CN106552646B - Supported catalyst, preparation method and application thereof, and method for catalyzing ring opening of naphthenic hydrocarbon by hydrogenolysis - Google Patents
Supported catalyst, preparation method and application thereof, and method for catalyzing ring opening of naphthenic hydrocarbon by hydrogenolysis Download PDFInfo
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Abstract
The invention discloses a supported catalyst, which comprises a carrier, a hydrogenation activity bimetallic component and an alkali metal component, wherein the hydrogenation activity bimetallic component and the alkali metal component are loaded on the carrier, and the supported catalyst is characterized in that the weight ratio of the bimetallic component calculated by metal elements satisfies (M)2/M1)XPS/(M2/M1)XRF2.0-20.0, wherein (M)2/M1)XPSThe weight ratio of the second metal component to the first metal component of the catalyst, calculated as the metal element, is characterized by X-ray photoelectron spectroscopy (M)2/M1)XRFThe weight ratio of the second metal component to the first metal component in the catalyst is characterized by X-ray fluorescence spectrum. The first metal component of the present invention is Co and/or Ni, and the second metal component is a transition metal element of group VIII of the fifth and/or sixth period. The invention also provides a preparation method of the catalyst and a method for catalyzing ring opening of naphthenic hydrocarbon by hydrogenolysis. Compared with the catalyst with the same metal content prepared by the prior art, the supported catalyst has obviously higher catalytic activity and selectivity for the ring opening of the hydrogenolysis of the cycloalkane.
Description
Technical Field
The invention relates to a 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 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 H2S and NH3Separating the sulfur and the nitrogen by a separation device, and when the S content in the material is lower than 50ppm and the N content is lower than 10ppm, feeding the material into a second reactor for selective ring-opening reaction, wherein 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.
However, there is still room for improvement and improvement in the naphthene hydrogenolysis ring-opening activity and selectivity of the above-disclosed catalysts.
Disclosure of Invention
The invention aims to provide a supported catalyst with higher naphthene hydrogenolysis ring-opening activity and selectivity, a preparation method and application thereof, and a method for catalyzing naphthene hydrogenolysis ring-opening.
The invention provides a supported catalyst, which comprises a carrier, a hydrogenation activity bimetallic component and an alkali metal component, wherein the hydrogenation activity bimetallic component and the alkali metal component are loaded on the carrier, and the supported catalyst is characterized in that the weight ratio of the bimetallic component calculated by metal elements satisfies (M)2/M1)XPS/(M2/M1)XRF2-20, wherein (M)2/M1)XPSThe weight ratio of the second metal component to the first metal component of the catalyst, calculated as the metal element, is characterized by X-ray photoelectron spectroscopy (M)2/M1)XRFThe catalyst is characterized by X-ray fluorescence spectrum, wherein the weight ratio of a second metal component to a first metal component is calculated by metal elements, the first metal component is selected from cobalt and/or nickel elements, and the second metal component is a transition metal element of a VIII group in a fifth and/or sixth period.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps:
1) impregnating the support with a solution containing a compound of the first metal component and a compound of the second metal component;
2) reducing and activating the impregnated carrier obtained in the step 1);
3) impregnating the product after the reduction activation in the step 2) with a solution containing a compound of a second metal active component in a reducing or inert atmosphere;
4) impregnating the support with a solution containing a compound of the alkali metal component;
wherein, the weight ratio of the compound of the first metal active component to the compound of the second metal active component in the step 1) calculated by metal elements is 10-600: 1, the weight ratio of the compound of the second metal active component in terms of metal element in step 1) and step 3) is 0.01-0.8:1, the first metal component is cobalt and/or nickel element, the second metal component is transition metal element of group VIII of the fifth and/or sixth period, and the step 4) is performed at any one period before, during, after, and before, during, and after step 3) of step 1).
The invention also provides a supported catalyst prepared by the method.
The invention also provides application of the supported catalyst in catalyzing ring opening reaction of naphthenic hydrocarbon hydrogenolysis.
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 supported catalyst.
