CN112090443B - Hydrodeoxygenation catalyst, application thereof and preparation method of cyclohexane - Google Patents
Hydrodeoxygenation catalyst, application thereof and preparation method of cyclohexane Download PDFInfo
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Abstract
The invention relates to the field of catalysis, and discloses a hydrodeoxygenation catalyst, application thereof and a preparation method of cyclohexane. The hydrodeoxygenation catalyst has high hydrodeoxygenation catalytic activity, shows high catalytic activity when being used as a catalyst for preparing cyclohexane by hydrodeoxygenation of a raw material containing oxygen-containing compounds of benzene, and can obtain high raw material conversion rate and high selectivity of product cyclohexane.
Description
Technical Field
The invention relates to a hydrodeoxygenation catalyst and application thereof, and also relates to a method for preparing cyclohexane from a raw material containing oxygen-containing compounds of benzene by using the hydrodeoxygenation catalyst.
Background
At present, the yield of light crude oil in the global crude oil reserves is continuously reduced, and the yield of heavy crude oil is continuously increased. In addition to the difficulty of extraction and transportation, the difficulty of processing heavy oil is increasing due to the increasing degree of crude oil heaviness. Under the condition that fossil energy in the world is increasingly deficient, alternative energy is actively sought so as to relieve energy pressure and environmental problems and realize sustainable development. In recent years, the alternative energy has been paid much attention in the world, and many countries have put forward definite development targets, made relevant laws and policies, promoted the improvement of the technical level of the alternative energy and the expansion of the industrial scale, and finally realized the diversification of the energy consumption structure. Alternative energy sources include nuclear, hydroelectric, and renewable energy sources (solar, wind, biomass, geothermal, ocean, etc.) by international convention. To date, hydroelectric and nuclear power have had significant success. The biomass energy is renewable green energy and is a high-efficiency and cheap concentrated form of solar energy. Because the biomass energy storage is very rich and various, the biomass energy storage has low S and N contents and CO 2 The emission is low, and the development and utilization of biomass energy have attracted global attention. According to the existing form, the biomass energy mainly comprises various plants which can be used as energy sources in the nature, human and animal excreta and energy sources of urban and rural organic waste conversion cities, such as firewood, marsh gas, biodiesel, fuel ethanol, forestry processing waste, crop straws and the like. Biomass thermal-chemical conversion is the production of gaseous fuels, liquid fuels and chemicals by gasification, carbonization, pyrolysis or catalytic liquefaction of biomass under certain conditions. Since biomass can be the only energy source from all alternative energy sources that can produce liquid fuel for storage and transportation, biomass liquid fuel (also called bio-fuel oil) will play an important role in transportation in the 21 st century. Pyrolysis oil from lignocellulosic biomass contains many different oxygenates. Hydrodeoxygenation (HDO) is a reaction that removes this atomic oxygen and can increase the heating value and stability of the bio-oil. The composition of the bio-oil is complex, and representative model compounds such as anisole and the like can be used for researching the effectiveness of the bio-oil hydrodeoxygenation catalyst. Anisole HDO reactionThere should be four main routes: (1) demethylation; (2) Direct Deoxygenation (DDO); (3) hydro-deoxygenation (HYD); and (4) methyl transfer. Firstly, demethylating anisole to generate phenol and methane; the intermediate phenol is converted to benzene via the DDO pathway or cyclohexane via the HYD pathway. In the reaction process, except for generating methane by hydrogenation, partial methyl is subjected to transfer reaction to generate o-cresol, 2, 6-dimethylphenol and the like. The following formula gives the reaction path for hydrodeoxygenation of anisole.
In the existing hydrodeoxygenation catalytic technology, a metal sulfide catalyst has high selectivity and activity, but sulfides need to be introduced to maintain the activity, and the introduction of the sulfides is easy to pollute products. The currently developed noble metal catalyst has higher reaction activity and high efficiency, but the catalyst has poor stability and high cost and cannot meet the industrial requirement.
Disclosure of Invention
The invention aims to solve the problems of low conversion rate of raw materials and low selectivity of cyclohexane in the preparation of cyclohexane from benzene oxygen-containing compounds by using a hydrodeoxygenation catalyst in the prior art, and provides a hydrodeoxygenation catalyst, application thereof and a preparation method of cyclohexane.
The inventors of the present invention have found that, as a carrier of a hydrodeoxygenation catalyst, both a sufficiently large specific surface area and mesopores are provided to facilitate dispersion of a metal element having hydrogenation activity, and suitable acidity is required to facilitate removal of an intermediate product having hydroxyl groups. The nanometer IM-5 molecular sieve has high specific surface area and mesopore volume and good thermal and hydrothermal stability, and is used in hydrocarbon shape-selective catalytic reactions catalyzed by a plurality of mesoporous molecular sieves, particularly in hydrocarbon catalytic cracking, hydrocracking, disproportionation and alkylation reactions.
