CN112742478B

CN112742478B - Preparation method of hydrogenation catalyst, hydrogenation catalyst and application thereof

Info

Publication number: CN112742478B
Application number: CN201911047233.6A
Authority: CN
Inventors: 王红; 申海平; 王翠红; 佘玉成
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: 2019-10-30
Filing date: 2019-10-30
Publication date: 2022-07-12
Anticipated expiration: 2039-10-30
Also published as: CN112742478A

Abstract

The present disclosure relates to a preparation method of a hydrogenation catalyst, a hydrogenation catalyst and an application thereof, wherein the catalyst contains an organic molybdenum compound and an organic iron salt, and the organic molybdenum compound has a structure shown in formula (1):

formula (1), wherein a + b is 2, 3, 4, 5 or 6, m + n is 0, 1, 2, 3, 4, 5 or 6, R₁Is C1-C6 oxygen-containing organic acid radical, R₂Is C6-C18 oxygen-containing organic acid radical. The catalyst disclosed by the invention has high metal content, low cost and good hydrogenation performance, ring opening activity and denitrification effect.

Description

Preparation method of hydrogenation catalyst, hydrogenation catalyst and application thereof

Technical Field

The disclosure relates to a preparation method of a hydrogenation catalyst, the hydrogenation catalyst and application thereof.

Background

From the general trend of international oil price, the higher one-time investment and processing cost of the hydrogenation process are no longer outstanding problems in the process of heavy oil conversion, and the hydrogenation technical route is more and more widely applied because of the advantages of high yield of high-quality liquid products, high return on investment and the like. The slurry bed has strong adaptability to the raw materials, can process various inferior raw materials with high metal and high carbon residue value, has the advantages of high residual oil conversion rate, flexible process operation and the like, and has better development prospect.

The slurry bed residual oil hydrogenation technology is that after dispersed catalyst and material oil are mixed fully, the mixture enters from the bottom of the slurry bed reactor and is hydrocracked with hydrogen at high temperature and high pressure, the reaction product is separated from the top of the reactor and further processed into product, and a small amount of residue is thrown away. Slurry bed residue oil hydrogenation generally adopts a dispersive catalyst, and because the dispersion degree of a precursor of the dispersive catalyst in heavy oil is very high, the catalyst precursor can be heated to form suspended sulfides under certain hydrogen pressure after the catalyst precursor is mixed with the residue oil. The catalyst has small particle size, high dispersity and strong hydrogen activation capacity, and macromolecules such as asphaltene and colloid can directly contact with the active center on the surface of the catalyst to react. Slurry bed residual oil hydrogenation catalysts are classified into inorganic powder catalysts, water-soluble catalysts and oil-soluble catalysts according to solubility and state. The most important advantage of using the solid powder catalyst is that the operation process allows coke formation, so that the operation can be performed at a higher reaction temperature to obtain a higher conversion rate of light oil, and the coke is adhered to the catalyst particles and discharged together, and the disadvantage is that the hydrogenation activity is low, so that the addition amount in the reaction process is large. The tail oil is difficult to utilize and process; in addition, the equipment is heavily worn.

The water-soluble catalyst is relatively low in price, but the water-soluble catalyst is difficult to highly disperse or completely vulcanize in a residual oil system due to complex dispersion operation in the links of emulsification dispersion, vulcanization and emulsion breaking in the using process, so that the activity of the catalyst is greatly influenced, and the energy consumption is high.

Compared with water-soluble catalysts, the oil-soluble catalyst containing the same metal elements has the characteristics of high hydrogenation activity, good coke inhibition performance, low solid content in tailings, easy treatment and the like.

The type of the active metal of the oil-soluble catalyst is a key factor influencing the hydrogenation coke inhibition performance. The active metal of the existing hydrogenation catalyst can be transition metal of IVB, VB, VIB, VIIB and VIII groups, and is commonly used Mo, Ni, V, Fe and the like, wherein the molybdenum-based catalyst has better hydrogenation activity and coke inhibition performance, high dispersity, large specific surface area, high probability of contact of active sites and reaction molecules, good hydrogenation coke inhibition effect and molybdenum-based catalysisAfter being pre-vulcanized, the catalyst can be decomposed into unsupported MoS in the form of nano-scale thin layer in situ₂Active centers of the catalyst are uniformly dispersed in the raw oil, and the hydrogenation active centers are directly exposed on the surface of the catalyst to contact with hydrogen to react, so that MoS₂The distance between the thin layers and the distance between oil molecules are smaller than that of the supported catalyst by several orders of magnitude, so that the hydrogenation reaction activity of the catalyst is greatly improved, and the coking reaction is inhibited.

At present, the global petrochemical industry has increasingly strict requirements on sulfur and phosphorus-containing elements of products, so that the development of a cheap, efficient and environment-friendly sulfur and phosphorus-free compound catalyst has great significance for the development of slurry beds.

Disclosure of Invention

The purpose of the disclosure is to provide a preparation method of a hydrogenation catalyst, the hydrogenation catalyst and application thereof, wherein the catalyst is low in cost and has good catalytic performance.

In order to achieve the above object, a first aspect of the present disclosure provides a hydrogenation catalyst comprising an organomolybdenum compound and an organic iron salt, the organomolybdenum compound having a structure represented by formula (1):

wherein a + b is 2, 3, 4, 5 or 6, m + n is 0, 1, 2, 3, 4, 5 or 6, R₁Is C1-C6 oxygen-containing organic acid radical, R₂Is C6-C18 oxygen-containing organic acid radical.

Alternatively, a and b are equal, and a + b is 2, 4 or 6; m is equal to n, and m + n is 0, 2 or 4.

Optionally, the C1-C6 oxygen-containing organic acid radical is a monocarboxylate, a dicarboxylates or a multi-carboxylate, preferably a dicarboxylates or a multi-carboxylate; the C6-C18 oxygen-containing organic acid radical is a monocarboxylate, a dicarboxylates, a polybasic carboxylate, a thiocarboxylate, a sulfonate or a sulfinate, and is preferably a monocarboxylate, a dicarboxylate or a sulfonate.

