Use of a bimetallic supported perovskite catalyst in the industrial gaseous hydrogenation of dipentene at atmospheric pressure to produce bio-jet fuel

Abstract

The application discloses a use of a bimetallic supported perovskite catalyst in industrial dipentene atmospheric gaseous hydrogenation for preparing bio-jet fuel, and a composition of the hydrogenation catalyst is Co-Ni / La2O3-LaMO3, wherein M is Al or Cr; the catalyst can maintain an ordered macroporous structure of a precursor; the catalyst is filled into a hydrogenation reactor and hydrogen is introduced; after the reactor is heated to a specified temperature, industrial dipentene can be vaporized by a vaporizer and then enters the hydrogenation reactor to perform hydrogenation reaction under atmospheric pressure to generate bio-jet fuel p-menthane with high selectivity; the hydrogenation catalyst has an ordered macroporous structure, a synergistic effect of high-dispersed Co-Ni nanometer alloy and a strong interaction between active metals and a carrier, and thus has excellent catalytic activity and stability in the preparation of p-menthane through the atmospheric gaseous hydrogenation of industrial dipentene; the conversion rate of dipentene reaches 100%, the selectivity of p-menthane reaches 100% at most, and the content of p-menthane in the product reaches 97.2% at most.

Description

TECHNICAL FIELD

[0001] The application relates to a use of a bimetallic supported perovskite catalyst in industrial dipentene atmospheric gaseous hydrogenation to prepare bio-jet fuel, and belongs to the field of application of catalysts in preparing paraffin. BACKGROUND

[0002] Industrial dipentene is a by-product produced in the preparation of terpineol or camphor from turpentine, and is a renewable resource derived from biomass. It is mainly a mixture of monocyclic monoterpene compounds with the same molecular mass and similar structures, usually having multiple isomers (such as limonene, alpha-terpinene, gamma-terpinene, isoterpinene, alpha-phellandrene and beta-phellandrene, etc.). Industrial dipentene has important applications in the synthesis of fragrances, the synthesis of organic intermediates and as an oil stain cleaning agent due to its high yield, low price and rich reactive structures. However, the utilization rate and economic benefits of industrial dipentene are limited in these applications. Converting it into bio-jet fuel (C10 naphthenic paraffin) to high-value use of industrial dipentene has more environmental, economic and social benefits.

[0003] At present, the production of paraffin from industrial dipentene mainly adopts a liquid-phase hydrogenation method. Invention patent CN108250009B discloses a preparation method of paraffin. The method first mixes hydrogen and dipentene into a gas-liquid fluid, then sequentially passes through two hydrogenation reactors under a reaction pressure of 0.5-7 MPa (hydrogen is supplemented during the period), and finally passes through gas-liquid separation to obtain a product with a paraffin content of greater than 96.0%. Invention patent CN114751802A discloses an industrial preparation method of paraffin. The method first mixes dipentene and hydrogen, heats it, and then sends it into a tubular fixed-bed reactor for hydrogenation reaction under a reaction pressure of 9-12 MPa. The conversion rate of dipentene can reach 99.9%, and the paraffin content in the product is greater than 95%. We see that the hydrogenation reaction of dipentene in the liquid phase requires very high hydrogen pressure to promote the contact reaction between dipentene and hydrogen. In order to solve the problem of high hydrogen pressure, invention patent CN108101728B discloses a preparation method of paraffin. The method first puts dipentene and a catalyst into a high-pressure reaction kettle, and then performs hydrogenation reaction under a certain hydrogen pressure. During the reaction process, sampling analysis is continuously performed. When the content of dipentene is less than or equal to 60%, 30% and 10% in turn, the hydrogen pressure is appropriately increased in turn to continue the hydrogenation reaction. When the content of dipentene is ≤0.5%, paraffin is obtained. The entire reaction pressure is between 0.5-2.6 MPa. Although this process reduces the hydrogen pressure to some extent, it still belongs to liquid-phase hydrogenation reaction and still requires a large reaction pressure (≥0.5 MPa). In addition, the existing process also has problems such as complex reaction process and easy deactivation of liquid-phase hydrogenation catalyst.