After further intensive research, the inventor of the invention finds that, until now, the IM-5 molecular sieve supported non-noble metal catalyst has higher selectivity, even approaching 100 percent selectivity of product cyclohexane by adopting the IM-5 molecular sieve supported Ni for the hydrodeoxygenation process, and the result is not reported. The hydrodeoxygenation catalyst has high activity and high selectivity of a target product cyclohexane, and can realize the directional conversion of an epoxy compound of benzene to the target product. Thereby greatly improving the efficiency of the catalytic process, reducing the separation process, saving energy and protecting environment.
In order to achieve the above object, in one aspect, the present invention provides a hydrodeoxygenation catalyst, wherein the catalyst comprises a carrier and an active element supported on the carrier, the carrier is an IM-5 molecular sieve, and the active element is Ni.
In a second aspect, the invention provides the use of a hydrodeoxygenation catalyst according to the invention as a catalyst for the hydrodeoxygenation of a feedstock containing an oxygenate to benzene to produce cyclohexane.
In a third aspect of the present invention, a method for preparing cyclohexane is provided, wherein the method comprises contacting and reacting a feedstock containing oxygen-containing compounds of benzene with hydrogen and a hydrodeoxygenation catalyst under hydrodeoxygenation reaction conditions, wherein the hydrodeoxygenation catalyst is the hydrodeoxygenation catalyst according to the present invention.
The hydrodeoxygenation catalyst has high hydrodeoxygenation catalytic activity, shows high catalytic activity when being used as a catalyst for preparing cyclohexane by hydrodeoxygenation of a raw material containing oxygen-containing compounds of benzene, and can obtain high raw material conversion rate and high selectivity of product cyclohexane. In addition, the product does not need to be separated, thereby greatly improving the efficiency of the catalytic process and reducing the energy consumption.
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.
FIG. 1 is an XRD spectrum of a hydrodeoxygenation catalyst C3 obtained by the method of preparation example 3 of the present invention;
FIG. 2 is a low-temperature nitrogen physisorption-desorption curve of a hydrodeoxygenation catalyst C3 obtained by the method of preparation example 3 of the invention;
FIG. 3 is a TEM image of hydrodeoxygenation catalyst C3 obtained by the process of preparation example 3 of the present invention;
FIG. 4 is a TEM image of hydrodeoxygenation catalyst C3 obtained by the method of preparation example 3 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
According to the first aspect of the present invention, the hydrodeoxygenation catalyst contains a carrier and an active element loaded on the carrier, the carrier is an IM-5 molecular sieve, and the active element is Ni.
According to the invention, the IM-5 molecular sieve with IMF structure is a silicon-aluminum molecular sieve synthesized by Benazzi et al in 1997 for the first time, orthorhombic system, space group is CmCm, unit cell parameters:
the three-dimensional ten-membered ring channel has the following dimensions: [001]：
[100]：
[010]：
[001]：
[100]:5.1x5.3. The inventor of the invention finds that the IM-5 molecular sieve has rich pore structure and better thermal and hydrothermal stability. After the IM-5 molecular sieve with the IMF structure is used as a carrier to load a Ni active component, the catalyst shows higher catalytic activity when being used as a catalyst for preparing cyclohexane by hydrodeoxygenation of a raw material containing oxygen-containing compounds of benzene, and can obtain higher raw material conversion rate and higher selectivity of product cyclohexane even reaching 100 percent.
According to the invention, the IM-5 molecular sieve preferably has a mesoporous area of 40-120m from the viewpoint of obtaining higher raw material conversion rate and selectivity of cyclohexane product 2 Per g, the mesoporous volume is 0.1-0.5cm 3 (ii)/g; the total specific surface area of the IM-5 molecular sieve is 300 to 450m 2 Per g, the micropore area is 200-350m 2 Per g, micropore volume of 0.1-0.2cm 3 Per g, total pore volume of 0.3-0.55cm 3 /g。
The contents of the IM-5 molecular sieve and the active element Ni in the hydrodeoxygenation catalyst are not particularly limited, and the contents of the IM-5 molecular sieve and the active element Ni in the hydrodeoxygenation catalyst are based on the catalytic action capable of realizing hydrodeoxygenation. More preferably, the content of the active element Ni, calculated as element, is 0.5-15 wt%, more preferably 3-10 wt%, based on the total amount of the catalyst.
According to the invention, in order to further improve the catalytic activity of the hydrodeoxygenation catalyst, the IM-5 molecular sieve is an H-IM-5 (hydrogen type IM-5 structure molecular sieve) molecular sieve.
The hydrodeoxygenation catalyst according to the invention can be prepared by a method conventional in the art, for example, by a conventional wet impregnation method, and optionally, for example, by a dry impregnation method (solid phase ion exchange). According to one embodiment of the present invention, the preparation of the catalyst may be carried out as follows: the IM-5 molecular sieve is impregnated with a solution of a soluble compound containing nickel, and the impregnated IM-5 molecular sieve is dried.
