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CN120815537A - A nickel-based catalyst and its preparation method and application - Google Patents

A nickel-based catalyst and its preparation method and application

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Publication number
CN120815537A
CN120815537A CN202410449946.XA CN202410449946A CN120815537A CN 120815537 A CN120815537 A CN 120815537A CN 202410449946 A CN202410449946 A CN 202410449946A CN 120815537 A CN120815537 A CN 120815537A
Authority
CN
China
Prior art keywords
nickel
based catalyst
precursor
carrier
oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202410449946.XA
Other languages
Chinese (zh)
Inventor
朱俊华
陈梁锋
王黎敏
郭凯
王健
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Shanghai Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
Sinopec Shanghai Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Shanghai Petrochemical Research Institute Co ltd, China Petroleum and Chemical Corp filed Critical Sinopec Shanghai Petrochemical Research Institute Co ltd
Priority to CN202410449946.XA priority Critical patent/CN120815537A/en
Publication of CN120815537A publication Critical patent/CN120815537A/en
Pending legal-status Critical Current

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    • 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
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
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    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
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    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/182—Phosphorus; Compounds thereof with silicon
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
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    • B01J35/615—100-500 m2/g
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    • B01J35/647—2-50 nm
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metals, or compounds thereof

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Abstract

本发明涉及催化剂技术领域，提供了一种镍基催化剂及其制备方法及应用。所述镍基催化剂包括载体和负载在载体上的氧化镍，所述载体包括氧化铝、氧化钼、锂和钾中的至少一种金属氧化物、以及磷氧化物和氟单质中的至少一种；所述镍基催化剂中各组分的含量如下：氧化镍10～30wt％；氧化钼1～10wt％；锂和钾中的至少一种金属氧化物0.5～3wt％；以P计的磷氧化物和氟单质中的至少一种3～8wt％；余量的氧化铝。本发明提供的镍基催化剂可以作为选择性加氢的催化剂，在用于富苯乙烯的碳八馏分中苯乙炔的选择性加氢时，具有良好的低温活性、选择性和稳定性，并且具有较高的苯乙炔加氢率以及极低的苯乙烯损失率。The present invention relates to the field of catalyst technology, and provides a nickel-based catalyst, a preparation method thereof, and an application thereof. The nickel-based catalyst comprises a carrier and nickel oxide supported on the carrier, wherein the carrier comprises aluminum oxide, molybdenum oxide, at least one metal oxide selected from lithium and potassium, and at least one selected from phosphorus oxide and fluorine. The content of each component in the nickel-based catalyst is as follows: 10-30 wt% nickel oxide; 1-10 wt% molybdenum oxide; 0.5-3 wt% of at least one metal oxide selected from lithium and potassium; 3-8 wt% of at least one selected from phosphorus oxide and fluorine, calculated as P; and the balance aluminum oxide. The nickel-based catalyst provided by the present invention can be used as a catalyst for selective hydrogenation. When used for the selective hydrogenation of phenylacetylene in a styrene-rich C8 fraction, it has good low-temperature activity, selectivity, and stability, and has a high phenylacetylene hydrogenation rate and an extremely low styrene loss rate.

Description

Nickel-based catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a nickel-based catalyst, a preparation method and application thereof.
Background
Styrene (ST) is an important monomer for producing Polystyrene (PS), ABS resin, styrene-butadiene rubber, and the like. At present, the world production methods of styrene mainly comprise an ethylbenzene dehydrogenation method, a propylene oxide-styrene (PO/SM) co-production method, a pyrolysis gasoline extractive distillation recovery method and the like. The production capacity of the ethylbenzene dehydrogenation method for preparing styrene accounts for about 90% of the total production capacity of the styrene in the world, and is the main method for producing the styrene at home and abroad at present. However, in recent years, with the increase in the production scale of ethylene, particularly in the case of a multi-megaton ethylene plant, the technology of recovering styrene by extraction from pyrolysis gasoline has become one of the technologies of increasing yield of styrene of great interest.