Optionally, in the catalyst, the molar ratio of the iron element in the organic iron salt to the molybdenum element in the organic molybdenum compound is (0.01-1.5): 1.

optionally, in the catalyst, a molar ratio of the iron element in the organo iron salt to the molybdenum element in the organo molybdenum compound is (0.2-0.7): 1.

optionally, the C1-C6 oxygen-containing organic acid group is selected from formate, acetate, propionate, 2-methylbutyrate, hydroxyacetate, isobutyrate, valerate, ethanedioate, malonate, succinate, glutarate, 2-hydroxysuccinate, 3-hydroxypropanetricarboxylate, or citrate.

Optionally, the C6-C18 oxygen containing organic acid radical is selected from the group consisting of hexanoate, heptanoate, 2-propyl heptanoate, octanoate, 2-ethylhexanoate, nonanoate, decanoate, oleate, palmitate, stearate, and naphthenate having 6-18 carbon atoms.

Optionally, the anion of the organic iron salt is a C6-C18 oxygen-containing organic acid radical; preferably, the organic iron salt is selected from one or more of iron oleate, iron 2-ethylhexanoate and iron dodecyl benzene sulfonate.

Optionally, the catalyst further contains a third metal organic salt, and the third metal organic salt contains at least one metal element in VIB group and VIII group; preferably, the third metal organic salt is an organic nickel salt and/or an organic cobalt salt.

Optionally, in the catalyst, the content of the organic molybdenum compound in terms of molybdenum element and the organic salt of the third metal in terms of third metal element is in a molar ratio of 1: (0.01-1).

Optionally, the anion of the third metal organic salt is a C6-C18 oxygen containing organic acid radical; preferably, the third metal organic salt is selected from one or more of nickel naphthenate, nickel oleate, nickel 2-ethyl hexanoate, nickel stearate, cobalt naphthenate, cobalt oleate, cobalt 2-ethyl hexanoate and cobalt stearate.

A second aspect of the present disclosure provides a method of preparing a dehydrogenation catalyst, the method comprising:

(1) mixing a molybdenum source, a solvent and C1-C6 oxygen-containing organic acid, reacting at 20-150 ℃ to obtain a reaction mixture, and adjusting the pH value of the reaction mixture to 2.5-5 to obtain a first product;

(2) mixing the first product with a first organic acid and reacting at 145-300 ℃, and performing first separation and purification on the obtained product to obtain an organic molybdenum compound;

(3) reacting a second organic acid with a solution of alkali at 40-90 ℃, mixing the obtained mixed solution with an iron source, reacting at 30-110 ℃, and carrying out second separation and purification on the obtained product to obtain an organic iron salt;

(4) mixing the organomolybdenum compound with the ferric organometal salt; wherein the first organic acid and the second organic acid are each independently selected from one of C6-C18 oxygen-containing organic acids.

Optionally, in the step (1), the weight ratio of the molybdenum source to the solvent is 1: (1-20); the molar ratio of the molybdenum source to the C1-C6 oxygen-containing organic acid calculated by molybdenum element is 1: (0.5-4).

The molar ratio of the molybdenum source to the first organic acid in the step (2) is 1: (1-10).

Optionally, in the step (3), the molar ratio of the iron source, the second organic acid and the base in terms of iron element is 1: (2-7): (2-4).

Optionally, in the step (4), the molar ratio of the organic iron salt calculated by iron element to the organic molybdenum compound calculated by molybdenum element is (0.1-1.5): 1.

optionally, the reaction time in step (1) is 0.3-9 hours;

the reaction time in the step (2) is 1-12 hours;

the step (3) comprises the following steps: dropwise adding the alkali solution into the second organic acid at 40-90 ℃, reacting for 0.5-2 hours, adding the iron source into the mixed solution within 0.2-30min, and continuously reacting for 0.5-4.0 hours at 30-100 ℃;

in the step (4), the mixing temperature is 25-100 ℃, and the mixing time is 0.1-2 hours.

Optionally, the solvent is selected from water and/or an organic solvent; the organic solvent is selected from benzene, toluene, ethanol or petroleum ether;

the C1-C6 oxygen-containing organic acid is selected from formic acid, acetic acid, propionic acid, 2-methyl butyric acid, glycolic acid, isobutyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 2-hydroxysuccinic acid, 3-hydroxypropanetricarboxylic acid or citric acid;

the first organic acid and the second organic acid are each independently selected from caproic acid, heptanoic acid, 2-propylheptanoic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, oleic acid, palmitic acid, stearic acid, or naphthenic acid having 6 to 18 carbon atoms;

the alkali is selected from sodium carbonate, sodium bicarbonate or sodium hydroxide.

Optionally, the molybdenum source is selected from one or more of molybdic acid, ammonium molybdate, ammonium paramolybdate and molybdenum trioxide;

the iron source is selected from one or more of ferric oxide, ferric sulfate, ferrous sulfate and iron halide.

Optionally, the method further comprises, at least one of steps (1) - (4) is performed in an inert atmosphere.

Optionally, step (4) comprises: mixing the organomolybdenum compound, the organic iron salt, and the third metal organic salt;

the third metal organic salt contains at least one metal element in VIB group and VIII group;

preferably, the third metal organic salt is an organic nickel salt and/or an organic cobalt salt;

in the catalyst, the content of the organic molybdenum compound calculated by molybdenum element and the third metal organic salt calculated by third metal element has a molar ratio of 1: (0.01-1);

the anion of the third metal organic salt is C6-C18 oxygen-containing organic acid radical; preferably, the third metal organic salt is selected from one or more of nickel naphthenate, nickel oleate, nickel 2-ethyl hexanoate, nickel stearate, cobalt naphthenate, cobalt oleate, cobalt 2-ethyl hexanoate and cobalt stearate.

In a third aspect of the present disclosure, a hydrogenation catalyst prepared by the method provided in the second aspect of the present disclosure is provided.

