CN114471570A - Naphthalene selective hydrogenation catalyst, and preparation method and application thereof - Google Patents

Naphthalene selective hydrogenation catalyst, and preparation method and application thereof Download PDF

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CN114471570A
CN114471570A CN202011148428.2A CN202011148428A CN114471570A CN 114471570 A CN114471570 A CN 114471570A CN 202011148428 A CN202011148428 A CN 202011148428A CN 114471570 A CN114471570 A CN 114471570A
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catalyst
selective hydrogenation
naphthalene
hydrogenation catalyst
nickel
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CN114471570B (en
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马宇春
王德举
韩亚梅
刘仲能
唐之勤
钱斌
刘师前
赵斌
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C07C5/11—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

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Abstract

The invention relates to a catalyst for producing tetrahydronaphthalene by naphthalene selective hydrogenation and a preparation method and application thereof, wherein the catalyst comprises 1-30 parts of one or more of non-noble metals selected from VIII groups; 1-20 parts of one or more metals selected from IB group metals; the carrier with the content of 50 to 98 portions is selected from one or more of silicon dioxide or aluminum oxide. The catalyst has obvious performance advantages in the reaction of producing tetrahydronaphthalene by naphthalene selective hydrogenation, and compared with a vulcanized catalyst, the metal catalyst does not need a pre-vulcanization process before use, tail gas does not need to be treated, the operation in the starting process is simple, and the cost is obviously reduced.

Description

Naphthalene selective hydrogenation catalyst, and preparation method and application thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a naphthalene selective hydrogenation catalyst, and a preparation method and application thereof.
Background
Tetrahydronaphthalene, also known as tetralin, is an alicyclic aromatic hydrocarbon. It is a colorless liquid with a naphthalene odor and is also an important derivative product of naphthalene. The tetrahydronaphthalene is insoluble in water, is miscible with all common solvents, is an ideal high-boiling point solvent, can dissolve grease, oxidized linseed oil, rubber, wax, asphalt, phenolic resin, naphthalene, iodine, paint and the like, and is widely applied to the production of an intermediate methylnaphthol of insecticide buvinin; also used for producing lubricant, reduce the viscosity of high-viscosity oil; mixing with alcohol and benzene as fuel for internal combustion engine; also useful as degreasers, softeners, absorbents for low boiling organic compound vapors, insect repellents, and substitutes for turpentine.
The production process of the tetrahydronaphthalene mainly comes from naphthalene hydrogenation, the naphthalene hydrogenation is a two-stage series reaction, firstly, a first benzene ring is hydrogenated to generate a target product of the tetrahydronaphthalene, but a second benzene ring is hydrogenated to generate a side reaction of decahydronaphthalene, so that the control of the selectivity of the hydrogenation process is particularly critical for improving the yield of the tetrahydronaphthalene. At present, due to the difficulty of controlling hydrogenation selectivity, the research on producing tetrahydronaphthalene by naphthalene hydrogenation is less, and the selectivity of the tetrahydronaphthalene is lower.
CN200310106565 discloses a method for intermittently hydrogenating to synthesize decahydronaphthalene, which uses naphthalene as raw material, on nickel catalyst, at 6 MPa-12 MPa, 180 deg.C-220 deg.C and liquid hourly space velocity of 0.5h-1～1.0h-1Under the condition, the conversion rate of naphthalene is more than 98 percent, and the yield of decalin is 98 percent. However, this process is a batch operation, is inefficient, and is not suitable for the production of tetrahydronaphthalene. CN200510041404.6 discloses a method for producing decahydronaphthalene by continuous hydrogenation, which adopts decahydronaphthalene or tetrahydronaphthalene as solvent of naphthalene, adopts platinum aluminum or nickel aluminum catalyst, and has a liquid hourly volume space velocity of 0.1h at 2 MPa-15 MPa, 120-280 ℃ and-1～5.0h-1and under the condition that the volume ratio of hydrogen to oil is 1-3000, the naphthalene conversion rate is 70% -99%, but the method is not suitable for producing tetrahydronaphthalene.