Pyrolysis gasoline is an important byproduct of the ethylene industry, the yield is about 60-70% of the ethylene production capacity, and the pyrolysis gasoline contains about 4-6% of styrene. The traditional processing method is to carry out two-stage hydrogenation on the C 6～C8 fraction in pyrolysis gasoline, wherein styrene is saturated to ethylbenzene, and the ethylbenzene is taken as a gasoline blending component or a raw material for C 8 aromatic hydrocarbon isomerization together with dimethylbenzene. The ratio of ethylbenzene to xylene isomers in the hydrogenated pyrolysis gasoline is about 1:1, the high ethylbenzene content reduces the value of the material as a raw material of a xylene device, the ethylbenzene influences the processing capacity of the paraxylene production device, and the circulation amount of a xylene isomerization loop is increased.
For ethylene enterprises with larger scale, if styrene can be separated before pyrolysis gasoline hydrogenation, considerable benefits are generated, and considerable economic benefits are brought by ① that styrene with purity of more than 99.7 percent can be separated, styrene is upgraded from fuel price to chemical value, mixed xylene can be recovered for producing isomers such as paraxylene, and xylene fraction is upgraded from fuel value to chemical value. Taking a set of 100 ten thousand tons/a ethylene device as an example, 2.4-4.2 kt/a of styrene can be obtained at low cost, ② can greatly reduce the hydrogenation load of the device and reduce the hydrogen consumption, and ③ has the production cost of 1/2 of ethylbenzene dehydrogenation.
The recovery of styrene from pyrolysis gasoline is generally accomplished by extractive distillation. Because Phenylacetylene (PA) and styrene have similar chemical structures and similar interactions with the extractant, effective separation of styrene from PA cannot be realized by extractive distillation, and styrene must be extracted after the selective hydrogenation removal of phenylacetylene. And PA is also a poison for styrene block copolymerization reaction, which increases the consumption of catalyst during styrene anion polymerization, affects chain growth and polymerization, and also causes deterioration of polystyrene performance such as discoloration, degradation, odor change, odor release and the like. Therefore, the development of a high-selectivity phenylacetylene selective hydrogenation catalyst becomes the core of a technology for recycling styrene from pyrolysis gasoline. In addition, it is important to note how to minimize the loss rate of styrene is critical to whether pyrolysis gasoline recovery of styrene is competitive.
Chinese patent CN1298376a discloses a method for hydrogenating phenylacetylene in a styrene-containing medium by means of a catalyst, which hydrogenates phenylacetylene in a styrene-containing medium by using a nickel catalyst having a nickel content of 10 to 25wt% supported on a carrier and a bubbling bed reactor, but the patent describes a method for selectively hydrogenating phenylacetylene only from the viewpoint of process control, but the hydrogenation performance of the catalyst is not ideal under high severe process conditions, and the loss of styrene in the process is not described in detail.
Chinese patent CN1087892a describes a method and apparatus for purifying phenylacetylene from a styrene stream by adding a diluent such as nitrogen to dilute the hydrogen, mixing the hydrogen with a catalyst selectivity improver such as carbon monoxide, dehydrogenating the effluent gas to provide hydrogen and hydrogenating phenylacetylene impurities to styrene using a multistage catalytic reactor, but only describes a method for selective hydrogenation and desyne with a low concentration of phenylacetylene content such as 300ppm, with a low hydrogenation rate of p-phenylacetylene (about 95%) and a styrene loss rate of about 0.2%. The process is only slightly improved from the point of view of the process and the catalyst is not described in detail.
Chinese patent CN1852877a discloses a process for hydrogenating phenylacetylene impurities in the presence of styrene monomer. A styrene monomer stream containing a small amount of phenylacetylene and a hydrogenation gas comprising hydrogen are fed to a hydrogenation reactor. The styrene monomer stream and hydrogen are contacted with a bed comprising a catalyst comprising a reduced copper compound on a theta alumina support. The hydrogenation reaction temperature is operated at a temperature of at least 60 ℃ and a pressure of at least 30psig to hydrogenate phenylacetylene to produce styrene. The hydrogenation gas is a mixture of nitrogen and hydrogen, the reaction temperature of the catalyst is high, the phenylacetylene hydrogenation rate is low, about 70%, the service life of the catalyst is short, and the loss rate of styrene is high (about 3%).
