CN112063415B

CN112063415B - Up-flow residual oil hydrotreating method

Info

Publication number: CN112063415B
Application number: CN201910498779.7A
Authority: CN
Inventors: 刘铁斌; 韩坤鹏; 袁胜华; 金建辉
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2019-06-10
Filing date: 2019-06-10
Publication date: 2022-01-04
Anticipated expiration: 2039-06-10
Also published as: CN112063415A

Abstract

The invention discloses an upflow residual oil hydrotreating method. The method comprises the following steps: the method comprises the following steps that residual oil feeding and hydrogen enter a hydrogenation reactor from the lower part, contact with a hydrotreating catalyst to carry out hydrotreating reaction, and a product is discharged from the upper part of the hydrogenation reactor. The method not only has good hydrogenation performance and metal removing capacity, but also has certain desulfurization and carbon residue and asphaltene conversion capacity, high hydrogenation activity and long service cycle, and also solves the problems that the prior upflow reactor has various catalysts, is cumbersome to load and unload, and the catalyst bed is unstable due to different active catalysts, thereby influencing the performance of the catalyst and the stable operation of the device.

Description

Up-flow residual oil hydrotreating method

Technical Field

The invention relates to a hydrocarbon feed hydrotreating technology, in particular to an up-flow residual oil hydrotreating method.

Background

As crude oil gets heavier and worse, more and more heavy oil and residual oil need to be processed. The processing treatment of heavy oil and residual oil not only needs to crack the heavy oil and residual oil into low boiling point products, such as naphtha, middle distillate oil, vacuum gas oil and the like, but also needs to improve the hydrogen-carbon ratio of the heavy oil and residual oil, and the processing treatment needs to be realized by a decarburization or hydrogenation method. Wherein the decarbonization process comprises coking, solvent deasphalting, heavy oil catalytic cracking and the like; the hydrogenation process comprises hydrocracking, hydrofining, hydrotreating and the like. The hydrogenation process can not only hydrogenate and convert residual oil and improve the yield of liquid products, but also remove heteroatoms in the residual oil, has good product quality and has obvious advantages. However, the hydrogenation process is a catalytic processing process, and the problem of deactivation of the hydrogenation catalyst exists, and particularly, the problem of deactivation of the catalyst is more serious when inferior and heavy hydrocarbon raw materials are processed. In order to reduce the cost of processing heavy and poor residual oil and increase the profit of oil refineries, the process for processing heavy and poor residual oil still mainly uses a decarburization process, but the product quality is poor and can be utilized only by post-treatment, wherein particularly, deasphalted oil and coker gas oil fractions need to be subjected to hydrotreating so as to be processed by using lightening devices such as catalytic cracking or hydrocracking, and therefore, each oil refinery is additionally provided with a hydrotreating device for deasphalted oil and coker gas oil.

The fixed bed hydrotreating technology for heavy oil and residual oil has relatively low residual oil cracking rate and is used mainly in providing material for downstream material lightening equipment, such as catalytic cracking, coking and other equipment. The impurity content of sulfur, nitrogen, metal and the like in the inferior residual oil and the carbon residue value are obviously reduced through hydrotreating, so that the feed which can be accepted by a downstream raw material lightening device is obtained.

In the fixed bed residue hydrotreating technology, the reactor types can be classified into general fixed bed reactors, i.e., downflow mode reactors and upflow reactors, according to the flow pattern of the reactant stream in the reactor. The upflow reactor is characterized in that the oil-gas mixture is fed from the bottom of the reactor to pass through the upflow catalyst bed layer upwards, the liquid phase is continuous in the reactor, the gas phase passes through the reactor in a bubbling mode, the whole catalyst bed layer slightly expands, the deposits of metal, coke and the like can be uniformly deposited on the whole catalyst bed layer, the deposits are prevented from being concentrated on a certain part, the performance of all catalysts is well exerted, and the rapid increase of the pressure drop of the catalyst bed layer is slowed down.

