CN112300834B

CN112300834B - Heavy oil hydrotreating method

Info

Publication number: CN112300834B
Application number: CN201910696530.7A
Authority: CN
Inventors: 邓中活; 胡大为; 戴立顺; 刘涛; 邵志才; 牛传峰; 施瑢; 聂鑫鹏; 任亮; 杨清河; 孙淑玲; 贾燕子
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-07-30
Filing date: 2019-07-30
Publication date: 2022-03-11
Anticipated expiration: 2039-07-30
Also published as: CN112300834A

Abstract

A heavy oil hydrotreating method in heavy oil hydrotreating unit along material flow directionAt least one catalyst is sequentially filled with a hydrogenation protection catalyst, a hydrogenation demetallization catalyst, a hydrogenation desulfurization catalyst and a hydrogenation carbon residue removal catalyst, and has the following characteristics: the catalyst contains a carrier and metal components loaded on the carrier, wherein the metal components comprise at least one VIB group metal and at least one VIII group metal, the content of the VIB group metal is 8-30 wt% and the content of the VIII group metal is 2-8 wt% based on the total weight of the catalyst, and when the catalyst is measured by diffuse reflection ultraviolet visible spectrum DRUVS, the absorbances at 630nm and 500nm are respectively F₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3-3.0. The method provided by the invention has good hydrogenation activity and better reaction stability, and can effectively prolong the running period of a heavy oil hydrogenation unit.

Description

Heavy oil hydrotreating method

Technical Field

The invention relates to a treatment method for removing impurities from heavy oil in the presence of hydrogen.

Background

The fixed bed heavy oil hydrogenation treatment technology has the advantages of mature process, simple operation, good product quality and the like, and is the most common heavy oil hydrogenation technology in the industry at present. However, the fixed bed heavy oil hydrogenation device has the disadvantage of short operation period, generally about 12-18 months, and the rapid deactivation of the catalyst is one of the main factors. Therefore, the service life of the heavy oil hydrogenation catalyst is prolonged, which is beneficial to prolonging the operation period of the fixed bed heavy oil hydrogenation device.

The main purpose of the fixed bed heavy oil hydrotreating process is to remove a large amount of impurities contained in the residual oil feedstock, such as sulfur, nitrogen, metals, and asphaltenes, and to provide a feedstock for the catalytic cracking unit. The main reactions of the process include hydrodemetallization, hydrodesulfurization, hydrodenitrogenation, aromatic saturation, hydrocarbon hydrocracking and the like. The inactivation of the fixed bed heavy oil hydrogenation catalyst is caused by two factors, namely, the deposition of metal to destroy the original active phase structure of the catalyst, and carbon deposit on the surface of the active phase to cover the active center, so that the reaction performance of the catalyst is reduced. Therefore, how to improve the stability of the active phase structure of the catalyst and reduce the damage, aggregation and poisoning of the active phase structure of the catalyst in the reaction process is a key technology for improving the activity stability of the catalyst.

CN107583659A discloses a gasoline selective hydrodesulfurization catalyst, wherein a composite alumina carrier containing zinc aluminate spinel is prepared by a non-constant pH alternative titration method, and the catalyst prepared by loading cobalt and molybdenum has good selectivity and reaction stability in the gasoline hydrodesulfurization process.

CN1252220C provides a heavy oil and residual oil fixed bed hydrotreatment method, which is characterized in that a hydrodecarbonization catalyst is arranged between a hydrodesulfurization catalyst and a hydrodenitrogenation catalyst, and the pore diameter of the hydrodecarbonization catalyst is larger than that of the hydrodesulfurization catalyst and the hydrodenitrogenation catalyst, so that a two-pass grading scheme is formed, but the reaction activity of the method is not obviously improved.

Heavy oil hydrogenation catalysts require higher reactivity than distillate oils and also have higher requirements for activity stability. An industrial fixed bed heavy oil hydrogenation device generally adopts a complex multi-catalyst system, and the prior art has no technology which can well meet the requirements of both the activity and the stability of the catalyst, so that the actual industrial application effect of the catalyst is seriously influenced.

Disclosure of Invention

The invention aims to solve the technical problem that the activity and stability of a catalyst cannot be considered in the heavy oil hydrotreating process provided by the prior art, and provides a heavy oil hydrotreating method which is remarkably improved in catalyst activity stability and has better desulfurization, denitrification and carbon residue removal activities.