Chinese patent CN101475438a discloses a process for the selective hydrogenation of phenylacetylene in the presence of styrene. The method takes nickel or palladium oxide containing carbon as a catalyst, hydrocarbon materials containing phenylacetylene and hydrogen are contacted with the catalyst in a reactor, so that the phenylacetylene in the materials is hydrogenated into styrene, but the method needs to perform a pre-carbon deposition process on the catalyst at a certain temperature in the use process, which is not beneficial to practical application.
Therefore, how to increase the phenylacetylene hydrogenation rate in the phenylacetylene selective hydrogenation process in the presence of styrene and simultaneously reduce the loss rate of styrene is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide a nickel-based catalyst and a preparation method and application thereof, and aims to solve the technical problems of low phenylacetylene hydrogenation rate and high styrene loss rate in the prior art when phenylacetylene is selectively hydrogenated in styrene-rich carbon eight fractions.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a nickel-based catalyst comprising a support and nickel oxide supported on the support, the support comprising at least one metal oxide of alumina, molybdenum oxide, lithium and potassium, and at least one of phosphorus oxide and elemental fluorine;
The nickel-based catalyst comprises the following components in percentage by weight:
The balance being alumina.
In the present invention, the content of phosphorus oxide in the nickel-based catalyst is calculated as the mass of elemental phosphorus (P).
According to some embodiments of the invention, the alumina comprises θ -alumina.
In the nickel-based catalyst provided by the invention, if gamma-alumina is adopted, the acidity is too strong, styrene is easy to polymerize and cross, the acidity of alpha-alumina is weak, but the specific surface area is too small, the metal loading is low, and the catalyst activity is insufficient, so that the catalyst is more suitable for selecting theta-alumina with low acidity and high specific surface area.
According to some embodiments of the invention, the specific surface area of the nickel-based catalyst is 90-150 cm 2/g, and the average pore diameter is 12-20 nm.
In a second aspect, the present invention provides a method for preparing a nickel-based catalyst, comprising:
S1, mixing a solution comprising a molybdenum precursor, a phosphorus and/or fluorine precursor, a lithium and/or potassium precursor, sesbania powder and aluminum oxide, molding, drying for the first time, and roasting for the first time to obtain a carrier;
S2, impregnating the carrier by adopting a solution containing a nickel precursor, drying for the second time, and roasting for the second time to obtain the nickel-based catalyst.
The performance of the nickel-based catalyst provided by the invention is closely related to the performance of the carrier. Other elements except nickel are added in the preparation of the carrier, the carrier with optimized acidity and proper physical properties can be obtained after heat treatment, and the catalyst obtained by adopting the carrier to load the nickel component can have higher phenylacetylene hydrogenation rate and extremely low styrene loss rate when applied to the selective hydrogenation of phenylacetylene in the carbon eight fraction rich in styrene.
According to some embodiments of the invention, the alumina comprises θ -alumina.
According to some embodiments of the invention, the molybdenum precursor comprises any one of ammonium molybdate and ammonium heptamolybdate.
According to some embodiments of the invention, the phosphorus precursor comprises phosphoric acid.
According to some embodiments of the invention, the fluorine precursor comprises ammonium fluoride.
According to some embodiments of the invention, the lithium precursor comprises lithium carbonate.
According to some embodiments of the invention, the precursor of potassium comprises potassium carbonate.
According to some embodiments of the invention, the precursor of nickel comprises nickel nitrate.
According to some embodiments of the present invention, the mass ratio of the nickel precursor calculated as nickel oxide, the molybdenum precursor calculated as molybdenum oxide, the lithium and/or potassium precursor calculated as metal oxide, the phosphorus and/or fluorine precursor calculated as elemental phosphorus and/or fluorine, and the aluminum oxide is (10-30): (1-10): (0.5-5): (3-8): (47-85.5).
According to some embodiments of the invention, the mass ratio of sesbania powder to alumina is (0.008-0.046): 1.
