CN110734782A

CN110734782A - Hydrogenation treatment method of inferior heavy oil

Info

Publication number: CN110734782A
Application number: CN201810797571.0A
Authority: CN
Inventors: 王鼎聪
Original assignee: Zhongshan Yiding Jie Nanotechnology Co Ltd
Current assignee: Zhongshan Yiding Jie Nanotechnology Co Ltd
Priority date: 2018-07-19
Filing date: 2018-07-19
Publication date: 2020-01-31
Anticipated expiration: 2038-07-19
Also published as: CN110734782B

Abstract

The invention discloses a poor heavy oil hydrotreating method, which adopts a vertical membrane core type reactor, wherein the reactor comprises a reactor body, a feeding distribution disc and a hollow catalyst membrane core element, wherein the reactor body is provided with a feeding hole and a discharging hole, the hollow catalyst membrane core element is vertically arranged in the reactor body, the hollow catalyst membrane core is a membrane catalyst provided with a hollow channel, and the hollow catalyst membrane core comprises a carrier component and a hydrogenation active metal component.

Description

Hydrogenation treatment method of inferior heavy oil

Technical Field

The invention relates to a hydrotreatment method of inferior heavy oils, in particular to a hydrotreatment method of inferior heavy oils with high metal impurity content and high carbon residue content.

Background

With the increasing weight and quality of petroleum, petroleum processing is more and more difficult. Heavy oil contains a large amount of metal impurities such as Ni, V, etc., and most of the metal impurities are present in asphaltenes, which are difficult components to remove.

When the content of the metal impurities V + Ni is more than 200 mug/g and the carbon residue value is more than 15%, a boiling bed or a suspension bed process is adopted like , but the boiling bed process is extremely complex, the device investment is large, the maintenance is difficult, which is an important reason for the difficulty in pushing , the suspension bed process is also relatively complex, the process has many problems, and is difficult to push.

At present, solvent deasphalting is used to obtain deasphalted oil as the raw material for catalytic cracking, fixed bed hydrogenation and other processes, but as the main component of deasphalted asphalt is asphaltene, the basic structural unit of asphaltene is a condensed aromatic ring system formed from several aromatic rings, and its periphery is connected with several naphthenic rings and aromatic rings, and said rings have several alkyl side chains whose length is less than , and in the aromatic nucleus structure also S, N, O heteroatom group and simultaneously contain several metals of complex V and Ni.

CN200910162163.9 discloses a combined process for processing inferior crude oil, which comprises subjecting an inferior crude oil raw material to solvent deasphalting to obtain deasphalted oil, preheating the deasphalted oil, introducing the deasphalted oil into a reaction zone of a catalytic conversion reactor, optionally mixing oil gas generated by the reaction with a used catalyst with a light raw material oil, introducing the mixture into a second reaction zone to perform cracking reaction, hydrogen transfer reaction and isomerization reaction, performing liquid-solid separation, and separating a reaction product into dry gas, liquefied gas, gasoline, diesel oil and catalytic wax oil in steps, wherein the reaction conditions of the reaction zone and the second reaction zone are enough to obtain the catalytic wax oil accounting for 12-60% of the raw material oil, introducing the catalytic wax oil after hydrogenation into a catalytic conversion device to perform reaction in steps to obtain a light fuel oil product, especially high-octane gasoline.

CN 201110352418.5 discloses a poor-quality heavy oil processing method, which comprises the steps of (1) feeding a poor-quality heavy oil raw material into a solvent deasphalting device to obtain deasphalted oil and deasphalted asphalt, (2) feeding the deasphalted asphalt obtained in the step (1) into a fluidized bed hydrotreatment device, and carrying out fluidized bed hydrotreatment in the presence of hydrogen and a fluidized bed hydrotreatment catalyst, and (3) mixing the fluidized bed hydrotreatment reaction effluent obtained in the step (2) and the deasphalted oil into a fixed bed hydrotreatment device, and carrying out fixed bed hydrotreatment in the presence of hydrogen and the fixed bed hydrotreatment catalyst, wherein the generated oil obtained from the fixed bed hydrotreatment reaction effluent is used as a raw material of a catalytic cracking device.

