CN111729690A - A kind of ammonia passivation method and passivation catalyst outside a sulfurized hydrocracking catalyst - Google Patents

Abstract

The invention relates to an ammonia passivation method and a passivation catalyst outside a sulfurized hydrocracking catalyst. The method comprises: loading an organic nitrogen compound on a sulfurized hydrocracking catalyst in the presence of an organic solvent to obtain a nitrogen-supported catalyst wherein, the nitrogen content in element terms on the nitrogen-supported catalyst accounts for 0.1-10% by weight of the weight of the nitrogen-supported catalyst; the obtained nitrogen-supported catalyst is subjected to drying treatment to obtain a passivation catalyst; wherein, the conditions of the drying treatment Including: the temperature is 30‑200℃, the absolute pressure is 0.01‑1MPa, and the time is 0.5‑10 hours. The method of the invention has good passivation effect and shortens the start-up time of the hydrogenation device.

Description

A kind of ammonia passivation method and passivation catalyst outside a sulfurized hydrocracking catalyst

technical field

The present invention relates to a method for ammonia passivation outside a sulfurized hydrocracking catalyst and a passivation catalyst.

Background technique

With the increasingly stringent environmental regulations around the world, the demand for clean fuels is also increasing. Hydroprocessing technology is an effective means of producing clean fuels. Therefore, the number of hydrogenation units in major refineries is also increasing. more.

Hydrocracking technology is an effective means of converting heavy distillates into light and clean products. Hydrocracking technology uses dual-function catalysts, including cracking function and hydrogenation function. The cracking function is usually provided by molecular sieves with acid sites. Currently, Y-type molecular sieves, Beta-type molecular sieves, ZSM series molecular sieves, and MCM series molecular sieves are widely used. and composite molecular sieves. The hydrogenation function is mainly derived from active metals, including Co and/or Ni of Group VIII, Mo and/or W of Group VIB. The hydrogenation catalyst has high hydrogenation performance only when the metal is converted into sulfide state. Therefore, in order to optimize the hydrogenation performance of the catalyst, the catalyst needs to be sulfided before use. There are two forms of vulcanization and external vulcanization. Among them, the in-vessel sulfidation is carried out in the reactor, and the waste gas and waste water produced will pollute the environment. The out-of-vessel sulfidation is that the catalyst completes the sulfidation treatment outside the vessel, generating highly active metal sulfides, which can be directly loaded into the reactor. It is the vulcanization method that is more advocated and popularized at present.

The hydrocracking unit generally requires a higher operating temperature. During the start-up process, the temperature of the reactor needs to be raised to a higher temperature. During the heating process, the feed oil will undergo a cracking reaction and a hydrogenation reaction on a catalyst with high cracking activity. And the whole is in an exothermic state. During the heating process, the catalyst bed will be "fly temperature" due to excessive hydrocracking reaction, which will not only accelerate carbon deposition but also affect the activity of the catalyst and the stability of the device. In the process, the hydrocracking catalyst is passivated to suppress its high initial activity and ensure the safety of the catalyst, equipment and people.

At present, the injection of anhydrous liquid ammonia during the start-up process of a hydrocracking unit is a common passivation method for hydrocracking catalysts. The injected anhydrous liquid ammonia is adsorbed by the catalyst, which can temporarily inhibit the initial cracking activity of the catalyst. With the increase of the start-up reaction temperature and the extension of the operation time, the catalyst can recover its own activity. However, anhydrous liquid ammonia is an irritating toxic liquid with flammable and explosive characteristics. The use of anhydrous liquid ammonia in industry is dangerous to a certain extent. If it leaks, it will cause great harm to the environment and people. The concept of safety, health and environmental protection. CN101492613A discloses a method for starting a hydrocracking unit. In the starting process, anhydrous liquid ammonia is used to carry out the passivation treatment of the catalyst, which has the above-mentioned drawbacks 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 reacting high-nitrogen raw materials with hydrogen gas to generate ammonia gas as a passivating agent during the start-up process, so as to achieve the purpose of reducing the use of anhydrous liquid ammonia, although it can be temporarily It has the effect of inhibiting cracking activity, but the operation is complicated, the stability is poor, and it is difficult to ensure the passivation effect of molecular sieves. At the same time, the additional introduction of high nitrogen feedstock oil is likely to introduce new impurities into the reaction system, affecting the activity of the catalyst.

CN103566963A discloses a method of introducing basic nitrides into catalysts at a low temperature stage, and then performing in-vessel vulcanization and activation processes. Although the cracking reaction can be controlled to a certain extent, the nitrides are introduced into the sulfided catalysts in the form of an aqueous solution. This will greatly affect the hydrogenation activity of the catalyst, resulting in the destruction of the active center of the catalyst. At the same time, if nitrogen-containing compounds are introduced into the catalyst in the oxidation state stage, the nitrides will decompose rapidly during the sulfidation process, and it is difficult to play the role of passivation protection, and the start-up process also requires sulfidation treatment, and the start-up time is relatively long.