A fourth aspect of the present disclosure provides a process for hydrogenating residuum or coal, the process comprising: contacting the residuum or coal with a catalyst provided by the first aspect of the disclosure or the third aspect of the disclosure under conditions of a residuum or coal hydrogenation reaction.

Through the technical scheme, the catalyst disclosed by the invention contains the organic molybdenum compound and the organic iron salt, and has low cost while ensuring good hydrogenation performance, ring-opening activity and selectivity. The method disclosed by the invention is simple in preparation process and low in cost, and can be used for preparing the catalyst with good catalytic performance.

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

Detailed Description

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

In a first aspect of the present disclosure, there is provided a hydrogenation catalyst comprising an organomolybdenum compound and an organic iron salt, the organomolybdenum compound having a structure represented by formula (1):

wherein m + n is 0, 1, 2, 3, 4, 5 or 6, a + b is 2, 3, 4, 5 or 6, R₁Is C1-C6 oxygen-containing organic acid radical, R₂Is C6-C18 oxygen-containing organic acid radical. Wherein the C1-C6 oxygen-containing organic acid radical refers to anion or atomic group of oxygen-containing organic acid with 1-6 carbon atoms after losing hydrogen ions, and the C6-C18 oxygen-containing organic acid radical refers to anion or atomic group of oxygen-containing organic acid with 6-18 carbon atoms after losing hydrogen ions.

According to the disclosure, the catalyst contains the organic molybdenum compound and the organic iron salt, and the active sites of the organic molybdenum compound and the organic iron salt have a synergistic effect, so that the catalyst has better dispersion performance and lower cost, and meanwhile, the catalyst can keep good hydrogenation capacity, ring-opening activity and selectivity, and can effectively reduce the cost of the slurry bed catalyst.

According to the disclosure, the values of m and n can be the same or different, and when the values of m and n are the same, the number of the C1-C6 oxygen-containing organic acid radicals connected to two Mo atoms is the same; when the values of m and n are different, the number of the C1-C6 oxygen-containing organic acid radicals connected to two Mo atoms is different. Preferably, m and n have the same value, and m + n is 0, 2 or 4. The values of a and b can be the same or different, and when the values of a and b are the same, the number of the C6-C18 oxygen-containing organic acid radicals connected to two Mo atoms is the same; when the values of a and b are different, the number of the C6-C18 oxygen-containing organic acid radicals connected to two Mo atoms is different. Preferably, a and b have the same value, and a + b is 2, 4 or 6.

According to the present disclosure, the molar ratio of the iron element in the organic iron salt to the molybdenum element in the organic molybdenum compound in the catalyst may vary within a wide range, preferably (0.01-1.5): 1, more preferably (0.05-1.3): 1, more preferably (0.2 to 0.7): 1. within the above range, the hydrogenation ability, ring-opening activity and selectivity of the catalyst can be further improved.

In the organomolybdenum compounds according to the present disclosure, the C1-C6 oxygen-containing organic acid group means an anion or an atomic group obtained by dehydrogenation of an oxygen-containing organic acid having 1 to 6 carbon atoms, and may be, for example, 2-methylbutyrate obtained by dehydrogenation of 2-methylbutyrate, 2-hydroxysuccinate obtained by dehydrogenation of 2-hydroxysuccinate, formate obtained by dehydrogenation of formate, acetate obtained by dehydrogenation of acetate, or propionate obtained by dehydrogenation of propionate. The C1-C6 oxygen-containing organic acid radical can be a monocarboxylate radical, dicarboxylic acid or a polybasic carboxylate radical with 1-6 carbon atoms, and is preferably a dicarboxylic acid radical or a polybasic carboxylate radical.

In a preferred embodiment, the C1-C6 oxygen-containing organic acid radical may be selected from formate, acetate, propionate, 2-methylbutyrate, hydroxyacetate, isobutyrate, valerate, oxalate, malonate, succinate, glutarate, 2-hydroxysuccinate, 3-hydroxypropanetricarboxylate, or citrate.

According to the present disclosure, in the organomolybdenum compounds, the C6-C18 oxygen-containing organic acid group refers to an anion or an atomic group obtained by removing hydrogen from an oxygen-containing organic acid having 6 to 18 carbon atoms. For example, it may be a 2-propylheptanoate obtained by dehydrogenation of 2-propylheptanoic acid, a 2-ethylhexanoate obtained by dehydrogenation of 2-ethylhexanoic acid, an octanoate obtained by dehydrogenation of octanoic acid, a hexanoate obtained by dehydrogenation of hexanoic acid or a heptanoate obtained by dehydrogenation of heptanoic acid. The C6-C18 oxygen-containing organic acid radical can be a monocarboxylic acid radical, a dicarboxylic acid radical, a polycarboxylic acid radical, a thiocarboxylate radical, a sulfonate radical or a sulfinate radical with 6-18 carbon atoms, and is preferably a monocarboxylic acid radical, a dicarboxylic acid radical or a sulfonate radical.

In a preferred embodiment, the C6-C18 oxygen-containing organic acid radical may be selected from the group consisting of hexanoate, heptanoate, 2-propyl heptanoate, octanoate, 2-ethylhexanoate, nonanoate, decanoate, oleate, palmitate, stearate, and naphthenates having 6-18 carbon atoms.

In accordance with the present disclosure, the organic iron salt may be well known to those skilled in the art, and the anion of the organic iron salt is preferably a C6-C18 oxygen-containing organic acid radical, and the C6-C18 oxygen-containing organic acid radical may be a monocarboxylic acid radical, a dicarboxylic acid radical, or a polycarboxylic acid radical having 6-18 carbon atoms. In a preferred embodiment, the C6-C18 oxygen-containing organic acid radical contained in the organic iron salt may be selected from the group consisting of hexanoate, heptanoate, 2-propylheptanoate, octanoate, 2-ethylhexanoate, nonanoate, decanoate, adipate, ethylenediaminetetraacetate, and phenylacetate.