CN200410050788.3 discloses a method for treating inferior heavy oils or residual oils, which comprises the steps of feeding heavy oils or residual oils into a solvent extraction device, feeding the obtained deasphalted oils into a fixed bed hydrotreatment device for hydrotreatment, feeding the obtained hydrogenated tail oils into a catalytic cracking device, feeding the obtained slurry oil and the deasphalted oils into a suspension bed hydrogenation device, separating the products to obtain light fractions and unconverted tail oils, wherein the unconverted tail oils are circulated to the solvent extraction device.

In conclusion, for the hydrotreatment of the inferior heavy oil with high metal impurity content and high carbon residue content, the fixed bed process, the fluidized bed process and the suspended bed process in the prior art all have disadvantages, and methods which are more suitable for the hydrotreatment of the inferior heavy oil are research hotspots in the field.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a hydrotreatment method for poor-quality heavy oils, which can convert the full fraction of the poor-quality heavy oils into light fuel oil and heavy fuel oil, and has good properties of the heavy fuel oil and long running period of the device.

The invention provides a hydrotreatment method of inferior heavy oils, which adopts a vertical membrane core type reactor, wherein the reactor comprises a reactor body, a feeding distribution disc and a hollow catalyst membrane core element, the reactor body is provided with a feeding hole and a discharging hole, the hollow catalyst membrane core element is vertically arranged in the reactor body, the hollow catalyst membrane core is a membrane catalyst provided with a hollow channel, a material space is formed between the reactor body and the peripheral side of the hollow catalyst membrane core element, the hollow catalyst membrane core comprises a carrier component and a hydrogenation active metal component, preferably, the content of the hydrogenation active metal is 30-70%, preferably 40-70% by taking the weight of the hollow catalyst membrane core as a reference, the inferior heavy oils and hydrogen enter the vertical membrane core type reactor from the feeding hole, contact with the hollow catalyst membrane core to carry out hydrotreatment reaction under the hydrotreatment condition, and the obtained hydrotreatment products are discharged out of the reactor from the discharging hole.

The membrane core type reactor can adopt , also can adopt a plurality of reactors to establish ties, in every membrane core type reactor, adopt hollow catalyst membrane core components or adopt a plurality of hollow catalyst membrane core components that connect in parallel, this hollow catalyst membrane core component adopts hollow catalyst membrane cores or adopts a plurality of hollow catalyst membrane cores that connect in parallel, in every membrane core type reactor, the total number of hollow catalyst membrane cores is 1 ~ 24.

The properties of the hollow catalyst membrane core are as follows: the bulk density is 0.36-0.65 g/cm³The lateral pressure strength is more than or equal to 12N/mm, is 12-30N/mm, the pore volume is 0.5-1.2 mL/g, and the specific surface area is 40-150 m²(ii)/g, the average pore diameter is 20 to 65 nm.

Preferably, the pore volume of the hollow catalyst membrane core is more than 80% of the total pore volume and preferably more than 90% of the total pore volume, the pore volume of the hollow catalyst membrane core is less than 20% of the total pore volume and preferably less than 10% of the total pore volume, the pore volume of the hollow catalyst membrane core is less than 20% of the total pore volume, preferably less than 10% of the total pore volume, the pore volume of the hollow catalyst membrane core is less than 35% of the total pore volume and preferably less than 12% to 35% of the total pore volume, the pore volume of the hollow catalyst membrane core is more than 40% of the total pore volume, preferably 45% to 80% of the total pore volume, and the pore volume of the hollow catalyst membrane core is more than 100nm and preferably less than 50% to 30% of the total pore volume.

The hollow catalyst membrane core in the membrane core type reactor is preferably a concentric annular cylinder, the ratio of the height to the outer diameter of the hollow catalyst membrane core is 1-20: 1, preferably 1.5-15: 1, the ratio of the outer diameter to the inner diameter is 1.2-50: 1, preferably 2-30: 1, and the height of the hollow catalyst membrane core is mm which is less than 2000 mm.

In the hollow catalyst membrane core, the carrier is an alumina-based carrier, wherein the carrier also can contain auxiliary agent components, such as at least of silicon, magnesium, titanium and zirconium, the content of the auxiliary agent accounts for less than 15% of the weight of the carrier components in terms of elements, the hydrogenation active metal component adopts a VIB group and/or VIII group metal component, the VIB group metal is preferably at least of W, Mo, the VIII group metal is preferably at least of Ni and Co, steps are preferably carried out, the weight ratio of the VIB group metal in terms of oxide to the VIII group metal in terms of oxide is 1-8: 1, and preferably 1-6: 1.