CN107446616A discloses a method of loading low-molecular-weight nitrides on conventional hydrocracking catalysts or introducing low-molecular-weight nitrides in the process of catalyst kneading and kneading, so as to alleviate the risk of overheating of the hydrocracking unit during the start-up process, but the catalyst is During the start-up process, vulcanization treatment is also required, which will cause some nitrides to react with sulfides during the vulcanization process or to be desorbed in advance with the increase of vulcanization temperature, and the subsequent process of ammonia injection will not continue, resulting in the passivation process of molecular sieves. It is unstable, the passivation effect cannot be guaranteed, and there is still a certain risk of over-temperature.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide an ammonia passivation method and a passivation catalyst outside a sulfurized hydrocracking catalyst. The method of the present invention has a good passivation effect and shortens the start-up time of the hydrogenation unit.

In order to achieve the above-mentioned purpose, the present invention provides a kind of ammonia passivation method outside the sulfide type hydrocracking catalyst, the method comprises:

The organic nitrogen compound is supported on a sulfurized hydrocracking catalyst in the presence of an organic solvent to obtain a nitrogen-supported catalyst; wherein the nitrogen content on the nitrogen-supported catalyst in terms of elements accounts for 0.1-3.6 by weight of the nitrogen-supported catalyst %;

The obtained nitrogen-supported catalyst is subjected to drying treatment to obtain a passivation catalyst; wherein, the drying treatment conditions include: a temperature of 30-200° C., an absolute pressure of 0.01-1 MPa, and a time of 0.5-10 hours.

Optionally, the sulfurized hydrocracking catalyst includes a cracking component, a hydrogenation component and a carrier, and based on the weight of the sulfurized hydrocracking catalyst, the content of the cracking component is 10-60% by weight, The content of the carrier is 30-70% by weight.

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

The hydrogenation component includes an active metal, the active metal includes a Group VIII metal and a Group VIB metal, the Group VIII metal is Co and/or Ni, and the Group VIB metal is Mo and/or W ; Based on the weight of the sulfurized hydrocracking catalyst, the content of the Group VIII metal in terms of oxides is 1-15% by weight, and the content of Group VIB metals in terms of oxides is 5-30% by weight;

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

Optionally, the active metal in the sulfurized hydrocracking catalyst exists in the form of metal sulfide.

Optionally, the organic nitrogen compound is selected from one of alkylamines, arylamines, anilines, methylanilines, amides, alcoholamines and polyamines or more; preferably selected from propylamine, butylamine, pentylamine, hexylamine, tri-n-butylamine, triethylamine, tert-butylamine, dodecylamine, trioctylamine, hexadecylamine, N,N-dihydroxyethylamine Aniline, acetanilide, diethanolamine, triethanolamine, diisopropanolamine, N,N-diethylhydroxylamine ethylenediamine, 1,2-cyclohexanediamine, 1,3-propanediamine, triethylenediamine , one or more of N,N-dimethyldipropylenetriamine, triethylenetetramine and hexamethylenetetramine and derivatives of the above compounds;

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

The organic carboxylic acid ester is preferably selected from fatty acid glycerides, more preferably selected 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 number of carbon atoms of the organic solvent is 2-35, preferably 2-15, more preferably 2-10.

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

(1), impregnating the sulfurized hydrocracking catalyst in the organic solution containing organic solvent and organic nitrogen compound;

(2), the organic solution containing organic solvent and organic nitrogen compound is sprayed in the described sulfurized hydrocracking catalyst;

(3), immersing the sulfurized 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° C., preferably 20-90° C. ℃, 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 the modes (1)-(3), the dipping or spraying is saturated dipping, supersaturated dipping or unsaturated dipping, and the temperature of the dipping or spraying is 10-100°C, preferably 20-80°C.

Optionally, under normal pressure, the boiling point of the organic nitride is 20-200° C. higher than the boiling point of the organic solvent.

Optionally, the method further comprises: performing the drying treatment after the nitrogen-supported catalyst is left to stand; wherein, the time of the stand treatment is 1-10 hours, preferably 2-4 hours.

Optionally, the nitrogen content of the nitrogen-supported catalyst in element terms accounts for 0.1-3 wt % of the weight of the nitrogen-supported catalyst, preferably 0.5-3 wt %.

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

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

Carry out in an inert atmosphere or an oxygen atmosphere with an oxygen content of 0.1-15% by volume, the inert atmosphere is selected from an atmosphere containing 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 performed in a no-flow atmosphere, a natural-flow atmosphere, or a forced-flow atmosphere.

The present invention also provides passivated catalysts obtained by the provided methods.

