CN108654610B - Preparation method of noble metal supported catalyst, catalyst and naphthenic hydrocarbon hydrogenolysis ring-opening method - Google Patents
Preparation method of noble metal supported catalyst, catalyst and naphthenic hydrocarbon hydrogenolysis ring-opening method Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/307—Cetane number, cetane index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method of a noble metal supported catalyst, the catalyst obtained by the method and a ring opening method for naphthenic hydrocarbon hydrogenolysis, wherein the preparation method comprises the following steps: (1) preparing a mixed solution containing a first component containing a VIII group noble metal element compound, a second component containing an alkali metal and/or alkaline earth metal element compound and a third component containing a VIB group and/or VIIB group metal element compound, and reacting under certain conditions to obtain a colloidal solution; (2) dispersing a carrier in a solvent to obtain suspension containing the carrier; (3) and (3) mixing the colloidal solution obtained in the step (1) with the suspension obtained in the step (2), and then drying and optionally roasting to obtain the noble metal supported catalyst. Compared with the catalyst with the same noble metal content prepared by the prior art, the noble metal supported catalyst has obviously higher catalytic activity and selectivity for the ring opening of the hydrogenolysis of the cycloalkane when being used for the ring opening of the cycloalkane by hydrogenolysis.
Description
Technical Field
The invention relates to a noble metal supported catalyst, a preparation method and application thereof, and a method for catalyzing ring opening of naphthenic hydrocarbon by hydrogenolysis by using the catalyst.
Background
With the development of the world economy, the demand of diesel oil is increasing. This requirement cannot be met by straight-run diesel alone, which requires blending in secondary process diesel, such as catalytic cracking diesel and coker diesel. The secondary processing diesel contains a large amount of sulfur, nitrogen and aromatic hydrocarbon, the sulfur and the nitrogen can be removed by using the traditional sulfide catalyst at present, and the technical difficulty is the conversion of the aromatic hydrocarbon. The high aromatics content in diesel fuel not only reduces the quality of the oil, but also increases particulate emissions in the combustion exhaust of diesel fuel. Normally normal or short-side chain paraffins have the highest cetane number, long-side chain paraffins and aromatics are higher in cetane number, and short-side chain or side chain-free naphthenes and aromatics are the lowest in cetane number. Thus, the aromatics hydrogenation saturation process is limited to increasing the cetane number of diesel fuel, and the ring-opening reaction is expected to increase the cetane number of diesel fuel. With the increasing severity of environmental regulations on clean energy, dearomatization upgrading of diesel fuels has become a focus of research. Therefore, the realization of the high-selectivity ring-opening reaction of the cyclanes has important significance for improving the quality of the diesel oil.
The cycloalkane ring-opening reaction can proceed by three mechanisms: a radical reaction mechanism, a carbonium ion mechanism and a hydrogenolysis mechanism (Journal of Catalysis,2002,210, 137-148). In contrast, metal catalyzed hydrogenolysis mechanisms have higher activity and selectivity for selective ring opening of cycloalkanes, primarily because ring opening is easier than side chain scission due to the intra-ring tension of the cycloalkane molecule.
WO/2002/007881 discloses a catalyst and process for ring opening of cycloalkanes by use of iridium catalysts supported on a composite support of alumina and an acidic aluminosilicate molecular sieve. Moreover, the catalyst is exposed to oxygen atmosphere of 250 ℃ for calcination and regeneration, and the ring-opening activity of the catalyst is not significantly deactivated.
CN200480043382.0 discloses a catalyst and a method for opening cyclic alkane using the catalyst. The catalyst comprises a group VIII metal component, a molecular sieve, a refractory inorganic oxide, and optionally a modifier component. The molecular sieves include MAPSO, SAPO, UZM-8 and UZM-15, the group VIII metals include platinum, palladium and rhodium, and the inorganic oxide is preferably alumina.
CN200910013536.6 discloses a naphthenic hydrocarbon hydroconversion catalyst, a preparation method and an application thereof. The catalyst comprises a carrier and active metal Pt, wherein the carrier consists of a hydrogen type Y-Beta composite molecular sieve and an inorganic refractory oxide, the content of the hydrogen type Y-Beta composite molecular sieve in the catalyst carrier is 10-90 wt%, and the content of the active metal Pt in the catalyst is 0.05-0.6%. The catalyst is prepared by adopting an impregnation method, and the obtained catalyst can be used for the hydro-conversion of various raw materials containing cycloparaffin.