The upflow reactor is generally arranged before the fixed bed reactor (downflow mode), which can greatly reduce the metal content in the feeding material entering the downflow fixed bed reactor, protect the fixed bed reactor catalyst and prevent the premature deactivation of the fixed bed reactor catalyst. The upflow reaction has the technical characteristics that reactant flows from bottom to top, so that a catalyst bed layer is slightly expanded, and the pressure drop is small, thereby solving the problem of large pressure drop change at the initial stage and the final stage when the conventional fixed bed reactor processes inferior residual oil. The upflow reactor can better remove metal impurities so as to protect a downstream fixed bed reactor and prolong the running period of the device. The combined process can fully exert the respective advantages of the upflow reaction zone and the fixed bed reactor.

The current grading loading of residuum hydroprocessing catalysts follows the general principle: along the direction of liquid phase reactant flow, the activity of the catalyst is changed from low to high, and the particle size is changed from large to small, so that the whole catalyst bed layer maintains smooth transition of the physical property and the chemical property of the catalyst. Such as: CN1315994C discloses an upflow reactor system, which employs at least two catalyst layers of different hydrogenation activity, wherein the catalyst in the lower horizontal catalyst layer has lower hydrogenation activity than the catalyst in the upper horizontal catalyst layer. The upflow reactor adopts a conventional catalyst filling mode, the catalyst activity is gradually increased along the material flow direction, the hydrogen consumption of a high-activity catalyst bed layer is gradually increased, the heat release is increased, and the upflow reactor easily causes the local hydrogen deficiency of the catalyst bed layer and the disturbance of the bed layer due to the limitation of the hydrogen-oil ratio, thereby influencing the performance of the catalyst and the stable operation of the device.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides an upflow residual oil hydrotreating method. The method has good hydrogenation performance and metal removing capacity, simultaneously has certain desulfurization and carbon residue and asphaltene conversion capacity, has high hydrogenation activity and long service cycle, and also solves the problems that the prior upflow reactor has various catalysts, is cumbersome to load and unload, and has the defects of unstable catalyst bed layers caused by different active catalysts, thereby influencing the performance of the catalyst, the stable operation of the device and the like.

In the field, the grading mode of a catalyst in an upflow hydrogenation reactor is generally along the direction of a liquid phase reactant flow, the activity of the catalyst is from low to high, in industrial application, the time interval of monitoring the upper temperature of the upflow hydrogenation reactor is generally 1 hour, the average temperature of the upper part of the reactor per day is kept basically stable, and the inventor accidentally finds that the time interval of monitoring the upper temperature of the reactor is shortened to 10 seconds, the local temperature fluctuation of the upper part of each catalyst bed in the upflow residual oil hydrogenation reactor is severe, the local high point temperature is suddenly increased by 20-100 ℃ within the range of 1-10 minutes, and the local high point temperature is restored to the previous value within 1-30 minutes, and the fluctuation is frequent, so that the activity and the long-term stability of the catalyst are finally influenced. This phenomenon is even more pronounced when a high sulfur content feed is used. When the catalyst grading mode is adopted, the temperature fluctuation at the upper part of the upflow reactor is obviously reduced, the reaction is continuous and stable, the catalyst hydrogenation performance is good, and the device stably operates.

The invention provides an up-flow residual oil hydrotreating method, wherein residual oil feed and hydrogen enter a hydrogenation reactor from the lower part, contact with a hydrotreating catalyst to carry out hydrotreating reaction, and a product is discharged from the upper part of the hydrogenation reactor.

In the upflow residual oil hydrotreating method, the hydrotreating catalyst can be a commonly used hydrotreating catalyst in an upflow residual oil hydrotreating reactor, generally mainly a catalyst with a hydrodemetallization function, and also has certain hydrodesulfurization and hydrodecarbonization functions. The hydrotreating catalyst generally comprises a carrier component and a hydrogenation active metal component, wherein the hydrogenation active metal component comprises a VIB group metal element and/or a VIII group metal element, the VIB group metal element is preferably Mo, and the VIII group metal element is preferably Ni and/or Co. Wherein, the content of the VIB group metal calculated by oxide is 7.0-16.0 percent, preferably 8.0-15.0 percent, and the content of the VIII group metal calculated by oxide is 2.0-7.0 percent, preferably 2.0-5.0 percent. The support component is typically an alumina-based support. The hydroprocessing catalyst can also include conventional adjunct components such as at least one of phosphorus, boron, silicon and the like. For example, FZC series commercial catalysts developed by the institute for petrochemical and comforting petrochemical industries of China, such as FZC-11UA, FZC-11UB and the like, can be used.