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

1. Carry out ammonia passivation treatment outside the sulfide type hydrocracking catalyst, and use organic nitrides as passivation agents to maximize the passivation effect of organic nitrides and reduce the amount of toxic substances such as ammonia during the start-up process. Use and discharge, while reducing the waste of passivating agents, has the advantages of saving resources, low carbon and environmental protection.

2. The passivation effect brought by the method of the present invention is stable, which can ensure that the cracking activity of the catalyst is suppressed at a certain temperature, and targeted passivation treatment can be carried out according to the strength of the acid site, avoiding the passivation caused by the high nitrogen oil. It has the characteristics of unstable passivation and the possibility of introducing other impurities, and has a highly efficient and stable passivation effect.

3. Compared with the existing passivation method, the method of the present invention has been upgraded and innovated, and the ammonia passivation treatment is carried out on the basis of the sulfurized hydrocracking catalyst, which will not affect the hydrogenation activity and sulfurization process of the catalyst, and will not affect the catalyst. On the basis of its activity, it minimizes the consumption of passivating agents, saves a lot of manpower and material resources, and also avoids environmental pollution and the difficulty and danger of operation, and simplifies the operation steps in the start-up process. It needs to be vulcanized and then injected with ammonia or high nitrogen oil to reduce the investment during the start-up process, which has certain economic and practical value.

4. The method adopted in the present invention allows only organic nitrogen-containing compounds to be adsorbed on the sulfurized hydrocracking catalyst, which has a targeted passivation effect, no other organic matter, and no contact with aqueous solution in the process, which has better temporary effect on molecular sieves. Passivation effect, and will not affect the hydrogenation activity.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, but not to limit the present invention.

The invention provides a method for ammonia passivation outside a sulfurized hydrocracking catalyst. The method comprises: loading an organic nitrogen compound on a sulfurized hydrocracking catalyst in the presence of an organic solvent to obtain a nitrogen-supported catalyst; The nitrogen content of the nitrogen-supported catalyst in terms of elements accounts for 0.1-3.6% by weight of the weight of the nitrogen-supported catalyst, preferably 0.1-3% by weight, more preferably 0.5-3% by weight; drying the obtained nitrogen-supported catalyst, A passivation catalyst is obtained; wherein, the conditions of the drying treatment include: a temperature of 30-200° C., an absolute pressure of 0.01-1 MPa, and a time of 0.5-10 hours.

Aiming at the problems existing in passivation during 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 of poor passivation effect or ammonia injection during the start-up process At the same time, the method of the invention has a short start-up time and a fast heating rate, and can directly heat up the oil to start the operation, enter a stable production state in a short time, reduce the risk of flying temperature, not only save energy consumption, but also reduce passivation agents Pollution of the environment and harm to the human body. The invention achieves the purpose of not using a passivating agent during the start-up process by performing an off-site ammonia passivation treatment on the sulfurized hydrocracking catalyst, effectively weakens the initial cracking activity, and avoids the environmental pollution and environmental pollution caused by the passivating agent. The difficulty and danger of operation can effectively reduce the start-up time of the device, and it is suitable for the passivation process of various types of hydrogenation catalysts containing molecular sieves.

According to the present invention, the hydrocracking catalyst of the present invention is a hydrocracking catalyst in a broad sense. In addition to conventional hydrocracking catalysts, the present invention may also include various types of molecular sieve-containing hydrogenation catalysts (such as hydro-upgrading catalysts) As well as employing specific hydrocracking catalysts known to common knowledge in the art. The sulfidation method of the hydrocracking catalyst is well known to those skilled in the art, and will not be repeated in the present invention. The sulfide-type hydrocracking catalyst may include a cracking component, a hydrogenation component and a carrier. Based on the weight of the sulfide-type hydrocracking catalyst, the content of the cracking component may be 10-60% by weight, preferably 10-60% by weight. 13-50% by weight, the content of the carrier may be 30-70% by weight; the cracking component may include amorphous acidic components and/or molecular sieves, and the amorphous acidic components may include amorphous silica-alumina and /or amorphous silicon-magnesium, the molecular sieve can be selected from one or more of Y-type molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesoporous molecular sieve; the hydrogenation component can include active metal, The active metal may include a Group VIII metal and a Group VIB metal, the Group VIII metal may be Co and/or Ni, and the Group VIB metal may be Mo and/or W; hydrocracking in a sulfurized form Based on the weight of the catalyst, the content of the Group VIII metal in terms of oxides may be 1-15 wt%, preferably 3-12 wt%, and the content of Group VIB metals in terms of oxides may be 5-30 wt% %, preferably 8-28% by weight; the carrier includes a refractory porous substance, such as one or more selected from alumina, silica, titania, magnesia and zirconia.