Compared with the catalyst with the same metal content prepared by the prior art, the bimetallic catalyst has obviously higher catalytic activity for the ring opening by the hydrogenolysis of cycloalkane and has lower cracking rate. Specifically, methylcyclopentane is used as a raw material, and the hydrogenolysis ring-opening performance of the catalyst is compared; as a result, the catalyst R1 prepared by the method is obviously superior to the catalyst D1 prepared by a co-impregnation method, the conversion rate of the methylcyclopentane is improved from 45 percent to 63 percent, and the cetane number of diesel oil is increased from 8.9 to 10.8; compared with the catalyst D2 without alkali metal, the catalyst R1 prepared by the method of the invention has similar conversion rate to methylcyclopentane, but the selectivity of straight-chain alkane is improved from 30 percent to 43 percent, and the cetane number is also improved from 9.1 to 10.8 when the actual oil is treated.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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 Ni 2p of catalyst R1 obtained in example 1 of the present invention and comparative catalyst D1 obtained in comparative example 1;
FIG. 2 is an X-ray photoelectron spectrum of Ir 4f for catalyst R1 prepared in example 1 according to the present invention and comparative catalyst D1 prepared 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 supported catalyst, which comprises a carrier, a hydrogenation activity bimetallic component and alkali metal, wherein the hydrogenation activity bimetallic component and the alkali metal are loaded on the carrier, and the supported catalyst is characterized in that the weight ratio of the bimetallic component calculated by metal elements satisfies (M)2/M1)XPS/(M2/M1)XRF2.0 to 20.0, preferably 2.5 to 10, more preferably 3 to 5, wherein (M)2/M1)XPSThe weight ratio of the second metal component to the first metal component of the catalyst, calculated as the metal element, is characterized by X-ray photoelectron spectroscopy (M)2/M1)XPSThe catalyst is characterized by X-ray fluorescence spectrum, wherein the weight ratio of a second metal component to a first metal component is calculated by metal elements, the first metal component is cobalt and/or nickel elements, and the second metal component is a transition metal element of a VIII group in a fifth and/or sixth period.
In the present invention, (M)2/M1)XPSThe catalyst is characterized by X-ray photoelectron spectroscopy, wherein the weight ratio of a second metal component to a first metal component in the catalyst is calculated by metal elements, and the weight ratio is converted by the area of a peak of a characteristic peak of the corresponding metal element, a measuring instrument of the X-ray photoelectron spectroscopy is an ESCALB 250 instrument of Thermo Scientific company, and the measuring condition is that an excitation light source is a monochromator Al K α X-ray of 150kW, and the combination energy is corrected by adopting a C1 s peak (284.8 eV).
In the present invention, (M)2/M1)XRFRefers to the metal of the second metal component and the first metal component in the catalyst characterized by X-ray fluorescence spectrumThe weight ratio of the elements. Wherein the measuring instrument of the X-ray fluorescence spectrum is a 3271 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.
According to the catalyst provided by the invention, based on the total weight of the catalyst, the content of the carrier is 69-94 wt%, the content of the first metal component loaded on the carrier is 5-30 wt%, the content of the second metal component is 0.05-2 wt%, and the content of the alkali metal component is 0.05-2 wt%. Preferably, the content of the carrier is 74 to 89% by weight, the content of the first metal component supported on the carrier is 10 to 25% by weight, the content of the second metal component is 0.1 to 1% by weight, and the content of the alkali metal component is 0.1 to 1% by weight, based on the total weight of the catalyst.
The difference between the supported catalyst of the invention and the prior art is the structural characteristic of hydrogenation activity bimetal, so the hydrogenation activity bimetal component can be various conventional hydrogenation activity metals in the field of hydrogenation catalysis. Preferably, the first metal component is at least one of Co or Ni, and the second metal component is at least one of Pt, Pd, Ru, Rh, Ir.
Preferably, the alkali metal component is at least one of Li, Na, K, Rb, Cs.
Preferably, the carrier is one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieve and activated carbon, and more preferably one or more of silica, alumina, Y-Beta and silica-alumina. The carrier can also be one or more of the carriers modified by one or more of phosphorus, silicon, fluorine and boron. The modified carrier can be obtained commercially or modified by the existing method.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps:
1) impregnating the support with a solution containing a compound of the first metal component and a compound of the second metal component;
2) reducing and activating the impregnated carrier obtained in the step 1);
3) impregnating the product after the reduction activation in the step 2) with a solution containing a compound of a second metal active component in a reducing or inert atmosphere;
4) impregnating the support with a solution containing a compound of the alkali metal component;
wherein, the weight ratio of the compound of the first metal active component to the compound of the second metal active component in the step 1) calculated by metal elements is 10-600: 1, the weight ratio of the compound of the second metal active component in terms of metal element in step 1) and step 3) is 0.01-0.8:1, the first metal component is cobalt and/or nickel element, the second metal component is transition metal element of group VIII of the fifth and/or sixth period of the periodic table, and the step 4) is performed at any one period before, during, after, before, during and after step 1) and step 3).