According to the invention, the impregnation can be carried out under conventional conditions. In general, the conditions for impregnating the IM-5 molecular sieve with the solution containing the soluble compound of nickel generally include a temperature and a time, and the impregnation temperature may generally be ambient temperature, and may for example be in the range of 10 to 60 ℃. The impregnation time may be appropriately selected depending on the concentration of the soluble compound of nickel, and is preferably 1 to 5 hours. Furthermore, the amount of solvent in the solution of soluble compounds containing nickel is such that, on the one hand, the soluble compounds containing nickel are sufficiently soluble in the solvent and, on the other hand, sufficient dispersion of the IM-5 molecular sieve is ensured, preferably the amount of solvent in the solution of soluble compounds containing nickel is between 1 and 50ml, preferably between 4 and 20ml, based on 1g of the weight of the IM-5 molecular sieve. The solvent may be at least one of water, ethanol, and propanol (including n-propanol and its isomer, isopropanol).
According to the invention, the impregnation of the IM-5 sieve with the solution containing the soluble compound of nickel is generally carried out with stirring, which may be a conventional mechanical stirring or ball milling with a ball mill.
According to the present invention, the form of impregnating the IM-5 molecular sieve with the solution of the soluble compound containing nickel is not particularly limited, and preferably, in order to make the solution of the soluble compound containing nickel more sufficient for the impregnation of the IM-5 molecular sieve, the IM-5 molecular sieve may be dispersed in the above-mentioned solvent to form a dispersion of the IM-5 molecular sieve, and then the soluble compound containing nickel or the solution of the soluble compound containing nickel may be added to the dispersion of the IM-5 molecular sieve to achieve the impregnation of the IM-5 molecular sieve with the solution of the soluble compound containing nickel.
According to the invention, the amounts of the IM-5 molecular sieve and the soluble compound containing nickel can be selected within wide limits, preferably, in order to further improve the catalytic performance of the catalyst, the amounts of the IM-5 molecular sieve and the soluble compound containing nickel are such that the content of the active element Ni, calculated as the element, is from 0.5 to 15% by weight, preferably from 3 to 10% by weight, and the content of the IM-5 molecular sieve is from 85 to 99.5% by weight, preferably from 90 to 97% by weight, based on the total weight of the catalyst.
According to the present invention, the soluble compound of nickel generally includes a water-soluble compound and an alcohol-soluble compound of nickel, and specifically, the soluble metal compound of nickel is preferably one or more of nickel nitrate hexahydrate, nickel chloride hexahydrate, and nickel sulfate hexahydrate.
According to the invention, after impregnating the IM-5 molecular sieve with a solution containing a soluble compound of nickel, the conditions for drying the impregnated IM-5 molecular sieve may be conventional drying conditions to remove the solvent therefrom. In general, the drying can be carried out at a temperature of from 40 to 150 ℃ and preferably at a temperature of from 50 to 120 ℃. The duration of the drying may be selected based on the temperature at which the drying is carried out, so as to remove or substantially remove the solvent therefrom. In general, the duration of the drying may be 8 to 24 hours. The drying may be performed in an air atmosphere, or may be performed in a non-oxidizing atmosphere, for example, a nitrogen atmosphere and/or a group zero atmosphere (e.g., argon). The drying may be performed under normal pressure (i.e., 1 atm), or under reduced pressure, and is not particularly limited.
According to the present invention, preferably, in order to further improve the catalytic activity of the catalyst, the preparation method of the catalyst comprises: the IM-5 molecular sieve is converted into the H-IM-5 molecular sieve, and the H-IM-5 molecular sieve is impregnated with a solution containing soluble compounds of nickel.
The method for converting the IM-5 molecular sieve into the H-IM-5 molecular sieve can be carried out by referring to the conventional method in the field. For example: performing ammonium salt exchange and deamination roasting on the molecular sieve (including IM-5 molecular sieve raw powder or the IM-5 molecular sieve obtained after roasting). Wherein the ammonium salt exchange conditions comprise: the temperature can be 70-90 ℃, the water-soluble ammonium salt used for ammonium salt exchange can be one or more selected from ammonium nitrate, ammonium chloride and ammonium sulfate, and the concentration of the ammonium salt aqueous solution is generally 1-10mol/L. In addition, the number and time of ammonia exchange depends on the degree of exchange of sodium ions in the molecular sieve during actual operation.
The conditions of the deamination calcination in the conversion of the IM-5 molecular sieve to the H-IM-5 molecular sieve according to the present invention generally comprise a calcination temperature and a calcination time, the calcination temperature can be 500 to 600 ℃, and the duration of the calcination can be selected according to the calcination temperature and can generally be 2 to 8 hours. The calcination is generally carried out in an air atmosphere, which includes both a flowing atmosphere and a static atmosphere.