In one embodiment, the organic iron salt may be one or more selected from iron oleate, iron 2-ethylhexanoate and iron dodecyl benzene sulfonate, preferably iron oleate and iron 2-ethylhexanoate.

According to the disclosure, the catalyst may further contain a third metal organic salt, and the third metal organic salt may contain at least one metal element in group VIB and group VIII; preferably, the third metal organic salt is an organic nickel salt and/or an organic cobalt salt. The catalyst has good hydrogenation performance, and the cost of the catalyst is further reduced.

According to the present disclosure, the molar ratio of the contents of the organomolybdenum compound calculated as molybdenum element and the third metal organic salt calculated as the third metal element in the catalyst may vary within a wide range, and is preferably 1: (0.01-1), more preferably 1: (0.05-0.5).

According to the present disclosure, the anion of the third metal organic salt may be a C6-C18 oxygen-containing organic acid group, such as a naphthenate, oleate, palmitate, stearate having 6-18 carbon atoms; preferably, the third metal organic salt is selected from one or more of nickel naphthenate, nickel oleate, nickel 2-ethyl hexanoate, nickel stearate, cobalt naphthenate, cobalt oleate, cobalt 2-ethyl hexanoate and cobalt stearate.

A second aspect of the present disclosure provides a method of preparing a hydrogenation catalyst, the method comprising:

(2) mixing the first product with a first organic acid and reacting at 160-320 ℃, and carrying out first separation and purification on the obtained product to obtain an organic molybdenum compound;

(4) mixing an organic molybdenum compound with an organic iron salt; wherein the first organic acid and the second organic acid are respectively and independently selected from one of C6-C18 oxygen-containing organic acids.

The method disclosed by the invention can be used for preparing the catalyst with good hydrogenation capacity, ring-opening activity and selectivity, and is simple in preparation process and low in synthesis cost.

According to the present disclosure, the weight ratio of the molybdenum source to the solvent in the molybdenum element in the step (1) may be 1: (1-20), preferably 1: (1.5-15). The molar ratio of the molybdenum source to the C1-C6 oxygen-containing organic acid calculated by molybdenum element can be 1: (0.5-4), preferably 1: (0.7-3). Preferably, the pH of the reaction mixture is adjusted to a value of 2.5 to 4.5.

According to the present disclosure, the molar ratio of the molybdenum source to the first organic acid in step (2) may be 1: (1-10), preferably 1: (1.5-9).

According to the present disclosure, in the step (3), the molar ratio of the iron source, the second organic acid and the base may be 1: (2-7): (2-4), preferably 1: (2.5-6.5): (2.2-3.5).

According to the present disclosure, in the step (4), the molar ratio of the organic molybdenum compound calculated as molybdenum element to the organic iron salt calculated as iron element may be (0.1 to 1.5): 1, preferably (0.15-1.3): 1.

in one embodiment, step (1) may comprise: the molybdenum source, solvent and C1-C6 oxygen-containing organic acid are mixed and reacted at 20-150 deg.C for 0.3-9 hours, preferably 30-130 deg.C for 0.5-8 hours.

In one embodiment, step (2) may include: the first product is mixed with the first organic acid and reacted at 145-300 ℃ for 1-12 hours, preferably, at 150-260 ℃ for 2-10 hours.

In one embodiment, step (3) may include: dripping alkali solution into the second organic acid at 40-90 deg.C, reacting for 0.5-2 hr, adding iron source into the mixed solution within 0.2-30min, and reacting at 30-100 deg.C for 0.5-4 hr.

In one embodiment, in step (4), the mixing temperature may be 25 to 100 ℃ and the mixing time may be 0.1 to 2 hours, preferably, the mixing temperature is 30 to 60 ℃ and the mixing time is 0.15 to 0.6 hours.

According to the present disclosure, the solvent may be selected from water and/or organic solvents, wherein the organic solvents may be well known to those skilled in the art, such as benzene, toluene, ethanol or petroleum ether.

According to the present disclosure, in the step (1), the C1-C6 oxygen-containing organic acid may be a monocarboxylic acid, a dicarboxylic acid or a polycarboxylic acid having 1 to 6 carbon atoms. In a preferred embodiment, in step (1), the C1-C6 oxygen-containing organic acid may be selected from formic acid, acetic acid, propionic acid, 2-methylbutyric acid, glycolic acid, isobutyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 2-hydroxysuccinic acid, 3-hydroxypropanetricarboxylic acid or citric acid.

According to the present disclosure, in the step (2), the first organic acid may be a monocarboxylic acid, a dicarboxylic acid or a polycarboxylic acid having 6 to 18 carbon atoms. In a preferred embodiment, in step (2), the first organic acid may be selected from the group consisting of hexanoic acid, heptanoic acid, 2-propylheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, oleic acid, palmitic acid, stearic acid, and naphthenic acid having 6 to 18 carbon atoms.

According to the present disclosure, in the step (3), the second organic acid may be a monocarboxylic acid, a dicarboxylic acid or a tricarboxylic acid having 6 to 18 carbon atoms. In a preferred embodiment, in step (3), the second organic acid may be selected from the group consisting of hexanoic acid, heptanoic acid, 2-propylheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, oleic acid, palmitic acid, stearic acid, and naphthenic acid having 6 to 18 carbon atoms.

Bases, according to the present disclosure, may be well known to those skilled in the art, for example selected from sodium carbonate, sodium bicarbonate, or sodium hydroxide.

In accordance with the present disclosure, the molybdenum source and the iron source may be conventionally employed by those skilled in the art, for example, one or more selected from molybdic acid, ammonium molybdate, ammonium paramolybdate and molybdenum trioxide, and the iron source may be one or more selected from iron oxide, iron sulfate, ferrous sulfate and iron halide.