As described above, the method of the present invention further comprises introducing an alkali metal into the support, wherein the manner of adding the alkali metal may be any of the existing various methods, and the order of introduction thereof is not particularly limited as long as the alkali metal element is introduced into the finally obtained catalyst. Wherein, step 1) may be preceded by modifying the support with a compound containing an alkali metal element prior to step 1). In the method, the impregnation solution in the step 1) or the step 3) may contain a compound containing an alkali metal element, and the method preferably contains a compound containing an alkali metal element in the impregnation solution in the step 3). This may be followed by impregnating the support loaded with the first metal component and/or the second metal component with an impregnation solution of a compound containing an alkali metal element after step 1) and before step 2) and/or after step 3).
The compound containing the alkali metal element can be at least one of nitrate, acetate, sulfate, basic carbonate, chloride and hydroxide containing at least one of Li, Na, K, Rb and Cs.
In the present invention, "impregnating the support with a solution containing a compound of the first metal component and a compound of the second metal component" may be carried out by one or more of the following ways:
1) impregnating the support with a solution containing a compound of the first metal component and then impregnating the support with a solution containing a compound of the second metal component;
2) impregnating the support with a solution containing a compound of the second metal component and then impregnating the support with a solution containing a compound of the first metal component;
3) simultaneously impregnating the support with a solution containing a compound of the first metal component and a solution containing a compound of the second metal component;
4) the compound of the first metal component and the compound of the second metal component are formulated into an impregnation solution, and then the carrier is impregnated with the impregnation solution.
Wherein, in the step 1), the weight ratio of the compound of the first metal active component to the compound of the second metal active component in terms of metal elements is preferably 50 to 200: 1, the ratio of the amount of the compound of the second metal active component used in step 1) and step 3) is preferably 0.1 to 0.5: 1.
The compound of the first metal active component is at least one of nitrate, acetate, sulfate, basic carbonate and chloride which take Co and/or Ni as cations.
In the solution containing the compound of the first metal active component and the compound of the second metal active component, the concentration of the compound of the first metal active component is preferably 500-2000 g/l, and more preferably 800-1500 g/l, based on the first metal active component.
The compound of the second metal active component can be various soluble compounds of noble metals, and preferably at least one of nitrate, acetate, sulfate, basic carbonate and chloride containing at least one of Pt, Pd, Ru, Rh and Ir.
According to the present invention, in step 1), the presence of the second metal active component serves to promote the progress of the reduction reaction in step 2) and the loading of the second metal active component in step 3), and therefore the amount is small relative to the total amount of the second metal active component, and preferably, the weight ratio of the compound of the first metal active component to the compound of the second metal active component in step 1) is 50 to 200 in terms of metal element: 1, more preferably 100-: 1.
the impregnation method in step 1) of the present invention is not particularly limited, and various methods known to those skilled in the art, for example, an equivalent-volume impregnation method and a supersaturation impregnation method, may be used. Specifically, the impregnation conditions of step 1) include a temperature of 10 to 90 ℃, preferably 15 to 40 ℃ and a time of 1 to 10 hours, preferably 2 to 6 hours.
The step 2) reduction activation is preferably carried out in a pure hydrogen atmosphere or a mixed gas atmosphere of hydrogen and an inert gas, such as a mixed gas atmosphere of hydrogen and nitrogen and/or argon, and the conditions of the reduction activation include a temperature of 200-500 ℃, preferably 300-500 ℃, more preferably 350-450 ℃, and a time of 1-12 hours, preferably 1-5 hours, more preferably 2-4 hours. The pressure of the reduction may be normal pressure or increased pressure, and specifically, the pressure of hydrogen may be 0.1 to 4MPa, preferably 0.1 to 2 MPa. The pressure in the present invention means an absolute pressure.
The concentration of the compound of the second metal active component in the solution containing the compound of the second metal active component in the step 3) is preferably 0.2 to 100 g/l, preferably 1 to 50 g/l, in terms of the second metal active component.
Preferably, the solvent used in step 1) is water, and the solvent used in step 2) is at least one of water, ethanol, propanol, ethylene glycol, hexane and cyclohexane.
The impregnation conditions of step 3) include a temperature of 10 to 90 c, preferably 15 to 40 c, and a time of 0.1 to 10 hours, preferably 0.5 to 2 hours. An equal volume impregnation or a supersaturation impregnation method may be used.
Preferably, the step 1) adopts equal volume impregnation, the volume of the impregnation liquid used is calculated according to the water absorption of the carrier, and the volume of the impregnation liquid used in the step 3) is 0.5 to 10 times, preferably 1 to 3 times of the volume of the impregnation liquid in the step 1).
According to the present invention, the above method preferably further comprises drying or further calcining the impregnated carrier obtained in step 1) in sequence, and then performing the reduction activation.
