CN113908888B

CN113908888B - Pre-vulcanization method of heavy oil hydrogenation catalyst and heavy oil hydrogenation pre-vulcanization catalyst

Info

Publication number: CN113908888B
Application number: CN202010656980.6A
Authority: CN
Inventors: 刘凯; 赵元生; 赵愉生; 李阳; 任静
Original assignee: Petrochina Co Ltd
Current assignee: Petrochina Co Ltd
Priority date: 2020-07-09
Filing date: 2020-07-09
Publication date: 2024-10-01
Anticipated expiration: 2040-07-09
Also published as: CN113908888A

Abstract

The invention relates to a presulfiding method of a heavy oil hydrogenation catalyst, which comprises the following steps: (1) Adding an oxidation state catalyst or a baking-free catalyst into a vulcanization reactor, and increasing the pressure to 0.5-20 MPa in an inert atmosphere; (2) Introducing a vulcanization raw material into the vulcanization reactor for vulcanization; and (3) after the vulcanization is finished, introducing passivation gas to carry out passivation. The invention also relates to a heavy oil hydrogenation presulfiding catalyst. The heavy oil hydrogenation presulfiding catalyst provided by the invention has excellent performance, uniform passivation, safe storage, transportation and filling, and shortened start-up time.

Description

Pre-vulcanization method of heavy oil hydrogenation catalyst and heavy oil hydrogenation pre-vulcanization catalyst

Technical Field

The invention relates to a presulfiding method of a heavy oil hydrogenation catalyst, in particular to a presulfiding method of a heavy oil hydrogenation catalyst used for conversion and modification of heavy oil products such as wax oil, deasphalted oil, residual oil and the like, and a heavy oil hydrogenation presulfiding catalyst prepared by the presulfiding method.

Background

The main index of heavy oil hydrotreating is to carry out hydrodemetallization, hydrodesulphurization, hydrodenitrogenation, aromatic saturation, olefin saturation and hydrocracking reactions on fractions such as oil residues. Most of the metals in crude oil exist in residuum, and the content of metals (mainly Ni, V, fe, etc.) in residuum is only in the order of parts per million, but it is easy to permanently poison and deactivate residuum hydrodesulfurization catalysts, hydrodenitrogenation catalysts, and catalytic cracking catalysts. Therefore, trace metals in the residuum feedstock must be removed. The residual oil hydrodemetallization reaction is an important chemical reaction occurring in the residual oil hydrotreatment process, and under the action of a catalyst, a metal compound reacts with hydrogen sulfide to generate a metal sulfide, and then the generated metal sulfide is deposited on the catalyst, so that the removal is achieved. In order to ensure the performance of the catalyst packed in the subsequent reactor, the best approach is to force the metal to deposit on the hydrodemetallization catalyst of the guard reactor to prevent premature deactivation of the catalyst in the subsequent reactor, since the catalyst pores in the subsequent reactor are small and the hydrotreating and conversion reactions are mostly carried out in the subsequent reactor; the hydrodesulfurization reaction of residuum is the most predominant chemical reaction occurring during the hydrotreating of residuum, by which various sulfur-containing compounds are converted into sulfur-free hydrocarbons and hydrogen sulfide in the presence of a catalyst and hydrogen. Hydrocarbons remain in the product, while hydrogen sulfide is removed from the reactants; nitrogen in crude oil is also mostly present in residuum, and nitrides in residuum can be classified into basic and non-basic. In the residual oil hydrogenation process, various nitrogen compounds generate ammonia and hydrocarbons under the action of a catalyst, the ammonia is removed from reactants, and the hydrocarbons are left in products; the aromatic hydrocarbon hydrogenation saturation reaction of the residual oil is mainly the hydrogenation of the polycyclic aromatic hydrocarbon, the reaction is the reaction which is most difficult to carry out in all hydrogenation reactions in the residual oil hydrotreating process, the monocyclic aromatic hydrocarbon is difficult to be hydrogenated and saturated, the polycyclic aromatic hydrocarbon is hydrogenated and saturated sequentially ring by ring, and the hydrogenation difficulty is increased ring by ring. The hydrogenation reaction of each ring of the polycyclic aromatic hydrocarbon is reversible and in an equilibrium state, and the hydrogenation depth is often limited by chemical equilibrium. If substituents are attached to the benzene ring, the hydrogenation saturation of aromatic hydrocarbons is more difficult. The temperature of the residual oil hydrodenitrogenation catalyst is not too high, and the higher hydrogen partial pressure is kept as much as possible, so that the occurrence of aromatic hydrocarbon hydrogenation saturation reaction is facilitated; the olefin saturation reaction is faster in the hydrotreating reaction process of all residual oil, is only next to hydrodemetallization reaction, and basically reaches full saturation at the hydrodesulphurization reaction temperature; hydrocracking reactions are reactions that change larger hydrocarbon molecules in a feed into smaller molecules in the presence of hydrogen and a catalyst, which occur almost throughout the reaction.