CN102838438 discloses a synthesis method of tetrahydronaphthalene, which takes naphthalene as a raw material, adopts sulfide NiMo containing 10-80% of ZSM-5 molecular sieve as a catalyst, and has hydrogen partial pressure of 0.5-20 MPa, 200-400 ℃ and volume space velocity of 0.5h in a fixed bed reactor-1～10h-1Under the condition that the volume ratio of hydrogen to oil is 200-1000, the conversion rate of naphthalene reaches 91.7%, and the selectivity of a target product, namely tetrahydronaphthalene reaches 97.8%. The method can obtain tetrahydronaphthalene with high selectivity, but needs to use a sulfide type catalyst. CN109550525 discloses a presulfurization method of a catalyst for preparing tetrahydronaphthalene, and also relates to a method for producing tetrahydronaphthalene by adopting a sulfur-type catalyst. The sulfide catalyst needs to be subjected to a pre-vulcanization process before use, namely, the oxide catalyst precursor adopts vulcanizing agents such as dimethyl disulfide (DMDS) and the like, and has catalytic activity after being subjected to pre-vulcanization at 200-400 ℃. The operation of the pre-vulcanization process is complex, and the use of the vulcanizing agent can bring about environmental problems such as treatment of tail gas containing hydrogen sulfide.
CN104741124A discloses a catalyst for naphthalene selective hydrogenation using an aluminum-based intermetallic compound and a preparation method thereof, wherein the catalyst uses a Ni-Al intermetallic compound as a hydrogenation catalyst, and the catalyst does not need to be vulcanized before being used in hydrogenation reaction, but the preparation process is complex, a strong reducing agent lithium naphthyl is needed, the catalyst cost is high, and the problem of waste liquid environmental protection exists at the same time.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problems of low selectivity of tetrahydronaphthalene and complex pretreatment of sulfide catalyst of the existing hydrogenation catalyst, and the like, and provides a naphthalene selective hydrogenation metal catalyst and a preparation method and application thereof, namely a first purpose of the invention is to provide a naphthalene selective hydrogenation catalyst which comprises the following components in parts by weight:
1-30 parts of VIII non-noble metal elements;
1-20 parts of IB metal elements;
50-98 parts of a carrier.
According to some embodiments of the invention, the group VIII non-noble metal element comprises one or more of nickel, iron, cobalt.
According to some embodiments of the invention, the group VIII non-noble metal element comprises nickel.
According to some embodiments of the invention, the nickel content comprises 5.0 parts to 20 parts by weight.
According to some embodiments of the invention, the group IB metal element comprises one or more of Cu, Ag, Au.
According to some embodiments of the invention, the group IB metal element comprises copper.
According to some embodiments of the invention, the copper content comprises 3.0 parts to 12.0 parts by weight.
According to some embodiments of the present invention, the photoelectron diffraction spectrum peak of the non-noble group VIII metal element in the naphthalene selective hydrogenation catalyst is shifted by 0.5 to 2.0eV toward the high binding energy direction of the photoelectron diffraction spectrum peak in the presence of the non-noble group VIII metal element alone. According to some specific embodiments of the present invention, the peak of photoelectron diffraction spectrum of Ni element in the naphthalene selective hydrogenation catalyst is shifted by 0.5 to 2.0eV toward the high binding energy direction of the peak of photoelectron diffraction spectrum in the presence of Ni element alone; according to some more specific embodiments of the present invention, the peak of the photoelectron diffraction spectrum of the Ni element in the naphthalene selective hydrogenation catalyst is shifted by 1.6eV toward the high binding energy direction of the peak of the photoelectron diffraction spectrum in the presence of the Ni element alone. Wherein the photoelectron diffraction spectrum peak of the group VIII non-noble metal element in the independent existence or the photoelectron diffraction spectrum peak of the group Ni element in the independent existence refers to the photoelectron diffraction spectrum peak only containing the group VIII non-noble metal element or the Ni element as an active element.