The drying temperature may be 80-150 ℃.
The temperature of the calcination can be 220-600 ℃, and the time can be 1-6 hours.
According to the present invention, the above method preferably further comprises cooling the product after the reduction activation in step 2) to room temperature or the desired temperature in step 3) in a hydrogen and/or inert atmosphere, such as nitrogen and/or argon, and then performing the impregnation in step 3). After the step 3) is finished, O can be further introduced2/N2The mixed gas with the volume ratio of 0.05-1.0% is used for 0.5-4 hours to passivate the metal active components in the mixed gas, and the catalyst which can be directly stored in the air is obtained.
According to the present invention, the above method preferably further comprises drying the impregnated product of step 3). In order to prevent the metal active components in the catalyst from being oxidized, the drying is preferably performed under vacuum conditions or under the protection of inert gas or reducing gas, and the product obtained by the impregnation is preferably dried by using a gas blow drying mode of the impregnation atmosphere in the step 3).
The carrier is used in an amount of 69 to 94% by weight, preferably 74 to 89% by weight, based on the total weight of the catalyst, the first metal component supported on the carrier is contained in an amount of 5 to 30% by weight, preferably 10 to 25% by weight, the second metal component is contained in an amount of 0.05 to 2% by weight, preferably 0.1 to 1% by weight, and the alkali metal component is contained in an amount of 0.05 to 2% by weight, preferably 0.1 to 1% by weight. The composition of the catalyst is calculated from the charge.
According to the present invention, the carrier may be any one or more of various carriers commonly used in hydrogenation catalysts, such as alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves, activated carbon, and particularly preferably at least one of alumina, silica, Y-Beta and silica-alumina carriers. The carrier can also be one or more of the carriers modified by one or more of phosphorus, silicon, fluorine and boron. The modified carrier can be obtained commercially or modified by the existing method.
Compared with the catalyst with the same metal content prepared by the prior artThe bimetallic component catalyst of the invention has obviously higher catalytic naphthene hydrogenolysis ring-opening activity and lower cracking rate. The reason for this is probably that the bimetallic catalyst forming a special structure has more suitable naphthene hydrogenolysis ring-opening active site. Therefore, the atomic composition of the surface layer of the catalyst is represented by X-ray photoelectron spectroscopy, the atomic composition of the bulk phase of the catalyst is represented by X-ray fluorescence spectroscopy, and the second metal component M of the catalyst is found2In the first metal component M1Surface enrichment; and the weight ratio of the bimetal component calculated by the metal element satisfies (M)2/M1)XPS/(M2/M1)XRFThe catalyst has better catalytic hydrogenolysis ring-opening performance in the range of 2.0-20.0, preferably 2.5-10, more preferably 3-5.
The invention also provides a supported catalyst prepared by the method.
The invention also provides the application of the supported catalyst in the ring opening reaction of the hydrogenolysis of cycloalkanes.
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 supported catalyst.
The catalyst of the invention can be used for hydrogenolysis ring-opening reaction (preferably, the mass content of aromatic hydrocarbon is less than 15%, and the mass content of sulfur is less than 30ppm) of various raw materials containing naphthene, such as naphthene model compounds, or gasoline fraction, kerosene fraction or diesel fraction containing naphthene.
The conditions for the contact reaction (i.e., the hydrogenolysis ring-opening reaction) may be carried out with reference to the prior art, for example, at a temperature of 180-450 deg.C, preferably 220-400 deg.C, a pressure of 1-18MPa, preferably 2-12MPa, and a hydrogen-oil volume ratio of 50-10000: 1 preferably from 50 to 5000: 1, the mass space velocity is 0.1-100 hours-1Preferably 0.2 to 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 bimetallic catalyst under hydrogenation reaction conditions, such as a fixed bed reactor, a slurry bed reactor, a moving bed reactor or an ebullating bed reactor.
In the following examples, the measuring apparatus for X-ray photoelectron spectroscopy is an ESCALB 250 type apparatus from Thermo Scientific, under the measurement conditions of a monochromator Al K α X ray having an excitation light source of 150kW, the binding energy being corrected by a peak C1 s (284.8eV), and the measuring apparatus for X-ray fluorescence spectroscopy is a 3271 type apparatus from Nippon Denshi electric Motor industries, Inc., under the measurement conditions of tablet forming of a powder sample, a rhodium target, a laser voltage of 50kV, a laser current of 50 mA., and the like, which are simple and convenient, and provide only the corresponding spectra of example 1 and comparative example 1, and other examples and comparative examples directly provide the calculation results.
In the following examples, the catalyst composition is calculated based on the total weight of the catalyst, and the mass percentages of the hydrogenation active metal element and the alkali metal element are calculated according to the charging amount.
