CN111729690A

CN111729690A - Method for passivating sulfuration type hydrocracking catalyst by using ammonia outside reactor and passivated catalyst

Info

Publication number: CN111729690A
Application number: CN201910228842.5A
Authority: CN
Inventors: 翟维明; 刘锋; 晋超; 杨平; 莫昌艺; 褚阳; 夏国富
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: 2019-03-25
Filing date: 2019-03-25
Publication date: 2020-10-02

Abstract

The invention relates to an off-site ammonia passivation method for a vulcanization type hydrocracking catalyst and a passivated catalyst, wherein the method comprises the following steps: loading an organic nitrogen compound on a vulcanization type hydrocracking catalyst in the presence of an organic solvent to obtain a nitrogen-loaded catalyst; wherein the content of nitrogen on the nitrogen-supported catalyst calculated by element accounts for 0.1-10 wt% of the weight of the nitrogen-supported catalyst; drying the obtained nitrogen-supported catalyst to obtain a passivated catalyst; wherein the drying treatment conditions include: the temperature is 30-200 ℃, the absolute pressure is 0.01-1MPa, and the time is 0.5-10 hours. The method has good passivation effect and shortens the start-up time of the hydrogenation device.

Description

Method for passivating sulfuration type hydrocracking catalyst by using ammonia outside reactor and passivated catalyst

Technical Field

The invention relates to an ex-situ ammonia passivation method for a vulcanization type hydrocracking catalyst and a passivation catalyst.

Background

With the stricter environmental regulations around the world, the demand for clean fuels is increasing, and hydrotreating technology is an effective means for producing clean fuels, so that the number of hydrogenation units in each large refinery is also increasing.

Hydrocracking technology is an effective means for converting heavy distillate oil into light clean products. The hydrocracking technology uses a bifunctional catalyst, which comprises a cracking function and a hydrogenation function, wherein the cracking function is usually provided by a molecular sieve with an acid site, and the bifunctional catalyst is a Y-type molecular sieve, a Beta-type molecular sieve, a ZSM series molecular sieve, an MCM series molecular sieve, a composite molecular sieve and the like which are widely used at present. The hydrogenation function is mainly from active metals, including Co and/or Ni of group VIII, Mo and/or W of group VIB. The hydrogenation catalyst has higher hydrogenation performance only by converting metal into a vulcanization state, so that the catalyst needs to be subjected to vulcanization treatment before use in order to ensure that the hydrogenation performance of the catalyst is optimal, and the vulcanization of the hydrogenation catalyst is divided into two forms of in-situ vulcanization and ex-situ vulcanization at present. The in-reactor vulcanization is carried out in a reactor, the produced waste gas and waste water can pollute the environment, the outside-reactor vulcanization is carried out by completing the vulcanization treatment of a catalyst outside the reactor to generate high-activity metal sulfides, and the high-activity metal sulfides can be directly fed into the reactor to start working, so that the method is a vulcanization mode which is advocated and popularized at present.

The hydrocracking device generally needs higher operating temperature, the temperature of the reactor needs to be raised to higher temperature in the startup process, raw oil can generate cracking reaction and hydrogenation reaction on a high-cracking-activity catalyst in the temperature raising process, the whole reactor is in an exothermic state, and a catalyst bed layer flies due to excessive hydrocracking reaction in the temperature raising process, so that carbon deposition can be accelerated, the activity of the catalyst and the stability of the device can be influenced, the hydrocracking catalyst is passivated in the startup temperature raising process, the excessive initial activity of the hydrocracking catalyst is inhibited, and the safety of the catalyst, equipment and a human body is ensured.

At present, anhydrous liquid ammonia is injected into a hydrocracking device in the start-up process, which is a common passivation mode for a hydrocracking catalyst, the injected anhydrous liquid ammonia is adsorbed by the catalyst, the initial cracking activity of the catalyst can be temporarily inhibited, and the catalyst can recover the activity of the catalyst along with the increase of the start-up reaction temperature and the extension of the running time. However, anhydrous liquid ammonia is an irritant toxic liquid and has the characteristics of flammability and explosiveness, and the industrial use of anhydrous liquid ammonia has certain dangerousness, causes great harm to the environment and human bodies if leaked, and is not in accordance with the safe, healthy and environment-friendly concept. CN101492613A discloses a method for starting up a hydrocracking device, in which anhydrous liquid ammonia is used for passivation of a catalyst during the start-up process, which has the disadvantages caused by ammonia injection in the prior art, and has certain hidden dangers and hazards.

CN103059969A and CN103789023A disclose a method for passivating a cracking agent by using ammonia gas generated by the reaction of a high-nitrogen raw material and hydrogen gas as a passivating agent during startup, so as to achieve the purpose of reducing the use of anhydrous liquid ammonia, and although the method can play a role in temporarily inhibiting cracking activity, the method is relatively complex in operation and poor in stability, and is difficult to ensure the passivation effect of a molecular sieve, and meanwhile, the additional introduction of the high-nitrogen raw material oil is likely to introduce new impurities into a reaction system to influence the activity of a catalyst.