The preparation method of the hollow catalyst membrane core can adopt at least methods of a foaming method, a sol-gel pore-forming method and a micelle template method to prepare a mixture containing aluminum hydroxide, then the mixture is pressed into a hollow catalyst membrane core intermediate with a hollow channel by a mould, and the hollow catalyst membrane core is obtained by drying and roasting.

The foaming method can adopt pseudo-boehmite, water, a binder and resin to be mixed, the mixture is pressed into a hollow catalyst membrane core with a hollow channel by a mould, the hollow catalyst membrane core is dried at 100-120 ℃ and roasted at 800-1100 ℃ to obtain the hollow catalyst membrane core.

The sol-gel pore-forming method is to prepare pseudo-boehmite by a sol-gel method, add a pore-forming agent, peptizing acid and water for kneading, press the mixture into a hollow catalyst membrane core with a hollow channel by a mould, dry the hollow catalyst membrane core at 100-120 ℃, and roast the hollow catalyst membrane core at 550-1100 ℃ to obtain the hollow catalyst membrane core.

The micelle template method is to prepare pseudo-boehmite by adopting a forward micelle method or a reverse micelle method, add peptizing acid and water for kneading, press the mixture into a hollow catalyst membrane core with a hollow channel by utilizing a mold, dry the hollow catalyst membrane core at 100-120 ℃ and roast the hollow catalyst membrane core at 550-1100 ℃ to obtain the hollow catalyst membrane core.

The membrane core type reactor can adopt an upper feeding mode and a lower feeding mode, and preferably adopts a lower feeding mode.

The membrane core type reactor material can flow to the hollow channel from the outside of the membrane core through the membrane layer, and also can flow to the outside of the membrane core through the membrane layer by adopting the hollow channel, and the pressure difference formed between the external material space of the membrane core and the hollow channel in the membrane core is less than 2MPa, preferably 0.2-1.0 MPa.

The process of the present invention is preferably operated with downfeed and flow from the outside of the membrane core through the membrane layers to the hollow channels. Wherein, the lower part of the reactor body is provided with a feed inlet. The feed distribution tray is disposed below the hollow catalyst membrane core element. The feeding distribution disc is evenly provided with openings, and the openings are communicated with the material space. The upper part of the body is provided with a discharge hole which is communicated with the hollow channel of the hollow catalyst membrane core.

The outer layer of the hollow catalyst membrane core can be provided with a detachable protective structural member.

The protective structural member may be a net structure including at least kinds of punched mesh, welded mesh, cast mesh, wire mesh, diamond metal mesh, gabion mesh, patterned stainless steel rolled mesh, mat type mesh, sieve plate or sieve sheet, but not limited to the above-exemplified net structure.

The number of the mesh plate or the hollow member may be or more, and if there are a plurality of the mesh plate or the hollow member, the mesh plate or the hollow member may be connected by welding or the like.

The screen plate or the hollow member is arranged on the outer layer of the hollow catalyst membrane core and is used for protecting the hollow catalyst membrane core.

The inferior heavy oil is heavy oil containing asphaltene and can be derived from petroleum hydrocarbon and/or other mineral oil, wherein the petroleum hydrocarbon can be derived from residual oil and/or crude oil, wherein the residual oil can be types or more selected from vacuum residual oil and atmospheric residual oil, and the crude oil can be selected from thickened oil, and the other mineral oil is types or more selected from coal liquefaction oil, oil sand oil and shale oil.

In the inferior heavy oil, the content of metal impurities V and Ni can be more than 150 mu g/g, and can also be more than 200 mu g/g, can be 150-900 mu g/g, and can also be 200-900 mu g/g, the weight content of carbon residue can be more than 10%, and can also be more than 15%, can be 10-28%, and can also be 15-28%, and the weight content of sulfur in the inferior heavy oil can be more than 3%, can be more than 4%, and can also be more than 5%.

The hydroprocessed feedstock may also include other sources of bituminous components such as or more of coal tar pitch, straight run pitch, and natural pitch.