The heavy oil hydrotreating method provided by the invention comprises the following steps that a heavy oil raw material enters a heavy oil hydrotreating unit, and reacts under the heavy oil hydrotreating reaction condition, and a hydrogenation protection catalyst, a hydrodemetallization catalyst, a hydrodesulfurization catalyst and a hydrodecarbonization catalyst are sequentially filled in the heavy oil hydrotreating unit along the material flow direction, wherein at least one of the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydrodecarbonization catalyst has the following characteristics: the catalyst contains a carrier and metal components loaded on the carrier, wherein the metal components comprise at least one VIB group metal and at least one VIII group metal, the content of the VIB group metal is 8-30 wt% and the content of the VIII group metal is 2-8 wt% based on the total weight of the catalyst, and when the catalyst is measured by diffuse reflection ultraviolet visible spectrum DRUVS, the absorbances at 630nm and 500nm are respectively F₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3-3.0.

Preferably, the ratio Q ═ F₆₃₀/F₅₀₀Is 1.4-2.8.

In a preferred aspect, the support in the catalyst is an alumina-containing support. The VIB group metal in the catalyst is molybdenum and/or tungsten; the group VIII metal is cobalt and/or nickel.

Further preferably, the group VIB metal is molybdenum and the group VIII metal is cobalt or nickel.

In order to obtain better hydrogenation activity and stability of heavy oil, the carrier of the catalyst also contains sulfur, and the content of the sulfur in the carrier is 0.7-3.0 wt% calculated by element and based on the total weight of the carrier.

In one preferred embodiment of the present invention, the loading amount of the hydrogenation protection catalyst is 1-20 vol%, the loading amount of the hydrodemetallization catalyst is 5-55 vol%, the loading amount of the hydrodesulfurization catalyst is 5-55 vol%, and the loading amount of the hydrodecarbonization catalyst is 5-55 vol%, based on the total volume of the catalyst loaded in the heavy oil hydrotreating unit.

In one preferred embodiment of the present invention, the loading amount of the hydrogenation protection catalyst is 2-15 vol%, the loading amount of the hydrodemetallization catalyst is 20-50 vol%, the loading amount of the hydrodesulfurization catalyst is 10-50 vol%, and the loading amount of the hydrodecarbonization catalyst is 10-50 vol%, based on the total volume of the catalyst loaded in the heavy oil hydrotreating unit.

In one preferred embodiment of the present invention, the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydrodecarbon residue removal catalyst are each loaded with one or more species.

In a further preferred embodiment, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydrodecarbonization catalyst are each loaded with one or more catalysts having the following characteristics: the catalyst contains a carrier and metal components loaded on the carrier, wherein the metal components comprise at least one VIB group metal and at least one VIII group metal, the content of the VIB group metal is 8-30 wt% and the content of the VIII group metal is 2-8 wt% based on the total weight of the catalyst, and when the catalyst is measured by diffuse reflection ultraviolet visible spectrum DRUVS, the absorbances at 630nm and 500nm are respectively F₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3-3.0. Preferably, the ratio Q ═ F₆₃₀/F₅₀₀Is 1.4-2.8.

Preferably, the carrier in the above catalyst is a carrier containing alumina. In the catalyst, the VIB group metal is molybdenum and/or tungsten; the group-VIII metal is cobalt and/or nickel. Further preferably, the group VIB metal is molybdenum and the group-VIII metal is cobalt or nickel.

Preferably, the carrier of the above catalyst further contains sulfur, and the content of sulfur in the carrier is 0.7 to 3.0% by weight in terms of element and based on the total weight of the carrier.

The inventor of the invention intensively studies and discovers that although the initial activity of the catalyst is influenced by the formation of the spinel structure, the formation of a proper amount of the spinel structure does not bring too much influence on the total activity of the catalyst, and the formed spinel structure gradually releases the reaction activity along with the extension of the catalyst participating in the reaction process, so that the activity stability of the catalyst is better, the service life of the catalyst is greatly prolonged on the premise of meeting the basic activity requirement, and the production efficiency is improved.