The aim of the residuum hydrotreater is to provide a good quality feedstock to its downstream heavy oil catalytic cracker. For reactions such as hydrodemetallization, hydrodesulphurisation, hydrodenitrogenation, aromatic saturation, olefin saturation and hydrocracking of residuum, fixed bed residuum hydrogenation processes generally comprise a plurality of reactors (mostly four or five reactors in series), and catalysts with different functions need to be loaded in the reactors. During the start-up of the plant, the catalyst needs to be presulfided in order to react the supported oxidized metal with the sulfur-containing compound to convert it to sulfided metal to activate the catalyst activity.

The vulcanizing process mainly comprises two vulcanizing processes, namely in-device vulcanizing and out-device vulcanizing. In-situ sulfiding refers to in-situ sulfiding performed after loading the catalyst into the reactor. The in-reactor vulcanization can adopt two modes of dry vulcanization and wet vulcanization. Dry sulfiding refers to mixing sulfiding agent with hydrogen in a certain proportion and directly introducing into catalyst bed, while wet sulfiding refers to sulfiding catalyst with oil carried sulfiding agent. The purpose of converting the oxidized metal into the vulcanized metal is achieved by controlling the flow rate of the sulfide and adjusting the temperature and the pressure of the bed. For the residuum hydrogenation process, dimethyl disulfide is generally adopted as a vulcanizing agent, and diesel oil and wax oil are adopted as solvents to carry out vulcanization operation on the catalyst. In the process of startup vulcanization of a residual oil device, the control over the temperature is extremely strict. Because in the oxidized state, the residuum hydrogenation catalyst is contacted with pure hot H ₂ (free of hydrogen sulfide) which causes reduction of the catalyst's active metals, resulting in permanent deactivation of the catalyst. Generally, if the hydrogen temperature exceeds 260 ℃, deactivation of the catalyst will occur within hours, so the hot H ₂ temperature is controlled. And the maximum temperature of the catalyst bed during sulfiding also needs to be controlled to prevent the reduction reaction from occurring before hydrogen sulfide is not detected in the recycle hydrogen. At present, typical in-reactor presulfiding processes are: heating the reactor to about 180 ℃ under the hydrogen atmosphere, introducing vulcanized oil containing a vulcanizing agent, continuously heating to about 230 ℃ and keeping the constant temperature for a period of time, heating to 360-380 ℃ and keeping the constant temperature, and then adjusting to the required reaction temperature and then switching the raw oil to perform normal reaction. In-reactor vulcanization has certain disadvantages, firstly, in order to ensure the vulcanization degree, several reactors are required to reach the optimal vulcanization temperature, and the vulcanization time is long, so that the operation time of an industrial device is long, and the production progress of a refinery is influenced. Secondly, the catalyst bed temperature is easy to generate, the activity of the catalyst is temporarily or permanently lost, and the catalyst is easy to be vulcanized incompletely due to in-situ vulcanization, so that the activity of the catalyst is influenced. In addition, the in-device vulcanizing method is adopted, special equipment is required to be provided, the vulcanizing agent is generally toxic, and particularly under the high-temperature condition, the vulcanizing agent can react with hydrogen to generate hydrogen sulfide and methane, and once the vulcanizing agent leaks, the environment is polluted, so that the vulcanizing agent is harmful to operators.