In the upflow residuum hydrotreating process of the present invention, the hydrotreating catalyst preferably has the following properties: the specific surface area is 70m²A ratio of 80 to 150 m/g or more²The pore volume is 0.70mL/g or more, preferably 0.70 to 1.20mL/g, and the shape may be spherical. Said hydrogenationThe particle size of the treated catalyst is 2.0-5.0 mm, preferably 2.8-3.5 mm, and the loading density of the catalyst is 500-700 kg/m³。

In the upflow residual oil hydrotreating method of the present invention, one or two upflow hydrogenation reactors are generally adopted. Wherein each upflow hydrogenation reactor can be provided with 2-5 catalyst beds, preferably 2-3 catalyst beds. The catalyst bed height may be set the same or different depending on the process feed.

The upflow type residual oil hydrotreating method adopts an upflow type hydrogenation reactor, when the upflow type hydrogenation reactor is provided with two catalyst beds, the lower part is a first bed layer, and the upper part is a second bed layer, wherein the first bed layer accounts for 35-50% of the total filling volume of the catalyst in the upflow type reactor, and the second bed layer accounts for 50-65% of the total filling volume of the catalyst in the upflow type reactor.

The upflow type residual oil hydrotreating method adopts an upflow type hydrogenation reactor, when the upflow type hydrogenation reactor is provided with three catalyst beds, the lower part is a first bed layer, the middle part is a second bed layer, and the upper part is a third bed layer, the first bed layer accounts for 25% -45% of the total filling volume of the catalyst in the upflow type reactor, the second bed layer accounts for 25% -45% of the total filling volume of the catalyst in the upflow type reactor, and the third bed layer accounts for 25% -45% of the total filling volume of the catalyst in the upflow type reactor.

In the upflow residual oil hydrotreating method, further, ceramic balls with a certain proportion are respectively filled at the upper part and/or the lower part of the catalyst bed layer, the proportion of the ceramic balls filled at the upper part is 5-15%, preferably 7-10% of the volume of the catalyst filled in the adjacent catalyst bed layer, the proportion of the ceramic balls filled at the lower part is 3-15%, preferably 5-8% of the volume of the catalyst filled in the catalyst bed layer, the particle size of the ceramic balls is 3-8 mm, preferably 4-5 mm, and the ceramic ball filling density can be 800-1000 kg/m³。

In the upflow residual oil hydrotreating method, a material distributor, a cold hydrogen pipe and the like can be arranged between catalyst beds of the upflow hydrogenation reactor and are used for adjusting material distribution and controlling the temperature of the catalyst beds.

In the upflow residual oil hydrotreating method, a temperature measuring instrument, such as a thermocouple, for measuring the temperature of the upper part of each catalyst bed in the upflow hydrogenation reactor is arranged, and the time interval of temperature measurement can be 10-60 seconds.

In the upflow residual oil hydrotreating method, the upflow hydrogenation reactor adopts the following operating conditions: the reaction pressure is 5-25 MPa, the reaction temperature is 300-420 ℃, and the liquid hourly space velocity is 0.05-5.0 h^-1The volume ratio of hydrogen to oil is 150: 1-400: 1.

In the upflow residuum hydroprocessing process of this invention, the feed can be the residuum feedstock of a conventional residuum hydroprocessing process. The residual oil feedstock may include atmospheric or vacuum residue oils and the like. The residua feedstock typically contains impurities such as metals, sulfur, nitrogen, and carbon residue. Optionally, the residual oil feedstock may further include conventional auxiliary materials for improving residual oil properties, facilitating processing, etc., such as adding a low-density, low-viscosity light oil for controlling proper feedstock viscosity, etc., wherein the light oil may be one from straight run, vacuum, or secondary processing, such as at least one of wax oil, diesel oil, gas oil, etc., and wherein the secondary processing may be at least one of coking, catalytic cracking, visbreaking, etc. For example, the wax oil may be one or more of straight-run wax oil, vacuum wax oil, and coker wax oil, and the light oil obtained by catalytic cracking may be at least one of catalytic cracking diesel oil, catalytic cracking cycle oil, and catalytic cracking cycle oil. The addition amount of the conventional auxiliary raw materials can be adjusted by those skilled in the art according to the properties of the raw materials and the like.