According to the present invention, the active metal in the sulfurized hydrocracking catalyst can exist in the form of metal sulfide, for example, Co exists in the form of Co ₉ S ₈ , Ni exists in the form of Ni ₃ S ₂ , and Mo exists in the form of MoS ₂ exists in the form of , W exists in the form of WS ₂ , 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 selected from alkylamine compounds, arylamine compounds, aniline compounds, methylaniline compounds, amide compounds One or more of compounds, alcoholamine compounds and polyamine compounds (referring to compounds with two or more amine groups), preferably alkylamine compounds; specific compounds can be selected from propylamine, butylamine, pentylamine Amine, hexylamine, tri-n-butylamine, triethylamine, tert-butylamine, dodecylamine, trioctylamine, hexadecylamine, N,N-dihydroxyethylaniline, acetanilide, diethanolamine, triethanolamine, diethanolamine Isopropanolamine, N,N-diethylhydroxylamine ethylenediamine, 1,2-cyclohexanediamine, 1,3-propanediamine, triethylenediamine, N,N-dimethyldipropylene One or more of triamine, triethylenetetramine and hexamethylenetetramine and derivatives of the above compounds (such as esters containing amino groups); the number of carbon atoms of the organic nitrogen compound (if the organic nitrogen compound is a simple substance, the number of carbon atoms refers to the specific number of carbon atoms in the organic nitrogen compound; if the organic nitrogen compound is a mixture, the number of carbon atoms refers to the range of the number of carbon atoms of all compounds in the mixture) can be 1-20, preferably 2 -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 oils, oxygen-containing derivatives of hydrocarbon oils and organic carboxylic acid esters, the hydrocarbon oils and hydrocarbons Oil oxygen-containing derivatives are preferably selected from one or more of alcohols, ethers and light end hydrocarbon oils, more preferably selected from ethanol, propanol, butanediol, diethyl ether, cyclohexane, n-heptane, n-decane , one or more of methylcyclopentane, naphtha, gasoline, kerosene, diesel oil, white oil, kerosene and lubricating oil base oil; the organic carboxylic acid ester is preferably selected from fatty acid glycerides, more preferably from corn One or more of oil, soybean oil, peanut oil, olive oil, and cottonseed oil. The number of carbon atoms of the organic solvent (if the organic solvent is a simple substance, the number of carbon atoms refers to the specific number of carbon atoms in the organic solvent; if the organic solvent is a mixture, the number of carbon atoms refers to the range of carbon atoms of all compounds in the mixture ) may be 2-35, preferably 2-15, more preferably 2-10.

According to the present invention, the loading is a catalyst preparation method well known to those skilled in the art, and the loading can be selected from one or more of the following ways: (1), impregnating the sulfurized hydrocracking catalyst in an organic solvent containing and (2), spraying the organic solution containing the organic solvent and the organic nitrogen compound into the sulfurized hydrocracking catalyst; (3), impregnating the sulfurized hydrocracking catalyst The organic solvent and organic nitrogen compound in the organic solution, and then evaporate the organic solvent, this method can make the nitride directly adsorb on the hydrocracking catalyst, in order to facilitate the evaporation, under normal pressure, the organic nitride The boiling point is higher than the boiling point of the organic solvent, for example, 20-200°C higher, wherein the evaporation temperature may be 10-150°C, preferably 20-90°C, and the absolute pressure may be 0.01-0.5MPa, preferably 0.03 -0.3MPa, the evaporation is preferably carried out in a rotary evaporator, in the form of rotary evaporation, the sulfurized hydrocracking catalyst is immersed in an excess of organic solution, and a certain temperature is set, so that the low-boiling organic solvent is preferentially heated and volatilized , and finally the high-boiling organic nitrides are adsorbed on the sulfurized hydrocracking catalyst; in modes (1)-(3), the impregnation or spray can be saturated impregnation, supersaturated impregnation or unsaturated impregnation, and the mode ( 1) is preferably saturated immersion, and mode (3) is preferably supersaturated immersion. The temperature of the dipping or spraying can be 10-100°C, preferably 20-80°C.

According to the present invention, the method may further comprise: performing the drying treatment after the nitrogen-supported catalyst is left to stand; wherein, the time of the standstill is 1-10 hours, preferably 2-4 hours , the temperature can be the same as the supported temperature or adjusted as needed, so as to improve the loading effect of the organic nitrogen compound on the catalyst.

According to the present invention, the drying treatment is used to remove the organic solvent and unadsorbed organic nitrogen-containing compounds under the condition that the properties of the sulfurized hydrocracking catalyst are not substantially changed. Preferably 50-180°C, more preferably 60-180°C, absolute pressure is 0.01-0.8MPa, preferably 0.03-0.6MPa, time is 1-8 hours, preferably 2-6 hours. The drying treatment can meet one or more of the following conditions: it is carried out in an inert atmosphere or an aerobic atmosphere with an oxygen content of 0.1-15% by volume, and the inert gas, as an equilibrium gas, can be selected from the group consisting of nitrogen, helium An atmosphere of one or more of gas and argon; the drying process is performed in a rotary heat treatment equipment or a stationary heat treatment equipment; the drying process is performed in a no-flow atmosphere, a natural-flow atmosphere or a forced-flow atmosphere.