According to some embodiments of the invention, the peak of the photoelectron diffraction spectrum of the group IB metal element is shifted by 0.2 to 0.5eV toward the high binding energy direction of the peak of the photoelectron diffraction spectrum in the presence of the group VIII non-noble metal element alone. According to some embodiments of the present invention, the peak of photoelectron diffraction spectrum of Cu element in the naphthalene selective hydrogenation catalyst is shifted by 0.2-0.5 eV toward the high binding energy direction in the presence of Cu element alone; according to some more specific embodiments of the present invention, the photoelectron diffraction spectrum peak of the Cu element in the naphthalene selective hydrogenation catalyst is shifted by 0.5eV toward the high binding energy direction in the presence of the Cu element alone. Wherein the photoelectron diffraction spectrum peak in the presence of the group IB metal element alone or the photoelectron diffraction spectrum peak in the presence of the Cu element alone refers to a photoelectron diffraction spectrum peak containing only the group IB metal element or the Cu element as an active element.
The invention also aims to provide a preparation method of the naphthalene selective hydrogenation catalyst, which comprises the steps of preparing a metal complexing solution from the VIII group non-noble metal element compound, the IB group metal element compound and a complexing agent, loading the metal complexing solution on a catalyst carrier, and drying and roasting the catalyst carrier to obtain the naphthalene selective hydrogenation catalyst.
According to some embodiments of the invention, the complexing agent comprises a polyamine complexing agent; preferably, the complexing agent comprises an aqueous solution of an organic amine or inorganic ammonia; more preferably, the complexing agent comprises an aqueous solution of ethylenediamine.
According to some embodiments of the invention, the group VIII non-noble metal element compound comprises a nickel-containing compound; preferably comprises one or more of nickel chloride, nickel nitrate, nickel sulphate and nickel carbonate, preferably nickel nitrate.
According to some embodiments of the invention, the group IB metal element compound comprises a copper-containing compound, preferably comprising one or more of copper chloride, copper nitrate, copper sulfate and basic copper carbonate, preferably copper nitrate.
According to some embodiments of the invention, the loading method comprises one or both of an impregnation method, a precipitation method.
According to some embodiments of the invention, the impregnation method comprises mixing or spraying the metal complexing solution onto a catalyst support; preferably, the saturated adsorption capacity of the metal complexing solution and the carrier is 1: 1.
According to some embodiments of the invention, the precipitation method comprises reacting the metal complex solution with a precipitant solution to precipitate the metal complex solution on the catalyst support; preferably, the precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, ammonium carbonate, basic sodium carbonate and ammonia water, and preferably ammonium carbonate. More preferably, the saturated adsorption capacity of the metal complex solution and the carrier is 10: 1-1: 1.
According to some embodiments of the present invention, the catalyst support comprises, for example, silica, alkali, extrusion aid and water, which are kneaded thoroughly, extruded into a strip, dried and calcined to obtain the catalyst support. Preferably, the catalyst support may comprise, for example, silica, alumina, an all-silicon molecular sieve.
According to some embodiments of the present invention, the silica is a powdery substance having a silica content of more than 99% by weight, and the silica content in the catalyst is 73 to 92 parts by weight; the silicon dioxide is selected from one or more of white carbon black, silica gel and colloidal silica; the alkali is selected from one or more of sodium hydroxide and potassium hydroxide, preferably sodium hydroxide, and the addition amount of the alkali is 0.1-10.0 parts by weight, preferably 1.0-5.0 parts by weight of the carrier on a dry basis; the extrusion aid is a substance which is beneficial to extrusion molding, can be one or more of starch, hydroxymethyl cellulose and sesbania powder, and is preferably sesbania powder, and the addition amount of the extrusion aid is 1.0-10.0 parts by weight, preferably 1.0-5.0 parts by weight of the dry basis of the carrier.
According to some embodiments of the present invention, the loading mode may be one or two of an impregnation method and a deposition precipitation method, and the nickel and copper-containing complex solution may be prepared by a conventional method, that is, a nickel-containing compound and a copper-containing compound are dissolved in an aqueous solution containing a complexing agent organic amine or inorganic ammonia, the nickel-containing compound is selected from one or more of nickel chloride, nickel nitrate, nickel sulfate and nickel carbonate, and is preferably nickel nitrate; the copper-containing compound is selected from one or more of copper chloride, copper nitrate, copper sulfate and basic copper carbonate, and is preferably copper nitrate.
According to some embodiments of the invention, the impregnation method comprises an equal volume impregnation method, i.e. the volume of the nickel-containing and copper-containing solutions formulated to saturate the adsorption capacity of the catalyst support is mixed directly or sprayed onto the catalyst support.