In the preparation method of the nickel-based catalyst provided by the invention, sesbania powder is mainly used for enabling the nickel-based catalyst to be easier to form, and the sesbania powder can be decomposed in the roasting process and cannot become constituent components of the prepared nickel-based catalyst and influence the performance of the nickel-based catalyst.
According to some embodiments of the invention, the temperature of the first drying is 100-120 ℃ and the time is 12-20 hours.
According to some embodiments of the invention, the first firing is performed at a temperature of 400-600 ℃ for a time of 6-10 hours.
According to some embodiments of the invention, the temperature of the second drying is 100-140 ℃ and the time is 6-10 hours.
According to some embodiments of the invention, the temperature of the second firing is 400-600 ℃ and the time is 2-6 hours.
According to some embodiments of the invention, the impregnation is performed at normal temperature for 0.5-5.0 h.
According to some embodiments of the invention, the volume of the nickel nitrate solution is not less than the water absorption of the carrier.
In a third aspect, the present invention provides a nickel-based catalyst prepared by the preparation method of the second aspect.
In a fourth aspect, the present invention provides the use of a nickel-based catalyst according to the first aspect or a nickel-based catalyst according to the third aspect for the selective hydrogenation of phenylacetylene in a styrene-rich carbon eight fraction.
It should be noted that the styrene-rich fraction means that the styrene content in the carbon eight fraction is far greater than the phenylacetylene content.
The phenylacetylene content in the carbon eight fraction is 0.1-1.0%.
In a fifth aspect, the invention provides a method for selectively hydrogenating phenylacetylene in a styrene-rich carbon eight fraction, comprising the steps of reducing the nickel-based catalyst in the first aspect or the nickel-based catalyst in the third aspect with hydrogen, vulcanizing with dimethyl disulfide to obtain a vulcanized nickel-based catalyst, and then using the vulcanized nickel-based catalyst for selectively hydrogenating phenylacetylene in the styrene-rich carbon eight fraction.
According to some embodiments of the invention, the temperature of the vulcanization is 40-80 ℃.
According to some embodiments of the invention, the hydrogen reduction condition is that the hydrogen pressure is 0.2-0.5 MPa, the hydrogen flow is 800-1200 mL/min, the reduction temperature is 350-550 ℃, and the reduction time is 12-24 h.
According to some embodiments of the invention, the conditions of the selective hydrogenation reaction comprise a reaction temperature of 20-50 ℃, a reaction pressure of 0.2-0.5 mpa, and a molar ratio of hydrogen to phenylacetylene of (2-6): 1, and a raw material volume space velocity of 3-5 h -1.
The invention has the advantages that:
the nickel-based catalyst provided by the invention can be used as a catalyst for selective hydrogenation, has good low-temperature activity, selectivity and stability when being used for selective hydrogenation of phenylacetylene in the carbon eight fraction rich in styrene, and has higher phenylacetylene hydrogenation rate and extremely low styrene loss rate.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to specific embodiments. It should be understood that the detailed description is presented herein only to illustrate the present patent and is not intended to limit the scope of the invention in any way.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The reagents used in the following examples are all conventional biochemical reagents unless otherwise specified, the raw materials, instruments, equipment and the like used in the following examples are all commercially available or available by the existing methods, the amounts of the reagents are all the amounts of the reagents used in conventional experimental operations unless otherwise specified, and the experimental methods are all conventional methods unless otherwise specified.
In the present invention, the specific surface area and the average pore size were tested using low temperature N 2 physical adsorption desorption (BET). The specific method comprises the steps of carrying out vacuum degassing on a sample at 400 ℃ for 2 hours by adopting an automatic adsorption instrument of the type Digsorb-2600 in the United states, then carrying out specific surface area test on the sample by using a krypton adsorption capacity method in liquid nitrogen, and calculating the result according to a BET method.
Example 1
1) Preparation of the carrier:
Mixing 78.5g of theta-alumina, 1.0g of sesbania powder, 16.2g of 60% ammonium heptamolybdate solution, 20g of 50% phosphoric acid solution and 8.67g of 15% lithium carbonate solution, extruding into clover with the size phi=1.2 mm and the length of 2-15 mm, obtaining a green body, drying the green body at 120 ℃ for 12h, and roasting at 400 ℃ for 6h to obtain a carrier Z1.