The present invention also provides a passivation catalyst obtained by the provided method, which has weak cracking activity at a low temperature stage and strong cracking activity at a high temperature stage.

The following examples will further illustrate the method for ammonia passivation outside the sulfurized hydrocracking catalyst of the present invention.

In order to illustrate the characteristics of the present invention, the same batch of industrially produced Ni oxide content of 3.0 wt %, W oxide content of 27 wt %, Y-type molecular sieve content of 35 % and the balance of alumina are selected in both Examples and Comparative Examples. The commercial hydrocracking catalyst of this product, the sulfurized hydrocracking catalyst is prepared _on the basis of the same batch of oxidative hydrocracking catalyst. , In an atmosphere with a volume fraction of H ₂ of 98%, the temperature is raised to 230°C for 4 hours at a rate of 5°C/min, and then heated to a constant temperature of 320°C for 4 hours at a rate of 5°C/min.

Example 1

Take 200 g of oxidative hydrocracking catalyst, carry out sulfurization treatment outside the vessel, and convert it into a sulfurized hydrocracking catalyst for later use.

Take 100 g of sulfurized hydrocracking catalyst, add 21.4 g of diethanolamine to ethanol, and stir evenly at 30 °C to obtain a nitrogen-containing solution. Set for 3 hours to introduce nitrogen content of 2.35% by weight to obtain a nitrogen-supported catalyst; then dry at 100° C., normal pressure, and a flowing nitrogen atmosphere for 4 hours to prepare a passivation catalyst A.

The passivation catalyst A is loaded into the reactor to carry out the reaction, and when the temperature is raised to 100 °C, hydrogen and n-heptane raw materials are introduced, and the temperature is continued to be raised to 300 °C for 3 hours. After that, the temperature was raised to 320°C for 2 hours at a constant temperature, followed by 20°C and constant temperature for two hours each time until the end of the 380°C constant temperature. Reaction conditions: reaction pressure 4.0MPa, hydrogen oil volume ratio 1800, volume space velocity 3h ^-1 , and its hydrocracking activity (expressed in the form of conversion rate) is shown in Table 1.

Example 2

Take 100 g of the same sulfurized hydrocracking catalyst as in Example 1, add 11.1 g of tri-n-butylamine to diethyl ether, stir evenly at 30° C. to obtain a nitrogen-containing solution, and introduce the nitrogen-containing solution into the pore-saturated impregnation method. The sulfurized hydrocracking catalyst was allowed to stand for 3 hours to introduce a nitrogen content of 0.75% by weight to obtain a nitrogen-supported catalyst; and then dried for 4 hours at 90° C. under normal pressure and in a flowing nitrogen atmosphere to prepare a passivation catalyst B.

The passivation catalyst B was charged into the reactor to carry out the reaction, and the reaction conditions were the same as those in Example 1, and its hydrocracking activity (expressed in the form of conversion rate) was shown in Table 1.

Example 3

Take 100 g of the same sulfurized hydrocracking catalyst as in Example 1, add 25.0 g of tri-n-butylamine to diethyl ether, stir evenly at 30° C. to obtain a nitrogen-containing solution, and introduce the nitrogen-containing solution into the pore-saturated impregnation method. The sulfurized hydrocracking catalyst was allowed to stand for 3 hours to introduce a nitrogen content of 1.51% by weight to obtain a nitrogen-supported catalyst; and then dried for 4 hours at 90° C., under normal pressure, and in a flowing nitrogen atmosphere to prepare passivation catalyst C.

The passivation catalyst C was charged into the reactor to carry out the reaction, and the reaction conditions were the same as those in Example 1, and its hydrocracking activity (expressed in the form of conversion rate) was shown in Table 1.

Example 4

Take 100 g of the same sulfurized hydrocracking catalyst as in Example 1, add 11.1 g of N,N-diethylhydroxylamine ethylenediamine to ethanol, stir evenly at 30°C to obtain a nitrogen-containing solution, and impregnate it according to pore saturation. The nitrogen-containing solution was introduced into the sulfide-type hydrocracking catalyst and left to stand for 3 hours to introduce a nitrogen content of 2.70% by weight to obtain a nitrogen-supported catalyst; then dried at 100 ° C under normal pressure and a flowing nitrogen atmosphere After 4 hours, passivated catalyst D was prepared.