Example 1
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
According to the content of metal salt required by an equal-volume impregnation method, 32.4 ml of impregnation solution containing 167 g/L nickel and 2.22 g/L iridium nitrate and iridium chloride is prepared. The impregnation solution was decanted to 36 g SiO2-Al2O3The support (prepared according to example 2 of cn201110139331. x) was stirred at 25 ℃ and left to stand for 4 hours, then dried at 120 ℃, calcined at 350 ℃ for 4 hours, and reduced with hydrogen at 350 ℃ for 4 hours under 0.1 mpa. After reduction, the temperature is reduced to room temperature, 48.6 ml of mixed aqueous solution of iridium chloride and potassium chloride containing 2.96 g/l of iridium and 2.96 g/l of potassium is added under the atmosphere of hydrogen, and the mixture is kept stand for 1 hour and then dried by hydrogen. Then pass through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. 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. According to NCalculating corresponding peak areas of electron binding energy of i 2p and Ir 4f to obtain surface layer atomic ratio (M)2/M1)XPS。
Comparative example 1
This comparative example serves to illustrate a comparative catalyst and a process for its preparation.
Comparative catalyst D1, which had the same metal composition as catalyst R1, was prepared according to a co-impregnation method.
According to the content of metal salt required by an equal-volume impregnation method, 32.4 ml of nickel nitrate, iridium chloride and potassium chloride impregnation solution containing 167 g/L of nickel, 6.67 g/L of iridium and 4.44 g/L of potassium is prepared. The impregnation solution was decanted to 36 g SiO2-Al2O3The carrier (prepared by reference to example 2 of CN201110139331. X) is uniformly stirred at 25 ℃, is dried at 120 ℃ after being kept stand for 4 hours, is roasted at 350 ℃ for 4 hours, and is reduced by hydrogen at 350 ℃ for 4 hours, wherein the hydrogen pressure is 0.1 MPa. Reducing, cooling to room temperature, and treating with O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. 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
A catalyst was prepared as in example 1 except that the impregnation solution used in the second impregnation contained no alkali metal elements, giving comparative catalyst D2 whose composition, XPS and XRF characterization results are given in Table 1.
Comparative example 3
A catalyst was prepared according to the procedure of example 1, except that the first metal was supported and dried and calcined, and the support of the second metal was directly performed without reduction in a hydrogen atmosphere, to obtain comparative catalyst D3, whose composition, XPS and XRF characterization results are shown in Table 1.
Example 2
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
According to the content of metal salt required by the equal-volume impregnation method, 32.4 ml of cobalt nitrate and platinum tetraammine dichloride impregnation solution containing 167 g/l cobalt and 1.11 g/l platinum is prepared. The steep was decanted to 36 g of the H form of the Y-Beta complexA molecular sieve-alumina carrier (prepared according to CN101992120A, carrier D1 of example 1) was stirred at 25 deg.C, left to stand for 4 hours, dried at 110 deg.C, calcined at 500 deg.C for 4 hours, and reduced with hydrogen at 350 deg.C for 4 hours under a hydrogen pressure of 0.1 MPa. After reduction, the temperature is reduced to room temperature, 48.6 ml of mixed aqueous solution of platinum dichloride tetraammineplatinum and sodium chloride which contain 1.85 g/l of platinum and 1.48 g/l of sodium is added under the atmosphere of hydrogen, the mixture is kept stand for 1 hour and then is dried by hydrogen. Then pass through O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained was designated as R2 and its composition, XPS and XRF characterization results are given in Table 1.
Comparative example 4
A comparative catalyst and a method for its preparation are illustrated.
Catalyst D4 was prepared according to the method provided in CN101992120A example 1.
32.4 ml of impregnation solution containing platinum 3.89 g/l tetraammineplatinum dichloride is prepared according to the content of metal salt required by the equal volume impregnation method. Decanting the maceration extract to 41.4 g hydrogen type Y-Beta composite molecular sieve-alumina carrier, stirring at 25 deg.C, standing for 4 hr, oven drying at 110 deg.C, calcining at 500 deg.C for 4 hr, and reducing with hydrogen at 350 deg.C for 4 hr under hydrogen pressure of 0.1 MPa. Reducing, cooling to room temperature, and treating with O2/N2The mixed gas with the volume ratio of 0.5 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained is designated D4 and its composition is shown in Table 1.