CN201110102568.0 discloses an aromatic selectivity ring-opening reaction process, wherein the reaction is carried out in two reactors connected in series; the material enters a first reactor for deep desulfurization and denitrification reaction and passes through H 2 S and NH 3 When the S content and the N content in the material are lower than 50ppm and 10ppm respectively, the material enters a second reactor for selective ring-opening reaction, the reactor is provided with two reaction beds, the first reaction bed is used for hydrogenation saturation isomerization reaction, and the second reaction bed is used for selective ring-opening reaction; the first reactor selects a metal sulfide catalyst; the first bed of the second reactor is filled with a noble metal/molecular sieve-alumina catalyst.
Alcohol (generally polyhydric alcohol) is used as a reducing agent and a solvent in the alcohol thermal reduction process, and a stabilizing agent is mostly not used, so that the prepared catalyst has high particle dispersity, uniform and controllable particle size distribution, low cost and simple operation. Wang reported a method for preparing stable monometal nanoparticles of Pt, Rh, Ru and the like in an organic medium by an alcoholic thermal reduction method without using a stabilizer (Chemistry of Materials,2000,12(6): 1622-1627).
However, there is still room for improvement and improvement in the naphthene hydrogenolysis ring-opening activity and selectivity of the above-disclosed catalysts. The noble metal supported catalyst for the ring opening of the hydrogenolysis of the cycloalkane disclosed above is basically obtained by a conventional impregnation method or a co-impregnation method, however, the important method for preparing the highly dispersed nano metal catalyst developed in recent years, namely the alcoholic thermal reduction method, is rarely reported in the field of the catalyst suitable for the ring opening of the hydrogenolysis of the cycloalkane.
Disclosure of Invention
The invention aims to provide a preparation method of a noble metal supported catalyst, the catalyst obtained by the method and application thereof, and also provides a method for catalyzing the ring opening reaction of naphthenic hydrocarbon hydrogenolysis.
The invention provides a preparation method of a noble metal supported catalyst, which comprises the following steps:
(1) preparing a mixed solution containing a first component containing a VIII group noble metal element compound, a second component containing an alkali metal and/or alkaline earth metal element compound and a third component containing a VIB group metal element compound and/or VIIB group metal element compound, and reacting for 0.5-24 hours at 50-200 ℃ to obtain a colloidal solution;
(2) dispersing a carrier in a solvent to obtain suspension containing the carrier;
(3) and (3) mixing the colloidal solution obtained in the step (1) with the suspension obtained in the step (2), and then drying and optionally roasting to obtain the noble metal supported catalyst.
The invention also provides the noble metal supported catalyst prepared by the method and the application thereof in catalyzing the ring opening reaction of the hydrogenolysis of the cycloalkane.
The invention further provides a naphthenic hydrocarbon hydrogenolysis ring-opening method, which comprises the step of contacting a raw material containing naphthenic hydrocarbon and hydrogen with a catalyst under the condition of catalyzing the naphthenic hydrocarbon hydrogenolysis ring-opening, wherein the catalyst is the noble metal supported catalyst.
Compared with the catalyst with the same noble metal content prepared by the prior art, the noble metal supported catalyst has obviously higher catalytic activity for the hydrogenolysis ring opening of the cycloalkane and lower cracking rate. Additional features and advantages of the invention will be set forth in the detailed description which follows.
Description of the drawings:
the accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray photoelectron spectrum of Ir 4f for catalyst R1 prepared in inventive example 1 and comparative catalyst D1 prepared in comparative example 1;
FIG. 2 is an X-ray photoelectron spectrum of Re4f of catalyst R1 obtained in example 1 of the present invention and comparative catalyst D1 obtained in comparative example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a preparation method of a noble metal supported catalyst, which comprises the following steps:
(1) preparing a mixed solution containing a first component containing a VIII group noble metal element compound, a second component containing an alkali metal or alkaline earth metal element compound and a third component containing a VIB group and/or VIIB group metal element compound, and reacting at 50-200 ℃ for 0.5-24 hours, preferably at 100-180 ℃ for 2-10 hours to obtain a colloidal solution;
(2) dispersing a carrier in a solvent to obtain suspension containing the carrier;
(3) and (3) mixing the colloidal solution obtained in the step (1) with the suspension obtained in the step (2), and then drying and optionally roasting to obtain the noble metal supported catalyst.