CN103566963A discloses a method of introducing basic nitride on a catalyst at a low temperature stage, then carrying out an in-situ sulfurization and activation process, although the cracking reaction can be controlled to some extent, the nitride is introduced into the sulfurization type catalyst in the form of an aqueous solution, which will largely affect the hydrogenation activity of the catalyst, resulting in the destruction of the active center of the catalyst. Meanwhile, if a nitrogen-containing compound is introduced into the catalyst in an oxidation state, the nitride is decomposed quickly in the vulcanization process, so that the passivation protection effect is difficult to play, and the start-up process also needs vulcanization treatment and has long start-up time.

CN107446616A discloses a method for loading low molecular nitride on a conventional hydrocracking catalyst or introducing low molecular nitride during a catalyst kneading molding process, so as to alleviate the risk of temperature runaway of a hydrocracking apparatus during start-up, but the catalyst needs to be subjected to a sulfidation treatment during start-up, which may cause a reaction between part of the nitride and sulfide during the sulfidation process or desorption in advance along with the rise of the sulfidation temperature, and there is no subsequent ammonia injection process, which results in an unstable passivation process of a molecular sieve, which cannot ensure the passivation effect, and there is still a certain risk of over-temperature.

Disclosure of Invention

The invention aims to provide an ex-situ ammonia passivation method for a vulcanization type hydrocracking catalyst and a passivation catalyst.

In order to achieve the above object, the present invention provides an off-site ammonia passivation method for a sulfided hydrocracking catalyst, comprising:

loading an organic nitrogen compound on a vulcanization type hydrocracking catalyst in the presence of an organic solvent to obtain a nitrogen-loaded catalyst; wherein the content of nitrogen on the nitrogen-supported catalyst calculated by element accounts for 0.1-3.6 wt% of the weight of the nitrogen-supported catalyst;

drying the obtained nitrogen-supported catalyst to obtain a passivated catalyst; wherein the drying treatment conditions include: the temperature is 30-200 ℃, the absolute pressure is 0.01-1MPa, and the time is 0.5-10 hours.

Optionally, the sulfided hydrocracking catalyst comprises a cracking component, a hydrogenation component and a carrier, wherein the content of the cracking component is 10-60 wt% and the content of the carrier is 30-70 wt% based on the weight of the sulfided hydrocracking catalyst.

Optionally, the cracking component comprises an amorphous acidic component and/or a molecular sieve, the amorphous acidic component comprises amorphous silica-alumina and/or amorphous silica-magnesia, and the molecular sieve is selected from one or more of a Y-type molecular sieve, a ZSM-5 molecular sieve, a SAPO molecular sieve and an MCM-41 mesoporous molecular sieve;

the hydrogenation component comprises active metals, wherein the active metals comprise VIII group metals and VIB group metals, the VIII group metals are Co and/or Ni, and the VIB group metals are Mo and/or W; based on the weight of the vulcanized hydrocracking catalyst, the content of VIII group metal calculated by oxide is 1-15 wt%, and the content of VIB group metal calculated by oxide is 5-30 wt%;

the carrier is selected from one or more of alumina, silica, titania, magnesia and zirconia.

Optionally, the active metal in the sulphided hydrocracking catalyst is present as a metal sulphide.

Optionally, the organic nitrogen compound is selected from one or more of alkyl amine compounds, aryl amine compounds, aniline compounds, methylaniline compounds, amide compounds, alcohol amine compounds and polyamine compounds; preferably selected from propylamine, butylamine, pentylamine, hexylamine, tri-N-butylamine, triethylamine, t-butylamine, dodecylamine, trioctylamine, hexadecylamine, N-dihydroxyethylaniline, acetanilide, diethanolamine, triethanolamine, diisopropanolamine, N-diethylhydroxylamine ethylenediamine, 1, 2-cyclohexanediamine, 1, 3-propanediamine, triethylenediamine, N-dimethyldipropylenetriamine, triethylenetetramine and hexamethylenetetramine and one or more of the above derivatives;

the organic solvent is selected from one or more of hydrocarbon oil, hydrocarbon oil oxygen-containing derivatives and organic carboxylic acid esters, the hydrocarbon oil and the hydrocarbon oil oxygen-containing derivatives are preferably selected from one or more of alcohols, ethers and light fraction hydrocarbon oil, and more preferably from one or more of ethanol, propanol, butanediol, diethyl ether, cyclohexane, n-heptane, n-decane, methyl cyclopentane, naphtha, gasoline, kerosene, diesel oil, white oil, lamp oil and lubricating oil base oil;

the organic carboxylic acid ester is preferably selected from fatty acid glycerides, more preferably from one or more of corn oil, soybean oil, peanut oil, olive oil and cottonseed oil.