The hydrodeoxygenation catalyst according to the invention can be reductively activated in a reactor by conventional methods before use. For example, the reduction may be carried out at a temperature of 200 to 600 deg.C, preferably 400 to 500 deg.C, under a reducing atmosphere (e.g., under a hydrogen atmosphere) or under a mixed atmosphere of a reducing atmosphere and an inert atmosphere (e.g., under a hydrogen and argon atmosphere). The reducing atmosphere may be a flowing atmosphere or a static atmosphere. The temperature increase from room temperature to the reduction temperature can be performed by temperature programming, generally, the temperature programming speed can be 5-15 ℃/min, preferably 8-12 ℃/min, and in one embodiment of the invention, the temperature increase from room temperature to the reduction temperature is performed at a rate of 10 ℃/min. According to one embodiment of the invention, the gas flow rate of the reducing atmosphere provided as a flowing atmosphere may be in the range of 30-100ml/min, preferably 50-60ml/min.
According to a second aspect of the invention, the invention also provides the application of the hydrodeoxygenation catalyst as a catalyst for preparing cyclohexane by hydrodeoxygenation of a raw material containing oxygen-containing compounds of benzene.
According to the second aspect of the present invention, the benzene oxygenate may be conventionally selected. Specifically, the oxygen-containing compound of benzene is selected from one or more of phenol, anisole, methylphenol, 2, 6-dimethylphenol, 2, 5-dimethylphenol, 3, 5-dimethylphenol, 2, 4-dimethylphenol, 3, 4-dimethylphenol, 1, 3-dimethylphenol, and guaiacol. Preferably, the feedstock containing benzene oxygenates is derived from coal tar and/or biomass oil. In particular, the biomass oil contains high content of oxygen-containing compounds, which not only reduces the calorific value of the bio-oil, but also accelerates the aging of the bio-oil by the mutual reaction of various oxygen-containing compounds. The biomass oil contains a large amount of benzene oxygen-containing compounds, wherein the content of phenol and homologues of phenol is 1-20 wt%, and the content of anisole and homologues of anisole is 1-15 wt%. The biomass oil is used as the source of the raw material of the oxygen-containing compound containing benzene in the application of the invention, so that the problem of difficult treatment of the biomass oil can be solved, and the oxygen-containing compound containing benzene in the biomass oil can be utilized to convert the benzene into the high-value product cyclohexane with high conversion rate.
According to a third aspect of the present invention, the present invention further provides a method for preparing cyclohexane, wherein the method comprises a contact reaction of a feedstock containing oxygen-containing compounds of benzene with hydrogen and a hydrodeoxygenation catalyst under hydrodeoxygenation reaction conditions, and the hydrodeoxygenation catalyst is the hydrodeoxygenation catalyst according to the present invention.
According to the process of the third aspect of the present invention, the hydrodeoxygenation catalyst is the hydrodeoxygenation catalyst of the first aspect of the present invention. The hydrodeoxygenation catalyst has been described in detail above and will not be described in detail here.
According to the process of the third aspect of the present invention, the hydrodeoxygenation catalyst and benzene are used in an amount of 1 to 150mg, preferably 10 to 100mg, based on 1mmol of the oxygen-containing compound of benzene.
According to the process of the third aspect of the invention, the hydrodeoxygenation reaction conditions comprise: the reaction temperature can be 150-300 ℃, and the reaction time can be 30 minutes-24 hours. Preferably, the reaction temperature is 180-250 ℃ and the reaction time is 60 minutes-4 hours, from the viewpoint of further improving the conversion of the raw material and obtaining a higher, even 100%, conversion of cyclohexane. The temperature increase from room temperature to the reaction temperature can be performed by temperature programming, generally, the temperature programming speed can be 5-15 ℃/min, preferably 8-12 ℃/min, and in one embodiment of the invention, the temperature increase from room temperature to the reaction temperature is performed at a rate of 10 ℃/min.
According to the method of the third aspect of the invention, the hydrogen comprises a flowing atmosphere and also a static atmosphere, preferably a flowing atmosphere. The amount of hydrogen used is such that the reaction pressure in the reaction system is 1 to 8MPa in terms of gauge pressure, and from the viewpoint of further improving the conversion of the raw material and obtaining a higher, even close to 100%, conversion of cyclohexane, the preferred reaction pressure is 2 to 6MPa.
According to the method of the third aspect of the present invention, the reaction system may further contain a reaction solvent, in which case the reaction rate may be adjusted. The reaction solvent may be conventionally selected. In general, the reaction solvent may be a liquid substance capable of dissolving the raw material and cyclohexane as a product, and for example, an alcohol solvent may be used. Specific examples of the alcohol-based solvent may include, but are not limited to, one or a combination of two or more of methanol, ethanol, propanol, and butanol, and in addition, the reaction solvent may be water or a combination of water and the above alcohol-based solvent. The amount of the reaction solvent may be conventionally selected. Generally, the reaction solvent is used in an amount of 1 to 20ml, preferably 2 to 15ml, based on 1mmol of the oxygen-containing compound of benzene.