According to the present disclosure, the first separation and purification may include removing a solvent phase of a product obtained by reacting the C6-C18 oxygen-containing organic acid with the first product, and optionally, may include subjecting an oil phase to water washing and distillation under reduced pressure; the second separation and purification can comprise adding an extracting agent into the product obtained by the reaction of the mixed solution of the step (3) and the iron source for extraction and removing a solvent phase, and optionally can comprise water washing of the oil phase and reduced pressure distillation. The removal of the oil phase by washing with water, the removal of light components by distillation under reduced pressure, the extraction of the organic phase, the removal of the solvent phase, washing with water, distillation under reduced pressure and extraction are well known to the person skilled in the art and will not be described further here.

According to the present disclosure, the method may further include that at least one of the step (1) to the step (4) may be performed in an inert atmosphere. The inert gas atmosphere may be a nitrogen gas atmosphere or an inert gas atmosphere, and the inert gas may be argon and/or helium.

According to the present disclosure, the step (4) may include: mixing an organomolybdenum compound, an organic iron salt, and the third metal organic salt. The third metal organic salt may contain at least one metal element from group VIB and group VIII; preferably, the third metal organic salt is an organic nickel salt and/or an organic cobalt salt.

According to the present disclosure, the molar ratio of the contents of the organomolybdenum compound in terms of molybdenum element and the third metal organic salt in terms of the third metal element in the catalyst may vary within a wide range, and is preferably 1: (0.01-1).

According to the present disclosure, the anion of the third metal organic salt may be a C6-C18 oxygen containing organic acid group. Preferably, the third metal organic salt may be one or more selected from nickel naphthenate, nickel oleate, nickel 2-ethylhexanoate, nickel stearate, cobalt naphthenate, cobalt oleate, cobalt 2-ethylhexanoate, and cobalt stearate.

In one embodiment, to make the reaction more complete, the method may further comprise: adding an accelerant into the steps (1) to (4), wherein the accelerant is one or more selected from water, diethyl ether, benzene, toluene and chloroform. The added promoter can be removed after the end of the reaction by methods conventionally employed by those skilled in the art, and can be removed, for example, under atmospheric or reduced pressure.

In a fourth aspect of the present disclosure, there is provided a process for hydrogenating a residue, the process comprising: contacting a residuum under residuum hydrogenation reaction conditions with a catalyst provided by the first or third aspect of the disclosure.

A fifth aspect of the present disclosure provides a method of hydrogenating coal, the method comprising: contacting coal with a catalyst provided in the first or third aspect of the disclosure under conditions for a coal hydrogenation reaction.

In one embodiment, the method further comprises: the hydrogenation catalyst is subjected to a sulfurization treatment, which may be conventional in the art, for example, by contacting the catalyst, elemental sulfur and residual oil under the conditions of residual oil hydrogenation. The reaction conditions for residuum hydrogenation may be conventional in the art, and the present disclosure is not particularly limited.

The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.

The chemical reagents used in the examples and comparative examples of the present disclosure are products of national pharmaceutical group chemical reagents ltd, and the properties of the residual oil feedstock used in the examples and comparative examples are shown in table 1.

The content of insoluble substances in the oil phase of the organic molybdenum compound is measured by a filtration method.

Analysis of the metal content was determined according to the ICP-other method on a PerkinElmer NexION300X inductively coupled plasma emission spectrometer.

The infrared spectrum was tested on a model Nicolet6700 fourier infrared spectrometer.

The relative molecular mass of the organomolybdenum compound was determined by mass spectrometry.

Examples 1-2 and comparative examples 1-2 are examples of the preparation of organic molybdenum compounds.

Example 1

(1) Dispersing ammonium molybdate tetrahydrate and water in a flask, wherein the weight ratio of the ammonium molybdate tetrahydrate to the water is 1: 15. purging with inert gas, adding 3-hydroxypropanetricarboxylic acid at the temperature of 90 ℃ for reaction for 5 hours, wherein the molar ratio of the 3-hydroxypropanetricarboxylic acid to the tetrahydrate molybdate amine (calculated as molybdenum element) is 3: 1; after the reaction is finished, the pH value of the solution is adjusted to 3 by using dilute ammonia water to obtain a first product.

(2) Adding preheated hexanoic acid into the solution according to the molar ratio of amine molybdate tetrahydrate (calculated by molybdenum element) to the hexanoic acid being 1: 8, mixing, preheating caproic acid at 100 ℃, reacting at 195 ℃ for 10 hours after mixing, and separating the solvent after the reaction is finished to obtain an organic molybdenum compound A1 with the relative molecular mass of 865. The oil phase insoluble content of the obtained organomolybdenum compound is shown in table 1.

Analyzing the metal content of the product by inductively coupled plasma emission spectrometry (GB/T17476)) The content of metallic molybdenum was 22.2% by weight. And (3) testing the structure of the organic molybdenum compound by adopting an infrared spectrum, wherein the infrared spectrum is as follows: gamma 2961cm^-1、1532cm^-1、1454cm^-1、1423cm^-1、987cm^-1、773cm^-1、735cm^-1。

As can be seen from the infrared spectrum data, 690 and 790cm^-1An absorption peak ascribed to Mo-O-Mo appears nearby, and the absorption peak is 2961cm^-1，1454cm^-1Are each CH on an organic acid alkyl group₃Has a C-H bond antisymmetric stretching vibration and antisymmetric deformation vibration peak of 1532cm^-1、1423cm^-1Respectively shows the asymmetric stretching vibration and the symmetric stretching vibration peak of the coordinated carboxyl, which shows that the organic molybdenum compound A1 has a binuclear molybdenum structure shown in formula (1).