Optionally, the number of carbon atoms of the organic nitrogen compound is 1-20, preferably 2-15;

the organic solvent has 2 to 35 carbon atoms, preferably 2 to 15 carbon atoms, and more preferably 2 to 10 carbon atoms.

Optionally, the load is selected from one or more of the following modes:

(1) dipping a sulfuration type hydrocracking catalyst into an organic solution containing an organic solvent and an organic nitrogen compound;

(2) spraying an organic solution containing an organic solvent and an organic nitrogen compound into the vulcanization type hydrocracking catalyst;

(3) dipping a sulfided hydrocracking catalyst in an organic solution containing an organic solvent and an organic nitrogen compound, and then evaporating the organic solvent; wherein the temperature of the evaporation is 10-150 ℃, preferably 20-90 ℃, the absolute pressure is 0.01-0.5MPa, preferably 0.03-0.3MPa, and the evaporation is preferably carried out in a rotary evaporator;

in modes (1) to (3), the impregnation or spraying is saturated impregnation, supersaturated impregnation or unsaturated impregnation, and the temperature of the impregnation or spraying is 10 to 100 ℃, preferably 20 to 80 ℃.

Optionally, the boiling point of the organonitrogen compound is 20 to 200 ℃ higher than the boiling point of the organic solvent at normal pressure.

Optionally, the method further includes: after the nitrogen-supported catalyst is subjected to standing treatment, the nitrogen-supported catalyst is subjected to drying treatment; wherein the standing treatment time is 1-10 hours, preferably 2-4 hours.

Optionally, the nitrogen content on the nitrogen-supported catalyst, calculated as the element, is from 0.1 to 3% by weight, preferably from 0.5 to 3% by weight, based on the weight of the nitrogen-supported catalyst.

Optionally, the drying conditions include: the temperature is 40-200 deg.C, preferably 60-180 deg.C, the absolute pressure is 0.01-0.8MPa, preferably 0.03-0.6MPa, and the time is 1-8 hr, preferably 2-6 hr.

Optionally, the drying treatment satisfies one or more of the following conditions:

in an inert atmosphere or an oxygen-containing atmosphere with an oxygen content of 0.1-15 vol%, wherein the inert atmosphere is selected from one or more of nitrogen, helium and argon;

the drying treatment is carried out in a rotary heat treatment device or a stationary heat treatment device;

the drying treatment is carried out in a non-flowing atmosphere, a naturally flowing atmosphere or a forced flowing atmosphere.

The invention also provides a passivated catalyst obtained by the provided method.

Compared with the prior art, the invention has the following outstanding technical effects:

1. the method has the advantages that the method carries out ammonia passivation treatment outside a reactor on the vulcanized hydrocracking catalyst, utilizes organic nitride as a passivator, can exert the passivation effect of the organic nitride to the maximum extent, reduces the use and discharge of toxic substances such as ammonia gas and the like in the start-up process, simultaneously reduces the waste of the passivator, and has the advantages of resource saving, low carbon, environmental protection and the like.

2. The method provided by the invention has the advantages that the passivation effect is stable, the cracking activity of the catalyst can be inhibited at a certain temperature, the targeted passivation treatment can be carried out according to the strength of an acid site, the characteristics of unstable passivation and possible introduction of other impurities caused by high-nitrogen oil are avoided, and the efficient and stable passivation effect is realized.

3. Compared with the existing passivation method, the method of the invention is upgraded and innovated, ammonia passivation treatment is carried out on the basis of the vulcanized hydrocracking catalyst, the hydrogenation activity and the vulcanization process of the catalyst are not influenced, the consumption of the passivating agent is reduced to the maximum extent on the basis of not influencing the activity of the catalyst, a large amount of manpower and material resources are saved, meanwhile, the environmental pollution and the difficulty and the danger of operation are avoided, the operation steps in the start-up process are simplified, oil can be directly fed into the reactor for start-up after the temperature is raised, the vulcanization and ammonia injection or high-nitrogen oil introduction are not needed, the investment in the start-up process is reduced, and the method has certain economic performance and practical value.

4. The method adopted by the invention enables the sulfuration type hydrocracking catalyst to only adsorb organic nitrogen-containing compounds, has targeted passivation effect, does not contain other organic matters, does not contact aqueous solution in the process, has better temporary passivation effect on the molecular sieve, and does not influence the hydrogenation activity.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The invention provides an off-site ammonia passivation method for a vulcanization type hydrocracking catalyst, which comprises the following steps: loading an organic nitrogen compound on a vulcanization type hydrocracking catalyst in the presence of an organic solvent to obtain a nitrogen-loaded catalyst; wherein the nitrogen content on the nitrogen-supported catalyst, calculated as the element, is from 0.1 to 3.6% by weight, preferably from 0.1 to 3% by weight, more preferably from 0.5 to 3% by weight, based on the weight of the nitrogen-supported catalyst; drying the obtained nitrogen-supported catalyst to obtain a passivated catalyst; wherein the drying treatment conditions include: the temperature is 30-200 ℃, the absolute pressure is 0.01-1MPa, and the time is 0.5-10 hours.