2) Preparation of nickel-based catalyst:
mixing a carrier Z1 with 64.2g of nickel nitrate solution with the mass concentration of 40% for multiple times, dipping for 1h at normal temperature, wherein the volume of the nickel nitrate solution is not smaller than the water absorption capacity of the carrier, drying the dipped carrier at 120 ℃ for 8h, and roasting in air at 450 ℃ for 4h to obtain the nickel-based catalyst C1.
The composition, specific surface area and average pore diameter of the nickel-based catalyst C1 are shown in Table 1.
Example 2
1) Preparation of the carrier:
Mixing 56g of theta-alumina, 0.5g of sesbania powder, 6.5g of 20% ammonium heptamolybdate solution, 20.3g of 70% phosphoric acid solution, 15g of 60% ammonium fluoride solution, 13.7g of 50% lithium carbonate solution and 8.15g of 50% potassium carbonate solution, extruding into clover with the size phi=1.2 mm and the length of 2-15 mm, obtaining a green body, drying the green body at 120 ℃ for 12h, and roasting at 600 ℃ for 10h to obtain a carrier Z2.
2) Preparation of nickel-based catalyst:
mixing the carrier Z2 with 90.3g of nickel nitrate solution with the mass concentration of 90% for multiple times, dipping for 2 hours at normal temperature, wherein the volume of the nickel nitrate solution is not smaller than the water absorption capacity of the carrier, drying the dipped carrier at 120 ℃ for 8 hours, and roasting in air at 600 ℃ for 4 hours to obtain the nickel-based catalyst C2.
The composition, specific surface area and average pore diameter of the nickel-based catalyst C2 are shown in Table 1.
Example 3
1) Preparation of the carrier:
Mixing 65.5g of theta-alumina, 3g of sesbania powder, 19.4g of 60% ammonium heptamolybdate solution with mass concentration, 26.8g of 60% ammonium fluoride solution with mass concentration and 5.52g of 40% potassium carbonate solution with mass concentration, extruding the mixture into clover with the size phi=1.2 mm and the length of 2-15 mm to obtain a green body, drying the green body at 120 ℃ for 15h, and roasting the green body at 500 ℃ for 8h to obtain a carrier Z3.
2) Preparation of nickel-based catalyst:
Mixing a carrier Z3 with 61.5g of nickel nitrate solution with the mass concentration of 60% for multiple times, dipping for 3 hours at normal temperature, wherein the volume of the nickel nitrate solution is not smaller than the water absorption capacity of the carrier, drying the dipped carrier at 120 ℃ for 8 hours, and roasting in air at 450 ℃ for 10 hours to obtain the nickel-based catalyst C3.
The composition, specific surface area and average pore diameter of the nickel-based catalyst C3 are shown in Table 1.
Example 4
1) Preparation of the carrier:
Mixing 60g of theta-alumina, 2.5g of sesbania powder, 14g of ammonium heptamolybdate solution with the mass concentration of 30%, 36.1g of phosphoric acid solution with the mass concentration of 85%, 15g of lithium carbonate solution with the mass concentration of 40% and 11.9g of potassium carbonate solution with the mass concentration of 30%, extruding into clover with the size phi=1.2 mm and the length of 2-15 mm, obtaining a green body, drying the green body at 120 ℃ for 16h, and roasting at 600 ℃ for 10h, thus obtaining a carrier Z4.
2) Preparation of nickel-based catalyst:
Mixing the carrier Z4 with 92.5g of nickel nitrate solution with the mass concentration of 80% for multiple times, dipping for 5 hours at normal temperature, wherein the volume of the nickel nitrate solution is not smaller than the water absorption capacity of the carrier, drying the dipped carrier at 120 ℃ for 8 hours, and roasting for 4 hours at 600 ℃ in air to obtain the nickel-based catalyst C4.
The composition, specific surface area and average pore diameter of the nickel-based catalyst C4 are shown in Table 1.