According to the process of the third aspect of the present invention, the oxygen-containing compound of benzene may be conventionally selected. Specifically, the oxygen-containing compound of benzene is selected from one or more of phenol, anisole, methylphenol, 2, 6-dimethylphenol, 2, 5-dimethylphenol, 3, 5-dimethylphenol, 2, 4-dimethylphenol, 3, 4-dimethylphenol, 1, 3-dimethylphenol, and guaiacol. Preferably, the feedstock containing benzene oxygenates is derived from coal tar and/or biomass oil. In particular, the biomass oil has a high content of oxygen-containing compounds, which not only reduces the calorific value of the bio-oil, but also accelerates the aging of the bio-oil by the mutual reaction of various oxygen-containing compounds. The biomass oil contains a large amount of oxygenated compounds of benzene, wherein the content of phenol and homologues of phenol is 1-20 wt%, and the content of anisole and homologues of anisole is 1-15 wt%, and the biomass oil is used as a source of raw materials of oxygenated compounds of benzene in the application of the invention, so that the problem of difficult treatment of the biomass oil can be solved, and the oxygenated compounds of benzene in the biomass oil can be utilized to convert the biomass oil into high-value cyclohexane products with high conversion rate.
According to the method of the third aspect of the invention, compared with the existing method for preparing cyclohexane by hydrodeoxygenation of benzene-containing oxygen-containing compound raw materials, such as anisole, the hydrodeoxygenation catalyst of the invention has significantly improved catalytic activity, obtains more excellent hydrodeoxygenation reaction effect, not only can obtain higher conversion rate of raw materials, but also can obtain higher selectivity of product cyclohexane, even reaching 100%, so that the product does not need to be separated, thereby greatly improving the efficiency of the catalytic process, reducing the separation process and reducing the operation energy consumption.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the pressures are in gauge pressure.
In the following preparation examples, examples and comparative examples, the crystal structure of the product was determined by X-ray diffraction (XRD), and spectra with 2 θ angles of 5 ° to 80 ° were recorded.
In the following preparation examples, examples and comparative examples, specific surface area and pore structure parameters of the product were measured by low-temperature nitrogen adsorption and desorption. The mesoporous area, the mesoporous volume, the total specific surface area, the micropore volume and the total pore volume are obtained by adopting a low-temperature nitrogen static capacity adsorption method according to GB/T5816-1995 test.
In the following examples and comparative examples, quantitative analysis of raw materials and products was performed using shimadzu gas chromatograph (GC 2014, HP-65 column), and conversion of raw materials and selectivity of products were calculated from the measured composition data.
In the following preparation examples, the IM-5 molecular sieves used (as calcined hydrogen form, na) 2 O mass fraction of less than 0.1%, available from China petrochemical catalyst division) has a mesoporous area of 74m 2 (g) the mesoporous volume is 0.252cm 3 (iv) g; the total specific surface area of the IM-5 molecular sieve is 359m 2 (g) micropore area of 285m 2 In terms of a volume of micropores, 0.128cm 3 (ii)/g, total pore volume of 0.380cm 3 /g。
The following preparation examples 1 to 4 illustrate the preparation of the hydrodeoxygenation catalyst provided by the present invention.
Preparation examples 1 to 4
Respectively weighing 5g of IM-5 molecular sieve carrier, placing the carrier in a 100m1 round-bottom flask, adding 20m1 water, uniformly stirring to uniformly disperse the carrier, respectively weighing 0.423mmol, 2.536mmol, 4.227mmol and 8.454mmol of nickel nitrate hexahydrate, dissolving the nickel nitrate hexahydrate in 5m1 water, dropwise adding the nickel nitrate hexahydrate into the molecular sieve carrier dispersion liquid after the nickel nitrate hexahydrate is completely dissolved, continuing stirring for 24h, drying in a 110 ℃ oven for 24h, cooling to room temperature, and taking out to obtain the hydrodeoxygenation catalysts with Ni loading amounts of 0.5 wt%, 3 wt%, 5 wt% and 10 wt% respectively counted as C1-C4.
Wherein, fig. 1 is an XRD spectrogram of the hydrodeoxygenation catalyst C3, fig. 2 is a low-temperature nitrogen physical adsorption-desorption curve of the hydrodeoxygenation catalyst C3, and fig. 3 and fig. 4 are TEM images of the hydrodeoxygenation catalyst C3. As can be seen from fig. 1, the dispersibility of the active component Ni in the hydrodeoxygenation catalyst C3 is better; as can be seen from fig. 3 and 4, the active phase Ni of the hydrodeoxygenation catalyst C3 was uniformly supported.
The following examples 1 to 6 illustrate the method for producing cyclohexane by hydrodeoxygenation of anisole according to the invention.