Aiming at the problems of passivation in the start-up process of the existing hydrocracking catalyst, the method provided by the invention has the characteristics of simple operation, good passivation effect, safety and environmental protection, and avoids the potential danger caused by poor passivation effect or ammonia injection in the start-up process. The invention achieves the purpose of no need of using a passivating agent in the startup process by carrying out ammonia passivation treatment on the vulcanized hydrocracking catalyst, effectively weakens the initial cracking activity, avoids environmental pollution and operation difficulty and danger brought by the passivating agent, effectively reduces the startup time of the device, and is suitable for the passivation process of various types of hydrogenation catalysts containing molecular sieves.

The hydrocracking catalyst of the present invention is a hydrocracking catalyst in a broad sense according to the present invention, and the present invention may include various types of molecular sieve-containing hydrocracking catalysts (e.g., hydro-upgrading catalysts) in addition to conventional hydrocracking catalysts, as well as specific hydrocracking catalysts known by common general knowledge in the art. The manner of sulfiding the hydrocracking catalyst is well known to those skilled in the art and the present invention will not be described in detail. The sulfided hydrocracking catalyst may include a cracking component, a hydrogenation component, and a carrier, and the content of the cracking component may be 10 to 60 wt%, preferably 13 to 50 wt%, and the content of the carrier may be 30 to 70 wt%, based on the weight of the sulfided hydrocracking catalyst; the cracking component may include an amorphous acidic component, which may include amorphous silica alumina and/or amorphous silica magnesium, and/or a molecular sieve, which may be selected from one or more of a Y-type molecular sieve, a ZSM-5 molecular sieve, a SAPO molecular sieve, and a MCM-41 mesoporous molecular sieve; the hydrogenation component can comprise active metals, the active metals can comprise VIII group metals and VIB group metals, the VIII group metals can be Co and/or Ni, and the VIB group metals can be Mo and/or W; the group VIII metal may be present in an amount of from 1 to 15 wt.%, preferably from 3 to 12 wt.%, calculated as oxide, and the group VIB metal may be present in an amount of from 5 to 30 wt.%, preferably from 8 to 28 wt.%, calculated as oxide, based on the weight of the sulfided hydrocracking catalyst; the support comprises a refractory porous substance, for example one or more selected from alumina, silica, titania, magnesia and zirconia.

According to the invention, the active metal in the sulphided hydrocracking catalyst may be present as a metal sulphide, e.g. Co as Co₉S₈In the form of Ni₃S₂In the form of MoS, Mo₂The form (a) of (b) exists,w is as WS₂The form of (a) exists, etc.

According to the present invention, the organic nitrogen-containing compound refers to an organic substance containing nitrogen, for example, the organic nitrogen compound may be one or more selected from alkylamine compounds, arylamine compounds, aniline compounds, methylaniline compounds, amide compounds, alkanolamine compounds and polyamine compounds (refer to compounds having two or more amine groups), and is preferably an alkylamine compound; specific compounds may be selected from propylamine, butylamine, pentylamine, hexylamine, tri-N-butylamine, triethylamine, t-butylamine, dodecylamine, trioctylamine, hexadecylamine, N-dihydroxyethylaniline, acetanilide, diethanolamine, triethanolamine, diisopropanolamine, N-diethylhydroxylamine ethylenediamine, 1, 2-cyclohexanediamine, 1, 3-propanediamine, triethylenediamine, N-dimethyldipropylenetriamine, triethylenetetramine and hexamethylenetetramine, and one or more of their derivatives (e.g., amino group-containing esters); the number of carbon atoms of the organic nitrogen compound (if the organic nitrogen compound is a simple substance, the number of carbon atoms means a specific number of carbon atoms of the organic nitrogen compound; if the organic nitrogen compound is a mixture, the number of carbon atoms means a range of the number of carbon atoms of all compounds in the mixture) may be 1 to 20, preferably 2 to 15.

According to the present invention, the organic solvent is well known to those skilled in the art, for example, the organic solvent is selected from one or more of hydrocarbon oil, oxygenated derivatives of hydrocarbon oil, and organic carboxylic acid esters, the hydrocarbon oil and oxygenated derivatives of hydrocarbon oil are preferably selected from one or more of alcohols, ethers, and light fraction hydrocarbon oils, and more preferably from one or more of ethanol, propanol, butanediol, diethyl ether, cyclohexane, n-heptane, n-decane, methylcyclopentane, naphtha, gasoline, kerosene, diesel oil, white oil, lamp oil, and lubricant base oil; the organic carboxylic acid ester is preferably selected from fatty acid glycerides, more preferably from one or more of corn oil, soybean oil, peanut oil, olive oil and cottonseed oil. The number of carbon atoms of the organic solvent (the number of carbon atoms means the specific number of carbon atoms of the organic solvent if the organic solvent is a simple substance; and the number of carbon atoms means the range of the number of carbon atoms of all compounds in the mixture if the organic solvent is a mixture) may be 2 to 35, preferably 2 to 15, more preferably 2 to 10.