Wherein, the three components in the step (1) can be prepared into solutions separately according to the properties of respective solubility, compatibility and the like, and then mixed, or directly prepared in the same solution; for example, a solution containing the first component and a solution containing both the second component and the third component are prepared separately and then mixed; alternatively, a solution containing both the first component and the third component and a solution containing the second component are prepared separately and then mixed.
After mixing the three-component solution of step (1), the reaction is preferably carried out under an inert atmosphere and/or a reducing atmosphere, which may be nitrogen, argon, helium, hydrogen, or a mixture thereof.
Preferably, in the step (1), the group VIII noble metal element is at least one selected from Ir, Rh and Ru, and the group VIII noble metal element-containing compound is selected from H 2 IrCl 6 、(NH 4 ) 2 IrCl 6 、IrCl 3 、(NH 4 ) 3 IrCl 6 、RhCl 3 、(NH 4 ) 3 RhCl 6 、RhPO 4 、Rh 2 (SO 4 ) 3 、RuCl 3 、(NH 4 ) 3 RuCl 6 、Ru(CH 3 COO) 3 、Ru(NO)(NO 3 ) 3 At least one of (a); further preferably, the group VIII noble metal element is Ir, and the group VIII noble metal element-containing compound is selected from H 2 IrCl 6 、(NH 4 ) 2 IrCl 6 、IrCl 3 、(NH 4 ) 3 IrCl 6 At least one of (1).
In the step (1), the alkali metal or alkaline earth metal element is preferably at least one selected from Li, Na, K, Rb and Ba, the compound containing the alkali metal or alkaline earth metal element is preferably hydroxide, and the metal element in the VIB and/or VIIB group is preferably at least one selected from Mo, W, Re and Mn.
Preferably, the solvent used for preparing the three-component solution in step (1) and the solvent used in step (2) may be the same solvent or different solvents, and both of them may be independently selected from alcohol or a mixture of alcohol and water, the alcohol is at least one selected from monohydric alcohol, dihydric alcohol and trihydric alcohol with 1-6 carbon atoms, and the content of alcohol in the solvent is 40-100 wt%; more preferably, the alcohol is at least one of ethanol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol and glycerol, and the content of the alcohol in the solvent is 70-100 wt%.
For better performance of the final catalyst, in preparing the colloidal solution, the components in step (1) are preferably used in such amounts that the content of the first component in terms of noble metal elements of group VIII, the content of the second component in terms of alkali metal and/or alkaline earth metal elements is 1 to 200 g/l, and the content of the third component in terms of metal elements of group VIB and/or VIIB is 1 to 500 g/l, based on the weight of the colloidal solution.
The support of the step (2) is not particularly limited, and preferably, may be one or more selected from the group consisting of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves, and activated carbon.
The method for dispersing the carrier in the solvent in the step (2) is not particularly limited, and various methods known to those skilled in the art may be used; for example, electromagnetic stirring dispersion and ultrasonic dispersion may be used.
In the finally obtained catalyst, the components of the step (1) and the step (2) are preferably used in such amounts that the contents of the components in terms of elements in the catalyst are as follows: the content of noble metal elements is 0.2-15 wt%, the content of VIB and/or VIIB group metal elements is 0.2-15 wt%, the content of alkali metals and/or alkaline earth metals is 0-2 wt%, and the balance is carrier, and the total content is 100 wt%. Further preferably, the content of the noble metal elements is 0.5 to 10 weight percent, the content of the metal elements in the VIB group and/or the VIIB group is 0.5 to 10 weight percent, the content of the alkali metals and/or the alkaline earth metals is 0 to 1 percent, and the balance is the carrier.
