different blending schemes and blending products are shown in table 24, and the indexes of the low-sulfur residual oil 4, the hydrogenated residual oil 4 and the low-sulfur diesel oil meet the standard requirements of low-sulfur marine fuel oil GB/T17411-2015.

TABLE 18

TABLE 19

	Example 10	Example 11
			RG-30A/ml	10	/
RG-30B/ml	20	50
			RDM-35/ml	30	30
RMS-30/ml	20	20
			RCS-30/ml	20	/
Total/ml	100	100

Table 20

	Coal tar A	Coal tar B
			Density (g/cm) ³ )	1.13	1.21
Viscosity (mm) at 50 DEG C ² /s)	1.5	1.9
			Viscosity at 100 ℃ (mm) ² /s)	2.6	3.0
Sulfur, wt%	0.51	0.92
			Solid particulate matter content (μg/g)	5420	8632

Table 21

	Example 10	Example 11
			Reaction temperature, DEG C	350	370
Total pressure, MPa	10.0	12.0
			Hydrogen partial pressure, MPa	10.0	12.0
Hydrogen to oil ratio (volume)	200	300
			Liquid hourly space velocity, hr ^-1	3.0	1.5

Table 22

Project	Example 10	Example 11
			Filtering out oil (oil slurry)
Viscosity at 100 ℃ (mm) ² /s)	2.70	3.12
			Solid particle content, wt%	487	765
Filtering out oil after hydrogenation	Hydrogenated coal tar 1	Hydrogenated coal tar 2
			Density (20 ℃), g/cm ³	1.01	1.02
Viscosity (mm) at 50 DEG C ² /s)	1.2	1.8
			Sulfur, wt%	0.30	0.15
Solid particle content, wt%	10	12

Table 23

Table 24

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Claims

1. A system for producing low-sulfur marine fuel oil comprises a slurry oil filtering unit, an optional slurry oil hydrogenation unit and a low-sulfur marine fuel oil blending unit, wherein the slurry oil filtering unit is provided with a slurry oil inlet, a de-solidified slurry oil outlet and a filter residue outlet; the slurry hydrogenation unit is provided with a solid removal slurry inlet, an optional heavy oil raw material inlet and a hydrogenation slurry outlet; the low-sulfur marine fuel oil blending unit is provided with a solid removal slurry inlet and/or a hydrogenation slurry inlet, a blending component inlet and a low-sulfur marine fuel oil outlet;

the slurry oil filter unit is internally provided with a filter, the filter is internally provided with at least one filter component of a flexible filter material, and the flexible filter material is one or more selected from polyethylene, nylon, polyphenylene sulfide, polyimide, polytetrafluoroethylene, aramid fiber, polyurethane and glass fiber; the filtering precision of the flexible filter material is 0.1-15 micrometers, and the gram weight of the flexible filter material is 300-1000 g/m ² The warp breaking strength is 850N/5 cm-9000N/5 cm, the weft breaking strength is 1000N/5 cm-11000N/5 cm, and the thickness is 0.5-3.4 mm; the flexible filter material at least comprises a de-solidification layer and a base cloth layer, wherein the porosity of the de-solidification layer is 25% -98%, the porosity of the base cloth layer is 30% -40%, and the base cloth layer is made of polytetrafluoroethylene and/or polyphenylene sulfide;

the slurry oil filter unit is provided with a regeneration medium buffer tank and a regeneration medium inlet pipeline which is respectively communicated with each filter; the regeneration medium comprises a leaching oil and a purging medium; the upper part of the filter is provided with a leaching oil inlet and a spraying device, and the top of the filter and/or the upper part of the filter is provided with a purging medium inlet.

2. The system of claim 1, wherein the flexible filter material has a filtration accuracy of 0.1 to 10 microns.

3. The system of claim 1, wherein the flexible filter material has a filtration accuracy of 0.2 to 5 microns.

4. The system of claim 1, wherein the filter assembly of the flexible filter material is in the form of a pinhole-free filter bag.

5. The system of claim 4, wherein the pinhole-free filter bag is manufactured using a stitching process, the stitching aperture of which is sealed with an acidic sealant material.

6. The system of claim 4, wherein the pinhole-free filter bag is made from a flexible filter material woven directly into a cylinder.

7. The system of claim 1, wherein the flexible filter material has a grammage of 520-660 g/m ² The method comprises the steps of carrying out a first treatment on the surface of the The warp breaking strength is 1000N/5 cm-2400N/5 cm, and the weft breaking strength is 1200N/5 cm-2600N/5 cm; the thickness is 0.5-3.0 mm.