The upflow residual oil hydrotreating method is particularly suitable for treating residual oil feed with high sulfur content, wherein the sulfur content reaches more than 3.3wt percent, and further ranges from 3.3wt percent to 5.5wt percent. In the residual oil feed, the content of metal (calculated by nickel and vanadium) is 40-150 mu g/g, the content of residual carbon is 8.0-15.0 wt%, and the density is 950-1200 kg/m³。

Compared with the prior art, the invention has the advantages that:

1. in the upflow residual oil hydrotreating method provided by the invention, the inventor discovers that at least two catalyst beds are arranged in the upflow hydrogenation reactor and the same hydrotreating catalyst is filled in each catalyst bed, so that the severe fluctuation of the upper temperature of the catalyst beds can be reduced, the upper temperature of the catalyst beds is stable, the reaction is continuously and stably carried out, the catalyst has long-term stable catalytic performance, the hydrodemetallization reaction is favorably carried out, and the desulfurization, carbon residue and asphaltene conversion capability are favorably improved.

2. Because the drastic fluctuation of temperature is more obvious when the conventional upflow residual oil hydrotreating method is adopted to treat the residual oil raw material with high sulfur content, the temperature at the upper part of a catalyst bed layer can still be stable by adopting the residual oil hydrodemetallization method provided by the invention, and the drastic temperature fluctuation caused by the increase of the sulfur content can not occur.

Drawings

FIG. 1 is a graph of the reaction temperature in the upper part of a bed of the catalyst of example 1, the average value of the reaction temperature being measured at intervals of 10 seconds;

FIG. 2 is a graph showing the reaction temperature at the upper part of the second bed of the catalyst in example 1, the average value of the reaction temperature being measured at intervals of 10 seconds;

FIG. 3 is a graph showing the reaction temperature at the upper part of the three beds of the catalyst in example 1, the average value of the reaction temperatures being measured at intervals of 10 seconds;

FIG. 4 is a graph showing the reaction temperature in the upper part of the catalyst bed of comparative example 1, the average value of the reaction temperatures being measured at intervals of 10 seconds;

FIG. 5 is a graph showing the reaction temperature in the upper part of the second bed of the catalyst in comparative example 1, the average value of the reaction temperature being measured at intervals of 10 seconds;

FIG. 6 is a graph showing the reaction temperature at the upper part of the three beds of the catalyst in comparative example 1, the average value of the reaction temperature being measured at intervals of 10 seconds;

FIG. 7 is a graph showing the reaction temperature at the upper part of each catalyst bed in example 2, the average value of the reaction temperatures being measured at intervals of 10 seconds;

FIG. 8 is a graph showing the reaction temperature at the upper part of each catalyst bed in example 3, the average value of the reaction temperatures being measured at intervals of 10 seconds;

FIG. 9 is a graph showing the reaction temperature at the upper part of each catalyst bed in example 4, and the average value of the reaction temperatures was measured at intervals of 10 seconds.

Detailed Description

The technical solution of the present invention is further described in detail with reference to the following examples, which are not intended to limit the scope of the present invention. In the present invention, wt% is a mass fraction.

In the invention, the specific surface area, the pore volume, the pore diameter and the pore distribution are measured by adopting a low-temperature liquid nitrogen adsorption method.

Example 1

In this example, an upflow hydrogenation reactor was used to perform the residue hydrofinishing reaction. The upflow reactor is provided with three catalyst bed layers with the volume ratio of 1:1:1, each catalyst bed layer is filled with 300 mL of catalyst, and the total amount of the catalyst is 900 mL. The three catalyst beds all adopt a hydrotreating catalyst FZC-11UA, and the properties of the catalyst are shown in Table 1.

The used feed is typical middle east residual oil, and is subjected to hydrofining reaction in an upflow residual oil hydrogenation reactor, and upflow hydrogenation generated oil is obtained after impurities such as metal and the like are mainly removed. The main process conditions are shown in table 2. The properties of the hydrogenated oil obtained in the upflow reactor are shown in Table 3.