Tests have shown that a catalyst with a ratio Q of 1.3 to 3.0, representing the content of spinel structure in the catalyst, gives a better initial activity and better stability of the activity, preferably a ratio Q of 1.4 to 2.8. When the Q value is less than 1.3, the improvement of the activity stability is not obvious; when the Q value is more than 3.0, the initial activity is too low, which affects the normal use of the catalyst.

In a preferred case, the aforementioned catalyst having a certain spinel structure can be prepared by a method comprising the steps of:

s1: treating the support, wherein the support is an alumina-containing support, more preferably an alumina support;

s2: impregnating the support with a solution containing the metal component for a certain period of time, and then filtering off and drying the support; and

s3: the product from step S2 was activated at a temperature of 600-800 ℃ for 1-10 hours.

In the preparation process, the catalyst with the spinel structure can be formed by activating at the temperature of 600-800 ℃ for 1-10 hours through the S3 step. The activation temperature is too low or the activation time is too short, the content of spinel in the obtained catalyst is too low, and the activity stability improvement effect is not obvious; if the activation temperature is too high or the activation time is too long, the spinel content in the obtained catalyst is too high, and the initial activity of the catalyst is influenced.

In a further preferred case, the activation temperature is 780 ℃, more preferably 630-750 ℃, and most preferably 650-730 ℃. One skilled in the art should be able to select the appropriate activation time based on the different activation temperatures.

In the present invention, the above activation refers to activation that is conventional in the art, and the activation may be raised from an ambient temperature to an activation temperature, or may be raised from a drying temperature directly after the impregnation of the metal component to the activation temperature, and is not particularly limited. The temperature rise rate at the activation may be 50 to 600 deg.C/hr, preferably 100-.

In a preferred case, the step S1 of treating the support includes introducing a sulfur source into the support, followed by drying and calcining. Incorporation as referred to herein means impregnation of the support with an aqueous solution containing a sulfur source.

In one embodiment, the pseudoboehmite is mixed with a sulfur source and water prior to support shaping. The sulfur source is used in such an amount that the sulfur content in the final carrier is 0.7 to 3.0% by weight, respectively, in terms of elements. The amount of water is such that the solution containing the sulfur source is mixed with the pseudoboehmite to form a material sufficient to meet the requirements of subsequent molding. Sufficient for subsequent forming is to mean that the water/powder ratio in the mixed material is suitable, as is well known to those skilled in the art.

Alternatively, the introduction of the sulfur source may be synchronized with the introduction of the metal component.

Alternatively, if the support itself is selected to contain sulfur in the above-described amounts, the support need only be calcined at elevated temperatures for a period of time.

As the sulfur source, one or more of sulfuric acid and metal sulfate can be used. The sulfur source is used in an amount such that the resulting support contains 0.7 to 3.0% by weight of sulfur, calculated as the element and based on the total weight of the support.

In one embodiment, the support after introduction of the sulfur source is dried at 100-150 deg.C, preferably at 110-120 deg.C for 1-6 hours, preferably 2-3 hours, and then calcined at 600-1000 deg.C, preferably 700-900 deg.C, more preferably 800-850 deg.C for 1-10 hours, preferably 2-8 hours, more preferably 2.5-5 hours.

In the present invention, the carrier of the catalyst can be made into various easy-to-handle shapes, such as spheres, honeycombs, bird nests, tablets or strips (such as clover, butterfly, cylinder, etc.), according to different requirements.

In the present invention, the impregnation of the support with the solution containing the metal component for a certain period of time means that the support is impregnated with the aqueous solution containing the oxide or salt of the metal component for a certain period of time so as to ensure that the finally obtained catalyst contains the oxide of each metal component in the above-mentioned content.

Alternatively, the aqueous solution of the oxide or salt of the metal component may further contain ammonia, phosphoric acid, citric acid, or the like to facilitate the introduction of the metal component.

In the present invention, when the catalyst of the present invention contains an auxiliary, the method for introducing the auxiliary may be any conventional method, for example, a method of impregnating the carrier after separately preparing a solution containing the auxiliary, or a method of impregnating the carrier with a mixed solution containing the metal component and the auxiliary; can be introduced for a single time or can be introduced for multiple times; each introduction may be followed by a drying, firing or unfired step.