The external vulcanization is generally divided into a sulfur-carrying type and a vulcanization type, the former adopts elemental sulfur or organic sulfides with different decomposition temperatures to be carried on the catalyst by impregnation technology, and active metals on the catalyst are changed from an oxidation state to an oxygen vulcanization state. The prepared pre-vulcanized catalyst is stable in air, and hydrogen is introduced to complete the whole process of pre-vulcanization of the catalyst during start-up vulcanization, and the activation time and the activation temperature of the catalyst are basically equal to or slightly shorter than the online in-situ vulcanization time. For the activation of sulfur-supported catalysts, there are two general possible reaction pathways: the catalyst is contacted with hydrogen at a certain temperature, and the active components are directly converted into a vulcanized state from an oxidized state or an oxygen vulcanized state; or the catalyst generates hydrogen sulfide under the condition of hydrogen, and the hydrogen sulfide converts the oxidation state or oxygen sulfide state catalyst into a sulfide state catalyst. The metal component adopted by the vulcanized catalyst exists in a vulcanized state completely, oil is directly heated and fed during startup, vulcanization or activation is not needed, the startup time is very short, and no pollution is caused. The hydrogenation catalyst free of on-site startup activation is used by oil refiners at will, but the catalyst also has the problems that the sulfidic catalyst is easy to spontaneously ignite when being contacted with air, and can not be stored and transported for a long time, and the application of the technology is affected. It is therefore often necessary to deactivate the catalyst.

The passivation techniques presently disclosed are broadly divided into two types, gas phase passivation and liquid phase passivation. The gas phase passivation mainly uses a gas having oxidizing property to form an oxide film on the surface of the sulfided catalyst at a proper temperature, thereby protecting the sulfided catalyst. For gas phase passivation, the sulfidic catalyst formed after complete sulfidation of the oxidation state catalyst is subjected to trace oxygen passivation, and part of sulfur in the crystallites of the active metal sulfide is replaced by oxygen to form metal oxysulfide. This compound is easily activated under hydrogen conditions and provides acidic active sites other than metal sites, so that oxygen-passivated catalysts have more acidic active sites than sulfided catalysts, which also accounts for the increased activity after reactivation of gas phase passivated catalysts. The liquid phase passivation mainly adopts methods of spraying, dipping and the like, and organic oxygen-containing hydrocarbon is loaded on the surface of the sulfidic catalyst to form a protective film. The liquefied protective liquid can be uniformly sprayed on the surface of the solid catalyst with the temperature lower than the condensation point of the protective liquid by liquid phase passivation, so that the protective liquid can be crystallized to form a solid protective film; the hot hydrocarbon can be sprayed on the surface of the low-temperature catalyst by adopting heavy hydrocarbon substances (such as vacuum distillate oil), so that the viscosity of the hydrocarbon is increased, and the diffusion speed to the center of the particles is slowed down so as to achieve the effect of wrapping the surface of the catalyst and isolating air; the passivation substances can be diluted or emulsified in a solvent to form a mixed solution, and the mixed solution is sprayed on the surface of the catalyst under the condition that the temperature is higher than the boiling point of the solvent. The solvent evaporates rapidly, and the passivation substance forms a protective film on the surface of the catalyst. By adopting liquid passivation, the spraying amount of the protective liquid needs to be strictly controlled, if the protective substances are too much, the protective substances are not easy to remove at the beginning of the reaction, so that the activity of the catalyst is affected, otherwise, too little protective substances cannot play a role in isolating oxygen from invading the surface and pore channels of the catalyst. There are currently two main explanations for the mechanism of liquid phase passivation: firstly, it is considered that the passivation (such as organic hydrocarbon) does not change the physicochemical properties of the catalyst, but is a simple physical protection process, and the protective film is removed by heating or solvent dissolution and carrying. One is to consider that certain hydrocarbons contained in the passivation react with sulfides of the catalyst, and the generated new substances can prevent oxygen from entering and play a role in protecting the catalyst.