And a material distributor and a cold hydrogen pipe are arranged between catalyst bed layers of the upflow hydrogenation reactor. And a thermocouple for measuring the temperature of the upper part of each catalyst bed layer in the upflow hydrogenation reactor is arranged, and the time interval for measuring the temperature is 10 seconds. The reaction temperature at the upper part of each catalyst bed is shown in FIGS. 1 to 3. When the measurement was made on the 23 rd day of continuous operation, the reaction temperature was measured at intervals of 10 seconds, and it was found that the reaction was continuously and stably carried out, the temperature in the upper part of the three beds was uniform, and sharp fluctuations in the reaction temperature were not found. The results of the long cycle operation of this example are shown in Table 5.

Comparative example 1

In this comparative example, the same upflow hydrogenation reactor as in example 1 was provided, and the catalyst volumes of the respective beds were completely the same. Wherein, the first bed layer of the upflow reactor adopts a hydrotreating catalyst FZC-10U, the bottom of the second bed layer adopts FZC-10U, the upper part adopts a hydrotreating catalyst FZC-11UA with higher activity (in the second bed layer, the volume ratio of the FZC-10U to the FZC-11UA is 2: 8), the third bed layer adopts a hydrotreating catalyst FZC-11UB with high activity, and the properties of the catalyst are shown in Table 1.

And a material distributor and a cold hydrogen pipe are arranged between catalyst bed layers of the upflow hydrogenation reactor. And a thermocouple for measuring the temperature of the upper part of each catalyst bed layer in the upflow hydrogenation reactor is arranged, and the time interval for measuring the temperature is 10 seconds. The reaction temperature at the upper part of each catalyst bed is shown in FIGS. 4 to 6. When the measurement was carried out on the 23 rd day of continuous operation, the reaction temperature was measured at intervals of 10 seconds, and it was found that significant fluctuation occurred. The results of the long-cycle operation of this comparative example are shown in Table 5.

TABLE 1 Properties of catalysts used in examples and comparative examples

Catalyst brand	FZC-10U	FZC-11UA	FZC-11UB
				Packing density, kg/m³	533	565	580
Particle shape	Spherical shape	Spherical shape	Spherical shape
				Outer diameter of the granule mm	2.9	2.9	2.9
Strength, N/mm	32	30	30
				Specific surface area, m²/g	110	142	155
Pore volume, cm³/g	0.78	0.74	0.72
				Wear rate, wt%	0.3	0.4	0.4
Metal content, wt.%
				MoO₃	5.7	10.8	12.2
NiO	1.2	2.4	2.7

TABLE 2 Main Process conditions of the examples and comparative examples

Item	Example 1	Comparative example 1	Example 2	Example 3
					Upflow catalyst numbering	FZC11UA	FZC10U/FZC11UA/FZC11UB	FZC11UA	FZC11UB
Reaction pressure, MPa	16.0	16.0	16.5	18.5
					Liquid hourly volume space velocity, h^-1	0.45	0.45	0.55	0.60
Volume ratio of hydrogen to oil	310	310	280	320
					Average reaction temperature,. degree.C	374	374	380	383

Table 3 main properties of the feeds and hydrogenated oils used in example 1 and comparative example 1

Item	Feed 1	Example 1	Comparative example 1
				S，wt%	4.25	2.13	2.38
N，μg/g	3160	2362	2453
				CCR，wt%	12.83	8.82	9.04
Density (20 ℃), kg/m³	988.2	955.2	955.8
				Viscosity (100 ℃ C.), mm²/s	157.2	70.26	76.33
Ni+V，µg/g	102	56.31	62.52

Example 2

In this example, an upflow hydrogenation reactor was used to perform the residue hydrofinishing reaction. The upflow reactor is provided with three catalyst beds, wherein the first catalyst bed is filled with 260 mL of catalyst, the second catalyst bed is filled with 300 mL of catalyst, and the third catalyst bed is filled with 340 mL of catalyst, and the total amount of the catalyst filled in the third catalyst bed is 900 mL. The three catalyst beds all adopt a hydrotreating catalyst FZC-11 UA.

The used feed is typical middle east residual oil, and is subjected to hydrofining reaction in an upflow residual oil hydrogenation reactor, and upflow hydrogenation generated oil is obtained after impurities such as metal and the like are mainly removed. The main process conditions are shown in table 2. The properties of the hydrogenated oil obtained in the upflow reactor are shown in Table 4.