The passivation catalyst D was charged into the reactor to carry out the reaction, and the reaction conditions were the same as those in Example 1, and its hydrocracking activity (expressed in the form of conversion rate) was shown in Table 1.

Example 5

Take 100g of the same sulfurized hydrocracking catalyst as in Example 1, add 29.0g of diethanolamine to ethanol, stir evenly at room temperature, and obtain a nitrogen-containing solution, which will be equivalent to 2 times of the nitrogen-containing solution required for pore saturation impregnation. Put it in a rotary evaporation flask, and at the same time, put the sulfurized hydrocracking catalyst into the rotary flask, set the heating temperature of the rotary flask to 80 °C, and set the rotation speed to 30 r/min. After the organic solvent is completely evaporated, the sulfurized hydrocracking containing nitride is The catalyst was allowed to stand for 3 hours to introduce a nitrogen content of 3.0% by weight to obtain a nitrogen-supported catalyst; and then dried for 4 hours at 100° C. under normal pressure and a flowing nitrogen atmosphere to prepare a passivation catalyst E.

The passivation catalyst E was charged into the reactor for reaction, and the reaction conditions were the same as those in Example 1, and its hydrocracking activity (expressed in the form of conversion rate) was shown in Table 1.

Example 6

Take 100 g of the same sulfurized hydrocracking catalyst as in Example 1, add 15.2 g of tri-n-butylamine to diethyl ether, and stir evenly at room temperature to obtain a nitrogen-containing solution. The nitrogen solution is placed in a rotary evaporation flask, and the sulfurized hydrocracking catalyst is put into the rotary flask at the same time. The hydrogen cracking catalyst was allowed to stand for 3 hours to introduce a nitrogen content of 1.0% by weight to obtain a nitrogen-supported catalyst; and then dried for 4 hours at 90° C. under normal pressure in a flowing nitrogen atmosphere to prepare a passivation catalyst F.

The passivation catalyst F was charged into the reactor to carry out the reaction, and the reaction conditions were the same as those in Example 1, and its hydrocracking activity (expressed in the form of conversion rate) was shown in Table 1.

Example 7

Take 100 g of the same sulfurized hydrocracking catalyst as in Example 1, add 12.7 g of diethanolamine to ethanol, stir evenly at room temperature, and obtain a nitrogen-containing solution, which will be equivalent to 2 times of the nitrogen-containing solution required for pore saturation impregnation. Put it in a rotary evaporation flask, and at the same time, put the sulfurized hydrocracking catalyst into the rotary flask, set the heating temperature of the rotary flask to 80 °C, and set the rotation speed to 30 r/min. After the organic solvent is completely evaporated, the sulfurized hydrocracking containing nitride is The catalyst was allowed to stand for 3 hours to introduce a nitrogen content of 1.5% by weight to obtain a nitrogen-supported catalyst; and then dried for 4 hours at 100° C. under normal pressure in a flowing nitrogen atmosphere to prepare a passivation catalyst G.

The passivation catalyst G was charged into the reactor to carry out the reaction, and the reaction conditions were the same as those in Example 1, and its hydrocracking activity (expressed in the form of conversion rate) was shown in Table 1.

Example 8

Get 100g of the same sulfurized hydrocracking catalyst as in Example 1, add 24.7g of n-tributylamine solution to the ether solution, stir evenly at room temperature, and place the nitrogen-containing solution equivalent to 2 times the required solution amount for pore saturation impregnation in a rotating In the evaporating flask, put the sulfurized hydrocracking catalyst into the rotating flask at the same time, set the heating temperature of the rotating flask to 35 °C, and the rotation speed of 30 r/min. After 3 hours, the nitrogen content of 1.5 wt % was introduced, and then it was dried at 90° C., under normal pressure, and under a flowing nitrogen atmosphere for 4 hours, and the passivation catalyst H was prepared.

The passivation catalyst H was charged into the reactor, and the reaction conditions were the same as those in Example 1, and its hydrocracking activity (expressed in the form of conversion rate) was shown in Table 1.

Comparative Example 1

Take 100 g of the same sulfurized hydrocracking catalyst as in Example 1, add 20.0 g of N,N-diethylhydroxylamine ethylenediamine to ethanol, stir evenly at 30°C to obtain a nitrogen-containing solution, and impregnate it according to pore saturation. The nitrogen-containing solution was introduced into the sulfide-type hydrocracking catalyst and left to stand for 3 hours to introduce a nitrogen content of 4.49% by weight to obtain a nitrogen-supported catalyst; then dried at 100 ° C under normal pressure and a flowing nitrogen atmosphere After 4 hours, passivated catalyst I was prepared.

The passivation catalyst I was charged into the reactor to carry out the reaction, and the reaction conditions were the same as those in Example 1, and its hydrocracking activity (expressed in the form of conversion rate) was shown in Table 1.