According to some embodiments of the present invention, the volume of the solution containing nickel and copper prepared in the deposition precipitation method is 1 to 10 times of the water absorption rate of the carrier, the solution containing active metal nickel and copper reacts with a precipitant solution, and the precipitant solution is deposited on the catalyst carrier, wherein the precipitant is one or more selected from sodium hydroxide, potassium hydroxide, ammonium carbonate, basic sodium carbonate and ammonia water, and is preferably ammonium carbonate.
According to some embodiments of the invention, the drying conditions of the catalyst support and the catalyst may be the same, and the calcination conditions of the catalyst support and the catalyst may be the same.
According to some embodiments of the present invention, the drying conditions of the catalyst carrier and the catalyst include a temperature of 50 ℃ to 300 ℃ for 1 hour to 48 hours, and the calcination conditions of the catalyst carrier and the catalyst are 300 ℃ to 700 ℃ for 0.5 hour to 10.0 hours.
According to some embodiments of the present invention, the method for preparing the naphthalene selective hydrogenation catalyst further comprises the step of reducing and activating the naphthalene selective hydrogenation catalyst into an active metal in a reducing atmosphere before use; the preferable reduction activation conditions comprise that the hydrogen partial pressure is 0.1MPa to 5.0MPa, the reaction temperature is 150 ℃ to 350 ℃, and the volume space velocity is 50h-1～300h-1The reduction time is 1-12 h.
Still another object of the present invention is to provide a method for producing tetrahydronaphthalene by selective hydrogenation of naphthalene, using a fixed bed adiabatic reactor, comprising the steps of:
in the presence of the naphthalene selective hydrogenation catalyst which is subjected to reduction activation treatment, the reaction temperature is 100-350 ℃, the reaction pressure is 0.5-5.0 MPa, and the volume space velocity is 0.5h-1And (5.0 h < -1 >) and under the condition that the hydrogen-oil ratio is 50-1000, performing hydrogenation reaction on the raw material naphthalene to obtain the tetrahydronaphthalene.
According to some embodiments of the invention, the reaction is carried out in a fixed bed adiabatic reactor.
The invention further aims to provide the application of the catalyst in the selective hydrogenation reaction of naphthalene to obtain tetrahydronaphthalene.
Compared with the prior art, the invention has the following beneficial effects:
(1) the active component of the hydrogenation catalyst adopted by the method is in a metal state, no noble metal is used, only hydrogen needs to be introduced for reduction before use, and the hydrogen is excessive in the reaction process, so that the active center can be effectively maintained. Compared with the traditional vulcanization type catalyst, the problems of complex operation, sulfur-containing gas treatment, activity reduction caused by catalyst sulfur loss in the reaction process and the like caused by the vulcanization process are solved. The operation difficulty and the reaction severity are obviously reduced.
(2) The hydrogenation catalyst contains nickel and copper double metals, and after hydrogen reduction, the nickel and copper are subjected to synergistic action, so that a double metal system has higher hydrogenation activity compared with a single metal active center;
(3) the acidity of the catalyst can cause the further deep hydrogenation of the tetrahydronaphthalene into decahydronaphthalene and the side reactions such as saturated ring cracking of naphthalene hydrogenation products, and the like, while the traditional vulcanized catalyst carrier usually contains a large amount of molecular sieves such as ZSM-5, MOR, Y and the like, and the side reaction on the center of strong acid cannot be avoided, thereby causing the selectivity reduction of the tetrahydronaphthalene. In order to solve the problem that the side reaction is caused by the acidity of the catalyst, the hydrogenation catalyst carrier in the technology is silicon dioxide and does not contain an acid center, so that the side reaction is inhibited to the greatest extent. The pore diameter of the silicon dioxide carrier is mesoporous, which is beneficial to the diffusion of reactant and product molecules and further beneficial to improving the selectivity of a target product, namely tetrahydronaphthalene;
(4) the method adopts a specific hydrogenation catalyst, can adopt a fixed bed to continuously produce the tetrahydronaphthalene under proper reaction conditions, and has higher naphthalene conversion rate and tetrahydronaphthalene selectivity.