After the colloidal solution in the step (1) and the suspension in the step (2) are mixed, the mixture may be separated and then dried, or may be directly dried. Generally, when the solid content is low, for example, 50% or less, the separation and the drying are preferred, and when the solid content is high, for example, 50% or more, the drying is conducted directly. The separation method and drying method in the step (3) are not particularly limited, and various methods known to those skilled in the art may be used; the separation method can adopt normal pressure filtration washing, reduced pressure filtration washing and centrifugal separation washing, and the drying mode can be oven drying and vacuum drying in air atmosphere. The drying conditions are also not particularly limited, and preferred drying conditions include: the temperature is 40-200 ℃ and the time is 0.1-24 hours. The product after drying may be calcined or not calcined according to different requirements, and the calcination condition is not particularly limited, and preferably, the calcination can be carried out at 200-600 ℃ for 0.1-24 hours.
The invention also provides the noble metal supported catalyst prepared by the method. Under the preferable condition, the content of noble metal is 0.2-15 wt%, the content of VIB and/or VIIB group element is 0.2-15 wt%, the content of alkali metal and/or alkaline earth metal is 0-2 wt% and the rest is carrier; further preferably, the noble metal content is 0.5-10 wt%, the group VIB and/or VIIB element content is 0.5-10 wt%, the alkali metal and/or alkaline earth metal content is 0-1 wt%, and the remainder is the support.
The inventor tests the metal content of the catalyst obtained by the invention, and the result shows that the noble metal supported catalyst obtained by the method meets the requirement (M) 2 /M 1 ) XPS /(M 2 /M 1 ) XRF 2-20, preferably 2.5-10, more preferably 3-5, wherein M is 1 Is a noble metal element of group VIII, M 2 Is a metal element of group VIB and/or VIIB, (M) 2 /M 1 ) XPS M in catalyst characterized by X-ray photoelectron spectroscopy 2 And M 1 (M) weight ratio based on the metal element 2 /M 1 ) XRF M in catalyst characterized by X-ray fluorescence spectrum 2 And M 1 Weight ratio in terms of metal element. The X-ray photoelectron spectrum is measured by adopting a monochromator Al K alpha X ray with an excitation light source of 150kW, and the measurement conditions of the X-ray fluorescence spectrum comprise a rhodium target, laser voltage of 50kV and laser current of 50 mA.
The invention also provides application of the noble metal supported catalyst in catalyzing ring opening reaction of naphthenic hydrocarbon hydrogenolysis.
In addition, the invention also provides a catalytic naphthene hydrogenolysis ring-opening reaction method, which comprises the step of contacting a raw material containing naphthene and hydrogen with a catalyst under the catalytic naphthene hydrogenolysis ring-opening condition, wherein the catalyst is the noble metal supported catalyst. The catalyst of the invention can be used for hydrogenolysis ring-opening reaction of various raw materials containing naphthene, such as naphthene model compounds, gasoline fraction, kerosene fraction or diesel fraction containing naphthene, preferably the mass content of aromatic hydrocarbon is less than 15%, and the mass content of sulfur is less than 30 ppm.
The ring opening condition of catalytic naphthenic hydrocarbon hydrogenolysis can be carried out according to the prior art, and preferably, the temperature is 180-450 ℃, the pressure is 1-18MPa, and the volume ratio of hydrogen to oil is 50-10000: 1, qualityThe volume space velocity is 0.1-100 hours -1 (ii) a Further preferably: the temperature is 220 ℃ and 400 ℃, the pressure is 2-12MPa, and the volume ratio of hydrogen to oil is 50-5000: 1, the mass space velocity is 0.2-80 hours -1 。
The means for the contact reaction may be carried out in any reactor sufficient for the contact reaction of the feedstock oil with the noble metal supported catalyst under hydrogenation reaction conditions, such as a fixed bed reactor, a slurry bed reactor, a moving bed reactor or an ebullating bed reactor.
Compared with the catalyst with the same noble metal content prepared by the prior art, the catalyst prepared by the method has obviously higher catalytic activity for the ring opening of the hydrogenolysis of the cycloalkane and lower cracking rate. The reason for this is probably because the preparation method of the catalyst provided by the invention greatly improves the interaction interface of the noble metal and the species containing the VIB and/or VIIB elements, and is beneficial to the selective breakage of secondary carbon-tertiary carbon bonds in cycloalkanes, thereby improving the ring opening selectivity.