Examples 1 to 6
The hydrodeoxygenation catalysts C1 to C4 prepared in preparation examples 1 to 4 were taken out and reduced in a reduction tube under the following reduction conditions: the hydrogen/argon flow rate, 60ml/min, was increased from room temperature 10 ℃/min to 500 ℃ and held for 3h.
Adding l m mol of anisole into a 25m1 high-pressure reaction kettle, respectively adding 12m1 of reaction solvent ethanol and 100mg of the catalyst prepared in the preparation examples 1-4, then sealing the reaction kettle, filling hydrogen to 5-8MPa, heating the reaction kettle to 160-200 ℃ from room temperature after 30min, keeping the temperature for 140-180min, carrying out quantitative analysis on raw materials and products by using Shimadzu gas chromatograph (GC 2014, HP-65 chromatographic column) after the reaction is finished, and referring to table 1 for analysis data of reaction results obtained by using hydrodeoxygenation catalysts C1-C4 under different reaction conditions.
TABLE 1
The results in table 1 show that the method for preparing cyclohexane by hydrodeoxygenation of anisole by using the hydrodeoxygenation catalyst of the invention can obtain higher anisole conversion rate and higher cyclohexane selectivity. In particular, when the loading amount of the Ni active component in the catalyst is in the range of 3 to 10 wt%, a higher conversion of anisole and a higher selectivity of cyclohexane can be obtained under relatively mild reaction conditions. When the loading amount of the Ni active component in the catalyst is 3 wt% or 5 wt%, increasing the reaction temperature or increasing the reaction pressure while prolonging the reaction time not only increases the conversion rate of anisole but also increases the selectivity of cyclohexane, preferably close to 100%. When the loading amount of the Ni active component in the catalyst is 5 weight percent, higher anisole conversion rate and cyclohexane selectivity close to 100 percent can be obtained. When the loading amount of the Ni active component in the catalyst is 10 wt%, higher conversion rate of anisole and selectivity of cyclohexane close to 100% can be obtained under relatively mild reaction conditions.
The following examples 7-10 illustrate the present invention for the hydrodeoxygenation of phenol to produce cyclohexane.
Examples 7 to 10
The hydrodeoxygenation catalysts C1 to C4 prepared in preparation examples 1 to 4 were taken out and reduced in a reduction tube under the following reduction conditions: the hydrogen/argon flow rate, 60ml/min, was increased from room temperature 10 ℃/min to 400 ℃ and held for 3h.
Adding 6m mol of phenol into a 25m1 high-pressure reaction kettle, respectively adding 12m1 reaction solvent deionized water and 100mg of the catalyst prepared in preparation examples 1-4, sealing the reaction kettle, filling hydrogen to 5-8MPa, heating to 220 ℃ from room temperature after 30min, keeping for 60-140min, carrying out quantitative analysis on raw materials and products by using Shimadzu gas chromatograph (GC 2014, HP-65 chromatographic column) after the reaction is finished, and obtaining analysis data of reaction results under different reaction conditions by using hydrodeoxygenation catalysts C1-C4, which are shown in Table 2.
TABLE 2
The results in table 2 show that when the loading amount of the Ni active component in the catalyst is in the range of 5 to 10 wt%, the reaction temperature is increased to 220 ℃, the reaction pressure is 5 to 8MPa, the reaction time is maintained for more than 60min, the phenol can achieve 100% conversion, and the selectivity of cyclohexane reaches more than 95%.
Examples 11 to 12
The hydrodeoxygenation catalyst C3 prepared in preparation example 3 was taken out and reduced in a reduction tube under the following reduction conditions: the hydrogen/argon flow rate, 60ml/min, was increased from room temperature 10 ℃/min to 400 ℃ and held for 3h.
Adding l m mol of anisole into a 25m1 high-pressure reaction kettle, respectively adding 12m1 reaction solvent ethanol and 20mg of the catalyst prepared in preparation example 3, then sealing the reaction kettle, filling hydrogen to 5MPa, heating the reaction kettle to 200 ℃ from room temperature after 30min, keeping the temperature for 80-240min, carrying out quantitative analysis on raw materials and products by using Shimadzu gas chromatograph (GC 2014, HP-65 chromatographic column) after the reaction is finished, and referring to table 3 for analysis data of reaction results obtained by using hydrodeoxygenation catalyst C3 under the conditions of different reaction time, the same reaction temperature and the same reaction pressure.
TABLE 3
It can be seen from the results in table 3 that when the catalyst dosage is reduced to 20mg, a conversion rate of anisole close to 100% and a selectivity of cyclohexane close to 100% can still be obtained by extending the reaction time to 200 min.
The following preparation examples 5 to 7 illustrate the preparation of the hydrodeoxygenation catalyst provided by the present invention.