The naphthalene selective hydrogenation catalyst with special components and proportion and the method for preparing tetrahydronaphthalene by applying the naphthalene selective hydrogenation catalyst to carry out naphthalene selective hydrogenation reaction have the advantages of no need of a pre-vulcanization process, no need of tail gas treatment, high catalytic activity and high naphthalene conversion rate, and the preparation method of the naphthalene selective hydrogenation catalyst is simple and easy to carry out and is suitable for large-scale production and application.
Drawings
FIG. 1 is an XRD diffraction pattern of a naphthalene selective hydrogenation catalyst prepared according to one embodiment of the present invention;
FIG. 2 is a Cu photoelectron diffraction spectrum of a naphthalene selective hydrogenation catalyst prepared according to an embodiment of the present invention;
FIG. 3 is a diffraction diagram of a Ni photoelectron diffraction spectrum of a naphthalene selective hydrogenation catalyst prepared by one embodiment of the invention.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The performance of the invention was determined as follows:
the catalyst of the invention is evaluated by a 100ml fixed bed adiabatic reactor, the loading of the catalyst is 100ml, the catalyst is subjected to reduction activation treatment before feeding, and the reduction conditions and the evaluation conditions are shown in table 1. And (3) after the materials are fed and react for 2 hours, analyzing the composition of the product, and calculating the conversion rate of naphthalene and the selectivity of tetrahydronaphthalene by the following specific calculation method:
naphthalene conversion [ ((weight of naphthalene in starting Material-weight of naphthalene in product)/weight of naphthalene in starting Material) ] X100%
Tetrahydronaphthalene selectivity (moles of tetrahydronaphthalene in product/moles of naphthalene converted) × 100%.
XPS (X-ray photoelectron spectroscopy) analysis method: analyzing the element composition and valence state of the catalyst by a Kratos AXIS Ultra DLD type X-ray photoelectron spectrometer with a minimum energy spectrum beam spot of 15 μm; the energy resolution is +/-1%; the analysis chamber was evacuated < 7X 10-8 Pa.
Example 1
The preparation procedure of the catalyst of this example is as follows:
(1) taking 76.1 g of white carbon black, 5 g of sodium hydroxide, 6 g of sesbania powder and a proper amount of water, fully mixing and kneading, extruding into a cylindrical strip (the diameter is 1.2 mm), drying at 120 ℃ for 8 hours and roasting at 550 ℃ for 3 hours to obtain a catalyst carrier;
(2) dissolving 74.3 g of nickel nitrate hexahydrate and 19 g of copper nitrate trihydrate into an ethylenediamine aqueous solution with the concentration of 45 wt.% to prepare a complex impregnation solution, preparing a catalyst by an isometric impregnation method, spraying the salt solution onto the carrier prepared in the step (1) in a rotary pot, rotationally stirring for 1 hour, drying at 110 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to prepare the catalyst, wherein the catalyst comprises the following components: the nickel/copper/silica is 15/5/80 (by weight) and is numbered Cat-1, and the hydrogenation evaluation process conditions of the catalyst are as follows: the reaction temperature is 170 ℃, the reaction pressure is 2.5MPa, and the volume space velocity is 2.5h-1The hydrogen-oil ratio was 500, and the results are shown in Table 1.
When the catalyst prepared in example 1 is analyzed by XRD diffraction, as shown in fig. 1, the XRD diffraction of the catalyst in example 1 has no characteristic diffraction peak of Ni, Cu and their oxides, which indicates that active metals such as Ni and Cu or their precursors are highly dispersed on the catalyst, and the highly dispersed catalyst has high catalyst activity.
XPS analysis was performed on Cat-1 prepared in example 1 and a single-component catalyst in which Cu and Ni elements exist alone, respectively, to determine the interaction between Cu and Ni elements of the catalyst prepared in the present invention:
as shown in FIG. 2, the photoelectron diffraction spectrum of Cu element of Cat-1 prepared in example 1, in which the binding energy of the photoelectron diffraction peak of Cu element is 933.6eV, was shifted by 0.5eV in the direction of the high binding energy of the photoelectron diffraction peak of the catalyst containing only Cu element (example 9) compared with 933.1eV, which is the binding energy of the photoelectron diffraction peak of the catalyst containing only Cu element (example 9).