And a material distributor and a cold hydrogen pipe are arranged between catalyst bed layers of the upflow hydrogenation reactor. And a thermocouple for measuring the temperature of the upper part of each catalyst bed layer in the upflow hydrogenation reactor is arranged, and the time interval for measuring the temperature is 10 seconds. The reaction temperature at the upper part of each catalyst bed is shown in FIG. 7. When the measurement was carried out on the 23 rd day of continuous operation, the reaction temperature was measured at intervals of 10 seconds, and no drastic fluctuation in the reaction temperature was observed, and the temperatures in the upper portions of the three beds were uniform. The results of the long cycle operation of this example are shown in Table 5.

Example 3

In this example, an upflow hydrogenation reactor was used to perform the residue hydrofinishing reaction. The upflow reactor is provided with three catalyst beds, the first catalyst bed is filled with 300 mL of catalyst, the second catalyst bed is filled with 300 mL of catalyst, and the third catalyst bed is filled with 300 mL of catalyst and the total amount of the catalyst filled in the third catalyst bed is 900 mL. The three catalyst beds all adopt a hydrotreating catalyst FZC-11 UB.

And a material distributor and a cold hydrogen pipe are arranged between catalyst bed layers of the upflow hydrogenation reactor. And a thermocouple for measuring the temperature of the upper part of each catalyst bed layer in the upflow hydrogenation reactor is arranged, and the time interval for measuring the temperature is 10 seconds. The reaction temperature at the upper part of each catalyst bed is shown in FIG. 8. When the measurement was carried out on the 23 rd day of continuous operation, the reaction temperature was measured at intervals of 10 seconds, and no drastic fluctuation in the reaction temperature was observed, and the temperatures in the upper portions of the three beds were uniform. And the long-period operation result shows that the temperature of each bed layer does not fluctuate to indicate that the temperature of the whole catalyst bed layer is stable, so that the performance of the catalyst is favorably exerted on one hand, and the long-period stable operation of the device is favorably realized on the other hand. The results of the long cycle operation of this example are shown in Table 5.

Example 4

In this example, an upflow hydrogenation reactor was used to perform the residue hydrofinishing reaction. The upflow reactor was set up with three catalyst beds, the first catalyst bed was loaded with 275mL of catalyst, the second catalyst bed was loaded with 275mL of catalyst, and the third catalyst bed was loaded with 275mL of catalyst and a total amount of 825mL of catalyst. The three catalyst beds all adopt a hydrotreating catalyst FZC-11 UB. The upper part of each bed layer is filled with 25mL of porcelain balls, the diameter of each porcelain ball is 4mm, and the filling density of each porcelain ball is 860kg/m³The used feed is typical middle east residual oil, and is subjected to hydrofining reaction in an upflow residual oil hydrogenation reactor, and upflow hydrogenation generated oil is obtained after impurities such as metal and the like are mainly removed. The main process conditions are shown in table 3. The properties of the hydrogenated oil obtained in the upflow reactor are shown in Table 4.

And a material distributor and a cold hydrogen pipe are arranged between catalyst bed layers of the upflow hydrogenation reactor. And a thermocouple for measuring the temperature of the upper part of each catalyst bed layer in the upflow hydrogenation reactor is arranged, and the time interval for measuring the temperature is 10 seconds. The reaction temperature at the upper part of each catalyst bed is shown in FIG. 9. When the measurement was carried out on the 23 rd day of continuous operation, the reaction temperature was measured at intervals of 10 seconds, and no drastic fluctuation in the reaction temperature was observed, and the temperatures in the upper portions of the three beds were uniform. And the long-period operation result shows that the temperature of each bed layer does not fluctuate to indicate that the temperature of the whole catalyst bed layer is stable, so that the performance of the catalyst is favorably exerted on one hand, and the long-period stable operation of the device is favorably realized on the other hand. The results of the long cycle operation of this example are shown in Table 5.