The operating conditions of the hydrotreatment are as follows: the reaction pressure is 11.0-17.5 MPa, and the liquid hourly space velocity is 0.1-2.0 h^-1The volume ratio of hydrogen to oil is 380-1000: 1, the reaction temperature is 350-411 ℃, and the preferable operation conditions are as follows: the reaction pressure is 12.0-16.0 MPa, and the liquid hourly space velocity is 0.2-0.6 h^-1The volume ratio of hydrogen to oil is 500-1000: 1, the reaction temperature is 375-390 ℃.

The membrane core reactor, especially a plurality of membrane core reactors are adopted, the effluent of each membrane core reactor can be subjected to gas-liquid separation, and H is removed from the obtained gas-phase product₂S and NH₃And the recovered hydrogen can be recycled. Wherein H is removed₂S removing NH by alkali solution absorption₃ it is absorbed by sulfuric acid solution.

The hydrogenation product can be fractionated to obtain light distillate oil (such as gasoline and diesel oil) and heavy distillate oil, wherein the heavy distillate oil meets the requirements of the marine fuel and can be used as the marine fuel.

When a plurality of membrane core type reactors are connected in series, the membrane core type reactor is also provided with a cutting pipeline for cutting and cutting in each reactor, and when the activity of the catalyst can not meet the application requirement, a cutting regeneration method of the membrane core type reactor can be adopted. The method can monitor each membrane core type reactor, when the catalytic performance of a certain membrane core type reactor is monitored to be reduced, the membrane core type reactor is cut out to regenerate the hollow catalyst membrane core therein, and the membrane core type reactor is cut in to continue the reaction after the regeneration, preferably, the carbon residue content of the product obtained by each membrane core type reactor is monitored, the membrane core type reactor with the carbon residue removal rate reduced by 5 percent is cut out on the basis of the carbon residue removal rate at the initial reaction, the hollow catalyst membrane core therein is regenerated, and the membrane core type reactor is cut in to continue the reaction after the regeneration. Wherein the initial decarbonization rate of the reaction is the decarbonization rate when the reaction is stable after raw materials are fed into the reactor. The reactor raw material feeding includes the situation that the reactor needs to cut in the raw material again for various reasons, such as the new start-up of the device, the cutting-in after the regeneration of the catalyst cut out from the reactor, and the like, and the decarbonization rate at the initial stage of the reaction needs to be measured again.

The hollow catalyst membrane core in the membrane core type reactor adopts a cutting regeneration method, and the regeneration method can adopt a high-temperature roasting method, and specifically comprises the following steps:

when the hollow catalyst membrane core in the membrane core type reactor can not meet the application requirement, the temperature of the reactor is reduced to be below 100 ℃, the pressure of hydrogen is reduced to be normal pressure, materials in the device completely flow out of the reactor, the reactor is washed by light distillate oil, the membrane core type reactor is opened, the membrane element with reduced activity is taken out, the hollow catalyst membrane core is placed into a 100 ℃ drying oven to be dried for 1-5 hours, the hollow catalyst membrane core is placed into a roasting oven to be roasted for 1-5 hours at the temperature of 150-250 ℃ at the speed of 3-5 ℃/min, and then the hollow catalyst membrane core is continuously heated to 450-500 ℃ to be roasted for 4-6 hours.

For conventional fixed bed residue hydroprocessing catalysts, deactivation of the catalyst usually requires replacement with all fresh catalyst, and regeneration by a char-fired method is not possible.

The hydrotreating product has sulfur content below 0.5 wt%, carbon residue below 5 wt% and metal impurity content below 50 microgram/g in Ni and V content.

The processing method of the inferior heavy oil has the following advantages:

1. the method adopts the membrane core type reactor, not only can effectively remove sulfur, nitrogen and metal impurities in the inferior heavy oil, but also can obtain light fuel oil and heavy fuel oil through complete conversion, and the heavy fuel oil can be used as marine fuel. For poor heavy oil raw materials, if a conventional residual oil fixed bed process is adopted, the operation period of a reactor is short, the deactivated catalyst cannot be regenerated, and the deactivated catalyst needs to be replaced by a fresh catalyst, so that the utilization rate of each catalyst is extremely low for conventional residual oil fixed bed hydrogenation.