As shown in FIG. 3, the photoelectron diffraction spectrum of Ni element in the catalyst Cat-1 prepared in example 1, in which the binding energy of the photoelectron diffraction peak of Ni element is 856.6eV, was shifted by 1.6eV in the direction of the high binding energy of the photoelectron diffraction peak of the catalyst containing only Ni element (example 8) in comparison with 855.0eV of the binding energy of the photoelectron diffraction peak of the catalyst containing only Ni element (example 8).
The variation condition of the XPS binding energy corresponds to the surface states of Cu elements and Ni elements which are active components on the surface of the catalyst, and the XPS of the Cu elements and the Ni elements moves towards the direction of high binding energy, which shows that the active elements Ni and Cu of the catalyst have stronger interaction, and an active center of Ni-Cu alloy exists after reduction, so that the catalyst has high activity and high reaction selectivity compared with a catalyst in which the elements exist independently.
Example 2
The catalyst of this example was prepared as in example 1, except that the silicon source used was silica gel and the catalyst composition was the same: the catalyst was hydrogenated under the same conditions as in example 1, except that 15/5/80 weight parts of Ni/Cu/silica was used, which was numbered Cat-2, and the results are shown in Table 1.
Example 3
The catalyst of this example was prepared as in example 1, except that the nickel salt used was nickel chloride and the catalyst composition was the same: the catalyst was hydrogenated under the same conditions as in example 1, except that 15/5/80 weight parts of Ni/Cu/silica was used, which was numbered Cat-3, and the results are shown in Table 1.
Example 4
The catalyst of this example was prepared as in example 1, except that the copper salt used was cupric chloride and the catalyst composition was the same: the catalyst was hydrogenated under the same conditions as in example 1, except that 15/5/80 weight parts of Ni/Cu/silica was used, which was numbered Cat-4, and the results are shown in Table 1.
Example 5
The catalyst of this example was prepared in the same manner as in example 1, except that the copper salt used was copper chloride, the nickel salt was nickel chloride, and the catalyst composition was the same: the hydrogenation evaluation process conditions for the catalyst were the same as in example 1, and the results are shown in table 1, with No. 15/5/80 (wt.)/wt.) and No. Cat-5.
Example 6
The preparation method of the catalyst of this example is the same as that of example 1, except that the mixture ratio of nickel salt and copper salt is different, the composition of the catalyst is different, and the obtained catalyst has the following composition: the catalyst was hydrogenated under the same conditions as in example 1, except that 10/10/80 weight parts of Ni/Cu/silica was used, which was numbered Cat-6, and the results are shown in table 1.
Example 7
The preparation method of the catalyst of this example is the same as that of example 1, except that the mixture ratio of nickel salt and copper salt is different, the composition of the catalyst is different, and the obtained catalyst has the following composition: the hydrogenation evaluation process conditions for the catalyst were the same as in example 1, and the results are shown in table 1, wherein the catalyst was 5/15/80 (parts by weight) and was numbered Cat-7.
Example 8
The catalyst of this example was prepared according to the same method as that of example 1, except that the catalyst composition was different, and the composition of the obtained catalyst was: the catalyst was numbered Cat-8 with the nickel/silica (wt) 20/80 and the hydrogenation evaluation process conditions were the same as in example 1, and the results are shown in table 1.
Example 9
The catalyst of this example was prepared according to the same method as in example 1, except that the catalyst composition was different, and the composition of the obtained catalyst was: the process conditions for the hydrogenation evaluation of the catalyst were the same as in example 1, and the results are shown in table 1.
Comparative example 1
The comparative example carrier was prepared in the same manner as in example 1, except that the precipitation method was used during the active ingredient loading process.
Dissolving 74.3 g of nickel nitrate hexahydrate and 19 g of copper nitrate trihydrate into 68.2 g of water to prepare a salt solution, preparing 0.1M ammonium carbonate solution, adding the solution into a beaker containing 80 g of carrier and 20 g of water in a parallel flow manner under the stirring state at 50 ℃, controlling the pH value in the liquid adding process to be 8-9, aging the solution at 50 ℃ for 2 hours after the dropwise adding is finished, filtering and washing the obtained slurry, drying the slurry at 110 ℃ for 8 hours, and roasting the slurry at 450 ℃ for 4 hours to prepare the catalyst, wherein the catalyst comprises the following components: the catalyst was hydrogenated under the same conditions as in example 1, except that the catalyst was 15/5/80 (parts by weight) and numbered Cat-10, and the results are shown in table 1.