After the pre-vulcanized catalyst is subjected to passivation treatment, the stability of the catalyst can be improved, the storage and transportation are facilitated, and the equipment investment and the starting cost are reduced in the starting period of a refinery. Based on the requirements of refineries on quick start-up of devices, the preparation technology and means of the device are rapidly developed.

CN102041045B, CN1129609a and US2002000394A1 belong to the sulfur-loaded ex-situ presulfiding process. The selected vulcanizing agent is elemental sulfur or a sulfur-containing compound, and the organic solvent loaded on the catalyst together with the vulcanizing agent is an organic solvent containing unsaturated bonds. The method has simple process and cost saving, but the method uses a large amount of organic solvents in the production process, is not easy to obtain in refineries, and is unfavorable for safety and environmental protection.

CN102284299a discloses a process for presulfiding an oxidation state hydrogenation catalyst outside a hydrogenation reactor, which process differs from presulfiding and passivation in that a reactivation step, i.e. a process in which a passivated catalyst that has been loaded in the hydrogenation reactor is reactivated in an atmosphere containing a sulfiding agent, is added. The presulfiding process only involves the use of sulfur gas (sulfur content 0.5-3%), no requirement is made on the sulfiding pressure, and the catalyst active metal is Mo and/or Ni.

US6294498B1 discloses a method of protecting an active catalyst using external surface spraying. The method prepares a protective film by spraying an inert material on the outer surface of the catalyst to protect the core and the internal pore channels of the catalyst particles. The concentration of the protective substance gradually decreases from the outer surface to the core, and the protective film automatically disappears under the reaction condition. After passivation, the mechanical property and the abrasion of the catalyst are effectively improved, but the operation method for spraying the inert protective film disclosed by the method is slightly complicated.

CN105233867B discloses a pre-sulfided sulfur-tolerant shift catalyst and a preparation method. The surface of the vulcanized catalyst is coated by a surface layer formed by a high molecular compound so as to avoid the contact of active components with oxygen. The external wrapping compound is two or more of polyacrylamide, polystyrene acrylonitrile, polyamide, melamine or naphthalene, the mixing ratio is 1:1, and the compound can be gasified at 250-350 ℃. The preparation method of the pre-sulfurized sulfur-tolerant shift catalyst comprises the steps of enabling the gasified wrapping compound to pass through a sulfurized catalyst bed layer under the vacuum condition (0.2-1 psi), and cooling to obtain the stable catalyst. The polymer compound film can not react with the active center of the catalyst and can not influence the activity of the catalyst. Meanwhile, in the initial stage of activation in the catalyst, the polymer compound film is gasified at a certain temperature, discharged from the catalyst pore canal in a gaseous form, and has the effect of secondarily adjusting the catalyst pore structure. The catalyst prepared by the method has high activity and good stability, but has larger vacuumizing difficulty in industrial application.

In summary, the problems with the presently disclosed ex-situ presulfiding technique are: the sulfuration time is longer, the sulfur rate on the catalyst is low, the sulfuration is uneven, the catalyst passivation operation is complex, and the catalyst transportation is safe. And the heavy oil raw material has high content of sulfur, nitrogen and heavy metal impurities, is rich in polycyclic aromatic hydrocarbon, and has higher requirements on the hydrogenation performance of the catalyst. Heavy oil hydrogenation catalysts tend to have high metal content and some difficulties exist in passivation by the prior art.

Disclosure of Invention

In view of the foregoing problems of the prior art, an object of the present invention is to provide a method for presulfiding a heavy oil hydrogenation catalyst and a catalyst produced by the presulfiding method. The catalyst treated by the presulfiding method has high activity, is safe and reliable to store and transport, and can meet the safe and rapid start-up requirements of refineries.