According to the present invention, the support is a catalyst preparation means well known to the skilled person, and may be selected from one or more of the following ways: (1) dipping a sulfuration type hydrocracking catalyst into an organic solution containing an organic solvent and an organic nitrogen compound; (2) spraying an organic solution containing an organic solvent and an organic nitrogen compound into the vulcanization type hydrocracking catalyst; (3) dipping a sulfided hydrocracking catalyst in an organic solution containing an organic solvent and an organic nitrogen compound, and then evaporating the organic solvent, the mode can lead the nitride to be directly adsorbed on the hydrocracking catalyst, so as to facilitate the evaporation, the organonitride has a boiling point higher than that of the organic solvent, e.g., 20-200 c higher, wherein the evaporation temperature can be 10-150 ℃, preferably 20-90 ℃, the absolute pressure can be 0.01-0.5MPa, preferably 0.03-0.3MPa, the evaporation is preferably carried out in a rotary evaporator, in the form of which the sulfided hydrocracking catalyst is impregnated with an excess of organic solution, setting a certain temperature to ensure that the low-boiling organic solvent is heated and volatilized preferentially, and finally, the high-boiling organic nitride is adsorbed on the vulcanization type hydrocracking catalyst; in the modes (1) to (3), the impregnation or spraying may be saturated impregnation, supersaturated impregnation, or unsaturated impregnation, and the mode (1) is preferably saturated impregnation, and the mode (3) is preferably supersaturated impregnation. The temperature of the dipping or spraying can be 10 to 100 ℃, preferably 20 to 80 ℃.

According to the invention, the method may further comprise: after the nitrogen-supported catalyst is subjected to standing treatment, the nitrogen-supported catalyst is subjected to drying treatment; wherein, the time of the standing treatment is 1-10 hours, preferably 2-4 hours, and the temperature can be the same as the temperature of the load or adjusted according to the requirement, thereby improving the load effect of the organic nitrogen compound on the catalyst.

According to the present invention, the drying treatment for removing the organic solvent and the unadsorbed organic nitrogen-containing compounds without substantially changing the properties of the sulfided hydrocracking catalyst may comprise: the temperature is 40-200 deg.C, preferably 50-180 deg.C, more preferably 60-180 deg.C, the absolute pressure is 0.01-0.8MPa, preferably 0.03-0.6MPa, and the time is 1-8 hr, preferably 2-6 hr. The drying treatment may satisfy one or more of the following conditions: in an inert atmosphere or an oxygen atmosphere with an oxygen content of 0.1-15 vol%, wherein the inert gas is used as a balance gas and can be selected from one or more of nitrogen, helium and argon; the drying treatment is carried out in a rotary heat treatment device or a stationary heat treatment device; the drying treatment is carried out in a non-flowing atmosphere, a naturally flowing atmosphere or a forced flowing atmosphere.

The invention also provides a passivated catalyst obtained by the method, and the passivated catalyst has weak cracking activity in a low-temperature stage and strong cracking activity in a high-temperature stage.

The following examples further illustrate the ex-situ ammonia deactivation process for a sulfided hydrocracking catalyst of the present invention.

To illustrate the characteristics of the present invention, the examples and comparative examples each selected a commercial hydrocracking catalyst having 3.0 wt% of Ni oxide, 27 wt% of W oxide, 35% of Y-type molecular sieve and the balance of alumina, which was industrially produced in the same batch, and a sulfided hydrocracking catalyst prepared on the basis of the same batch of the oxidation hydrocracking catalyst, the sulfiding step was: oxidation type hydrocracking catalyst in H₂S volume fraction of 2% and H₂Heating to 230 ℃ at the speed of 5 ℃/min for 4 hours under the atmosphere with the volume fraction of 98%, and then heating to 320 ℃ at the speed of 5 ℃/min for 4 hours.

Example 1

200g of oxidation type hydrocracking catalyst is taken out of the reactor for vulcanization treatment, and the oxidation type hydrocracking catalyst is converted into a vulcanization type hydrocracking catalyst for later use.

Taking 100g of a vulcanization type hydrocracking catalyst, adding 21.4g of diethanolamine into ethanol, stirring uniformly at 30 ℃ to obtain a nitrogen-containing solution, introducing the nitrogen-containing solution into the vulcanization type hydrocracking catalyst in a pore saturation impregnation mode, standing for 3 hours to introduce 2.35 wt% of nitrogen content, and obtaining a nitrogen-loaded catalyst; then drying for 4 hours at 100 ℃ under normal pressure and in flowing nitrogen atmosphere to prepare the passivated catalyst A.