Comparative example 2
The preparation method of the catalyst of the comparative example is the same as that of comparative example 1, except that the copper salt used is copper chloride, the nickel salt is nickel chloride, and the catalyst composition is the same: the catalyst was hydrogenated under the same conditions as in example 1, except that 15/5/80 weight parts of Ni/Cu/silica was used, which was numbered Cat-11, and the results are shown in table 1.
Comparative example 3
The carrier of the catalyst of this comparative example was prepared by the same method as in example 1, except that the composition was changed, and 2 g of molybdenum trioxide was added during the molding process. The active component loading method was an isometric impregnation method, the metal salt solution contained only nickel salt and no copper salt, and the preparation procedure was the same as in example 8, to obtain a catalyst having a composition of nickel/molybdenum trioxide/silica 20/2/78 (by weight) and numbered Cat-12.
The comparative example is a vulcanized catalyst, dimethyl disulfide is adopted as a vulcanizing agent to be heated and presulfurized before use, and the presulfurization conditions are as follows: hydrogen partial pressure of 2.0MPa, temperature of 320 ℃, vulcanizing agent content of 3.0wt percent and vulcanizing volume space velocity of 1.0h-1The hydrogen-oil volume ratio is 400, and the vulcanization time is 12 h. The hydrogenation evaluation process conditions of the catalyst were the same as in example 1, and the results are shown in Table 1.
TABLE 1 evaluation results of different catalysts
Examples Catalyst numbering Naphthalene conversion, wt.% Tetrahydronaphthalene Selectivity, mol%
1 Cat-1 95.4 98.6
2 Cat-2 94.8 98.5
3 Cat-3 92.0 94.1
4 Cat-4 90.9 93.6
5 Cat-5 90.1 87.4
6 Cat-6 78.1 98.9
7 Cat-7 45.2 99.5
8 Cat-8 90.6 91.3
9 Cat-9 3.2 99.9
10 Cat-10 85.4 97.8
11 Cat-11 78.8 87.1
12 Cat-12 86.7 96.5
From the results in table 1, it can be seen that the metal catalyst Cat-1 of the present invention has very good reaction performance in the reaction of producing tetrahydronaphthalene by naphthalene selective hydrogenation, and both the naphthalene conversion rate and the target product tetrahydronaphthalene selectivity are greater than 95%. Compared with the vulcanized catalyst Cat-12 of the comparative example, the catalyst of the invention has obviously higher naphthalene conversion (95.4%) than the naphthalene conversion (86.7%) of the comparative example under the condition of basically equivalent tetrahydronaphthalene selectivity.
The results show that the catalyst has obvious performance advantages in the reaction of producing tetrahydronaphthalene by selective hydrogenation of naphthalene, and compared with a vulcanized catalyst, the metal catalyst does not need a pre-vulcanization process before use, tail gas does not need to be treated, the operation in the starting process is simple, and the cost is obviously reduced.

Claims (13)

1. A naphthalene selective hydrogenation catalyst comprises the following components in parts by weight:
1-30 parts of VIII non-noble metal elements;
1-20 parts of IB metal elements;
50-98 parts of a carrier; wherein,
the VIII group non-noble metal element comprises one or more of nickel, iron and cobalt; and/or the IB group metal element comprises one or more of Cu, Ag and Au.
2. The naphthalene selective hydrogenation catalyst of claim 2, wherein the group VIII non-noble metal element comprises nickel; preferred said nickel content includes 5.0 parts to 20 parts by weight; and/or said group IB metal element comprises copper, preferably said copper content comprises 3.0 parts to 12.0 parts by weight.