And (3) measuring overflowing components and relative contents in the thermal decomposition products at different temperatures by using gas chromatography. Washing the reaction product with 80 deg.C hot water for 5 times, and titrating the water washing solution with alkaline solution to obtain the mass m (R) of 3-hydroxypropanetricarboxylic acid₁) (ii) a Washing the oil phase with water, and removing light components by reduced pressure distillation to obtain the mass m (R) of free caproic acid₂). By calculation, the 3-hydroxypropanetricarboxylic acid radical in the reaction product: mo: molar ratio of hexanoate group ═ n (R)₁)-m(R₁)/M(R₁)-n(R_{1 decomposition})]: m (product molybdenum)/M (product molybdenum): [ n (R)₂)-m(R₂)/M(R₂)-n(R_{2 decomposition})]2: 1: 2. wherein n (R)₁) Represents R₁Total moles of (a); m (R)₁) Represents R₁Relative molecular mass of (a); n (R)_{1 decomposition}) R represents a thermal decomposition₁The number of moles of (a); m (product molybdenum) represents the mass of molybdenum element in the product; m (product molybdenum) represents the relative molecular mass of the molybdenum element; n (R)₂) Represents R₂Total moles of (a); m (R)₂) Represents R₂Relative molecular mass of (a); n (R)_{2 decomposition}) R represents a thermal decomposition₁The number of moles of (a).

Example 2

(1) Dispersing ammonium molybdate tetrahydrate and water in a flask, wherein the weight ratio of the ammonium molybdate tetrahydrate to the water is 1: 10. and (3) purging by inert gas, adding oxalic acid at the temperature of 70 ℃ and reacting for 6 hours, wherein the molar ratio of the oxalic acid to the ammonium molybdate tetrahydrate (calculated by molybdenum element) is 4: 1; after the reaction is finished, the pH value of the solution is adjusted to 3.7 by using dilute ammonia water to obtain a first product.

(2) Adding preheated hexanoic acid into the solution, wherein the molar ratio of amine molybdate tetrahydrate (calculated as molybdenum element) to the hexanoic acid is 1: 4, mixing, preheating caproic acid at 90 ℃, reacting for 8 hours at 205 ℃ after mixing, and obtaining the organic molybdenum compound A2 with the relative molecular mass of 947 after the reaction is finished.

The oil phase insoluble content of the obtained organomolybdenum compound is shown in Table 1. The product was analyzed for metal content using the method of example 1 and the content of metallic molybdenum was 20.3 wt%. Infrared spectrum: gamma 2942cm^-1、1506cm^-1、1462cm^-1、1435cm^-1、989cm^-1、776cm^-1、737cm^-1。

690cm from infrared spectrum data^-1-790cm^-1An absorption peak of 2942cm, which is attributed to Mo-O-Mo^-1，1462cm^-1Are each CH on an organic acid alkyl group₃The C-H bond antisymmetric stretching vibration and antisymmetric deformation vibration peak of 1506cm^-1、1435cm^-1Respectively shows the asymmetric stretching vibration and the symmetric stretching vibration peak of the coordinated carboxyl, which shows that the organic molybdenum compound A2 has a binuclear molybdenum structure shown in formula (1).

And (3) measuring overflowing components and relative contents in the thermal decomposition products at different temperatures by using gas chromatography. Repeatedly washing the reaction product for 5 times by using hot water at the temperature of 80 ℃, and titrating the water washing liquid by using alkali liquor to obtain the amount of oxalic acid, wherein the oxalic acid has completely reacted; washing the oil phase with water, and distilling under reduced pressure to obtain the amount of free caproic acid. By calculation, Mo in the reaction product: molar ratio of hexanoate group 1: 6.

comparative example 1

Adding caproic acid into a flask, and dropwise adding sodium hydroxide, wherein the molar ratio of caproic acid to sodium hydroxide is 1: 1, adding ammonium molybdate after the reaction is finished, adding caproic acid at the temperature of 205 ℃ for reacting for 6 hours, wherein the molar ratio of the caproic acid to the ammonium molybdate (calculated by molybdenum element) is 4: 1; after the reaction is finished, the pH value is about 6.5, the oil phase is washed by water, and the organic molybdenum compound A3 with the relative molecular mass of 354 can be obtained by reduced pressure distillation.

The oil phase insoluble content of the resulting product is shown in Table 1.

The product was analyzed for metal content using the method of example 1 and the content of metallic molybdenum was 5.2 wt%. Infrared spectrum: gamma 2954cm^-1，1711cm^-1，1698cm^-1，1341cm^-1，1257cm^-1，1128cm^-1，903cm^-1，684cm^-1。

690cm from infrared spectrum data^-1-790cm^-1The absorption peak of Mo-O-Mo is not present, which indicates that the organic molybdenum compound A3 does not have the binuclear molybdenum structure shown in formula (1).

Comparative example 2

An organomolybdenum compound was produced in the same manner as in example 1, except that the pH of the reaction mixture was adjusted to 0.5 in step (1). And after the reaction is finished, washing the reaction product with water to obtain an oil phase, and distilling under reduced pressure to obtain the organic molybdenum compound A4, wherein the relative molecular mass of the organic molybdenum compound A4 is 445.

The oil phase insoluble content of the resulting product is shown in Table 1.

The product was analyzed for metal content using the method of example 1 and the content of metallic molybdenum was 7.3 wt%. Infrared spectrum: gamma 2956cm^-1，1708cm^-1，1509cm^-1，1421cm^-1，1297cm^-1，1118cm^-1，983cm^-1，684cm^-1。

Analysis of the Infrared Spectrum 690cm^-1-790cm^-1The absorption peak of Mo-O-Mo is not existed, which indicates that the organic molybdenum compound A4 does not have the binuclear molybdenum structure shown in formula (1).

Examples 3 to 8 and comparative examples 3 to 6 are examples of the preparation of catalysts.

Example 3

Preparation of organic iron salt:

dropwise adding a sodium hydroxide solution into dodecylbenzene sulfonic acid, stirring at 70 ℃ for completely reacting for 1 hour, and then adding ferrous sulfate within 10min, wherein the molar ratio of the ferrous sulfate (calculated by iron element), the dodecylbenzene sulfonic acid and the sodium hydroxide is 1: 3: 2.7. reacting at 50 ℃ for 1 hour, adding petroleum ether into the reaction product after the reaction is finished to extract an organic phase, separating and removing a solvent phase, washing the oil phase with water, and removing light components by reduced pressure distillation to obtain the organic iron salt M1.