Example 3
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
According to the content of metal salt required by an equal-volume impregnation method, 32.4 ml of impregnation solution containing 111 g/L nickel and 2.22 g/L palladium and containing nickel nitrate and palladium nitrate is prepared. The impregnation solution was decanted to 36 g SiO2-Al2O3The carrier (prepared according to example 2 of cn201110139331. x), after being stirred and kept stand for 4 hours, is dried at 120 ℃, roasted at 350 ℃ for 4 hours, and reduced by hydrogen at 450 ℃ for 2 hours, and the hydrogen pressure is 1 mpa. After reduction, the temperature was lowered to room temperature, and 48.6 ml of a mixture of palladium nitrate and lithium nitrate containing 5.19 g/l of palladium and 3.70 g/l of lithium was added under a hydrogen atmosphereStirring the aqueous solution at 15 ℃, standing for 6 hours, and drying by using hydrogen. Then pass through O2/N2The mixed gas with the volume ratio of 1 percent is passivated for 0.5 hour and stored in a dryer for standby. The catalyst obtained was designated as R3 and its composition, XPS and XRF characterization results are given in Table 1.
Example 4
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
According to the content of metal salt required by an equal-volume impregnation method, 32.4 ml of impregnation solution containing 167 g/L nickel and 2.22 g/L ruthenium for nickel nitrate and ruthenium chloride is prepared. The steep liquor was decanted to 36 g of gamma-Al2O3The carrier (product of Changling catalyst factory, granularity 20-40 mesh, same at once), at 40 deg.C, stirring, standing for 2 hr, oven drying at 120 deg.C, calcining at 550 deg.C for 1 hr, and hydrogen reducing at 400 deg.C for 2 hr under MPa. After reduction, the temperature is reduced to room temperature, 48.6 ml of mixed water-ethanol solution (the volume ratio of water to ethanol is 1: 1) of ruthenium chloride and potassium chloride containing 2.96 g/L of ruthenium and 2.96 g/L of potassium is added under the atmosphere of hydrogen, and the mixture is kept stand for 1 hour and then dried by hydrogen. Then pass through O2/N2And passivating the mixed gas with the volume ratio of 0.5% for 2 hours, and storing the gas in a dryer for standby. The catalyst obtained was designated as R4 and its composition, XPS and XRF characterization results are given in Table 1.
Example 5
This example serves to illustrate the catalysts and the process for their preparation according to the invention.
32.4 ml of cobalt nitrate, iridium chloride and potassium nitrate impregnation solution containing 244 g/l of cobalt, 2.22 g/l of iridium and 4.44 g/l of potassium is prepared according to the metal salt content required by the equal-volume impregnation method. The steep liquor was decanted to 36 g of gamma-Al2O3The carrier is evenly stirred and kept stand for 4 hours, then is dried at 120 ℃, is roasted for 4 hours at 350 ℃, and is reduced for 4 hours by hydrogen at 350 ℃, and the pressure of the hydrogen is 0.1 MPa. After reduction, the temperature is reduced to room temperature, 48.6 ml of water-ethanol solution (the volume ratio of water to ethanol is 1: 1) containing iridium chloride with the concentration of 2.96 g/L of iridium is added under the atmosphere of hydrogen, and the mixture is kept stand for 1 hour and then dried by hydrogen. Then pass through O2/N2Inactivating the mixed gas with the volume ratio of 0.5% for 0.5 hour, and storing in a dryerAnd (5) standby. The catalyst obtained was designated as R4 and its composition, XPS and XRF characterization results are given in Table 1.
Examples 6 to 10
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, R4 and R5 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 5 to 8
These comparative examples serve to illustrate the hydrogenolysis ring opening activity of the comparative catalysts.
Comparative catalysts D1 to D4 were each evaluated in the same manner and under the same conditions as in example 6. The reaction results are shown in Table 2.
TABLE 1
TABLE 2
| Example numbering | Catalyst numbering | Methylcyclopentane conversion (%) | Straight chain alkane selectivity (%) |
| Example 6 | R1 | 63 | 43 |
| Comparative example 5 | D1 | 45 | 32 |
| Comparative example 6 | D2 | 61 | 30 |
| Comparative example 7 | D3 | 44 | 35 |
| Example 7 | R2 | 57 | 45 |
| Comparative example 8 | D4 | 46 | 39 |
| Example 8 | |
54 | 40 |
| Example 9 | |
56 | 40 |
| Example 10 | |
62 | 42 |
Examples 11 to 15
These examples illustrate the hydrogenolysis ring opening activity of the catalysts provided by the present invention when treating oils.
Catalysts R1, R2, R3, R4 and R5 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-1And 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 9 to 12
This comparative example serves to illustrate the ring opening activity of the comparative catalyst when treating an oil.
Comparative catalysts D1 to D4 were each evaluated in the same manner and under the same conditions as in example 11. The reaction results are shown in Table 3.