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. In the following examples, the percentages are by weight unless otherwise specified; the catalyst composition is calculated according to the feeding amount and is based on the total weight of the catalyst, and the mass percentage of the hydrogenation active metal elements is calculated; the measuring instrument for X-ray photoelectron spectroscopy is an ESCALB 250 instrument of Thermo Scientific company, and the measuring conditions are as follows: an excitation light source is a monochromator Al K alpha X ray of 150kW, and the combination energy is corrected by adopting a C1 s peak (284.8 eV); the measuring instrument for X-ray fluorescence spectrum is 3271 type instrument of Nippon science and Motor industry Co., Ltd, and the measuring conditions are as follows: and tabletting and molding the powder sample, wherein the rhodium target is subjected to laser voltage of 50kV and laser current of 50 mA.
Example 1
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
100 ml of ethylene glycol solution containing iridium 6.0 g/l chloroiridic acid and rhenium 10.0 g/l perrhenic acid is prepared, added into 100 ml of ethylene glycol solution containing potassium hydroxide 18.5 g/l under stirring, stirred for 1 hour at room temperature, and the obtained reactant is refluxed for 4 hours at 160 ℃ under the protection of nitrogen to prepare about 200 ml of iridium colloid solution, and cooled to room temperature for standby.
Taking 20 g of SiO 2 -Al 2 O 3 The carrier (prepared according to example 2 of cn201110139331.x, the same applies below) was dispersed in 50 ml of ethanol with magnetic stirring. 200 ml of the iridium colloidal solution was added dropwise to 50 ml of the carrier-dispersed ethanol under rapid electromagnetic stirring, and the electromagnetic stirring was continued for 2 hours. And (3) carrying out vacuum filtration on the solid under reduced pressure, washing with water for several times, and carrying out vacuum drying at 120 ℃ for 12 hours to obtain the iridium-containing supported catalyst, wherein the iridium-containing supported catalyst is stored in a dryer for later use. The obtained catalyst is marked as R1, and the composition, XPS and XRF characterization results are shown in Table 1, wherein X-ray photoelectron spectra are shown in figures 1 and 2. The atomic ratio (M) of the surface layer was obtained by converting the peak areas corresponding to the electron binding energies of Ir 4f and Re4f 2 /M 1 ) XPS . Wherein the composition is the weight percentage content of the iridium, the third component metal element and the second component metal element (the same below) calculated by element based on the total weight of the catalyst.
Comparative example 1
This comparative example serves to illustrate a comparative catalyst and a process for its preparation.
The iridium-containing supported catalyst is prepared by adopting a co-impregnation method. Preparing 44 ml of aqueous solution of chloroiridic acid containing 11.4 g/l of iridium and perrhenic acid containing 15.9 g/l of rhenium, and soaking the aqueous solution into 20 g of SiO 2 -Al 2 O 3 The carrier is evenly stirred at the temperature of 20 ℃, is dried at the temperature of 120 ℃ after being kept stand for 4 hours, is roasted at the temperature of 400 ℃ for 4 hours, and is reduced by hydrogen at the temperature of 400 ℃ for 4 hours, and the pressure of the hydrogen is 0.1 MPa. Reducing the temperature to room temperature after reduction, and storing in a dryer for later use. The catalyst obtained was designated as D1 and its composition, XPS and XRF characterization results are given in Table 1. Wherein the X-ray photoelectron spectrum is shown in figure 1 and figure 2.
Comparative example 2
This comparative example serves to illustrate a comparative catalyst and a process for its preparation.
A catalyst was prepared according to the procedure of example 1 except that the ethylene glycol solution used to prepare the iridium colloidal solution did not contain perrhenic acid. The catalyst obtained was designated as D2 and its composition, XPS and XRF characterization results are given in Table 1.
Example 2
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
100 ml of ethylene glycol solution containing iridium 6.0 g/l and rhenium 15.6 g/l of perrhenic acid is prepared, added to 100 ml of ethylene glycol solution containing potassium hydroxide 18.5 g/l under stirring, stirred at room temperature for 1 hour, the obtained reaction product is refluxed at 160 ℃ for 4 hours under the protection of nitrogen to prepare about 200 ml of iridium colloidal solution, and cooled to room temperature for standby.