[0004] In the hydrogenation reaction of dipentene, the hydrogenation catalyst plays a crucial role. At present, the hydrogenation catalyst of dipentene mainly includes noble metals (such as Pd, Pt, Ru, etc.) or transition metals (such as Fe, Co, Ni, etc.) supported on Al2O3, SiO2 and activated carbon carriers, which mainly adopts traditional methods such as impregnation, coprecipitation and sol-gel, and has the defects of easy agglomeration of active metals, large particle size and poor dispersion. The supported catalyst prepared by taking the perovskite ABO3 oxide as a precursor and after reduction has highly dispersed active metal nanoparticles, and has important applications in the methanation of CO2 and CO, the steam reforming of hydrocarbons and the synthesis of higher alcohols from synthesis gas. However, there is no report on the application of the supported catalyst derived from the ABO3 perovskite to the industrial preparation of p-menthane from dipentene by hydrogenation. SUMMARY

[0005] In view of the problems in the prior art, the technical problem to be solved by the present application is to provide a use of a bimetallic supported perovskite catalyst in the industrial preparation of bio-jet fuel from dipentene by atmospheric gaseous hydrogenation, wherein the catalyst has excellent catalytic activity and stability in the preparation of p-menthane from industrial dipentene by atmospheric gaseous hydrogenation, has the advantages of mild reaction conditions, simple reaction process and high hydrogenation efficiency, and solves the problems of complex process flow, harsh reaction conditions (high pressure), easy deactivation of the catalyst due to coke deposition and low catalytic activity of the catalyst in the preparation of p-menthane from industrial dipentene by catalytic hydrogenation.

[0006] In order to solve the above problems, the technical scheme adopted by the present application is as follows:

[0007] The use of a bimetallic supported perovskite catalyst in the industrial preparation of bio-jet fuel from dipentene by atmospheric gaseous hydrogenation, wherein the composition of the bimetallic supported perovskite catalyst is Co-Ni / La2O3-LaMO3, wherein M is Al or Cr; the gaseous dipentene is subjected to atmospheric hydrogenation reaction under the catalysis of the bimetallic supported perovskite catalyst to obtain bio-jet fuel (p-menthane).

[0008] By special selection of the bimetallic supported perovskite catalyst and gaseous hydrogenation, the industrial dipentene can be fully mixed with hydrogen gas, and the gaseous solid contact reaction with the catalyst can be carried out at atmospheric pressure, so that the low-temperature hydrogenation of industrial dipentene under atmospheric pressure is realized, and the advantages of mild reaction conditions, high hydrogenation activity and stability of the catalyst and high hydrogenation reaction efficiency are achieved, thereby simplifying the operation, saving energy consumption and having great production significance.

[0009] The inventors have found that in the general formula ABO3, the A site is usually occupied by rare earth, alkaline earth or other large ions and is difficult to reduce; the B site is usually filled with transition metal cations and is easy to reduce; in addition, the A and B sites can be substituted by other cations. LaCo 1-x Nix O3 is reduced by hydrogen, a Co-Ni nanometer alloy catalyst can be obtained, which is highly dispersed on the La2O3 carrier. At the same time, the Co-Ni nanoparticles have a strong interaction with the La2O3 carrier to inhibit the agglomeration of the metal nanoparticles. In addition, H2 chemical adsorption and dissociation is the rate-determining step in the catalytic hydrogenation of dipentene, and the existence of electron transfer between Co-Ni alloys is conducive to the adsorption, dissociation and desorption of H2, which will improve the catalytic activity of the catalyst. However, ABO3 type perovskite usually has a low specific surface area, which is not conducive to the contact of the catalyst active site with the reactants and H2. The use of a template method to prepare a perovskite with a three-dimensional ordered macroporous structure can increase the specific surface area of the catalyst precursor, thereby increasing the number of active sites and improving the mass transfer efficiency. However, after reduction, the perovskite structure disappears, causing the collapse of the three-dimensional macroporous structure, thereby reducing the specific surface area of the catalyst. In view of the fact that nickel ions and cobalt ions can be reduced to metal at a relatively low temperature, it is of great significance to construct LaM 1-x-y Co x Ni y O3 perovskite precursor (the reduction temperature of M metal is higher than that of Ni and Co) is of great significance because at a suitable reduction temperature, a Co-Ni / La2O3-LaMO3 catalyst with a three-dimensional ordered macroporous structure can be synthesized, in which the Co-Ni alloy nanoparticles have hydrogenation, anti-sintering and anti-carbon deposition properties, and the carrier can maintain a three-dimensional ordered macroporous framework structure. At the same time, the oxygen vacancies generated during the reduction process and the improvement of the oxygen mobility of the carrier help to reduce carbon deposition.