8. The system of claim 7, wherein the flexible filter material has a thickness of 1.8 mm to 2.9mm.

9. The system of claim 1, wherein the de-solidified layer has a porosity of 50% -95% when the flexible filter material has a filtration accuracy of 2-5 microns;

And when the filtering precision of the flexible filter material is 0.1-less than 2 microns, the porosity of the solid removing layer is 25-70%.

10. The system of claim 1, wherein the deaggregation layer is made of polytetrafluoroethylene.

11. The system of claim 10, wherein the de-anchoring layer is made of polytetrafluoroethylene having a three-dimensional void structure.

12. The system of claim 1, wherein the flexible filter material comprises at least a de-consolidation layer, a base cloth layer, and an inner layer, wherein the inner layer is positioned on the base cloth layer on the side opposite to the de-consolidation layer and is made of fibers with fineness of 1-3 d.

13. The system of claim 12, wherein the fibers forming the inner layer are one or more selected from the group consisting of polyethylene, nylon, polyester, polypropylene, polyphenylene sulfide, polyimide, polytetrafluoroethylene, aramid, polyurethane, and fiberglass.

14. The system of claim 1, wherein the filter is an upflow filter or a downflow filter, the filter having a slurry inlet, a de-solidified slurry outlet, a filter residue outlet, and a regeneration medium inlet.

15. The system of claim 1, wherein the filter assembly comprises a cake layer of filter aid disposed on the filter assembly; the filter aid is one or a mixture of a plurality of diatomite, cellulose, perlite, talcum powder, activated clay, filter residues obtained by a filter and waste catalytic cracking catalyst; the thickness of the filter cake layer formed by the filter aid is 0.1-10 mm.

16. The system of claim 15, wherein the filters are provided with a filter aid inlet, and the slurry filtration unit is provided with a filter aid buffer tank in communication with the filter aid inlet of each filter, respectively.

17. The system of claim 16, wherein the filter aid buffer tank is filled with filter aid and a mixing medium, the mixing medium being a liquid hydrocarbon.

18. A system according to any one of claims 1-3, characterized in that the rinse oil is one or more selected from the group consisting of slurry oil, catalytically cracked diesel oil, catalytically cracked heavy cycle oil;

the purging medium is inactive gas and/or flushing oil.

19. A system according to any one of claims 1-3, characterized in that the shower oil is a de-solidified slurry.

20. The system of claim 18, wherein the flushing oil is one or more selected from the group consisting of de-solidified slurry, catalytically cracked diesel, catalytically cracked heavy cycle oil.

21. The system according to claim 1, wherein the filter unit is provided with at least one filter group, each filter group being provided with at least two filters, each filter being provided with a slurry inlet, a de-solidified slurry outlet, a regeneration medium inlet and a filter residue outlet, and lines communicating with the respective inlets and outlets, respectively; in the same filter group, a communication pipeline is arranged between the solid-removing slurry outlet of each filter and the slurry inlet of each filter in the same group, and a communication valve is arranged on the communication pipeline; the filter accuracy of the plurality of filters included in each filter group is of the same order of magnitude.

22. The system according to claim 1 or 21, wherein the slurry filtration unit comprises a control system;

the control system comprises an online pressure difference monitoring module, a filter control module and a regeneration control module, wherein the online pressure difference monitoring module is used for monitoring the pressure difference of an online filter, the filter control module is used for controlling a single filter to be switched in and out of the filter system, and the regeneration control module is used for controlling the regeneration process of the filter.

23. The system of claim 1, wherein the slurry hydrogenation unit comprises a hydrogenation reaction zone and a gas-liquid separation zone, and the solids-free slurry outlet is in communication with the hydrogenation reaction zone inlet;

the hydrogenation reaction zone is provided with one or more reactors selected from a fixed bed reactor, a slurry bed reactor and a boiling bed reactor, and an outlet of the hydrogenation reaction zone is communicated with an inlet of the gas-liquid separation zone; the gas-liquid separation zone is provided with a gas outlet and a hydrogenated slurry oil outlet.

24. The system of claim 23, wherein the fixed bed reactor of the hydrogenation reaction zone is sequentially graded with a hydrogenation protecting agent, a hydrodemetallation agent and/or a hydrotreating agent.

25. The system of claim 24, wherein the fixed bed reactor of the hydrogenation reaction zone is sequentially filled with a hydrogenation protecting agent, a hydrodemetallization agent or a hydrotreating agent, wherein the filling volume fraction of the hydrogenation protecting agent is 5% -90%, the filling volume fraction of the hydrodemetallization agent or the hydrotreating agent is 5% -90%, the sum of the filling volume fractions of the hydrogenation protecting agent and the hydrodemetallization agent is 100%, or the sum of the filling volume fractions of the hydrogenation protecting agent and the hydrotreating agent is 100% based on the whole catalyst in the fixed bed reactor.