Taking 20 g of SiO 2 -Al 2 O 3 The carrier was dispersed in 50 ml of ethanol with electromagnetic stirring. 200 ml of the iridium colloidal solution was added dropwise to 50 ml of the carrier-dispersed ethanol under rapid electromagnetic stirring, and the electromagnetic stirring was continued for 2 hours. And (3) carrying out vacuum filtration on the solid under reduced pressure, washing with water for several times, and carrying out vacuum drying at 120 ℃ for 12 hours to obtain the iridium-containing supported catalyst, wherein the iridium-containing supported catalyst is stored in a dryer for later use. The catalyst obtained was designated as R2 and its composition, XPS and XRF characterization results are given in Table 1.
Example 3
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
100 ml of iridium chloride solution containing 10.3 g/l of iridium is prepared, added to 100 ml of ethylene glycol solution containing 3.2 g/l of potassium hydroxide and 15.6 g/l of tungsten ammonium tungstate under stirring, stirred at room temperature for 1 hour, the obtained reactant is refluxed at 160 ℃ for 6 hours under the protection of nitrogen to prepare about 200 ml of iridium colloidal solution, and cooled to room temperature for later use.
Taking 20 g of SiO 2 -Al 2 O 3 The carrier was dispersed in 50 ml of ethanol with electromagnetic stirring. 200 ml of the iridium colloidal solution was added dropwise to 50 ml of the carrier-dispersed ethanol under rapid electromagnetic stirring, and the electromagnetic stirring was continued for 2 hours. And (3) carrying out vacuum filtration on the solid under reduced pressure, washing with water for several times, and carrying out vacuum drying at 140 ℃ for 10 hours to obtain the iridium-containing supported catalyst, wherein the iridium-containing supported catalyst is stored in a dryer for later use. The obtained catalystThe composition, XPS and XRF characterization results are shown in Table 1 and recorded as R3.
Example 4
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
100 ml of a 1, 2-propanediol solution containing 6.0 g/l ruthenium chloride is prepared, added to 100 ml of a 1, 2-propanediol solution containing 8.4 g/l sodium hydroxide and 10.0 g/l ammonium molybdate with molybdenum under stirring, stirred at room temperature for 1 hour, the obtained reaction is refluxed at 160 ℃ for 4 hours under the protection of nitrogen to prepare about 200 ml of a ruthenium colloidal solution, and cooled to room temperature for later use.
20 g of gamma-Al is taken 2 O 3 The carrier (product of Changling catalyst plant, particle size 20-40 mesh), is dispersed in 50 ml ethanol by electromagnetic stirring. The 200 ml of ruthenium colloidal solution was added dropwise to the 50 ml of ethanol in which the carrier was dispersed under rapid electromagnetic stirring, and the electromagnetic stirring was continued for 4 hours. And (3) carrying out vacuum filtration on the solid under reduced pressure, washing with water for several times, and carrying out vacuum drying at 140 ℃ for 8 hours to obtain the ruthenium-containing supported catalyst, wherein the ruthenium-containing supported catalyst is stored in a dryer for later use. The catalyst obtained was designated as R4 and its composition, XPS and XRF characterization results are given in Table 1.
Examples 5 to 8
These examples serve to illustrate the catalytic hydrogenolysis ring opening results of the catalyst provided by the present invention on the model compound methylcyclopentane.
Catalysts R1, R2, R3 and R4 were each evaluated according to the following procedure.
The activity evaluation of the catalyst is carried out on a continuous flow fixed bed micro-reaction device, raw oil is a model compound methyl cyclopentane, the loading amount of the catalyst is 0.5 g, and the reaction conditions are as follows: the pressure is 3.0 MPa, the input amount of raw oil is 0.2 ml/min, the volume ratio of hydrogen to oil is 1000, the temperature is 260 ℃, and a sample is taken for on-line gas chromatographic analysis after 3 hours of reaction. Before the reaction, the reaction mixture was reduced at 260 ℃ under a hydrogen pressure of 3.0 MPa and a flow rate of 200 ml/min for 2 hours. The reaction results are shown in Table 2.
Comparative examples 3 to 4
These comparative examples serve to illustrate the hydrogenolysis ring opening activity of the comparative catalysts.