[0010] Preferably, the above-mentioned M is Al.

[0011] The temperature of the hydrogenation reaction of the present application is 170-230°C, preferably 190-210°C.

[0012] The present application is an industrial dipentene atmospheric gaseous hydrogenation to prepare bio-jet fuel, which comprises the following steps:

[0013] 1) Load the bimetallic supported perovskite catalyst into the hydrogenation reactor, and purge the vertically connected vaporizer and hydrogenation reactor with H2 for 10-15 min to remove air;

[0014] 2) Continue to pass H2, and increase the temperature of the vaporizer to 200-230°C and the temperature of the hydrogenation reactor to 170-230°C;

[0015] 3) Continuously add industrial dipentene to the vaporizer at a flow rate of 0.5 ml / min per 10-15 g of bimetallic supported perovskite catalyst, and the generated gaseous dipentene immediately enters the hydrogenation reactor for hydrogenation reaction at atmospheric pressure to obtain gaseous products, which are condensed to obtain bio-jet fuel (p-menthane).

[0016] The "flow rate of 0.5 ml / min per 10-15 g of double metal loaded perovskite catalyst" means that 0.5 ml / min of industrial dipentene needs to be passed per 10-15 g of catalyst. That is, when the amount of catalyst is increased or decreased by n times, the amount of industrial dipentene passed is also increased or decreased by the same multiple. In the reaction, industrial dipentene is continuously passed in, and 0.5 ml / min refers to the total amount of industrial dipentene passed in per minute. The above hydrogenation reaction is completed during the process of passing through the catalyst layer after the gaseous industrial dipentene enters the hydrogenation reactor. Industrial dipentene is continuously input during the reaction, and the product is continuously output.

[0017] In step 3), industrial dipentene is preferably continuously added to the vaporizer at a flow rate of 0.5 ml / min per 10-12 g of double metal loaded perovskite catalyst.

[0018] In order to ensure the reaction efficiency and selectivity, the precursor of the above double metal loaded perovskite catalyst has the general formula LaM 1-x-y Co x Ni y O3, wherein x is in the range of 0.05-0.15, y is in the range of 0.05-0.15, and M is Al or Cr.

[0019] The precursor of the above double metal loaded perovskite catalyst is preferably LaAl 0.8 Co 0.1 Ni 0.1 O3.

[0020] The preparation method of the above double metal loaded perovskite catalyst comprises the following steps:

[0021] 1) Take lanthanum nitrate, metal M nitrate, cobalt nitrate, nickel nitrate and citric acid in a ratio of lanthanum nitrate: metal M nitrate: cobalt nitrate: nickel nitrate: citric acid = 1: (0.7-0.9): (0.05-0.15): (0.05-0.15): 0.4 by mole, add them to a methanol-ethylene glycol solution (volume ratio 2:3) so that the total concentration of metal ions is kept at 2 mol / L, and stir at room temperature for 6-8 h to obtain solution A, wherein the sum of the mole amounts of metal M nitrate, cobalt nitrate and nickel nitrate is equal to the mole amount of lanthanum nitrate;

[0022] 2) Add a PMMA (polymethyl methacrylate) colloidal template to solution A, soak for 4-5 h, and then vacuum filter to obtain a filter residue; wherein the PMMA colloidal template is formed by self-assembly of monodisperse PMMA microspheres with a particle size of 80-500 nm, and 28-32 mL of solution A is needed per 3 g of PMMA colloidal template;

[0023] 3) The filter residue is dried in a vacuum at 35-40℃ for 20-24h, and then calcined in a tube furnace. The calcination process is as follows: under N2 atmosphere, the temperature is raised to 310℃ at a rate of 1℃ / min, and kept for 3h, then reduced to room temperature, and then under air atmosphere, the temperature is raised to 310℃ at a rate of 1℃ / min, and kept for 2h, then raised to 700℃ at a rate of 1℃ / min, and kept for 4h, and finally naturally cooled to room temperature, to obtain the precursor LaM 1-x-y Co x Ni y O3;

[0024] 4) The precursor is placed in a tube furnace, and heated to the reduction temperature under 20%H2 / Ar atmosphere at a rate of 1℃ / min, and kept for 1.5-2h, and then naturally cooled to room temperature, to obtain Co-Ni / La2O3-LaMO3.