Example 5
1) Preparation of the carrier:
Mixing 69g of theta-alumina, 2g of sesbania powder, 11.7g of 50% ammonium heptamolybdate solution with mass concentration, 12.2g of 50% ammonium fluoride solution with mass concentration and 22.3g of 20% potassium carbonate solution with mass concentration, extruding into clover with the dimension phi=1.2 mm and the length of 2-15 mm, obtaining a green body, drying the green body at 120 ℃ for 18h, and roasting at 550 ℃ for 10h, thus obtaining a carrier Z5.
2) Preparation of nickel-based catalyst:
Mixing a carrier Z5 with 70g of nickel nitrate solution with the mass concentration of 70% for multiple times, dipping for 4 hours at normal temperature, wherein the volume of the nickel nitrate solution is not smaller than the water absorption capacity of the carrier, drying the dipped carrier at 120 ℃ for 8 hours, and roasting in air at 500 ℃ for 4 hours to obtain the nickel-based catalyst C5.
The composition, specific surface area and average pore diameter of the nickel-based catalyst C5 are shown in Table 1.
Comparative example 1
1) Preparation of the carrier:
mixing 80g of theta-alumina, 3.3g of sesbania powder and water, extruding the mixture into clover with the size phi=1.2 mm and the length of 2-15 mm to obtain a green body, drying the green body at 120 ℃ for 18h, and roasting the green body at 550 ℃ for 10h to obtain the carrier D1.
2) Preparation of nickel-based catalyst:
Mixing the carrier D1 with 70g of nickel nitrate solution with the mass concentration of 70% for multiple times, soaking for 4 hours at normal temperature, wherein the volume of the nickel nitrate solution is not smaller than the water absorption capacity of the carrier, drying the soaked carrier at 120 ℃ for 8 hours, and roasting in air at 500 ℃ for 4 hours to obtain the nickel-based catalyst CD1.
The composition, specific surface area and average pore diameter of the nickel-based catalyst CD1 are shown in Table 1.
Comparative example 2
1) Preparation of the carrier:
Mixing 72g of theta-alumina, 2.9g of sesbania powder, 11.7g of 50% ammonium heptamolybdate solution and 22.3g of 20% potassium carbonate solution, extruding the mixture into clover with the size phi=1.2 mm and the length of 2-15 mm to obtain a green body, drying the green body at 120 ℃ for 18h, and roasting the green body at 550 ℃ for 10h to obtain a carrier D2.
2) Preparation of nickel-based catalyst:
Mixing the carrier D2 with 70g of nickel nitrate solution with the mass concentration of 70% for multiple times, dipping for 4 hours at normal temperature, wherein the volume of the nickel nitrate solution is not smaller than the water absorption capacity of the carrier, drying the dipped carrier at 120 ℃ for 8 hours, and roasting in air at 500 ℃ for 4 hours to obtain the nickel-based catalyst CD2.
The composition, specific surface area and average pore diameter of the nickel-based catalyst CD2 are shown in Table 1.
Comparative example 3
1) Preparation of the carrier:
Mixing 77g of theta-alumina, 1.8g of sesbania powder and 12g of 50% ammonium fluoride solution, extruding the mixture into clover with the size phi=1.2 mm and the length of 2-15 mm to obtain a green body, drying the green body at 120 ℃ for 18h, and roasting the green body at 550 ℃ for 10h to obtain a carrier D3.
2) Preparation of nickel-based catalyst:
Mixing the carrier D3 with 70g of nickel nitrate solution with the mass concentration of 70% for multiple times, dipping for 4 hours at normal temperature, wherein the volume of the nickel nitrate solution is not smaller than the water absorption capacity of the carrier, drying the dipped carrier at 120 ℃ for 8 hours, and roasting in air at 500 ℃ for 4 hours to obtain the nickel-based catalyst CD3.
The composition, specific surface area and average pore diameter of the nickel-based catalyst CD3 are shown in Table 1.
Comparative example 4
The difference from example 5 is that:
The theta alumina was replaced with alpha alumina, the resulting support was designated D4, and the resulting nickel-based catalyst was designated CD4.