And (2) loading the passivated catalyst A into a reactor for reaction, introducing hydrogen and n-heptane raw materials when the temperature is raised to 100 ℃, continuously raising the temperature to 300 ℃, keeping the temperature constant for 3 hours, then analyzing the composition of the product on line, calculating the cracking conversion rate of the n-heptane, raising the temperature to 320 ℃ after the constant temperature is finished, keeping the temperature constant for 2 hours, and subsequently raising the temperature to 20 ℃ each time and keeping the temperature constant for two hours until the constant temperature of 380 ℃ is finished. Reaction conditions are as follows: the reaction pressure is 4.0MPa, the volume ratio of hydrogen to oil is 1800, and the volume airspeed is 3h^-1The hydrocracking activity (expressed as conversion) is shown in table 1.

Example 2

Taking 100g of the same vulcanization type hydrocracking catalyst as in example 1, adding 11.1g of tri-n-butylamine into diethyl ether, stirring uniformly at 30 ℃ to obtain a nitrogen-containing solution, introducing the nitrogen-containing solution into the vulcanization type hydrocracking catalyst in a pore saturated impregnation mode, standing for 3 hours to introduce the nitrogen content of 0.75 wt% to obtain a nitrogen-loaded catalyst; then drying for 4 hours at 90 ℃, under normal pressure and in flowing nitrogen atmosphere to prepare the passivated catalyst B.

The passivated catalyst B was loaded into a reactor and reacted under the same conditions as in example 1, with the hydrocracking activity (expressed as conversion) shown in Table 1.

Example 3

Taking 100g of the same vulcanization type hydrocracking catalyst as in example 1, adding 25.0g of tri-n-butylamine into diethyl ether, stirring uniformly at 30 ℃ to obtain a nitrogen-containing solution, introducing the nitrogen-containing solution into the vulcanization type hydrocracking catalyst in a pore saturated impregnation mode, standing for 3 hours to introduce 1.51 wt% of nitrogen content, and obtaining a nitrogen-supported catalyst; then drying for 4 hours at 90 ℃, under normal pressure and in flowing nitrogen atmosphere to prepare the passivated catalyst C.

The reaction was carried out by charging the reactor with the passivated catalyst C under the same conditions as in example 1, the hydrocracking activity (expressed as conversion) of which is shown in Table 1.

Example 4

Taking 100g of the same vulcanization type hydrocracking catalyst as in example 1, adding 11.1g N, N-diethylhydroxylamine ethylenediamine into ethanol, stirring uniformly at 30 ℃ to obtain a nitrogen-containing solution, introducing the nitrogen-containing solution into the vulcanization type hydrocracking catalyst in a pore saturation impregnation mode, standing for 3 hours to introduce 2.70 wt% of nitrogen content, and thus obtaining a nitrogen-supported catalyst; then drying for 4 hours at 100 ℃, under normal pressure and in flowing nitrogen atmosphere to prepare the passivated catalyst D.

The passivated catalyst D was loaded into a reactor and reacted under the same conditions as in example 1, with the hydrocracking activity (expressed as conversion) as shown in Table 1.

Example 5

Taking 100g of the same vulcanization type hydrocracking catalyst as in example 1, adding 29.0g of diethanolamine into ethanol, stirring uniformly at normal temperature to obtain a nitrogen-containing solution, placing the nitrogen-containing solution which is 2 times of the solution required for saturated impregnation of the pores into a rotary evaporation bottle, simultaneously placing the vulcanization type hydrocracking catalyst into the rotary bottle, setting the heating temperature of the rotary bottle to be 80 ℃ and the rotating speed to be 30r/min, standing the vulcanization type hydrocracking catalyst containing nitride for 3 hours after the organic solvent is completely evaporated to introduce the nitrogen content of 3.0 weight percent to obtain a nitrogen-loaded catalyst; then drying for 4 hours at 100 ℃ under normal pressure and in flowing nitrogen atmosphere to prepare the passivated catalyst E.

The reaction was carried out by charging the reactor with the passivated catalyst E, under the same reaction conditions as in example 1, whose hydrocracking activity (expressed as conversion) is shown in Table 1.

Example 6

Taking 100g of the same vulcanization type hydrocracking catalyst as in example 1, adding 15.2g of tri-n-butylamine into diethyl ether, stirring uniformly at normal temperature to obtain a nitrogen-containing solution, placing the nitrogen-containing solution which is 2 times of the solution amount required for saturated impregnation of pores into a rotary evaporation bottle, simultaneously placing the vulcanization type hydrocracking catalyst into the rotary evaporation bottle, setting the heating temperature of the rotary evaporation bottle to be 35 ℃ and the rotating speed to be 30r/min, standing the vulcanization type hydrocracking catalyst containing nitride for 3 hours after the organic solvent is completely evaporated to introduce the nitrogen content of 1.0 weight percent to obtain a nitrogen-loaded catalyst; then drying for 4 hours at 90 ℃ under normal pressure and in flowing nitrogen atmosphere to prepare the passivated catalyst F.