2. In the method, although the hollow catalyst membrane core has no void ratio of a fixed bed catalyst, the metal impurities which are beneficial to removal are slowly deposited in the catalyst membrane layer from bottom to top, the problem of overhigh pressure drop of the membrane core can not occur, the utilization rate of the catalyst is high, and the catalytic effect is stable.

3. In the method, the membrane core type reactor is adopted, the regeneration method of the membrane core reactor for alternately roasting at high temperature can be adopted to restore the activity after the activity of the hollow catalyst membrane core is reduced, when a plurality of membrane core type reactors are connected in series, each reactor can be cut in and out at any time, the operation is convenient, and the operation period of the reactors is further prolonged in steps.

Drawings

FIG. 1 is a schematic view of a membrane core reactor of the present invention;

FIG. 2 is a schematic view of a hollow catalyst membrane core of the present invention;

FIG. 3 is a schematic view of four membrane core reactors in series;

fig. 4 is a membrane core element with five hollow catalyst membrane cores connected in parallel.

Detailed Description

The technical solution of the present invention is further illustrated in detail by the following examples, but the scope of the present invention is not limited by the following examples.

In the present invention, the specific surface area and pore properties (such as pore volume, average pore diameter, pore distribution) of the hollow catalyst membrane core are measured using mercury intrusion analysis.

The vertical membrane core reactor of the present invention is described with reference to fig. 1 and 2, wherein the membrane core reactor comprises a reactor body 4, a hollow catalyst membrane core element 5, a feeding distribution plate 3, a feeding port 1, a discharging port 2, and a material space 6, wherein the hollow catalyst membrane core element 5 is vertically disposed inside the body 4, fig. 2 is a schematic view of the hollow catalyst membrane core element 5 in fig. 1, the hollow catalyst membrane core element 5 employs hollow catalyst membrane cores, and the hollow catalyst membrane cores are catalysts provided with hollow channels 7 and membrane layers 8.

The reactor comprises a reactor body 4, a feeding port 1, a feeding distribution disc 3, a material space 6, a discharging port 2 and a hollow catalyst membrane core, wherein the feeding port 1 is positioned at the lower part of the reactor body 4, the feeding distribution disc 3 is arranged below a hollow catalyst membrane core element 5, openings are uniformly distributed on the feeding distribution disc, the openings are communicated with the material space 6, the upper part of the reactor body 4 is provided with the discharging port 2, and the discharging port 2 is communicated with a hollow channel 7 of the.

For example, when the activity of the catalyst in the membrane-core reactor 101 cannot meet the application requirement, the membrane-core reactor 101 is cut off by controlling the cut-off pipeline and the corresponding valve , so that the feed directly enters the membrane-core reactor 102 for reaction, and after the membrane-core reactor 101 is regenerated by a regeneration method, the feed is cut in by controlling the opening and closing of the corresponding valve , so that the feed enters the membrane-core reactor 101 again.

Each membrane core type reactor adopts 1 hollow catalyst membrane core element, each hollow catalyst membrane core element is provided with 5 hollow catalyst membrane cores which are connected in parallel, as shown in figure 4, wherein the flow direction of materials is diffused from the outside of the hollow catalyst membrane core to the hollow channel.

The properties of the starting materials used in the examples of the invention are shown in Table 1.

TABLE 1 Properties of the raw materials

	Raw materials
		Density (20 ℃ C.), g/cm³	0.998
Carbon residue in wt%	24.6
		Metal (V + Ni) content,. mu.g/g	760
Sulfur, wt.%	5.24
		Nitrogen,. mu.g/g	5320

In the embodiment of the invention, the carbon residue content of the product of each membrane core reactor is monitored, the membrane core type reactor with the carbon residue removal rate reduced by 5 percent is cut out on the basis of the initial carbon residue removal rate of the reaction, the hollow catalyst membrane core in the membrane core type reactor is regenerated, and the membrane core is cut in for continuous reaction after regeneration. Wherein the decarbonization rate at the initial reaction is the decarbonization rate measured when the reaction is stable after the reactor is fed with raw materials again (namely the reactor is switched into the raw materials to run for about 200 hours).