Comparative catalysts D1 and D2 were evaluated in the same manner and under the same conditions as in example 5. The reaction results are shown in Table 2.
TABLE 1
TABLE 2
| Examples | Catalyst and process for preparing same | Methylcyclopentane conversion (%) | Straight chain alkane selectivity (%) |
| Comparative example 3 | D1 | 47 | 46 |
| Comparative example 4 | D2 | 41 | 37 |
| Example 5 | R1 | 69 | 52 |
| Example 6 | R2 | 67 | 53 |
| Example 7 | |
66 | 50 |
| Example 8 | |
64 | 49 |
Examples 9 to 12
These examples illustrate the hydrogenolysis ring opening activity of the catalysts provided by the present invention when treating oils.
Catalysts R1, R2, R3 and R4 were each evaluated according to the following procedure.
The ring-opening activity of the oil was evaluated on a 30 ml hydrogenation apparatus using the deeply hydrodesulfurized and partially aromatic saturated catalytically cracked diesel as the reaction material (total aromatic content 9.5 wt%, sulfur content 8.1ppm, cetane number 39.2). The loading amount of the catalyst is 20 ml, and the catalyst is diluted to 30 ml by quartz sand, and the granularity is 20-40 meshes. Before the reaction, the reaction mixture was reduced at 290 ℃ under a hydrogen pressure of 6.0 MPa and a flow rate of 200 ml/min for 4 hours. Then, under the condition of constant temperature and pressure, the liquid volume space velocity is kept for 1.5 hours -1 And evaluating the activity of the catalyst under the condition of hydrogen-oil volume ratio of 800, sampling after 24 hours of reaction stabilization, and analyzing the cetane number of the generated diesel oil. The evaluation results are shown in Table 3.
Comparative examples 5 to 6
This comparative example serves to illustrate the ring opening activity of the comparative catalyst when treating an oil.
Comparative catalysts D1 and D2 were each evaluated in the same manner and under the same conditions as in example 9. The reaction results are shown in Table 3.
TABLE 3 evaluation results of oil treated with catalyst
| Examples | Catalyst and process for preparing same | Cetane number increase value |
| Comparative example 5 | D1 | 9.3 |
| Comparative example 6 | D2 | 8.8 |
| 9 | R1 | 11.8 |
| 10 | R2 | 11.1 |
| 11 | R3 | 11.7 |
| 12 | R4 | 10.9 |
The results of these examples demonstrate that the catalyst provided by the present invention has better naphthene ring opening activity and a greater increase in diesel cetane number than catalysts of the prior art with the same precious metal content.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (11)
1. A preparation method of a noble metal supported catalyst comprises the following steps:
(1) preparing a mixed solution containing a first component containing a VIII group noble metal compound, a second component containing an alkali metal and/or alkaline earth metal element compound and a third component containing a VIB group metal element compound and/or VIIB group metal element compound, and reacting for 0.5-24 hours at 50-200 ℃ to obtain a colloidal solution;
(2) dispersing a carrier in a solvent to obtain suspension containing the carrier;
(3) mixing the colloidal solution obtained in the step (1) with the suspension obtained in the step (2), and then drying and optionally roasting to obtain the noble metal supported catalyst;
the solvent of the solution in the step (1) and the solvent in the step (2) are the same or different and are respectively and independently selected from alcohol or a mixture of alcohol and water, the alcohol is at least one selected from monohydric alcohol, dihydric alcohol and trihydric alcohol with 1-6 carbon atoms, and the content of the alcohol in the solvent is 40-100 wt%;
the noble metal supported catalyst satisfies (M) 2 /M 1 ) XPS /(M 2 /M 1 ) XRF =2-20, wherein M 1 Is a noble metal element of group VIII, M 2 Is a metal element of group VIB and/or VIIB, (M) 2 /M 1 ) XPS M in catalyst characterized by X-ray photoelectron spectroscopy 2 And M 1 (M) weight ratio based on the metal element 2 /M 1 ) XRF M in catalyst characterized by X-ray fluorescence spectrum 2 And M 1 Weight ratio in terms of metal element; the X-ray photoelectron spectrum is measured by adopting a monochromator Al K alpha X ray with an excitation light source of 150kW, and the measurement conditions of the X-ray fluorescence spectrum comprise a rhodium target, laser voltage of 50kV and laser current of 50 mA.