TABLE 3 evaluation results of oil treated with catalyst
| Example numbering | Catalyst numbering | Cetane number increase value |
| Example 11 | R1 | 10.8 |
| Comparative example 9 | D1 | 8.9 |
| Comparative example 10 | D2 | 9.1 |
| Comparative example 11 | D3 | 8.9 |
| Example 12 | R2 | 10.4 |
| Comparative example 12 | D2 | 9.1 |
| Example 13 | R3 | 9.9 |
| Example 14 | R4 | 10.0 |
| Example 15 | R5 | 10.3 |
From the results of example 6 and comparative example 5, and example 11 and comparative example 9, it can be seen that the catalyst R1 prepared by the method of the present invention is significantly better than the catalyst D1 prepared by the co-impregnation method, the conversion rate of methylcyclopentane is increased from 45% to 63%, and the cetane number of diesel oil is increased from 8.9 to 10.8. From the results of example 6 and comparative example 6, and example 11 and comparative example 10, it can be seen that the conversion of methylcyclopentane by the catalyst R1 prepared by the process of the present invention is similar, but the linear alkane selectivity is increased from 30% to 43%, and the cetane number increase range is also increased from 9.1 to 10.8 when treating actual oil, compared with the catalyst D2 containing no alkali metal.
From the results of example 7 and comparative example 8, and example 12 and comparative example 12, it can be seen that the catalyst R2 prepared by the method of the present invention is superior to the composite molecular sieve supported single Pt catalyst D4, the conversion rate of methyl cyclopentane is improved from 46% to 57%, and the cetane number of diesel oil is increased from 9.1 to 10.4.
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 (24)
1. A supported catalyst comprising a carrier, a hydrogenation-active metal component comprising a first metal component and a second metal component and an alkali metal component supported on the carrier, characterized in that the catalyst satisfies (M)2/M1)XPS/(M2/M1)XRF2-20, wherein (M)2/M1)XPSThe weight ratio of the second metal component to the first metal component in the catalyst, calculated as the metal element, is characterized by X-ray photoelectron spectroscopy (M)2/M1)XRFThe catalyst is characterized by comprising a first metal component and a second metal component, wherein the first metal component is cobalt and/or nickel element, the second metal component is transition metal element of fifth and/or sixth periodic group VIII, the weight ratio of the second metal component to the first metal component is calculated by metal element, the catalyst is characterized by X-ray fluorescence spectrum, the content of the carrier is 69-94 wt%, the content of the first metal component loaded on the carrier is 5-30 wt%, the content of the second metal component is 0.05-2 wt%, and the content of the alkali metal component is 0.05-2 wt%;
the preparation method of the supported catalyst comprises the following steps:
1) impregnating the support with a solution containing a compound of the first metal component and a compound of the second metal component;
2) reducing and activating the impregnated carrier obtained in the step 1);
3) impregnating the product after the reduction activation in the step 2) with a solution containing a compound of the second metal component in a reducing or inert atmosphere;
4) impregnating the support with a solution containing a compound of the alkali metal component;
wherein, the weight ratio of the compound of the first metal component to the compound of the second metal component in the step 1) calculated by the metal element is 10-600: 1, the weight ratio of the compound of the second metal component in terms of the metal element in step 1) and step 3) is 0.01 to 0.8:1, and said step 4) is carried out at any one period of time before, during, after, before, during, and after step 1).
2. The catalyst of claim 1, wherein the catalyst satisfies (M)2/M1)XPS/(M2/M1)XRF＝2.5-10。
3. The catalyst of claim 1, wherein the catalyst satisfies (M)2/M1)XPS/(M2/M1)XRF＝3-5。
4. The catalyst according to claim 1, wherein the carrier is contained in an amount of 74 to 89% by weight, the first metal component supported on the carrier is contained in an amount of 10 to 25% by weight, the second metal component is contained in an amount of 0.1 to 1% by weight, and the alkali metal component is contained in an amount of 0.1 to 1% by weight, based on the total weight of the catalyst.
5. The catalyst of claim 1, wherein the second metal component is at least one of Pt, Pd, Ru, Rh, Ir and the alkali metal component is at least one of Li, Na, K, Rb, Cs.
6. The catalyst of claim 1, wherein the support is one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieves, activated carbon.
7. The catalyst according to claim 1, wherein the X-ray photoelectron spectroscopy is measured by using a monochromator AlK α X-ray with an excitation light source of 150kW, and the measurement conditions of the X-ray fluorescence spectroscopy include a rhodium target, a laser voltage of 50kV and a laser current of 50 mA.