Preparation of the catalyst:

the organomolybdenum compound a1 prepared in example 1 and the organic iron salt M1 prepared in this example were mixed and stirred at 30 ℃ for 0.5 hour to give catalyst C1 of the present disclosure. Wherein, the mol ratio of organic iron salt counted by iron element and organic molybdenum compound counted by molybdenum element in the catalyst is 0.3: 1.

example 4

Preparation of organic iron salt:

dropwise adding a sodium hydroxide solution into caprylic acid, stirring at 65 ℃ for completely reacting for 0.6 hour, and then adding ferric sulfate within 5min, wherein the molar ratio of the ferric sulfate (calculated by iron element), the caprylic acid and the sodium hydroxide is 1: 3: 2.3. reacting at 60 ℃ for 1 hour, adding petroleum ether into the reaction product after the reaction is finished to extract an organic phase, separating and removing a solvent phase, washing the oil phase with water, and removing light components by reduced pressure distillation to obtain the organic iron salt M2.

Preparation of the catalyst:

organomolybdenum compound a2 prepared in example 2 the organic iron salt M2 prepared in this example was mixed and stirred at 80 ℃ for 0.3 hour to afford catalyst C2 of the present disclosure. Wherein, the mol ratio of the organic iron salt counted by iron element and the organic molybdenum compound counted by molybdenum element in the catalyst is 0.5: 1.

example 5

With the organic iron salt M1 and the organic molybdenum compound a1, only the difference from example 3 was that the organic iron salt M1 in terms of iron element and the organic molybdenum compound a1 in terms of molybdenum element were used in a molar ratio of 1.3: 1 to give catalyst C3.

Example 6

With the organic iron salt M1 and the organic molybdenum compound a1, only the difference from example 3 was that the organic iron salt M1 in terms of iron element and the organic molybdenum compound a1 in terms of molybdenum element were used in a molar ratio of 1.8: 1 to give catalyst C4.

Example 7

The catalyst is prepared by compounding an organic iron salt M1, an organic molybdenum compound A1 and nickel naphthenate, and is different from the catalyst in example 3 only in that the organic iron salt M1 calculated by iron element, the organic molybdenum compound A1 calculated by molybdenum element and the nickel naphthenate calculated by nickel element are mixed according to the mol ratio of 0.2: 1: 0.4 to obtain catalyst C5.

Example 8

The catalyst is prepared by compounding an organic iron salt M1, an organic molybdenum compound A1, nickel naphthenate and cobalt naphthenate, and the difference from the embodiment 3 is only that the organic iron salt M1 calculated by iron element, the organic molybdenum compound A1 calculated by molybdenum element, the nickel naphthenate calculated by nickel element and the cobalt naphthenate calculated by cobalt element are mixed according to the mol ratio of 0.4: 1: 0.2: 0.2 to obtain catalyst C6.

Comparative example 3

Organic iron salt M1 was used as catalyst C7, and no organic molybdenum compound was added.

Comparative example 4

A catalyst was prepared by the method of example 3, except that the organic iron salt M1 was replaced with an equivalent amount of iron sulfate to give catalyst C8.

Comparative example 5

A catalyst was prepared by the method of example 3 except that the organomolybdenum compound A1 in the catalyst was replaced with an equivalent amount of the organomolybdenum compound A3 to provide catalyst C9.

Comparative example 6

A catalyst was prepared by the method of example 3 except that the organomolybdenum compound A1 in the catalyst was replaced with an equivalent amount of the organomolybdenum compound A4 to provide catalyst C10.

Test example

The properties of the middle east residue used in the test examples are shown in table 2.

350g of residual oil is weighed respectively, then 200 mu g/g of the catalysts C1-C9 prepared in the above examples and comparative examples are added into the residual oil raw material respectively, 0.36g of sulfur powder is added, hydrogenation reaction is carried out at the reaction temperature of 435 ℃, the initial pressure of reaction hydrogen is 9MPa, and the reaction time is 3 hours, and the distribution of products after reaction is measured by a standard test method (analytical method ASTM D5307) for measuring the boiling range distribution of crude oil by gas chromatography, and the results are shown in Table 3.

TABLE 1

Item	Mass fraction of molybdenum/% of the organic molybdenum compound	Oil phase insoluble content/%)
			Example 1	22.2	0.11
Example 2	20.3	0.13
			Comparative example 1	6.5	7.4
Comparative example 2	7.3	1.1

TABLE 2

Item	Residual oil
		Content of C, wt.%	83.49
H content, wt%	9.88
		N_H/N_C	1.42
S content, wt%	6.42
		N content, wt.%	0.38
Carbon residue value, wt%	23.74
		Ni content, μ g^-1	52.8
V content, μ g^-1	179
		524⁺Content of fraction (C)% by weight	>95
Asphaltenes% by weight	9.9

TABLE 3

The catalyst disclosed by the invention is low in cost, has good hydrogenation activity when being used for residual oil hydrocracking reaction after vulcanization, is high in residual oil conversion rate, is capable of obviously improving the gasoline yield and the diesel oil yield, reduces toluene insoluble substances, and also has good denitrification performance.

The preferred embodiments of the present disclosure have been described above in detail, however, the present disclosure 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 disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.

In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims

1. A hydrogenation catalyst comprising an organomolybdenum compound and an organic iron salt, the organomolybdenum compound having a structure represented by formula (1):

wherein a + b is 2, 3, 4, 5 or 6, m + n is 0, 1, 2, 3, 4, 5 or 6, R₁Is C1-C6 oxygen-containing organic acid radical, R₂Is C6-C18 oxygen-containing organic acid radical;

the hydrogenation catalyst is prepared by adopting a method comprising the following steps:

(4) mixing the organomolybdenum compound with the organic iron salt;

wherein the first organic acid and the second organic acid are each independently selected from one of C6-C18 oxygen-containing organic acids.