In a preferred case, when the metal component is molybdenum, the oxide or salt thereof is one or more selected from molybdenum oxide, ammonium molybdate, ammonium paramolybdate; when the metal component is tungsten, the oxide or salt thereof is one or more selected from tungsten oxide, ammonium tungstate and ammonium paratungstate; when the metal component is cobalt, the oxide or salt thereof is one or more selected from cobalt nitrate, cobalt sulfate and basic cobalt carbonate; when the metal component is nickel, the oxide or salt thereof is one or more selected from nickel nitrate, nickel sulfate and basic nickel carbonate. Of course, the person skilled in the art can select other water-soluble salts or complex salts of these metals in combination with the specific circumstances, and there is no particular limitation thereto.

Preferably, in the step of S2, the drying temperature is 60 to 150 ℃ and the drying time is 1 to 5 hours.

In the invention, in addition to the catalyst containing a carrier and metal components loaded on the carrier, the metal components comprise at least one VIB group metal and at least one VIII group metal, the content of the VIB group metal is 8-30 wt% and the content of the VIII group metal is 2-8 wt% based on the total weight of the catalyst, and the absorbance at 630nm and 500nm is respectively F when the catalyst is measured by diffuse reflection ultraviolet visible spectrum DRUVS₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀The remaining of the hydrogenation protecting catalyst, hydrodemetallization catalyst, hydrodesulfurization catalyst and hydrodecarbonization catalyst, in addition to the catalyst having the characteristics of 1.3-3.0 ", may be selected from commercial catalysts conventional in the art or catalysts prepared by other conventional methods, such as RG-series, RDM-series, RMS-series, RCS-series and RSN-series commercial catalysts developed by the institute of petrochemical science, petrochemical engineering, china. The active metal component of the hydrogenation protection catalyst, the hydrogenation demetallization catalyst, the hydrogenation desulfurization catalyst and the hydrogenation carbon residue removal catalyst can be selected from non-noble metals in group VIB and/or group VIII, preferably the combination of nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum, and the content of the active metal component is 0-30 wt%, preferably 0-25 wt%, calculated by the oxide of the active metal component. The carrier may be at least one selected from alumina, silica and titania. At least one element of boron, germanium, zirconium, phosphorus, chlorine, fluorine and the like can be added into the carrier for modification. The catalyst may be in the form of extrudates or spheres and may have a particle size of 0.5 to 50 mm.

In the present invention, the particle diameter refers to the maximum straight-line distance between two different points on the cross section of the particle, and when the catalyst particle is spherical, the particle diameter refers to the diameter of the particle.

According to a preferred embodiment of the invention, the active metal component content of each catalyst is gradually increased, the pore size is gradually decreased and the particle size is gradually decreased along the direction of flow.

Further preferably, the hydrogenation protection catalyst has a metal component content (calculated as metal oxide) of 0 to 15 wt%, an average pore diameter of 18 to 30nm, and a particle diameter of 1.3 to 50 mm.

Further preferably, the hydrodemetallization catalyst has a metal component content (calculated as metal oxide) of 10 to 25 wt.%, an average pore diameter of 10 to 20nm, and a particle diameter of 0.8 to 5 mm.

Further preferably, the hydrodesulfurization catalyst has a metal component content (calculated as metal oxide) of 13 to 30 wt%, an average pore diameter of 8 to 15nm, and a particle diameter of 0.6 to 2 mm.

Further preferably, the content of the metal component (calculated by metal oxide) of the hydrogenation carbon residue removal catalyst is 16-38 wt%, the average pore diameter is 0.5-15nm, and the particle size is 0.5-2 mm.

In the heavy oil hydrotreating method according to the present invention, preferably, the heavy oil hydrotreating unit is a fixed bed heavy oil hydrotreater conventional in the art.

In the heavy oil hydrotreating unit, a heavy oil raw material and hydrogen are mixed and then enter a fixed bed heavy oil hydrogenation device to be sequentially contacted with a hydrogenation protection catalyst, a hydrogenation demetalization catalyst, a hydrodesulfurization catalyst and a hydrogenation carbon residue removal catalyst for reaction, and oil gas after the reaction enters a subsequent separation device for separation.

In the present invention, the heavy oil hydrotreating process may be operated using heavy oil hydrotreating conditions that are conventional in the art. Preferably, the heavy oil hydrotreating conditions include: the reaction temperature is 300-460 ℃, and more preferably 350-440 ℃; the reaction pressure is 6-25MPa, and more preferably 12-20 MPa; the liquid hourly space velocity is 0.1-1-h^-1More preferably 0.2-0.4-h^-1(ii) a The hydrogen-oil volume ratio is 250-1500, and more preferably 300-1000. In the present invention, the pressure means an absolute pressure.