Comparative Example 2

Take 100 g of the same sulfurized hydrocracking catalyst as in Example 1, add 17.4 g of N,N-diethylhydroxylamine ethylenediamine to ethanol, stir evenly at room temperature, and obtain a nitrogen-containing solution, which is equivalent to pore-saturated impregnation. The nitrogen-containing solution required to be twice the amount of the solution is placed in a rotary evaporation flask, and the sulfurized hydrocracking catalyst is placed in the rotary flask. The sulfide-type hydrocracking catalyst containing nitride was allowed to stand for 3 hours to introduce a nitrogen content of 4.0% by weight to obtain a nitrogen-supported catalyst; and then dried for 4 hours at 100° C. under normal pressure and in a flowing nitrogen atmosphere to prepare the Passivated catalyst J.

The passivation catalyst J was charged into the reactor to carry out the reaction, and the reaction conditions were the same as those in Example 1, and its hydrocracking activity (expressed in the form of conversion rate) was shown in Table 1.

Comparative Example 3

Take 100 g of the same sulfurized hydrocracking catalyst as in Example 1, and name it catalyst K.

The catalyst K was charged into the reactor to carry out the reaction, and the reaction conditions were the same as those in Example 1, and its hydrocracking activity (expressed in the form of conversion rate) was shown in Table 1.

Comparative Example 4

Take 100 g of the same sulfurized hydrocracking catalyst as in Example 1, add 21.4 g of diethanolamine to deionized water, stir evenly at 30 ° C to obtain a nitrogen-containing solution, and introduce the nitrogen-containing solution into sulfurized solution according to the method of pore saturation impregnation. Type hydrocracking catalyst was left standing for 3 hours to introduce a nitrogen content of 2.35% by weight, and then dried for 4 hours at 120° C. under normal pressure and in a flowing nitrogen atmosphere to prepare a sulfurized type with ammonia passivation outside the vessel. Hydrocracking catalyst L.

The catalyst L was charged into the reactor to carry out the reaction, and the reaction conditions were the same as those in Example 1, and its hydrocracking activity (expressed in the form of conversion rate) was shown in Table 1.

Comparative Example 5

Get the oxidative hydrocracking catalyst (named as catalyst M) and load it into the reactor and carry out the reaction, utilize carbon disulfide to carry out in-vessel sulfurization treatment, and the step of sulfurization treatment is: with the cyclohexane containing 5% by weight of carbon disulfide as sulfurized oil, sulfurization The process pressure is 4.0MPa, the volume ratio of hydrogen to oil is 1800, the volumetric space velocity is 6h ^-1 , the temperature is raised at 10°C/min to 230°C for 2 hours, and then heated to 320°C at 10°C/min for 2 hours. The heptane raw material was adjusted to 300°C for 3 hours, and the product composition was analyzed online to calculate the n-heptane cracking conversion rate. Constant temperature ends. Reaction conditions: reaction pressure 4.0MPa, hydrogen oil volume ratio 1800, volume space velocity 3h ^-1 , and its hydrocracking activity (expressed in the form of conversion rate) is shown in Table 1.

It can be seen from the above examples that the most important feature of the ammonia passivation method outside the sulfurized hydrocracking catalyst is that it has a good passivation effect on the basis of not affecting the hydrogenation activity, and the corresponding organic nitrides are targeted. It is separately introduced into the sulfurized hydrocracking catalyst to weaken the cracking activity of the hydrocracking catalyst in the low temperature stage (300-360 ℃), and at the same time, it reduces the waste of passivation agent during the start-up process, and avoids the poisoning of the passivator during the start-up process. It is a safety hazard, and the catalyst does not need to be vulcanized and passivated during the start-up process. It can directly enter the oil to start the operation, and enter a stable production state in a short time, saving a lot of time. It is time-saving, labor-saving, safe and environmentally friendly. Features.

The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details of the above-mentioned embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the specific technical features described in the above-mentioned specific embodiments can be combined in any suitable manner unless they are inconsistent. In order to avoid unnecessary repetition, the present invention provides The combination method will not be specified otherwise.

In addition, the various embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the spirit of the present invention, they should also be regarded as the content of the present invention.