To this end, the present invention provides a method for presulfiding a heavy oil hydrogenation catalyst comprising the steps of:

(1) Adding an oxidation state catalyst or a baking-free catalyst into a vulcanization reactor, and increasing the pressure to 0.5-20 MPa in an inert atmosphere;

(2) Introducing a vulcanization raw material into the vulcanization reactor for vulcanization;

(3) And after the vulcanization is finished, introducing passivation gas to carry out passivation.

The pre-sulfiding method of heavy oil hydrogenation catalyst of the present invention, wherein preferably, the sulfiding conditions are: and vulcanizing at a constant temperature of 170-400 ℃ for 2-30 hours.

The presulfiding method of the heavy oil hydrogenation catalyst of the present invention, wherein preferably the passivation gas consists of 2 to 15wt% of gaseous olefin and the balance of CO.

The presulfiding method of the heavy oil hydrogenation catalyst of the present invention, wherein the time for the deactivation is preferably 0.5 to 5 hours.

The presulfiding method of the heavy oil hydrogenation catalyst of the invention, wherein the oxidation state catalyst or the baking-free catalyst supported active metal is preferably selected from at least one of a group VIB metal and a group VIII metal.

The presulfiding method of the heavy oil hydrogenation catalyst of the invention is characterized in that preferably, the VIB group metal is molybdenum and/or tungsten, and the VIII group metal is cobalt and/or nickel.

The presulfiding method of the heavy oil hydrogenation catalyst of the invention is characterized in that the carrier of the oxidation state catalyst or the baking-free catalyst is preferably a hydrogenation catalyst carrier. The hydrogenation catalyst support may be a conventional hydrogenation catalyst support including, but not limited to, alumina, silica alumina, molecular sieves, or combinations thereof.

The method for presulfiding the heavy oil hydrogenation catalyst according to the present invention is characterized in that the hydrogenation catalyst carrier preferably comprises at least one of alumina, silica alumina, molecular sieve, and magnesia.

The presulfiding method of the heavy oil hydrogenation catalyst of the invention is characterized in that the sulfidation raw material is mixed gas composed of hydrogen sulfide, hydrogen and inert gas, wherein the content of the hydrogen sulfide is 3-25%, the content of the hydrogen is 15-77% and the content of the inert gas is 20-60% by volume.

The presulfiding method of the heavy oil hydrogenation catalyst of the present invention, wherein preferably the inert gas comprises at least one of nitrogen, argon, xenon, helium, neon, krypton and carbon dioxide.

The presulfiding method of the heavy oil hydrogenation catalyst according to the present invention is preferred, wherein the gaseous olefin is at least one selected from mono-olefins and di-olefins.

The invention also provides a heavy oil hydrogenation presulfiding catalyst which is prepared by the presulfiding method, wherein the specific surface area of the catalyst is more than 10m ².g^-1, and the pore volume is more than 0.1cm ³.g^-1.

The heavy oil hydrogenation presulfiding catalyst is preferable to have a specific surface area of 11-500m ².g^-1 and a pore volume of 0.2-3cm ³.g^-1.

The heavy oil hydrogenation presulfiding catalyst is preferably prepared from Ni ₃S₂ serving as a VIII family metal sulfide, wherein the content of the Ni ₃S₂ is 1.0-10.0 wt%; the group VIB metal sulfide is MoS ₂, and the content of the group VIB metal sulfide is 3.0-35.0 wt%.

The presulfiding method of the heavy oil hydrogenation catalyst provided by the invention is suitable for heavy oil hydrogenation series catalysts, including hydrodemetallization agents, hydrodesulphurisation agents and hydrodenitrogenation agents. The presulfiding method comprises three steps of drying, vulcanizing and passivating. The specific process is as follows:

(1) And (3) drying a catalyst: the oxidation state catalyst or the catalyst which is immersed and dried but not baked is put into a vulcanization reactor, purged by inert gas and dried for 2 to 6 hours at the temperature of 100 to 150 ℃.