In the invention, the heavy oil raw material is selected from one or more of inferior raw materials such as atmospheric residue, vacuum residue, deasphalted oil, coal tar, coal liquefied heavy oil and the like.

The heavy oil hydrotreating method provided by the invention adopts an optimal catalyst grading mode, so that the catalyst has better activity stability, and can greatly prolong the service life of the catalyst on the premise of meeting the basic activity requirement, namely, the heavy oil hydrotreating method has good hydrogenation activity and better reaction stability, thereby effectively prolonging the operation period of a heavy oil hydrogenation device.

Detailed Description

The following examples further illustrate the invention but are not intended to limit the invention thereto.

The present invention is further illustrated by the following examples and comparative examples, which should not be construed as limiting the invention thereto.

In the following examples and comparative examples, the composition of the catalyst was determined by X-ray fluorescence spectroscopy (XRF), as specified in petrochemical analysis method RIPP 133-90.

In the following examples and comparative examples, the specific surface, pore volume and pore size distribution of the carrier were measured by low-temperature nitrogen adsorption, and the specific methods are shown in petrochemical analysis method RIPP 151-90.

In the following examples and comparative examples, the formation of nickel or cobalt aluminate spinel structures in the catalyst was determined by ultraviolet visible light spectroscopy (DRUVS). The instrument adopts a Cary300 ultraviolet visible light analyzer of Agilent company, and the wavelength ranges are as follows: 190nm-1100nm, wavelength precision: ± 0.1nm, wavelength reproducibility: ± 0.1nm, baseline stability: 0.0003/h, stray light: 0.02% or less, photometric accuracy: + -0.003.

In the following examples and comparative examples, G denotes a hydrogenation-protecting catalyst, M denotes a hydrodemetallization catalyst, S denotes a hydrodesulfurization catalyst, CCR denotes a hydrodemetallization catalyst, the numbers 1 and 2 following the letters denote different catalysts, for example M1 and M2 denote two hydrodemetallization catalysts, respectively, and the hydrodesulfurization catalyst and the hydrodemetallization catalyst are distinguished in the same manner.

The hydrogenation protection catalyst was prepared in a conventional manner, and the specific composition and properties are shown in table 1.

The hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydrodecarbonization catalyst are obtained by the following preparation processes, and the specific compositions and properties are shown in table 1.

M1 and M2 preparation processes:

the preparation method comprises the steps of uniformly mixing 1 kg of pseudoboehmite dry glue powder RPB90 produced by a Changling catalyst factory with 30 g of sesbania powder, uniformly mixing the mixture with 1.1 l of sulfuric acid aqueous solution with the weight percentage concentration of 2.7% at room temperature, finishing and forming, drying at 120 ℃ for 3 hours, and roasting at 850 ℃ for 3 hours to obtain a carrier Z1. Weighing 1100 g of carrier Z, soaking for 1 hour by using 220 ml of ammonia water mixed solution containing ammonium molybdate and nickel nitrate, filtering, and drying for 2 hours at 120 ℃. And (3) activating the dried catalyst, heating to 650 ℃ at 300 ℃/h, and keeping the temperature at 650 ℃ for 3 hours to obtain the catalyst M1.

The preparation of M2 was essentially the same as that of M1 except that no aqueous sulfuric acid solution was added during the preparation of the support. And after drying the impregnated catalyst, heating the dried catalyst to 400 ℃ at the speed of 300 ℃/h by adopting a conventional method, and keeping the temperature of 400 ℃ for 3 h to obtain the catalyst M2.

S1, S2 and S3 preparation processes:

the preparation method comprises the steps of uniformly mixing 1 kg of pseudoboehmite dry rubber powder RPB100 produced by a Changling catalyst factory and 30 g of sesbania powder, adding 1.2 l of sulfuric acid aqueous solution with the weight percentage concentration of 3.3%, uniformly mixing, finishing, forming, drying at 110 ℃ for 2 hours, and roasting at 800 ℃ for 3 hours to obtain the carrier Z2. 2100 g of carrier Z was weighed, impregnated with 110 ml of a mixed solution containing molybdenum oxide, basic cobalt carbonate and phosphoric acid for 0.5 hour, and dried at 120 ℃ for 2 hours. And (3) activating the dried catalyst, heating to 700 ℃ at 350 ℃/h, and keeping the temperature of 700 ℃ for 3 hours to obtain the catalyst S1.