The passivated catalyst F was loaded into a reactor and reacted under the same conditions as in example 1, with the hydrocracking activity (expressed as conversion) as shown in Table 1.

Example 7

Taking 100g of the same vulcanization type hydrocracking catalyst as in example 1, adding 12.7g of diethanolamine into ethanol, stirring uniformly at normal temperature to obtain a nitrogen-containing solution, placing the nitrogen-containing solution which is 2 times of the solution required for saturated impregnation of the pores into a rotary evaporation bottle, simultaneously placing the vulcanization type hydrocracking catalyst into the rotary bottle, setting the heating temperature of the rotary bottle to be 80 ℃ and the rotating speed to be 30r/min, standing the vulcanization type hydrocracking catalyst containing nitride for 3 hours after the organic solvent is completely evaporated to introduce the nitrogen content of 1.5 weight percent to obtain a nitrogen-loaded catalyst; then drying for 4 hours at 100 ℃ under normal pressure and in flowing nitrogen atmosphere to prepare the passivated catalyst G.

The passivated catalyst G was loaded into the reactor and reacted under the same conditions as in example 1, with the hydrocracking activity (expressed as conversion) as shown in Table 1.

Example 8

100g of the same vulcanization type hydrocracking catalyst as in example 1 was taken, 24.7g of n-tributylamine solution was added to the ether solution, stirred uniformly at room temperature, a nitrogen-containing solution 2 times the amount of the solution required for pore saturation impregnation was placed in a rotary evaporation flask, the vulcanization type hydrocracking catalyst was placed in the rotary flask, the rotary flask was set to a heating temperature of 35 ℃ and a rotation speed of 30r/min, the vulcanization type hydrocracking catalyst containing a nitride was allowed to stand for 3 hours after the organic solvent was completely evaporated to introduce a nitrogen content of 1.5 wt%, and then dried under a flowing nitrogen atmosphere at 90 ℃ and under normal pressure for 4 hours to prepare a passivated catalyst H.

The reactor was charged with passivated catalyst H, under the same reaction conditions as in example 1, and its hydrocracking activity (expressed as conversion) is shown in Table 1.

Comparative example 1

Taking 100g of the same vulcanization type hydrocracking catalyst as in example 1, adding 20.0g of 20.0g N, N-diethylhydroxylamine ethylenediamine into ethanol, stirring uniformly at 30 ℃ to obtain a nitrogen-containing solution, introducing the nitrogen-containing solution into the vulcanization type hydrocracking catalyst in a pore saturation impregnation mode, standing for 3 hours to introduce 4.49 wt% of nitrogen content, and thus obtaining a nitrogen-supported catalyst; then drying for 4 hours at 100 ℃, under normal pressure and in flowing nitrogen atmosphere to prepare the passivated catalyst I.

The passivated catalyst I was loaded into a reactor and reacted under the same conditions as in example 1, with the hydrocracking activity (expressed as conversion) as shown in Table 1.

Comparative example 2

Taking 100g of the same vulcanization type hydrocracking catalyst as in example 1, adding 17.4g N, N-diethylhydroxylamine ethylenediamine into ethanol, stirring uniformly at normal temperature to obtain a nitrogen-containing solution, placing the nitrogen-containing solution which is 2 times of the solution required for saturated impregnation of the pores into a rotary evaporation bottle, simultaneously placing the vulcanization type hydrocracking catalyst into the rotary evaporation bottle, setting the heating temperature of the rotary evaporation bottle to be 80 ℃, setting the rotating speed to be 30r/min, standing the vulcanization type hydrocracking catalyst containing nitrides for 3 hours after the organic solvent is completely evaporated to introduce the nitrogen content of 4.0 weight percent to obtain a nitrogen-supported catalyst; then drying for 4 hours at 100 ℃ under normal pressure and in flowing nitrogen atmosphere to prepare the passivated catalyst J.

The passivated catalyst J was loaded into a reactor and reacted under the same conditions as in example 1, with the hydrocracking activity (expressed as conversion) as shown in Table 1.

Comparative example 3

100g of the same sulfided hydrocracking catalyst as in example 1 was taken and designated catalyst K.

The catalyst K was charged into a reactor and reacted under the same conditions as in example 1, the hydrocracking activity (in terms of conversion) of which is shown in Table 1.

Comparative example 4

100g of the same vulcanization type hydrocracking catalyst as in example 1 was taken, 21.4g of diethanolamine was added to deionized water, and stirred uniformly at 30 ℃ to obtain a nitrogen-containing solution, the nitrogen-containing solution was introduced into the vulcanization type hydrocracking catalyst in a pore saturation impregnation manner, and then allowed to stand for 3 hours to introduce a nitrogen content of 2.35 wt%, and then dried at 120 ℃ under normal pressure under a flowing nitrogen atmosphere for 4 hours to prepare an ex-situ ammonia-passivated vulcanization type hydrocracking catalyst L.