(2) And (3) vulcanizing a catalyst: boosting to 0.5-20MPa, introducing a vulcanizing raw material for vulcanization, wherein the vulcanization temperature is 170-400 ℃, and the constant temperature is 2-10 hours.

(3) And (3) passivating the catalyst: introducing mixed gas consisting of 2-30wt% of gaseous olefin and the balance of CO for passivation for 0.5-5 hours.

The passivation gas adopted by the invention is composed of gaseous olefin and CO, so that uniform passivation can be ensured, spontaneous combustion of the catalyst is effectively avoided, and the device start-up step is simplified. Wherein the gaseous olefin can be one or a mixture of a plurality of mono-olefin and diolefin.

The presulfiding method provided by the invention can shorten the start-up time of a refinery, has the advantages of simple and uniform catalyst passivation process, good catalyst activity, stable existence in air and convenience in storage and transportation. The catalyst prepared by the invention has good economic benefit and wide application prospect.

Drawings

FIG. 1 is a process flow diagram of an evaluation apparatus for a heavy oil hydrogenation presulfiding catalyst obtained by the presulfiding method of the present invention.

Wherein,

A 1-buffer tank, wherein the buffer tank is provided with a plurality of buffer chambers,

2-A first hydrogenation reactor, wherein the first hydrogenation reactor comprises a first hydrogenation catalyst,

A 3-second hydrogenation reactor, wherein the second hydrogenation reactor is provided with a third hydrogenation catalyst,

A 4-third hydrogenation reactor, wherein the hydrogenation catalyst comprises a catalyst,

5-Gas-liquid separator combination (including high pressure separator and low pressure separator).

Detailed Description

The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.

Example 1

Pre-sulfiding of residuum hydrodemetallization catalysts

The residuum hydrodemetallization catalyst was prepared as described in example 1 of CN101928593a, with oxidation state catalyst properties as shown in table 1.

The oxidation state catalyst is added into a vulcanization reactor to be sealed, nitrogen is adopted to purge, the catalyst is dried for 4 hours at the temperature of 130 ℃ of the catalyst bed, mixed gas consisting of 6v percent hydrogen sulfide, 30v percent argon and 64v percent hydrogen is started to be introduced into the catalyst bed as vulcanized gas after the temperature of the catalyst bed is raised to 180 ℃ at 10 ℃/h, and the vulcanized gas pressure in the whole vulcanization process is ensured to be 1MPa. Heating the bed to 280 ℃, and keeping the temperature for 5 hours; a mixed gas consisting of 5% by volume of olefins (C3 and C4 mixed olefins, in a ratio of 50/50) and the balance CO was introduced as passivation gas and kept at a constant temperature for 1.5 hours. The device is cooled down, depressurized, and the catalyst is barreled and sealed.

Example 2

Pre-sulfiding of residuum hydrodesulfurization catalysts

The residuum hydrodesulfurization catalyst was prepared as described in example 1 of CN101928593a with the oxidation state catalyst properties shown in table 1.

The oxidation state catalyst is added into a vulcanization reactor to be sealed, nitrogen is adopted to purge, the catalyst is dried for 4 hours at the temperature of 130 ℃ of the catalyst bed, and mixed gas consisting of 10v percent of hydrogen sulfide, 40v percent of argon and 50v percent of hydrogen is started to be introduced into the catalyst bed as vulcanized gas after the temperature of the catalyst bed is raised to 170 ℃ at 10 ℃/h, and the vulcanized gas pressure in the whole vulcanization process is ensured to be 8MPa. Heating the bed to 290 ℃ and then keeping the temperature for 4 hours; introducing mixed gas consisting of 5v% of olefin (C2 and C3 mixed olefin, the ratio of which is 30/70 and the balance of CO as passivation gas, and keeping the temperature for 2 hours.