2. The production method according to claim 1, wherein the group VIII noble metal element is at least one selected from Ir, Rh and Ru, and the group VIII noble metal element-containing compound is at least one selected from H 2 IrCl 6 、(NH 4 ) 2 IrCl 6 、IrCl 3 、(NH 4 ) 3 IrCl 6 、RhCl 3 、(NH 4 ) 3 RhCl 6 、RhPO 4 、Rh 2 (SO 4 ) 3 、RuCl 3 、(NH 4 ) 3 RuCl 6 、Ru(CH 3 COO) 3 、Ru(NO)(NO 3 ) 3 At least one of; the alkali metal or alkaline earth metal element is at least one selected from Li, Na, K, Rb and Ba, and the compound containing the alkali metal and/or alkaline earth metal element is hydroxide; the metal element in VIB and/or VIIB is at least one selected from Mo, W, Re and Mn.
3. The method according to claim 1, wherein the alcohol is at least one of ethanol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, and glycerin, and the content of the alcohol in the solvent is 70 to 100% by weight.
4. The preparation method according to claim 1, wherein the components in step (1) are used in such amounts that the content of the first component in terms of group VIII noble metal elements is 1-200 g/l, the content of the second component in terms of alkali metal and/or alkaline earth metal elements is 1-500 g/l, and the content of the third component in terms of group VIB and/or VIIB metal elements is 1-500 g/l, based on the weight of the colloidal solution.
5. The preparation method according to claim 1, wherein the components in the step (1) and the step (2) are used in amounts such that the contents of the components in terms of elements in the final catalyst are as follows: the content of noble metal elements is 0.2-15 wt%, the content of VIB and/or VIIB group metal elements is 0.2-15 wt%, the content of alkali metals and/or alkaline earth metals is 0-2%, and the balance is carrier.
6. The preparation method according to claim 5, wherein the components in the step (1) and the step (2) are used in amounts such that the contents of the components in terms of elements in the final catalyst are as follows: 0.5-10 wt% of noble metal element, 0.5-10 wt% of VIB and/or VIIB group metal element, 0-1% of alkali metal and/or alkaline earth metal and the balance of carrier.
7. The production method according to claim 1, wherein the operating conditions of the drying in the step (3) include: the temperature is 40-200 ℃, and the time is 0.1-24 hours; the roasting operation conditions in the step (3) comprise: the temperature is 200 ℃ and 600 ℃ and the time is 0.1-24 hours.
8. The production method according to any one of claims 1 to 7, wherein the support is one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieve, activated carbon.
9. A noble metal supported catalyst made by the process of any one of claims 1-8.
10. Use of the noble metal supported catalyst of claim 9 for catalyzing the hydrogenolysis ring opening reaction of cycloalkanes.
11. Catalytic naphthenic hydrogen disentanglingA ring opening process comprising contacting a feedstock comprising cycloalkanes, hydrogen, and a catalyst under catalytic cycloalkane hydrogenolysis ring opening conditions, wherein the catalyst is the supported catalyst of claim 9, and the catalytic cycloalkane hydrogenolysis ring opening conditions comprise a temperature of 180-: 1, the mass space velocity is 0.1-100 hours -1 。
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| CN101670286A (en) * | 2008-09-12 | 2010-03-17 | 北京大学 | Supported transition metal or transition metal alloy nanocluster catalyst and preparation method and application thereof |
| CN104275181A (en) * | 2013-07-10 | 2015-01-14 | 清华大学 | Pd-Re catalyst for propylene glycol preparation by glycerol hydrogenolysis and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009045606A1 (en) * | 2007-09-28 | 2009-04-09 | Battelle Memorial Institute | Multi-metal hydrogenation catalysts |
| CN101670286A (en) * | 2008-09-12 | 2010-03-17 | 北京大学 | Supported transition metal or transition metal alloy nanocluster catalyst and preparation method and application thereof |
| CN104275181A (en) * | 2013-07-10 | 2015-01-14 | 清华大学 | Pd-Re catalyst for propylene glycol preparation by glycerol hydrogenolysis and preparation method thereof |
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