The preparation process of S2 was substantially the same as that of S1 except that no aqueous sulfuric acid solution was added during the preparation of the support. And the dried catalyst is activated in the same way, the temperature is raised to 700 ℃ at 350 ℃/h, and the temperature is kept constant at 700 ℃ for 3 h to obtain the catalyst S2.

The preparation process of S3 was substantially the same as that of S1 except that no aqueous sulfuric acid solution was added during the preparation of the support, and 1.2 liters of an aqueous nitric acid solution having a concentration of 1% by weight was added. And after drying the impregnated catalyst, heating the dried catalyst to 450 ℃ at the speed of 300 ℃/h by adopting a conventional method, and keeping the temperature of 450 ℃ for 3 hours to obtain the catalyst S3.

CCR1, CCR2 and CCR3 preparation processes:

the preparation method comprises the steps of uniformly mixing 1 kg of pseudoboehmite dry rubber powder RPB100 produced by a Changling catalyst factory and 30 g of sesbania powder, adding 1.2 l of sulfuric acid aqueous solution with the weight percentage concentration of 4.2%, uniformly mixing, finishing, forming, drying at 120 ℃ for 3 hours, and roasting at 750 ℃ for 3 hours to obtain a carrier Z3. 3100 g of the carrier Z was weighed, immersed in 120 ml of a mixed solution containing molybdenum oxide and nickel nitrate for 1 hour, and dried at 120 ℃ for 2 hours. And (3) activating the dried catalyst, heating to 750 ℃ at the speed of 400 ℃/h, and keeping the temperature of 750 ℃ for 3 h to obtain the catalyst CCR 1.

CCR2 was prepared in essentially the same manner as CCR1 except that no aqueous sulfuric acid solution was added during the preparation of the support. And the dried catalyst is activated, the temperature is raised to 750 ℃ at 400 ℃/h, and the temperature is kept at 750 ℃ for 3 h to obtain the catalyst CCR 2.

CCR3 was prepared in essentially the same manner as CCR1 except that no aqueous sulfuric acid solution was added during the preparation of the support. And after drying the impregnated catalyst, heating the dried catalyst to 450 ℃ at the speed of 300 ℃/h by adopting a conventional method, and keeping the temperature of 450 ℃ for 3 hours to obtain the catalyst CCR 3.

TABLE 1

The properties of the residual oil feedstock used in the following examples and comparative examples are shown in table 2.

TABLE 2

Properties of	Residual oil feedstock
		Density (20 ℃ C.)/(g/cm)³)	0.9687
Viscosity (100 ℃ C.)/(mm)²/s)	62.37
		MCR/(wt%)	12.40
Sulfur content/(wt%)	3.18
		Nitrogen content/(wt%)	0.34
(Ni + V) content/(μ g/g)	87.9
		Four components/(wt%)
Saturated hydrocarbons	32.2
		Aromatic hydrocarbons	41.5
Glue	22.3
		Asphaltenes (C)₇Insoluble matter)	4.0

Example 1

The residual oil raw material enters a heavy oil hydrotreating unit, and reacts under the heavy oil hydrotreating reaction condition, and a hydrogenation protection catalyst G1, a hydrodemetallization catalyst M1, a hydrodesulfurization catalyst S2 and a hydrodecarbonization catalyst CCR3 are sequentially filled in the heavy oil hydrotreating unit along the material flow direction, wherein the filling volume ratio is 5: 40: 25: 30. the conditions of the heavy oil hydrotreatment are shown in table 3, the impurity removal rate at 200 hours of operation is shown in table 4, the reaction temperature is adjusted to 70% of the carbon removal rate, the operation is stopped when the set value of 405 ℃ is reached, and the operation time is recorded as shown in table 4.