Example 3

(1) Preparation of residual oil hydrodenitrogenation catalyst

Taking 500g (dry basis) of silicon-containing pseudo-boehmite dry powder (SiO ₂ content is 39%), adding 15g of sesbania powder, and uniformly mixing. 395g of acetic acid solution having a concentration of 3.5% by weight was added to the above-mentioned materials, kneaded for 40 minutes, and then extruded into a cylindrical shape having a diameter of 2.0mm on a single screw extruder. Drying in a baking oven at 120 ℃ for 3 hours, then placing the baking oven, heating to 780 ℃ at a heating rate of 100-150 ℃/h, and baking for 3 hours.

150G of the above carrier having a water absorption of 1.10ml/g was weighed, and an aqueous ammonia solution of ammonium molybdate (MoO ₃ 82.0.0 wt%) and nickel nitrate (NiO 25.2 wt%) was sprayed and immersed in the saturated absorption solution. Homogenizing in spray leaching equipment for 5min, drying at 60deg.C for 2 hr, heating to 120deg.C, and drying for 3 hr to obtain roasting-free hydrodenitrogenation catalyst containing nickel and molybdenum.

To facilitate the characterization of the catalyst, the prepared calcination-free hydrodenitrogenation catalyst containing nickel and molybdenum was placed in 500 ℃ air for calcination for 3 hours, and after cooling, the catalyst properties were analyzed, and the results are shown in table 1.

(2) Pre-sulfiding of residuum hydrodenitrogenation agents

Adding the calcination-free hydrodenitrogenation catalyst into a vulcanization reactor, sealing, purging with nitrogen, drying for 4 hours at the temperature of 130 ℃ of the catalyst bed, heating the catalyst bed to 200 ℃ at 10 ℃/h, starting to introduce mixed gas consisting of 3v% hydrogen sulfide, 50v% neon and 47v% hydrogen as the vulcanization gas, and ensuring the vulcanization gas pressure of 15MPa in the whole vulcanization process. Heating the bed to 320 ℃ and then keeping the temperature for 3 hours; introducing mixed gas consisting of 5% of olefin (C2, C3, C4 and C5 mixed olefin, the proportion of the four is 15/40/10/35) and the balance of CO as passivation gas, continuously heating to 360 ℃ and keeping the temperature for 3 hours, and ending vulcanization. And after the device is cooled and depressurized, the catalyst is barreled and sealed.

Example 4

This example uses the pre-sulfided catalyst prepared according to the invention to test its performance. The hydrodemetallization presulfiding catalyst, the hydrodesulphurisation presulfiding catalyst and the hydrodenitrogenation presulfiding catalyst prepared in examples 1-3 were sequentially fed into a reaction apparatus (3X 300ml pilot scale evaluation apparatus) shown in FIG. 1, and were directly subjected to evaluation by feeding hydrogen gas and an evaluation oil in amounts of 40wt%, 40wt% and 20wt%, respectively. The properties of the raw oil are shown in Table 2. The process conditions and 2000 hours reaction results are shown in Table 3.

Referring to fig. 1, the evaluation process flow of the invention is as follows: raw oil and hydrogen for hydrogenation evaluation are mixed in a buffer tank 1, sequentially enter a first hydrogenation reactor 2, a second hydrogenation reactor 3 and a third hydrogenation reactor 4 for reaction, and are combined by a gas-liquid separator 5 (sequentially pass through a high-pressure separator and a low-pressure separator) to finally obtain gas and hydrogenated full distillate. The first hydrogenation reactor 2, the second hydrogenation reactor 3 and the third hydrogenation reactor 4 are arranged in series, and the reaction conditions are consistent.