Table 4 main properties of the feeds used in examples 2 to 4 and of the hydrorefined oils

Item	Feed 2	Example 2	Feed 3	Example 3	Feed 4	Example 4
							S，wt%	3.61	1.88	3.86	2.47	3.36	2.17
N，μg/g	3560	2457	3250	2287	3330	2217
							CCR，wt%	13.43	9.95	14.32	10.31	12.12	9.31
Density (20 ℃), kg/m³	982.2	953.2	1002.3	954.2	996.3	955.2
							Viscosity (100 ℃ C.), mm²/s	93.9	57.3	219.3	90.26	192.0	93.26
Ni+V，µg/g	84	47.2	122.4	68.5	92.2	60.5

TABLE 5 residual oil hydrogenation stability test

Item/run time	Catalyst and process for preparing same	500h	1000h	2000h	3000h	4000h	5000h
								Product oil S, wt%	Example 1	2.13	2.20	2.22	2.25	2.37	2.42
Product oil S, wt%	Comparative example 1	2.38	2.59	2.65	2.69	2.83	2.93
								Product oil S, wt%	Example 2	1.88	1.92	1.94	1.95	1.98	1.99
Product oil S, wt%	Example 3	2.47	2.49	2.53	2.58	2.60	2.64
								Product oil S, wt%	Example 4	2.17	2.18	2.20	2.30	2.33	2.38
Resulting oil CCR, wt%	Example 1	8.82	8.90	8.93	8.98	9.03	9.15
								Resulting oil CCR, wt%	Comparative example 1	9.04	9.33	9.43	9.58	9.79	10.22
Resulting oil CCR, wt%	Example 2	9.95	9.98	10.12	10.15	10.18	10.25
								Resulting oil CCR, wt%	Example 3	10.31	10.38	10.43	10.45	10.48	10.52
Resulting oil CCR, wt%	Example 4	9.31	9.43	9.45	9.48	9.55	9.58
								Oil (Ni + V) formation, mug/g	Example 1	56.3	56.8	57.0	58.4	58.9	59.5
Oil (Ni + V) formation, mug/g	Comparative example 1	62.5	64.5	65.8	68.8	69.2	72.3
								Oil (Ni + V) formation, mug/g	Example 2	47.2	47.5	47.8	48.2	48.7	48.8
Oil (Ni + V) formation, mug/g	Example 3	68.5	68.8	69.2	69.3	69.6	70.2
								Oil (Ni + V) formation, mug/g	Example 4	60.5	62.2	63.1	63.4	63.5	64.0

As can be seen from Table 5, the up-flow residual oil treatment method of example 1 can maintain good demetallization capability, and remove the generated oil metal (Ni + V) by up-flow hydrogenation to less than 60 mug/g. By adopting the upflow residual oil treatment method in the comparative example 1, when 5000 hours, the upflow generated oil metal (Ni + V) is increased to over 72 mug/g. Therefore, the method has outstanding demetallization performance and still shows good stability even after 5000 hours. Comparing the removal conditions of sulfur and carbon residue, at 5000 hours, the sulfur content of the upflow type formed oil in the example 1 is less than 2.50wt%, and the sulfur content of the upflow type formed oil in the comparative example 1 reaches 2.90 wt%; at 5000 hours, the carbon residue content of the upflow type produced oil of example 1 is less than 9.20wt%, and the carbon residue content of the upflow type produced oil of comparative example 1 exceeds 10.00wt%, so that the method of the invention has stable integral performance of the catalyst and is obviously superior to that of the comparative example. Also, the upflow residuum hydrotreating processes of example 2, example 3 and example 4 also exhibited excellent hydrogenation activity and stability.

Claims

1. An up-flow residual oil hydrotreating method, residual oil feed and hydrogen enter a hydrogenation reactor from the lower part, contact with a hydrotreating catalyst to carry out hydrotreating reaction, and discharge a product from the upper part of the hydrogenation reactor, wherein the hydrogenation reactor is an up-flow hydrogenation reactor and at least adopts one up-flow hydrogenation reactor, each up-flow hydrogenation reactor is provided with at least two catalyst beds, and each catalyst bed is filled with the same hydrotreating catalyst; in the residual oil feed, the sulfur content reaches more than 3.3 wt%; in the residual oil feeding material, the metal content is 40-150 mu g/g calculated by nickel and vanadium, the content of residual carbon is 8.0-15.0 wt%, and the density is 950-1200 kg/m³(ii) a The particle size of the hydrotreating catalyst is 2.0-5.0 mm, and hydrogenation is performedThe loading density of the treatment catalyst is 500-700 kg/m³。

2. The process of claim 1 wherein the hydrotreating catalyst comprises a support component and a hydrogenation-active metal component, wherein the hydrogenation-active metal component comprises a group vib metal element and/or a group viii metal element.