Example 1

The raw material (properties are shown in table 1) is mixed with hydrogen, and then the mixture enters a membrane core type reactor for carrying out hydrotreating reaction, and the properties of hydrogenated heavy distillate oil (boiling point is above 350 ℃) obtained by separating the obtained product are shown in table 4. It can be seen from table 4 that the hydrogenated heavy fraction oil is particularly suitable as a marine fuel.

The membrane core type reactor is shown in figure 3, namely 4 membrane core type reactors are connected in series, a gas-liquid separator is arranged between every two adjacent reactors, gas discharged from the gas-liquid separator enters sodium hydroxide alkali liquor to absorb hydrogen sulfide, enters sulfuric acid solution to absorb ammonia, and purified gas is used as circulating hydrogen to be continuously used, each membrane core type reactor is internally provided with membrane core elements formed by connecting 5 hollow catalyst membrane cores in parallel, as shown in figure 4, each hollow catalyst membrane core is a concentric annular cylinder, the outer diameter of each membrane core is 430mm, the height of each membrane core is 1000mm, and the inner diameter of each hollow channel is 30 mm.

Each hollow catalyst membrane core a used had the following composition: the hydrogenation active metals are Mo and Ni, wherein the content of Mo and Ni is 48 wt% calculated by oxide, and the content of Mo: the weight ratio of Ni calculated by oxide is 4: the carrier adopts alumina, and the properties of the catalyst are shown in Table 2. The operating conditions for the hydrotreatment were as follows: the liquid hourly space velocity is 0.22h^-1The volume ratio of hydrogen to oil is 800: 1, the reaction temperature is 385 ℃, and the reaction pressure is 15.5 MPa.

The deposited metal content after days of normal reactor operation is shown in Table 3.

Example 2

The hollow catalyst membrane core a used in example 1 was replaced with the hollow catalyst membrane core B, and the operating conditions were adjusted.

The hollow catalyst membrane core B comprises the following components: the hydrogenation active metals are Mo and Ni, wherein the content of Mo and Ni is 55 wt% in terms of oxides, and the content of Mo: the weight ratio of Ni calculated by oxide is 5: 1, the carrier adopts alumina, and the other catalyst adopts a hollow catalyst membrane core A, and the properties of the catalyst are shown in a table 2.

The operating conditions for the hydrotreatment were as follows: the liquid hourly space velocity is 0.24h^-1The volume ratio of hydrogen to oil is 800: 1, the reaction temperature is 385 ℃, and the reaction pressure is 15.0 MPa. Separating the obtained product to obtain hydrogenated heavy distillate oil (boiling oil)Dots above 350 c) are shown in table 4. It can be seen from table 4 that the hydrogenated heavy fraction oil is particularly suitable as a marine fuel.

Example 3

The hollow catalyst membrane core a used in example 1 was replaced with a hollow catalyst membrane core C, and the operating conditions were adjusted.

The composition of the hollow catalyst membrane core C is as follows: the hydrogenation active metals are Mo and Ni, wherein the content of Mo and Ni is 60 wt% calculated by oxide, and the content of Mo: the weight ratio of Ni calculated by oxide is 4: 1, the carrier adopts alumina, and the other catalyst adopts a hollow catalyst membrane core A, and the properties of the catalyst are shown in a table 2.

The operating conditions for the hydrotreatment were as follows: the liquid hourly space velocity is 0.25h^-1The volume ratio of hydrogen to oil is 1000: 1, the reaction temperature is 385 ℃, and the reaction pressure is 14.5 MPa. The properties of the hydrogenated heavy distillate (boiling point above 350 ℃) obtained by separation of the product obtained are shown in table 4. It can be seen from table 4 that the hydrogenated heavy fraction oil is particularly suitable as a marine fuel.

Example 4

The hollow catalyst membrane core a used in example 1 was replaced with a hollow catalyst membrane core D, and the hollow catalyst membrane core D was placed in a hollow member prepared from a stainless steel mesh plate to protect the membrane core from increasing its strength. While operating conditions were adjusted.

The composition of the hollow catalyst membrane core D is as follows: the hydrogenation active metals are Mo and Ni, wherein the content of Mo and Ni is 40 wt% calculated by oxide, and the content of Mo: the weight ratio of Ni calculated by oxide is 4: 1, the carrier adopts alumina, and the other catalyst adopts a hollow catalyst membrane core A, and the properties of the catalyst are shown in a table 2.