The catalyst L was charged into a reactor and reacted under the same conditions as in example 1, the hydrocracking activity (in terms of conversion) of which is shown in Table 1.

Comparative example 5

Loading an oxidation type hydrocracking catalyst (named as catalyst M) into a reactor for reaction, and carrying out in-reactor vulcanization treatment by using carbon disulfide, wherein the vulcanization treatment comprises the following steps: cyclohexane containing 5 weight percent of carbon disulfide is used as vulcanized oil, the pressure in the vulcanization process is 4.0MPa, the volume ratio of hydrogen to oil is 1800, and the volume space velocity is 6h^-1Heating to 230 ℃ at a speed of 10 ℃/min, keeping the temperature for 2 hours, heating to 320 ℃ at a speed of 10 ℃/min, keeping the temperature for 2 hours, switching n-heptane raw materials after vulcanization, adjusting to 300 ℃ and keeping the temperature for 3 hours, then analyzing the composition of the product on line, calculating the cracking conversion rate of n-heptane, heating to 320 ℃ after constant temperature is over, keeping the temperature for 2 hours, subsequently heating to 20 ℃ each time, keeping the temperature for two hours, and keeping the temperature until the constant temperature of 380 ℃ is over. Reaction conditions are as follows: the reaction pressure is 4.0MPa, the volume ratio of hydrogen to oil is 1800, and the volume airspeed is 3h^-1The hydrocracking activity (expressed as conversion) is shown in table 1.

The above embodiment can show that the method for passivating the in-situ ammonia of the vulcanized hydrocracking catalyst has the greatest characteristic of having a good passivation effect on the basis of not influencing the hydrogenation activity, specifically and independently introducing the corresponding organic nitride to the vulcanized hydrocracking catalyst, weakening the cracking activity of the hydrocracking catalyst at a low temperature stage (300-.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the content of the present invention as long as it does not depart from the gist of the present invention.

TABLE 1

Claims

1. An ex-situ ammonia passivation method for a sulfided hydrocracking catalyst, the method comprising:

2. The process of claim 1, wherein the sulfided hydrocracking catalyst comprises a cracking component, a hydrogenation component, and a support, wherein the cracking component is present in an amount of 10-60 wt% and the support is present in an amount of 30-70 wt%, based on the weight of the sulfided hydrocracking catalyst.

3. The process of claim 2, wherein the cracking component comprises an amorphous acidic component comprising amorphous silica alumina and/or amorphous silica magnesium and/or a molecular sieve selected from one or more of Y-type molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesoporous molecular sieve;

4. The process of claim 3, wherein the active metal in the sulfided hydrocracking catalyst is present as a metal sulfide.

5. The method according to claim 1, wherein the organic nitrogen compound is selected from one or more of alkylamine compound, arylamine compound, aniline compound, methylaniline compound, amide compound, alcoholamine compound and polyamine compound; preferably selected from propylamine, butylamine, pentylamine, hexylamine, tri-N-butylamine, triethylamine, t-butylamine, dodecylamine, trioctylamine, hexadecylamine, N-dihydroxyethylaniline, acetanilide, diethanolamine, triethanolamine, diisopropanolamine, N-diethylhydroxylamine ethylenediamine, 1, 2-cyclohexanediamine, 1, 3-propanediamine, triethylenediamine, N-dimethyldipropylenetriamine, triethylenetetramine and hexamethylenetetramine and one or more of the above derivatives;

6. The method according to claim 1 or 5, wherein the organic nitrogen compound has a carbon number of 1 to 20, preferably 2 to 15;

7. The method of claim 1, wherein the load is selected from one or more of the following:

8. The method according to claim 1 or 7, wherein the boiling point of the organonitride is 20-200 ℃ higher than the boiling point of the organic solvent at atmospheric pressure.

9. The method of claim 1, further comprising: after the nitrogen-supported catalyst is subjected to standing treatment, the nitrogen-supported catalyst is subjected to drying treatment; wherein the standing treatment time is 1-10 hours, preferably 2-4 hours.

10. A process according to claim 1, wherein the nitrogen content on the nitrogen supported catalyst, calculated as element, is from 0.1 to 3% by weight, preferably from 0.5 to 3% by weight, based on the weight of the nitrogen supported catalyst.

11. The method of claim 1, wherein the conditions of the drying process comprise: the temperature is 40-200 deg.C, preferably 60-180 deg.C, the absolute pressure is 0.01-0.8MPa, preferably 0.03-0.6MPa, and the time is 1-8 hr, preferably 2-6 hr.

12. The method of claim 1, wherein the drying process satisfies one or more of the following conditions:

13. A passivated catalyst obtained by the process of any one of claims 1 to 12.