Table 1

Claims (13)

1. an ammonia passivation method outside a sulfurized hydrocracking catalyst, the method comprising: The organic nitrogen compound is supported on a sulfurized hydrocracking catalyst in the presence of an organic solvent to obtain a nitrogen-supported catalyst; wherein the nitrogen content on the nitrogen-supported catalyst in terms of elements accounts for 0.1-3.6 by weight of the nitrogen-supported catalyst %; The obtained nitrogen-supported catalyst is subjected to drying treatment to obtain a passivation catalyst; wherein, the drying treatment conditions include: a temperature of 30-200° C., an absolute pressure of 0.01-1 MPa, and a time of 0.5-10 hours. 2. The method of claim 1, wherein the sulfided hydrocracking catalyst comprises a cracking component, a hydrogenation component and a support, the cracking component being based on the weight of the sulfided hydrocracking catalyst The content of the carrier is 10-60% by weight, and the content of the carrier is 30-70% by weight. 3. The method according to claim 2, wherein the cracking components comprise amorphous acidic components and/or molecular sieves, and the amorphous acidic components comprise amorphous silica-alumina and/or amorphous silica-magnesium, so The molecular sieve is selected from one or more of Y-type molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesoporous molecular sieve; The hydrogenation component includes an active metal, the active metal includes a Group VIII metal and a Group VIB metal, the Group VIII metal is Co and/or Ni, and the Group VIB metal is Mo and/or W ; Based on the weight of the sulfurized hydrocracking catalyst, the content of the Group VIII metal in terms of oxides is 1-15% by weight, and the content of Group VIB metals in terms of oxides is 5-30% by weight; The carrier is selected from one or more of alumina, silica, titania, magnesia and zirconia. 4. The method of claim 3, wherein the active metal in the sulfided hydrocracking catalyst is present in the form of metal sulfides. 5. The method according to claim 1, wherein the organic nitrogen compound is selected from the group consisting of alkylamine compounds, arylamine compounds, aniline compounds, methylaniline compounds, amide compounds, alcoholamine compounds and one or more of polyamine compounds; preferably selected from propylamine, butylamine, pentylamine, hexylamine, tri-n-butylamine, triethylamine, tert-butylamine, dodecylamine, trioctylamine, hexadecylamine , N,N-dihydroxyethylaniline, acetanilide, diethanolamine, triethanolamine, diisopropanolamine, N,N-diethylhydroxylamine ethylenediamine, 1,2-cyclohexanediamine, 1,3 - one or more of propylenediamine, triethylenediamine, N,N-dimethyldipropylenetriamine, triethylenetetramine and hexamethylenetetramine and derivatives of the above compounds; The organic solvent is selected from one or more of hydrocarbon oils, hydrocarbon oil oxygen-containing derivatives and organic carboxylic acid esters, and the hydrocarbon oils and hydrocarbon oil oxygen-containing derivatives are preferably selected from alcohols, ethers and light end hydrocarbons One or more of oil, more preferably selected from ethanol, propanol, butanediol, diethyl ether, cyclohexane, n-heptane, n-decane, methylcyclopentane, naphtha, gasoline, kerosene, diesel , one or more of white oil, kerosene and lubricating oil base oils; The organic carboxylic acid ester is preferably selected from fatty acid glycerides, more preferably selected from one or more of corn oil, soybean oil, peanut oil, olive oil and cottonseed oil. 6. The method according to claim 1 or 5, wherein the number of carbon atoms of the organic nitrogen compound is 1-20, preferably 2-15; The number of carbon atoms of the organic solvent is 2-35, preferably 2-15, more preferably 2-10. 7. The method of claim 1, wherein the load is selected from one or more of the following: (1), impregnating the sulfurized hydrocracking catalyst in the organic solution containing organic solvent and organic nitrogen compound; (2), the organic solution containing organic solvent and organic nitrogen compound is sprayed in the described sulfurized hydrocracking catalyst; (3), immersing the sulfurized 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° C., preferably 20-90° C. ℃, 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 the modes (1)-(3), the dipping or spraying is saturated dipping, supersaturated dipping or unsaturated dipping, and the temperature of the dipping or spraying is 10-100°C, preferably 20-80°C. The method according to claim 1 or 7, wherein, under normal pressure, the boiling point of the organic nitride is 20-200°C higher than the boiling point of the organic solvent. 9 . The method according to claim 1 , further comprising: performing the drying treatment after the nitrogen-supported catalyst is subjected to a standing treatment; wherein, the period of the standing treatment is 1-10 hours. 10 . , preferably 2-4 hours. 10. The method according to claim 1, wherein the nitrogen content on the nitrogen-supported catalyst as an element is 0.1-3% by weight, preferably 0.5-3% by weight, based on the weight of the nitrogen-supported catalyst. 11. The method according to claim 1, wherein the conditions of the drying treatment include: the temperature is 40-200°C, preferably 60-180°C, the absolute pressure is 0.01-0.8MPa, preferably 0.03-0.6MPa, and the time is 1-8 hours, preferably 2-6 hours. 12. The method of claim 1, wherein the drying process satisfies one or more of the following conditions: Carry out in an inert atmosphere or an oxygen atmosphere with an oxygen content of 0.1-15% by volume, the inert atmosphere is selected from an atmosphere containing 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 process is performed in a no-flow atmosphere, a natural-flow atmosphere, or a forced-flow atmosphere. 13. The passivated catalyst obtained by the method of any one of claims 1-12.