Preparation examples 5 to 7
Weighing 5g of IM-5 molecular sieve carrier, placing the carrier in a 100m1 round-bottom flask, adding 20m1 of water, uniformly stirring to uniformly disperse the carrier, respectively weighing 0.423mmol, 4.227mmol and 8.454mmol of nickel nitrate hexahydrate, mixing the mixture with the molecular sieve carrier dispersion liquid, ball-milling for 10 minutes in a ball mill, drying in an oven at 110 ℃ for 24 hours, cooling to room temperature, taking out, and obtaining the hydrodeoxygenation catalyst with Ni loading amounts of 0.5 wt%, 5 wt% and 10 wt% respectively calculated by elements, which is marked as C5-C7.
The following examples 13-15 illustrate the process of the present invention for the hydrodeoxygenation of guaiacol to produce cyclohexane.
Examples 13 to 15
The hydrodeoxygenation catalysts C5 to C7 prepared in preparation examples 5 to 7 were taken out and reduced in a reduction tube under the following reduction conditions: the hydrogen/argon flow rate, 60ml/min, was increased from room temperature 10 ℃/min to 600 ℃ and held for 3h.
Adding l m mol of guaiacol into a 25m1 high-pressure reaction kettle, respectively adding 12m1 reaction solvent ethanol and 100mg of the catalyst prepared in preparation examples 5-7, sealing the reaction kettle, filling hydrogen to 5MPa, heating to 220 ℃ from room temperature after 30min, keeping for 140min, carrying out quantitative analysis on raw materials and products by using Shimadzu gas chromatograph (GC 2014, HP-65 chromatographic column) after the reaction is finished, and obtaining analysis data of reaction results under the same reaction conditions by using hydrodeoxygenation catalysts C5-C7, which are shown in Table 4.
TABLE 4
It can be seen from the results of table 4 that when the supported amounts of Ni active component in the catalyst were 5 wt% and 10 wt%, respectively, the conversion of guaiacol of 98% or more and the selectivity of cyclohexane of 96% or more were obtained by maintaining the reaction temperature to 220 ℃, the reaction pressure to 5MPa, and the reaction time to 140 min.
Comparative preparation examples 1 to 2
Weighing 5g of molecular sieve carrier H-ZSM-5, placing the molecular sieve carrier H-ZSM-5 in a 100m1 round-bottom flask, adding 20m1 water, uniformly stirring to uniformly disperse the carrier, respectively weighing 4.227mmol and 8.454mmol of nickel nitrate hexahydrate to dissolve in the 5m1 water, dropwise adding the mixture into a molecular sieve carrier dispersion liquid after the mixture is completely dissolved, continuously stirring for 24 hours, taking out the mixture, drying the mixture in a 110 ℃ oven for 24 hours, cooling the mixture to room temperature, and taking out the mixture to obtain hydrodeoxygenation catalysts with Ni loading of 5 weight percent and 10 weight percent respectively, wherein the hydrodeoxygenation catalysts are recorded as DC1-DC2.
Comparative preparation example 3
Weighing 5g of molecular sieve carrier alpha-Al 2 O 3 Placing the mixture into a 100m1 round-bottom flask, adding 20m1 water, uniformly stirring to uniformly disperse the carrier, weighing 4.277mmol of nickel nitrate hexahydrate, dissolving the nickel nitrate hexahydrate in 5m1 water, dropwise adding the nickel nitrate hexahydrate into the molecular sieve carrier dispersion liquid after the nickel nitrate hexahydrate is completely dissolved, continuously stirring for 24 hours, taking out, drying in a drying oven at the temperature of 110 ℃ for 24 hours, cooling to room temperature, and taking out to obtain the hydrodeoxygenation catalyst with the Ni loading of 5 weight percent, wherein the hydrodeoxygenation catalyst is marked as DC3.
Comparative examples 1 to 3
The hydrodeoxygenation catalysts DC1 to DC3 prepared in comparative preparation examples 1 to 3 were taken out and reduced in a reduction tube under the following conditions: the hydrogen/argon flow rate, 60ml/min, was increased from room temperature 10 ℃/min to 500 ℃ and held for 3h.
Adding l mmol of anisole into a 25m1 high-pressure reaction kettle, respectively adding 100mg of the catalyst prepared in comparative preparation examples 1-3 and 12m1 reaction solvent ethanol, sealing the reaction kettle, filling hydrogen to 5-6MPa, heating to 200-220 ℃ from room temperature after 30min, keeping for 140min, carrying out quantitative analysis on raw materials and products by using Shimadzu gas chromatograph (GC 2014, HP-65 chromatographic column) after the reaction is finished, and referring to Table 5 for analysis data of reaction results obtained by using hydrodeoxygenation catalysts DC1-DC3 under different reaction conditions.