The composition, specific surface area and average pore diameter of the nickel-based catalyst CD4 are shown in Table 1.
Comparative example 5
The difference from example 5 is that:
The theta-alumina was replaced with gamma-alumina, the resulting support was designated D5, and the resulting nickel-based catalyst was designated CD5.
The composition, specific surface area and average pore diameter of the nickel-based catalyst CD5 are shown in Table 1.
Comparative example 6
The difference from example 5 is that:
69g of theta alumina was replaced with 100g of pseudo-boehmite (69 wt% Al 2O3), the resulting support was designated D6, and the resulting nickel-based catalyst was designated CD6.
The composition, specific surface area and average pore diameter of the nickel-based catalyst CD6 are shown in Table 1.
Comparative example 7
1) Preparation of the carrier:
Mixing 69g of theta-alumina, 2g of sesbania powder, 12.2g of ammonium fluoride solution with the mass concentration of 50% and 22.3g of potassium carbonate solution with the mass concentration of 20%, extruding into clover with the size phi=1.2 mm and the length of 2-15 mm to obtain a green body, drying the green body at 120 ℃ for 18h, and roasting at 550 ℃ for 10h to obtain a carrier D7.
2) Preparation of nickel-based catalyst:
The method comprises the steps of mixing a carrier D7 with 11.7g of 50% ammonium heptamolybdate solution and 70g of 70% nickel nitrate solution for multiple times, soaking for 4 hours at normal temperature, wherein the volume of the nickel nitrate solution is not smaller than the water absorption capacity of the carrier, drying the soaked carrier at 120 ℃ for 8 hours, and roasting the carrier at 500 ℃ in air for 4 hours to obtain the nickel-based catalyst CD7.
The composition, specific surface area and average pore diameter of the nickel-based catalyst CD7 are shown in Table 1.
TABLE 1 composition, specific surface area, average pore size of Nickel-based catalysts of examples and comparative examples
Application example 1
Use of the catalysts obtained in the examples and comparative examples for the selective hydrogenation of phenylacetylene in a carbon eight fraction:
Taking 100mL of the catalysts obtained in each example and comparative example, reducing for 16h under the conditions of hydrogen pressure of 0.3MPa, temperature of 450 ℃ and hydrogen flow of 1000mL/min, cooling to 50 ℃, introducing cyclohexane solution of dimethyl disulfide (with the mass concentration of 0.044% and the sulfur content of 300 ppm) under the conditions of maintaining the hydrogen flow and pressure, vulcanizing for 15h, and introducing a carbon eight fraction raw material under the conditions of temperature of 30 ℃ and reaction pressure of 0.3MPa, the molar ratio of hydrogen to phenylacetylene of 4:1 and the volume space velocity of 4h -1 for selective hydrogenation. The mass percentage composition of the carbon eight fraction raw material is shown in table 2, and the hydrogenation result is shown in table 3.
TABLE 2 carbon eight fraction raw material mass percent composition
TABLE 3 Selective hydrogenation reaction results for Nickel-based catalysts of examples and comparative examples
As shown in tables 1-3, the nickel-based catalyst provided by the invention is used in the selective hydrogenation of phenylacetylene, has higher phenylacetylene hydrogenation rate and extremely low styrene loss rate, has the output phenylacetylene content of not more than 5ppm and has an increment of styrene, and can be used in the industrial production of the selective hydrogenation of trace phenylacetylene in a carbon eight fraction.
Comparative example 1 was used
The catalyst obtained in example 5 was examined for its use in the selective hydrogenation of phenylacetylene in a carbon eight fraction (the composition of the raw materials in mass% is shown in Table 2) by the method of application example 1, except that the "cooling to 50℃was not conducted, and a cyclohexane solution of dimethyl disulfide (0.044% in mass concentration, wherein the sulfur content is 300 ppm) was introduced under the condition of maintaining the flow rate and pressure of hydrogen gas, and sulfided for 15 hours". The hydrogenation results are shown in Table 4.