8. A method for preparing a supported catalyst, comprising the steps of:
1) impregnating the support with a solution containing a compound of the first metal component and a compound of the second metal component;
2) reducing and activating the impregnated carrier obtained in the step 1);
3) impregnating the product after the reduction activation in the step 2) with a solution containing a compound of the second metal component in a reducing or inert atmosphere;
4) impregnating the support with a solution containing a compound of the alkali metal component;
wherein, the weight ratio of the compound of the first metal component to the compound of the second metal component in the step 1) calculated by the metal element is 10-600: 1, the weight ratio of the compound of the second metal component in terms of metal element in step 1) and step 3) is 0.01-0.8:1, the first metal component is cobalt and/or nickel element, the second metal component is transition metal element of group VIII of the fifth and/or sixth period, and the step 4) is performed at any one period before, during, after, and before, during, and after step 1).
9. The production method according to claim 8, wherein the weight ratio of the compound of the first metal component to the compound of the second metal component in the step 1) in terms of the metal element is 50 to 200: 1, the compound of the second metal component is used in a ratio of 0.1-0.5:1 in step 1) and step 3).
10. The production method according to claim 8 or 9, wherein the compound of the alkali metal component is at least one of nitrate, acetate, sulfate, hydroxycarbonate, chloride, hydroxide containing one or more of Li, Na, K, Rb, Cs.
11. The method of claim 8, wherein the impregnating conditions of step 1) include a temperature of 10-90 ℃ and a time of 1-10 hours.
12. The method of claim 8, wherein the impregnating conditions of step 1) include a temperature of 15-40 ℃ and a time of 2-6 hours.
13. The preparation method according to claim 8, wherein the reduction activation in step 2) is carried out under a hydrogen atmosphere, and the conditions of the reduction activation include a temperature of 200 ℃ and 500 ℃ and a time of 1-12 hours.
14. The method of claim 8, wherein the impregnating conditions of step 3) include a temperature of 10-90 ℃ and a time of 0.1-10 hours.
15. The method according to claim 8, further comprising drying and calcining the impregnated support obtained in step 1) in sequence, and then performing the reduction activation.
16. The method according to claim 8, further comprising cooling the product after the reduction activation in step 2) to room temperature or the desired temperature in step 3) under hydrogen or inert atmosphere, and then performing the impregnation in step 3).
17. The method according to claim 8, further comprising introducing O into the solid obtained in step 3)2/N2The mixed gas with the volume ratio of 0.05-1.0% is used for 0.5-4 hours to passivate the metal active components in the mixed gas, and the catalyst which can be directly stored in the air is obtained.
18. The production method according to claim 8, wherein the first metal component, the second metal component and the alkali metal component are used in an amount such that the carrier is contained in an amount of 69 to 94% by weight, the first metal component is contained in an amount of 5 to 30% by weight, the second metal component is contained in an amount of 0.05 to 2% by weight and the alkali metal component is contained in an amount of 0.05 to 2% by weight, based on the total weight of the catalyst.
19. The production method according to claim 8, wherein the support is one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay, molecular sieve, activated carbon.
20. A supported catalyst prepared by the process of any one of claims 8 to 19.
21. Use of the supported catalyst of any one of claims 1-7 and 20 in the hydrogenolysis ring opening reaction of cycloalkanes.
22. A process for the hydrogenolysis ring opening of cycloalkanes comprising contacting a feedstock containing cycloalkanes, hydrogen, and a catalyst under conditions to catalyze the hydrogenolysis ring opening of cycloalkanes, wherein the catalyst is the supported catalyst of any one of claims 1-7 and 20.
23. The hydrogenolysis ring-opening method of cycloalkane as claimed in claim 22, wherein the hydrogenolysis ring-opening conditions of catalytic cycloalkane include a temperature of 180 ℃ to 450 ℃, a pressure of 1 to 18MPa, a hydrogen to oil volume ratio of 50 to 10000: 1, the mass space velocity is 0.1-100 hours-1。
24. The hydrogenolysis ring-opening method of cycloalkane according to claim 22, wherein the hydrogenolysis ring-opening conditions of catalytic cycloalkane include a temperature of 220-: 1, the mass space velocity is 0.2-80 hours-1。
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| CN110882710B (en) * | 2018-09-07 | 2022-10-21 | 中国石油化工股份有限公司 | Carbide-based catalyst, preparation method thereof and glycerol hydrogenolysis method |
| KR102009364B1 (en) * | 2018-11-02 | 2019-08-09 | 에스케이이노베이션 주식회사 | Catalyst for Hydrofinishing and Production Method of Lubricating Base Oil using Thereof |
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