The operating conditions for the hydrotreatment were as follows: the liquid hourly space velocity is 0.24h^-1The volume ratio of hydrogen to oil is 800: 1, the reaction temperature is 385 ℃, and the reaction pressure is 15.5 MPa. The properties of the hydrogenated heavy distillate (boiling point above 350 ℃) obtained by separation of the product obtained are shown in table 4. As can be seen from Table 4, the hydrogenated heavy distillate is particularlyIs suitable for being used as marine fuel.

After days of normal operation, the content of deposited metals is shown in Table 3, and the properties and yield of the hydrogenated heavy distillate oil are shown in Table 4.

TABLE 2 Properties of hollow catalyst membrane cores used in the examples of the invention

Catalyst sample	Example 1	Example 2	Example 3	Example 4
					Pore volume, cm³/g	0.72	0.63	0.65	0.70
Specific surface area, m²/g	102	105	106	105
					Average pore diameter, nm	60	51	48	58
Hole distribution,%
					10nm or less	7	2	4	6
10-30nm	23	20	34	28
					30-100nm	61	65	51	49
Over 100nm	9	13	11	17
					Bulk density, g/cm³	0.57	0.58	0.62	0.52
Lateral pressure strength, N/mm	27	25	28	24

TABLE 3 evaluation results of hydrotreating catalysts of examples of the invention

	Content of deposit metal%	Days of operation
			Example 1	63	255
Example 2	64	260
			Example 3	58	262
Example 4	65	263

Note: the precipitated metal content is the weight percent of V and Ni precipitated in the spent hydroprocessing catalyst based on the spent hydroprocessing catalyst, wherein the amount of V and Ni is determined by plasma emission spectroscopy (ICP).

Table 4 properties and yields of hydrogenated heavy distillates

	Yield, wt.%	Sulfur, wt.%	V+Ni，μg/g	Carbon residue in wt%
					Raw materials	-	5.24	760	24.6
Example 1	68	0.45	42	5.5
					Example 2	69	0.42	38	4.8
Example 3	69	0.39	39	4.0
					Example 4	68	0.41	40	5.3

In conclusion, the method can convert the poor-quality heavy oil full fraction into the light fuel oil and the heavy fuel oil, and the heavy fuel oil has good property and long running period, which cannot be realized by other processes.

It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and do not limit the technical solutions of the present invention; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that: various changes in form and details may be made therein without departing from the spirit and scope defined by the appended claims and their equivalents.

Claims

A process for hydrogenating poor-quality heavy oils includes such steps as providing a vertical membrane-core reactor with a main body, a feeding distribution disk and a hollow catalyst membrane-core element with a feeding inlet and a discharging outlet, vertically arranging said hollow catalyst membrane-core element in said main body, preparing a membrane catalyst with a hollow channel, forming a material space between said main body and said hollow catalyst membrane-core element, preparing a hollow catalyst membrane-core containing carrier component and hydrogenating active metal component, contacting said hollow catalyst membrane-core with said carrier component, hydrogenating active metal content by 30-70%, preferably 40-70%, introducing poor-quality heavy oil and hydrogen gas into said reactor, hydrogenating, and discharging the hydrogenated product from said discharging outlet.
2. The method of claim 1, wherein or a plurality of reactors connected in series are used as the membrane-core reactor, each membrane-core reactor contains or a plurality of hollow catalyst membrane core elements connected in parallel, each hollow catalyst membrane core element contains or a plurality of hollow catalyst membrane cores connected in parallel, and the total number of the hollow catalyst membrane cores in each membrane-core reactor is 1-24.
3. A method according to claim 1 or 2, characterized in that: the properties of the hollow catalyst membrane core are as follows: the bulk density is 0.36-0.65 g/cm³The lateral pressure strength is more than or equal to 12N/mm, the preferable lateral pressure strength is 12-30N/mm, the pore volume is 0.5-1.2 mL/g, and the specific surface area is 40-150 m²(ii)/g, the average pore diameter is 20-65 nm;