3. The method of claim 1, wherein the hydrotreating catalyst comprises a support component and a hydrogenation-active metal component, wherein the hydrogenation-active metal component comprises a group vib metal element and/or a group viii metal element, wherein the group vib metal element is Mo and the group viii metal element is Ni and/or Co.

4. The process of claim 2 wherein the group VIB metal is present in an amount of from 7.0% to 16.0% by weight on an oxide basis and the group VIII metal is present in an amount of from 2.0% to 7.0% by weight on an oxide basis, based on the weight of the catalyst.

5. The process of claim 2 wherein the group VIB metal is present in an amount of from 8.0% to 15.0% by weight and the group VIII metal is present in an amount of from 2.0% to 5.0% by weight, based on the weight of the catalyst; the support component is an alumina-based support.

6. The process of claim 1, wherein the hydrotreating catalyst has a specific surface area of 70m²A pore volume of 0.70mL/g or more.

7. The method of claim 1, wherein the specific surface area of the hydrotreating catalyst is 80 to 150m²The pore volume is 0.70-1.20 mL/g; the hydrotreating catalyst is spherical in shape.

8. The method of claim 1, wherein the hydrotreating catalyst has a particle size of 2.8 to 3.5 mm.

9. The process of claim 1, wherein one or two upflow hydrogenation reactors are employed; wherein each upflow hydrogenation reactor is provided with 2-5 catalyst beds.

10. The process of claim 9, wherein one or two upflow hydrogenation reactors are employed; wherein each upflow hydrogenation reactor is provided with 2-3 catalyst beds.

11. The method according to claim 1, wherein an upflow hydrogenation reactor is used, and when two catalyst beds are arranged in the upflow hydrogenation reactor, the lower part is a first bed, and the upper part is a second bed, wherein the first bed accounts for 35-50% of the total loading volume of the catalyst in the upflow reactor, and the second bed accounts for 50-65% of the total loading volume of the catalyst in the upflow reactor.

12. The method according to claim 1, wherein an upflow hydrogenation reactor is used, and when three catalyst beds are provided in the upflow hydrogenation reactor, the lower part is a first bed, the middle part is a second bed, and the upper part is a third bed, the first bed accounts for 25% -45% of the total loading volume of the catalyst in the upflow reactor, the second bed accounts for 25% -45% of the total loading volume of the catalyst in the upflow reactor, and the third bed accounts for 25% -45% of the total loading volume of the catalyst in the upflow reactor.

13. The method according to claim 1, wherein ceramic balls are respectively filled at the upper part and/or the lower part of the catalyst bed layers, the proportion of the ceramic balls filled at the upper part is 5-15% of the volume of the catalyst filled in the adjacent catalyst bed layers, the proportion of the ceramic balls filled at the lower part is 3-15% of the volume of the catalyst filled in the adjacent catalyst bed layers, and the particle size of the ceramic balls is 3-8 mm.

14. The method according to claim 1, wherein the upper part and/or the lower part of the catalyst bed layer are/is respectively filled with ceramic balls, the upper part is filled with the ceramic balls according to the proportion of 7-10% of the volume of the catalyst filled in the adjacent catalyst bed layer, the lower part is filled with the ceramic balls according to the proportion of 5-8% of the volume of the catalyst filled in the adjacent catalyst bed layer, the particle size of the ceramic balls is 4-5 mm, and the filling density of the ceramic balls is 800-1000 kg/m³。

15. The method according to claim 1, characterized in that a material distributor and a cold hydrogen pipe are arranged between each catalyst bed layer of the upflow hydrogenation reactor; and arranging a temperature measuring instrument for measuring the temperature of the upper part of each catalyst bed in the up-flow hydrogenation reactor, wherein the time interval of temperature measurement is 10-60 seconds.

16. The process of claim 15 wherein the temperature measuring device for measuring the temperature of the upper portion of each catalyst bed in the upflow hydrogenation reactor is a thermocouple.

17. The process of claim 1 wherein the upflow hydrogenation reactor is operated under the following conditions: the reaction pressure is 5-25 MPa, the reaction temperature is 300-420 ℃, and the liquid hourly space velocity is 0.05-5.0 h^-1The volume ratio of hydrogen to oil is 150: 1-400: 1.

18. The process of claim 1 wherein the sulfur content of the residua feedstock is from 3.3 wt.% to 5.5 wt.%.