2. The catalyst of claim 1, wherein a and b are equal, and a + b is 2, 4 or 6; m is equal to n, and m + n is 0, 2 or 4.

3. The catalyst of claim 1, wherein the C1-C6 oxoorganic acid group is a monocarboxylate, a dicarboxylate, or a polycarboxylate; the C6-C18 oxygen-containing organic acid radical is monocarboxylate, dicarboxylates, polycarboxylates, sulfonates or sulfinates.

4. The catalyst of claim 3, wherein the C1-C6 oxoorganic acid is a dicarboxylate or a polycarboxylate.

5. The catalyst of claim 3, wherein the C6-C18 oxygen-containing organic acid radical is a monocarboxylic acid radical, a dicarboxylic acid radical, or a sulfonic acid radical.

6. The catalyst of claim 1, wherein the molar ratio of the iron element in the ferric organo salt to the molybdenum element in the organo-molybdenum compound in the catalyst is (0.01-1.5): 1.

7. the catalyst of claim 1, wherein the molar ratio of the iron element in the ferric organo salt to the molybdenum element in the organo-molybdenum compound in the catalyst is (0.2-0.7): 1.

8. the catalyst of claim 1, wherein the C1-C6 oxygen-containing organic acid group is selected from formate, acetate, propionate, 2-methylbutyrate, hydroxyacetate, isobutyrate, valerate, oxalate, malonate, succinate, glutarate, 2-hydroxysuccinate, 3-hydroxypropanetricarboxylate, or citrate.

9. The catalyst of claim 1, wherein the C6-C18 oxygen-containing organic acid is selected from the group consisting of hexanoate, heptanoate, 2-propyl heptanoate, octanoate, 2-ethyl hexanoate, nonanoate, decanoate, oleate, palmitate, stearate, and naphthenate having 6-18 carbon atoms.

10. The catalyst of claim 1, wherein the anion of the organic iron salt is a C6-C18 oxygen containing organic acid radical.

11. The catalyst of claim 10, wherein the organic iron salt is selected from one or more of iron petroleate, iron 2-ethylhexanoate and iron dodecyl benzene sulfonate.

12. The catalyst according to claim 1, wherein the catalyst further comprises a third metal organic salt, the third metal organic salt being an organic nickel salt and/or an organic cobalt salt.

13. The catalyst according to claim 12, wherein the molar ratio of the contents of the organomolybdenum compound by molybdenum element and the third metal organic salt by third metal element in the catalyst is 1: (0.01-1).

14. The catalyst of claim 12, wherein the anion of the third metal organic salt is a C6-C18 oxoorganyl.

15. The catalyst of claim 12, wherein the third metal organic salt is selected from one or more of nickel naphthenate, nickel oleate, nickel 2-ethylhexanoate, nickel stearate, cobalt naphthenate, cobalt oleate, cobalt 2-ethylhexanoate, and cobalt stearate.

16. A process for preparing a hydrogenation catalyst as claimed in claim 1, characterized in that the process comprises:

(1) mixing a molybdenum source, a solvent and a C1-C6 oxygen-containing organic acid, reacting at 20-150 ℃ to obtain a reaction mixture, and adjusting the pH value of the reaction mixture to 2.5-5 to obtain a first product;

(4) mixing the organomolybdenum compound with the ferric organometal salt;

17. The method of claim 16, wherein in step (1), the weight ratio of the molybdenum source to the solvent, calculated as elemental molybdenum, is from 1: (1-20); the molar ratio of the molybdenum source to the C1-C6 oxygen-containing organic acid is 1: (0.5-4).

18. The method of claim 16, wherein the molar ratio of the molybdenum source, calculated as elemental molybdenum, to the first organic acid in step (2) is 1: (1-10).

19. The method according to claim 16, wherein in step (3), the molar ratio of the iron source, the second organic acid and the base, calculated as iron element, is 1: (2-7): (2-4).

20. The method according to claim 16, wherein in step (4), the molar ratio of the organic iron salt, calculated as iron element, to the organic molybdenum compound, calculated as molybdenum element, is (0.1-1.5): 1.

21. the method according to claim 16, wherein the reaction time in step (1) is 0.3 to 9 hours;

the reaction time in the step (2) is 1-12 hours;

the step (3) comprises the following steps: dropwise adding the alkali solution into the second organic acid at 40-90 ℃, reacting for 0.5-2 hours, adding the iron source into the mixed solution within 0.2-30min, and continuing to react for 0.5-4 hours at 30-100 ℃;

22. The method of claim 16, wherein the solvent is selected from water and/or an organic solvent; the organic solvent is selected from benzene, toluene, ethanol or petroleum ether;

the C1-C6 oxygen-containing organic acid is selected from formic acid, acetic acid, propionic acid, 2-methylbutyric acid, glycolic acid, isobutyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, 2-hydroxysuccinic acid, 3-hydroxypropanetricarboxylic acid or citric acid;

the base is selected from sodium hydroxide.

23. The method of claim 16, wherein the molybdenum source is selected from one or more of molybdic acid, ammonium molybdate, ammonium paramolybdate, and molybdenum trioxide;

24. The method of claim 16, wherein the method further comprises: at least one of steps (1) - (4) is carried out in an inert atmosphere.

25. The method of claim 16, wherein step (4) comprises: mixing the organomolybdenum compound, the organic iron salt, and a third metal organic salt;

the third metal organic salt is organic nickel salt and/or organic cobalt salt;

the anion of the third metal organic salt is C6-C18 oxygen-containing organic acid radical.

26. The method of claim 25, wherein the third metal organic salt is selected from one or more of nickel naphthenate, nickel oleate, nickel 2-ethylhexanoate, nickel stearate, cobalt naphthenate, cobalt oleate, cobalt 2-ethylhexanoate, and cobalt stearate.

27. A hydrogenation catalyst prepared by the process of any one of claims 16 to 26.

28. A process for hydrogenating residuum or coal, comprising: contacting a residuum or coal with the catalyst of any one of claims 1-15 and claim 27 under residuum or coal liquefaction hydrogenation conditions.