preferably, the pore volume of the hollow catalyst membrane core is more than 80% of the total pore volume and preferably more than 90% of the total pore volume, the pore volume of the hollow catalyst membrane core is less than 20% of the total pore volume and preferably less than 10% of the total pore volume, the pore volume of the hollow catalyst membrane core is less than 20% of the total pore volume, preferably less than 10% of the total pore volume, the pore volume of the hollow catalyst membrane core is less than 35% of the total pore volume and preferably less than 12% to 35% of the total pore volume, the pore volume of the hollow catalyst membrane core is more than 40% of the total pore volume, preferably 45% to 80% of the total pore volume, and the pore volume of the hollow catalyst membrane core is more than 100nm and preferably less than 50% to 30% of the total pore volume.
4. A method according to claim 1 or 2, characterized in that: in the membrane core type reactor, the hollow catalyst membrane core is a concentric annular cylinder, and the ratio of the height to the outer diameter of the hollow catalyst membrane core is 1-20: 1, preferably 1.5-15: 1, the ratio of the outer diameter to the inner diameter is 1.2 to 50: 1, preferably 2 to 30: 1; preferably, the height of the hollow catalyst membrane core used is below 2000 mm.
5. The method according to claim 1 or 2, characterized in that in the hollow catalyst membrane core, an alumina-based carrier is adopted as the carrier, the hydrogenation active metal component adopts VIB group and/or VIII group metal components, the VIB group metal is preferably at least in W, Mo, the VIII group metal is preferably at least in Ni and Co, and the weight content ratio of the VIB group metal calculated by oxide to the VIII group metal calculated by oxide is further , and is 1-8: 1, preferably 1-6: 1.
6. A method according to claim 1 or 2, characterized in that: the membrane core type reactor is operated in a mode of feeding materials downwards and flowing from the outside of a hollow catalyst membrane core to a hollow channel through a membrane layer; the pressure difference formed between the external material space of the hollow catalyst membrane core and the hollow channel in the membrane core is less than 2MPa, and preferably 0.2-1.0 MPa.
7. A method according to claim 1 or 2, characterized in that: the outer layer of the hollow catalyst membrane core is provided with a detachable protective structural member.
8. The method of claim 1, wherein: the operating conditions of the hydrotreatment are as follows: the reaction pressure is 11.0-17.5 MPa, and the liquid hourly space velocity is 0.1-2.0 h^-1The volume ratio of hydrogen to oil is 380-1000: 1, the reaction temperature is 350-411 ℃, and the preferable operation conditions are as follows: the reaction pressure is 12.0-16.0 MPa, and the liquid hourly space velocity is 0.2-0.6 h^-1The volume ratio of hydrogen to oil is 500-1000: 1, the reaction temperature is 375-390 ℃.
9. The method of as claimed in any one of claims 1-8, wherein the low-grade heavy oil is heavy oil containing asphaltene and is derived from petroleum hydrocarbon and/or other mineral oil, wherein the petroleum hydrocarbon is derived from residual oil and/or crude oil, wherein the residual oil is selected from or more of vacuum residual oil and atmospheric residual oil, and the crude oil is selected from viscous crude oil, and the other mineral oil is selected from or more of coal liquefaction oil, oil sand oil and shale oil, preferably, the low-grade heavy oil has a content of metallic impurities V and Ni of 150 μ g/g or more, preferably 200 μ g/g or more, a content of carbon residue of 10% or more, preferably 15% or more, and a content of sulfur of 3 wt% or more;

the hydrotreating product has sulfur content below 0.5 wt%, carbon residue below 5 wt% and metal impurity content below 50 microgram/g in Ni and V content.
10. A method according to claim 1 or 2, characterized in that: when a plurality of membrane core reactors are connected in series, each membrane core reactor is monitored, when the catalytic performance of a certain membrane core reactor is monitored to be reduced, the membrane core reactor is cut out to regenerate the hollow catalyst membrane core therein, the membrane core reactor is cut in to continue the reaction after the regeneration, preferably, the residual carbon content in the product obtained by each membrane core reactor is monitored, the membrane core reactor with the residual carbon removal rate reduced by 5 percent is cut out on the basis of the initial residual carbon removal rate of the reaction, the hollow catalyst membrane core therein is regenerated, and the membrane core reactor is cut in to continue the reaction after the regeneration.