Example 2

The residual oil raw material enters a heavy oil hydrotreating unit, and reacts under the heavy oil hydrotreating reaction condition, and a hydrogenation protection catalyst G1, a hydrodemetallization catalyst M1, a hydrodesulfurization catalyst S1 and a hydrodecarbonization catalyst CCR2 are sequentially filled in the heavy oil hydrotreating unit along the material flow direction, wherein the filling volume ratio is 5: 40: 25: 30. the conditions of the heavy oil hydrotreatment are shown in table 3, the impurity removal rate at 200 hours of operation is shown in table 4, the reaction temperature is adjusted to 70% of the carbon removal rate, the operation is stopped when the set value of 405 ℃ is reached, and the operation time is recorded as shown in table 4.

Example 3

The residual oil raw material enters a heavy oil hydrotreating unit, and reacts under the heavy oil hydrotreating reaction condition, and a hydrogenation protection catalyst G1, a hydrodemetallization catalyst M2, a hydrodesulfurization catalyst S3 and a hydrodecarbonization catalyst CCR1 are sequentially filled in the heavy oil hydrotreating unit along the material flow direction, wherein the filling volume ratio is 5: 40: 25: 30. the conditions of the heavy oil hydrotreatment are shown in table 3, the impurity removal rate at 200 hours of operation is shown in table 4, the reaction temperature is adjusted to 70% of the carbon removal rate, the operation is stopped when the set value of 405 ℃ is reached, and the operation time is recorded as shown in table 4.

Example 4

The residual oil raw material enters a heavy oil hydrotreating unit, and reacts under the heavy oil hydrotreating reaction condition, and a hydrogenation protection catalyst G1, a hydrodemetallization catalyst M1, a hydrodesulfurization catalyst S2 and a hydrodecarbonization catalyst CCR1 are sequentially filled in the heavy oil hydrotreating unit along the material flow direction, wherein the filling volume ratio is 5: 40: 25: 30. the conditions of the heavy oil hydrotreatment are shown in table 3, the impurity removal rate at 200 hours of operation is shown in table 4, the reaction temperature is adjusted to 70% of the carbon removal rate, the operation is stopped when the set value of 405 ℃ is reached, and the operation time is recorded as shown in table 4.

Example 5

The residual oil raw material enters a heavy oil hydrotreating unit, and reacts under the heavy oil hydrotreating reaction condition, and a hydrogenation protection catalyst G1, a hydrodemetallization catalyst M1, a hydrodesulfurization catalyst S1 and a hydrodecarbonization catalyst CCR1 are sequentially filled in the heavy oil hydrotreating unit along the material flow direction, wherein the filling volume ratio is 5: 40: 25: 30. the conditions of the heavy oil hydrotreatment are shown in table 3, the impurity removal rate at 200 hours of operation is shown in table 4, the reaction temperature is adjusted to 70% of the carbon removal rate, the operation is stopped when the set value of 405 ℃ is reached, and the operation time is recorded as shown in table 4.

Comparative example 1

The residual oil raw material enters a heavy oil hydrotreating unit, and reacts under the heavy oil hydrotreating reaction condition, and a hydrogenation protection catalyst G1, a hydrodemetallization catalyst M2, a hydrodesulfurization catalyst S3 and a hydrodecarbonization catalyst CCR3 are sequentially filled in the heavy oil hydrotreating unit along the material flow direction, wherein the filling volume ratio is 5: 40: 25: 30. the conditions of the heavy oil hydrotreatment are shown in table 3, the impurity removal rate at 200 hours of operation is shown in table 4, the reaction temperature is adjusted to 70% of the carbon removal rate, the operation is stopped when the set value of 405 ℃ is reached, and the operation time is recorded as shown in table 4.

TABLE 3

Reaction temperature of	380
		Partial pressure of hydrogen, MPa	15.0
Hydrogen to oil ratio (volume)	600
		Liquid hourly space velocity, hr^-1	0.20

TABLE 4

It can be seen from the above examples and comparative examples that, in the heavy oil hydrotreating process, the heavy oil hydrotreating method provided by the present invention can significantly improve the impurity removal rate and has better activity stability.