Comparative example 2 was used
The catalyst obtained in example 5 was examined for its use in the selective hydrogenation of phenylacetylene in a carbon eight fraction (the composition of the feedstock in mass% is shown in Table 2) by the method of application example 1, except that the sulfiding temperature was changed from 50℃to 100 ℃. The hydrogenation results are shown in Table 4.
TABLE 4 Selective hydrogenation reaction results for Nickel-based catalyst of example 5
Evaluation of catalyst stability
The catalyst stability evaluation test was carried out using 100 ml of each of the catalysts of example 5 and comparative example 3 by using the same apparatus, raw materials and reaction conditions as those of application example 1, and the results are shown in Table 5.
TABLE 5
As can be seen from Table 5, the nickel-based catalyst of the present invention has excellent catalytic stability.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (10)

1. A nickel-based catalyst, characterized by comprising a carrier and nickel oxide supported on the carrier, wherein the carrier comprises at least one metal oxide of aluminum oxide, molybdenum oxide, lithium and potassium, and at least one of phosphorus oxide and fluorine simple substance;
The nickel-based catalyst comprises the following components in percentage by weight:
The balance being alumina.
2. The nickel-based catalyst of claim 1, wherein the alumina comprises θ -alumina.
3. The nickel-based catalyst according to claim 1 or 2, wherein the specific surface area of the nickel-based catalyst is 90-150 cm 2/g and the average pore diameter is 12-20 nm.
4. A method for preparing a nickel-based catalyst, comprising:
S1, mixing a solution comprising a molybdenum precursor, a phosphorus and/or fluorine precursor, a lithium and/or potassium precursor, sesbania powder and aluminum oxide, molding, drying for the first time, and roasting for the first time to obtain a carrier;
S2, impregnating the carrier by adopting a solution containing a nickel precursor, drying for the second time, and roasting for the second time to obtain the nickel-based catalyst.
5. The method of preparing according to claim 4, wherein the alumina comprises θ -alumina;
And/or the molybdenum precursor comprises any one of ammonium molybdate and ammonium heptamolybdate;
And/or, the phosphorus precursor comprises phosphoric acid;
and/or, the fluorine precursor comprises ammonium fluoride;
and/or, the lithium precursor comprises lithium carbonate;
and/or, the precursor of potassium comprises potassium carbonate;
and/or, the precursor of nickel comprises nickel nitrate.
6. The production method according to claim 4 or 5, wherein the mass ratio of the precursor of nickel in terms of nickel oxide, the precursor of molybdenum in terms of molybdenum oxide, the precursor of lithium and/or potassium in terms of metal oxide, the precursor of phosphorus and/or fluorine in terms of elemental phosphorus and/or fluorine, and aluminum oxide is (10-30): 1-10): 0.5-5): 3-8): 47-85.5.
7. The method according to any one of claims 4 to 6, wherein the temperature of the first drying is 100 to 120 ℃ for 12 to 20 hours;
and/or the temperature of the first roasting is 400-600 ℃ and the time is 6-10 hours;
and/or the temperature of the second drying is 100-140 ℃ and the time is 6-10 h;
and/or the temperature of the second roasting is 400-600 ℃ and the time is 2-6 h.
8. A nickel-based catalyst prepared by the method of any one of claims 4-7.
9. Use of the nickel-based catalyst of any of claims 1-3 or the nickel-based catalyst of claim 8 for the selective hydrogenation of phenylacetylene, in particular in a styrene-rich carbon eight fraction.
10. A method for selectively hydrogenating phenylacetylene in a styrene-rich carbon eight fraction is characterized by comprising the steps of reducing the nickel-based catalyst according to any one of claims 1-3 or the nickel-based catalyst according to claim 8 with hydrogen and then vulcanizing with dimethyl disulfide to obtain a vulcanized nickel-based catalyst, and then using the vulcanized nickel-based catalyst for the selective hydrogenation of phenylacetylene in the styrene-rich carbon eight fraction;
preferably, the vulcanization temperature is 40-80 ℃.
CN202410449946.XA 2024-04-15 2024-04-15 A nickel-based catalyst and its preparation method and application Pending CN120815537A (en)

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