3. The naphthalene selective hydrogenation catalyst according to claim 1 or 2, wherein the binding energy of the photoelectron diffraction spectrum peak of the group VIII non-noble metal element in the naphthalene selective hydrogenation catalyst is shifted by 0.5 to 2.0eV toward the high binding energy of the photoelectron diffraction spectrum peak in the presence of the group VIII non-noble metal element alone; and/or
And the binding energy of the photoelectron diffraction spectrum peak of the IB group metal element to the photoelectron diffraction spectrum peak of the IB group metal element is shifted by 0.2-0.5 eV towards the high binding energy direction of the photoelectron diffraction spectrum peak in the presence of the IB group metal element alone.
4. The naphthalene selective hydrogenation catalyst according to claim 3, wherein the photoelectron diffraction spectrum peak of the Ni element in the naphthalene selective hydrogenation catalyst is shifted by 0.5-2.0 eV, preferably by 1.2-2.0 eV, toward the direction of the high binding energy of the photoelectron diffraction spectrum peak in the presence of the Ni element alone; and/or
The photoelectron diffraction spectrum peak of the Cu element in the naphthalene selective hydrogenation catalyst moves 0.2-0.5 eV, preferably 0.3-0.5 eV, towards the direction of high binding energy of the photoelectron diffraction spectrum peak in the presence of the Cu element alone.
5. A preparation method of a naphthalene selective hydrogenation catalyst comprises the steps of preparing a VIII group non-noble metal element compound, an IB group metal element compound and a complexing agent which are described in any one of claims 1-4 into a metal complexing solution, loading the metal complexing solution on a catalyst carrier, and drying and roasting the catalyst carrier to obtain the naphthalene selective hydrogenation catalyst.
6. The method of claim 5, wherein the complexing agent comprises a polyamine complexing agent; preferably an aqueous solution comprising an organic amine or inorganic ammonia; preferably comprising an aqueous solution of ethylenediamine.
7. The method of claim 5, wherein the group VIII non-noble metal compound comprises a nickel-containing compound; preferably comprises one or more of nickel chloride, nickel nitrate, nickel sulfate and nickel carbonate, preferably nickel nitrate; and/or the group IB metal element compound comprises a copper-containing compound, preferably comprising one or more of copper chloride, copper nitrate, copper sulfate and basic copper carbonate, preferably copper nitrate.
8. The method of claim 5, wherein the loading comprises one or both of impregnation and precipitation; and/or the impregnation method comprises mixing or spraying the metal complex solution onto a catalyst support; and/or the precipitation method comprises the step of reacting the metal complexing solution with a precipitator solution to precipitate on the catalyst carrier; preferably, the precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, ammonium carbonate, basic sodium carbonate and ammonia water, and preferably ammonium carbonate.
9. The method for preparing a naphthalene selective hydrogenation catalyst according to claim 5, wherein the metal complex solution has a saturated adsorption capacity to a carrier of 1: 1; and/or the saturated adsorption capacity of the metal complexing solution and the carrier is 10: 1-1: 1.
10. The method for preparing the naphthalene selective hydrogenation catalyst according to claim 5, wherein the drying condition is that the temperature is kept between 50 ℃ and 300 ℃ for 1h to 48 h; and/or the roasting condition is that the temperature is kept between 300 and 700 ℃ for 0.5 to 10.0 hours.
11. The method for preparing the naphthalene selective hydrogenation catalyst according to claim 5 to 10, wherein the catalyst further comprises a step of reducing and activating the naphthalene selective hydrogenation catalyst into an active metal in a reducing atmosphere before use; the preferable reduction activation conditions comprise that the hydrogen partial pressure is 0.1MPa to 5.0MPa, the reaction temperature is 150 ℃ to 350 ℃, and the volume space velocity is 50h-1～300h-1The reduction time is 1-12 h.
12. A method for producing tetrahydronaphthalene by naphthalene selective hydrogenation is characterized by comprising the following steps:
in the presence of naphthalene selective hydrogenation catalyst which is subjected to reduction activation treatment and is described in any one of claims 1 to 4, the reaction temperature is 100 ℃ to 350 ℃, the reaction pressure is 0.5MPa to 5.0MPa, and the volume space velocity is 0.5h-1～5.0h-1And under the condition that the hydrogen-oil ratio is 50-1000, performing hydrogenation reaction on the raw material naphthalene to obtain the tetrahydronaphthalene.
13. The process of claim 11, wherein the reaction is carried out in a fixed bed adiabatic reactor.
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