Claims

1. A heavy oil hydrotreating method, the heavy oil raw material enters the heavy oil hydrotreating unit, reacts under the heavy oil hydrotreating reaction condition, the heavy oil hydrotreating unit is sequentially filled with hydrogenation protection catalyst, hydrodemetallization catalyst, hydrodesulfurization catalyst and hydrogenation carbon residue removal catalyst along the material flow direction, wherein at least one of the hydrogenation demetallization catalyst, the hydrodesulfurization catalyst and the hydrogenation carbon residue removal catalyst has the following characteristics: the catalyst contains a carrier and metal components loaded on the carrier, wherein the metal components comprise at least one VIB group metal and at least one VIII group metal, the content of the VIB group metal is 8-30 wt% and the content of the VIII group metal is 2-8 wt% based on the total weight of the catalyst, and when the catalyst is measured by diffuse reflection ultraviolet visible spectrum DRUVS, the absorbances at 630nm and 500nm are respectively F₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3-3.0.

2. The method of claim 1, wherein the ratio Q ═ F₆₃₀/F₅₀₀Is 1.4-2.8.

3. The method of claim 1, wherein the support is an alumina-containing support; the VIB group metal is molybdenum and/or tungsten; the group VIII metal is cobalt and/or nickel.

4. The process according to claim 3, characterized in that the group VIB metal is molybdenum and the group VIII metal is cobalt or nickel.

5. The process of claim 1 wherein the support further comprises sulfur, and the amount of sulfur in the support is from 0.7 to 3.0 wt.% on an elemental basis and based on the total weight of the support.

6. The method of any one of claims 1 to 5, wherein the loading of the hydrogenation protection catalyst is from 1 to 20 vol%, the loading of the hydrodemetallization catalyst is from 5 to 55 vol%, the loading of the hydrodesulfurization catalyst is from 5 to 55 vol%, and the loading of the hydrodecarbonization catalyst is from 5 to 55 vol%, based on the total volume of the catalyst loaded in the heavy oil hydroprocessing unit.

7. The method of claim 6, wherein the loading of the hydrogenation protection catalyst is 2-15 vol%, the loading of the hydrodemetallization catalyst is 20-50 vol%, the loading of the hydrodesulfurization catalyst is 10-50 vol%, and the loading of the hydrodecarbonization catalyst is 10-50 vol%, based on the total volume of the catalyst loaded in the heavy oil hydroprocessing unit.

8. The process of any one of claims 1-5, wherein the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst, and the hydrodecarbonization catalyst are each loaded with one or more.

9. The process of claim 8, wherein the hydrodemetallization catalyst, the hydrodesulfurization catalyst, and the hydrodecarbonization catalyst are each loaded with one or more catalysts having the following characteristics: the catalyst contains a carrier and metal components loaded on the carrier, wherein the metal components comprise at least one VIB group metal and at least one VIII group metal, the content of the VIB group metal is 8-30 wt% and the content of the VIII group metal is 2-8 wt% based on the total weight of the catalyst, and when the catalyst is measured by diffuse reflection ultraviolet visible spectrum DRUVS, the absorbances at 630nm and 500nm are respectively F₆₃₀And F₅₀₀And the ratio Q ═ F of the two₆₃₀/F₅₀₀Is 1.3-3.0.

10. The method of claim 1, wherein the active metal component content of each catalyst is gradually increased, the pore size is gradually decreased, and the particle size is gradually decreased along the flow direction.

11. The process of claim 10, wherein the hydrogenation catalyst has a metal component content of 0 to 15 wt.% in terms of metal oxide, an average pore diameter of 18 to 30nm, and a particle diameter of 1.3 to 50 mm; the metal component of the hydrodemetallization catalyst accounts for 10-25 wt% of metal oxide, the average pore diameter is 10-20nm, and the particle size is 0.8-5 mm; the metal component of the hydrodesulfurization catalyst accounts for 13-30 wt% of metal oxide, the average pore diameter is 8-15nm, and the particle size is 0.6-2 mm; the content of metal components of the hydrogenation carbon residue removal catalyst calculated by metal oxides is 16-38 wt%, the average pore diameter is 0.5-15nm, and the particle size is 0.5-2 mm.

12. The method of claim 1, wherein the heavy oil hydroprocessing reaction conditions comprise: the reaction temperature is 300-The reaction pressure is 6-25MPa, and the liquid hourly space velocity is 0.1-1-h^-1The volume ratio of hydrogen to oil is 250-1500.

13. The method of claim 12, wherein the heavy oil hydroprocessing reaction conditions comprise: the reaction temperature is 350-440 ℃, the reaction pressure is 12-20MPa, and the liquid hourly space velocity is 0.2-0.4-h^-1The volume ratio of hydrogen to oil is 300-1000.