TABLE 5
As can be seen from the results in Table 5, H-ZSM-5 or alpha-Al supported on molecular sieve was used 2 O 3 When the catalyst prepared by loading the Ni active component is used as a hydrodeoxygenation catalyst for preparing cyclohexane by hydrodeoxygenation of anisole, the conversion rate of anisole is low, and the selectivity of cyclohexane is lower than 80%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (18)
1. The application of a hydrodeoxygenation catalyst as a catalyst for preparing cyclohexane by hydrodeoxygenation of a raw material containing oxygen-containing compounds of benzene; the catalyst comprises a carrier and an active element loaded on the carrier, wherein the carrier is an IM-5 molecular sieve, and the active element is Ni; the oxygen-containing compound of benzene is one or more selected from phenol, anisole, methylphenol, 2, 6-dimethylphenol, 2, 5-dimethylphenol, 3, 5-dimethylphenol, 2, 4-dimethylphenol, 3, 4-dimethylphenol, 1, 3-dimethylphenol and guaiacol.
2. Use according to claim 1, wherein the content of the active element Ni, calculated as element, is 0.5 to 15% by weight, based on the total amount of the catalyst.
3. Use according to claim 2, wherein the content of the active element Ni, calculated as element, is 3-10% by weight, based on the total amount of the catalyst.
4. The use of any one of claims 1 to 3, wherein the IM-5 molecular sieve has a mesopore area of 40 to 120m 2 Per g, the mesoporous volume is 0.1-0.5cm 3 (ii)/g; the total specific surface area of the IM-5 molecular sieve is 300 to 450m 2 Per g, the micropore area is 200-350m 2 Per g, micropore volume of 0.1-0.2cm 3 (ii)/g, total pore volume of 0.3-0.55cm 3 /g。
5. Use according to any one of claims 1 to 3, wherein the IM-5 molecular sieve is a H-IM-5 molecular sieve.
6. The use according to any one of claims 1 to 3, wherein the benzene-containing oxygenate feedstock is derived from coal tar and/or biomass oil, wherein the biomass oil has a phenol and phenol homologue content of 1 to 20 wt% and an anisole and anisole homologue content of 1 to 15 wt%.
7. The preparation method of the cyclohexane is characterized by comprising the steps of carrying out contact reaction on a raw material containing oxygen-containing compounds of benzene, hydrogen and a hydrodeoxygenation catalyst under the hydrodeoxygenation reaction condition, wherein the catalyst comprises a carrier and an active element loaded on the carrier, the carrier is an IM-5 molecular sieve, and the active element is Ni; the oxygen-containing compound of benzene is one or more selected from phenol, anisole, methylphenol, 2, 6-dimethylphenol, 2, 5-dimethylphenol, 3, 5-dimethylphenol, 2, 4-dimethylphenol, 3, 4-dimethylphenol, 1, 3-dimethylphenol and guaiacol.
8. The production method according to claim 7, wherein the content of the active element Ni in terms of element is 0.5 to 15% by weight based on the total amount of the catalyst.
9. The production method according to claim 8, wherein the content of the active element Ni in terms of element is 3 to 10% by weight based on the total amount of the catalyst.
10. The method of any one of claims 7 to 9, wherein the IM-5 molecular sieve has a mesopore area of 40 to 120m 2 Per g, the mesoporous volume is 0.1-0.5cm 3 (ii)/g; the total specific surface area of the IM-5 molecular sieve is 300 to 450m 2 G, the micropore area is 200-350m 2 Per g, micropore volume of 0.1-0.2cm 3 (ii)/g, total pore volume of 0.3-0.55cm 3 /g。
11. The process of any one of claims 7 to 9, wherein the IM-5 molecular sieve is a H-IM-5 molecular sieve.
12. The production process according to any one of claims 7 to 9, wherein the amount of the hydrodeoxygenation catalyst used is 1 to 150mg based on 1mmol of the oxygen-containing compound of benzene.
13. The production method according to claim 12, wherein the amount of the hydrodeoxygenation catalyst used is 10 to 100mg based on 1mmol of the oxygen-containing compound of benzene.
14. The production method according to any one of claims 7 to 9, wherein the hydrodeoxygenation reaction conditions include: the reaction temperature is 150-300 ℃, the reaction time is 30 minutes-24 hours, and the reaction pressure is 1-8MPa.
15. The process according to claim 14, wherein the reaction temperature is 180 to 250 ℃, the reaction time is 60 minutes to 4 hours, and the reaction pressure is 2 to 6MPa.
16. The production process according to any one of claims 7 to 9, wherein the contact reaction of the benzene-containing oxygen-containing compound-containing raw material with hydrogen and the hydrodeoxygenation catalyst is carried out in the presence of a reaction solvent selected from one or more of water, methanol, ethanol, propanol and butanol, the amount of the reaction solvent being 1 to 20ml based on 1mmol of the benzene-containing oxygen-containing compound.
17. The production method according to claim 16, wherein the reaction solvent is used in an amount of 2 to 15ml based on 1mmol of the oxygen-containing compound of benzene.
18. The production method according to any one of claims 7 to 9, wherein the benzene-containing oxygen-containing compound raw material is derived from coal tar and/or biomass oil, wherein the biomass oil contains 1 to 20 wt% of phenol and homologues of phenol, and 1 to 15 wt% of anisole and homologues of anisole.
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