26. The system of claim 24, wherein the fixed bed reactor of the hydrogenation reaction zone is sequentially filled with a hydrogenation protecting agent, a hydrodemetallization agent and a hydrotreating agent, wherein the filling volume fraction of the hydrogenation protecting agent is 10% -70%, the filling volume fraction of the hydrodemetallization agent is 10% -60% and the filling volume fraction of the hydrotreating agent is 20% -80% based on the whole catalyst in the fixed bed reactor.

27. The system of claim 1, wherein the low sulfur marine fuel oil blending unit is provided with a blending component line, a blending product tank; the blending component pipeline is selected from pipelines for transporting one or more of normal pressure residual oil, vacuum residual oil, catalytic diesel oil, straight-run wax oil, hydrogenated wax oil and hydrogenated residual oil.

28. The system according to claim 1, wherein the flexible filter material is a flexible filter material formed by compounding any two or more selected from the group consisting of polyethylene, nylon, polyphenylene sulfide, polyimide, polytetrafluoroethylene, aramid, polyurethane, and glass fibers.

29. A method of producing low sulfur marine fuel oil employing the system of any one of claims 1-28, comprising:

30. The method of claim 29, wherein the slurry filtration unit has a filter temperature of 30 to 250 ℃.

31. The method of claim 30, wherein the slurry filtration unit has a filter temperature of 50 to 240 ℃.

32. The method of claim 30, wherein the slurry filtration unit has a filter temperature of 60 to 180 ℃.

33. The method of claim 29, wherein the slurry filtration unit has a filter application pressure differential of 0.01 to 0.5mpa.

34. The method according to claim 29, wherein the heavy oil feedstock is one or more mixed oils selected from the group consisting of residuum, straight run wax oil, coker wax oil, catalytically cracked heavy cycle oil, catalytically cracked diesel oil, coal tar;

the slurry oil is liquid hydrocarbon with particulate impurities; the sulfur content of the obtained hydrogenated slurry oil is less than or equal to 0.5 weight percent.

35. The method of claim 34, wherein the slurry is a catalytic cracking slurry produced by a catalytic cracking process.

36. A method according to claim 29, wherein the method of regenerating the filter after use is such that the shower oil is sprayed on the filter cake forming surface of the flexible filter material and/or counter-purged with a purging medium;

the leaching oil is one or more selected from slurry oil, catalytic cracking diesel oil and catalytic cracking heavy cycle oil;

the purging medium is inactive gas and/or flushing oil, and the flushing oil is one or more selected from solid removal slurry, catalytic cracking diesel oil and catalytic cracking heavy cycle oil.

37. The method of claim 36, wherein the rinse oil is a de-solidified slurry.

38. The method of claim 29, wherein the slurry filtration unit filters the slurry, comprising the steps of:

(1) And (3) filtering: passing the slurry into at least one filter;

39. The method of claim 38, wherein prior to the step of (1) filtering in the slurry filtration unit, there is the step of (1-1) forming a cake layer: introducing a filter aid into a filter to form a filter cake layer of the filter aid on a filter element of the filter; the filter aid is one or a mixture of a plurality of diatomite, cellulose, perlite, talcum powder, activated clay, filter residues obtained by a filter and waste catalytic cracking catalyst;

When the online pressure difference monitoring module monitors that the pressure difference of the filter in the filter cake layer forming step reaches a set value II, the filter with the filter cake layer is cut into a filtering system through the filter control module to carry out the filtering step (1), and the set value II is in the range of 0.01-0.07 MPa.

40. The process of claim 29, wherein the slurry hydrogenation unit is operated under the following conditions: the reaction temperature is 100-400 ℃, the reaction pressure is 1.0-20.0 MPa, the volume ratio of hydrogen to oil is 10-1000, and the liquid hourly space velocity is 0.10-10.0 h ^-1 。

41. The process of claim 40 wherein the slurry hydrogenation unit is operated under the following conditions: the reaction temperature is 200-380 ℃, the reaction pressure is 2.0-16.0 MPa, the hydrogen-oil volume ratio is 50-500, and the liquid time volume is emptyThe speed is 0.2 to 5.0h ^-1 。

42. The process of claim 29 wherein the hydrogen-containing gas entering the slurry hydrogenation unit hydrogenation reaction zone is selected from one or more of the group consisting of catalytically cracked dry gas, coker dry gas, hydrotreater bottoms gas, and hydrogen.

43. The method of claim 29, wherein the de-solidified and/or hydrogenated slurry oil is present in an amount of 5% to 40% by weight based on the low sulfur marine fuel oil.

44. The method of claim 43, wherein the de-solidified and/or hydrogenated slurry oil is 15% to 35% by weight based on the low sulfur marine fuel oil.