Comparative example 1

The comparative example was vulcanized by a conventional in-vessel vulcanization method and performance comparative evaluation was performed. The non-presulfided oxidized hydrodemetallization catalyst, the non-presulfided oxidized hydrodesulphurization catalyst and the non-presulfided baking-free hydrodenitrogenation catalyst prepared in examples 1-3 were sequentially added to the reaction apparatus shown in FIG. 1 in the proportions of 40wt%, 40wt% and 20wt%, respectively. The in-reactor vulcanization adopts wet vulcanization, the vulcanization pressure is 10MPa, the vulcanizing agent adopts carbon disulfide, the addition amount is 2.0wt%, the vulcanized diesel oil is vulcanized for 10 hours at 240 ℃, and the vulcanized wax oil is vulcanized for 6 hours at 300 ℃. The raw oil and the process conditions were evaluated in the same manner as in example 4, and the reaction results for 2000 hours are shown in Table 3.

Table 1 catalyst properties table

Table 2 evaluation of raw oil Properties

Project	Raw oil
		Density 20 deg.c (g/cm ^-3)	0.9733
Residual carbon (w%)	9.2
		S(w％)	1.47
N(w％)	0.33
		Ni+V(wppm)	65.19

Table 3 2000 hours evaluation results

As can be seen from Table 3, the pre-sulfided catalysts of the present invention perform comparable to the conventional in-reactor sulfided catalysts used in the comparative examples. The performance of the heavy oil hydrogenation presulfiding catalyst prepared by the presulfiding method meets the use requirement, does not need to be reactivated during use, and can effectively reduce the device start-up time (2-4 days).

Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.

Claims

1. A method for presulfiding a heavy oil hydrogenation catalyst, comprising the steps of:

(1) Adding an oxidation state catalyst or a baking-free catalyst into a vulcanization reactor, and increasing the pressure to 0.5-20 MPa under inert atmosphere;

(3) After vulcanization is finished, introducing passivation gas to perform passivation;

The passivation gas consists of 2-15 wt% of gaseous olefin and the balance of CO;

The vulcanizing raw material is mixed gas composed of hydrogen sulfide, hydrogen and inert gas;

The gaseous olefin is at least one selected from mono-olefins and di-olefins.

2. The method for presulfiding a heavy oil hydrogenation catalyst according to claim 1, wherein said sulfiding conditions are: and vulcanizing at a constant temperature of 170-400 ℃ for 2-30 hours.

3. The method for presulfiding a heavy oil hydrogenation catalyst according to claim 1, wherein said time for deactivation is from 0.5 to 5 hours.

4. The method for presulfiding a heavy oil hydrogenation catalyst according to claim 1, wherein said oxidation state catalyst or baking-free catalyst-supported active metal is selected from at least one of group VIB and group VIII.

5. The method for presulfiding a heavy oil hydrogenation catalyst according to claim 1, wherein said oxidation state catalyst or calcination-free catalyst support is a hydrogenation catalyst support.

6. The method for presulfiding a heavy oil hydrogenation catalyst according to claim 5, wherein said hydrogenation catalyst support comprises at least one of alumina, silica alumina, molecular sieves, magnesia.

7. The method for presulfiding a heavy oil hydrogenation catalyst according to claim 1, wherein said sulfided raw material has a hydrogen sulfide content of 3 to 25%, a hydrogen gas content of 15 to 77% and an inert gas content of 20 to 60% by volume.

8. The method for presulfiding a heavy oil hydrogenation catalyst according to claim 1, wherein said inert gas comprises at least one of nitrogen, argon, xenon, helium, neon, krypton and carbon dioxide.

9. A heavy oil hydrogenation presulfiding catalyst prepared by the presulfiding process of any one of claims 1 to 8, characterized in that the catalyst has a specific surface area of greater than 10m ².g^-1 and a pore volume of greater than 0.1 cm ³.g^-1.

10. The heavy oil hydrosulfiding catalyst of claim 9, wherein the catalyst has a specific surface area of 11-500 m ².g^-1 and a pore volume of 0.2-3 cm ³.g^-1.

11. The heavy oil hydrogenation presulfiding catalyst according to claim 9, wherein in the catalyst, the group VIII metal sulfide is Ni ₃S₂, the content of which is 1.0 to 10.0: 10.0 wt%; the group VIB metal sulfide is MoS ₂, and the content of the group VIB metal sulfide is 3.0-35.0-wt%.