[0025] In the above step 1), the molar ratio of lanthanum nitrate: metal M nitrate: cobalt nitrate: nickel nitrate: citric acid is preferably 1:0.8:0.1:0.1:0.4.

[0026] The above 20%H2 / Ar atmosphere refers to the volume ratio of H2 being 20% and the volume ratio of Ar being 80%. The methanol-ethylene glycol solution is a solution obtained by mixing methanol and ethylene glycol in a volume ratio of 2:3.

[0027] When M is Al, the reduction temperature is 650-800℃, preferably 730℃; when M is Cr, the reduction temperature is 700-830℃, preferably 770℃.

[0028] The above industrial dipentene includes one or two or more of limonene, alpha-terpinene, beta-terpinene, gamma-terpinene, terpinolene, alpha-phellandrene, beta-phellandrene, and p-cymene.

[0029] Advantages: Compared with the prior art, the advantages of the present application include:

[0030] (1) The prepared dipentene hydrogenation catalyst has highly dispersed Co-Ni nano-alloy particles and a three-dimensional ordered macroporous perovskite carrier skeleton structure, and the active metal and the carrier have strong interaction force. There is electron transfer between the Co-Ni nano-alloy, and the synergistic effect is conducive to the adsorption, dissociation and desorption of H2, thereby promoting the hydrogenation reaction of dipentene. The three-dimensional ordered macroporous carrier structure is conducive to the mass transfer of dipentene and reduces the diffusion resistance, which is conducive to the contact reaction of reactants, H2 and active sites, and the separation of products. The interaction force between the active metal and the carrier can inhibit the agglomeration of the active metal in the reduction process and the catalytic reaction process, thereby improving the activity and stability of the catalyst. In addition, the La2O3-LaMO3 carrier generated by controlling the reduction conditions not only maintains the macroporous structure, but also the oxygen vacancies generated are conducive to eliminating carbon deposition.

[0031] (2) The B-site metal component M used in the present application is one of Al and Cr, and the reduction temperature is higher than that of Ni and Co. By controlling the reduction temperature, the three-dimensional ordered macroporous perovskite skeleton structure of the La2O3-LaMO3 carrier can be maintained on the basis of generating highly dispersed Co-Ni nano-alloy, and appropriate oxygen vacancies are generated and the oxygen mobility is improved.

[0032] (3) The gaseous hydrogenation process of dipentene is adopted in the present application, and the gaseous dipentene and H2 can be fully mixed and uniform, thereby fully undergoing gas-solid contact reaction, and under the excellent hydrogenation activity of the catalyst, the p-menthane can be efficiently generated at normal pressure, which has the beneficial effects of mild reaction conditions, simple reaction process and catalyst not easy to deactivate. DETAILED DESCRIPTION

[0033] In order to make the above-mentioned purposes, characteristics and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below.

[0034] The content of dipentene series components and p-menthane in industrial dipentene is obtained by using the gas chromatograph-mass spectrometer (8890 GC-5977B MS) of Agilent Company of the United States and HP-PONA chromatographic column.

[0035] The conversion rate of dipentene and the selectivity of the product p-menthane are calculated according to formula (1) and formula (2) respectively.

[0036] Conversion rate of dipentene / % = (MD1-MD2) / MD1x 100 (1)

[0037] Selectivity of p-menthane / % = M0 / (MD1-MD2)x 100 (2)

[0038] In the formula, MD1 represents the relative mass fraction of dipentene in the raw material; MD2 represents the relative mass fraction of dipentene in the reaction product; and M0 represents the relative mass fraction of p-menthol in the reaction product.

[0039] The composition of the industrial dipentene used in each example is shown in Table 3.

[0040] Example 1

[0041] 1) LaAl 0.8 Co 0.1 Ni 0.1 Preparation of O3 precursor: Each metal nitrate and citric acid were added to a methanol-ethylene glycol solution (where the volume ratio of methanol to ethylene glycol was 2:3) according to the molar ratio of lanthanum nitrate: aluminum nitrate: cobalt nitrate: nickel nitrate: citric acid = 1:0.8:0.1:0.1:0.4, so that the total metal ion concentration was maintained at 2 mol / L, and the solution was stirred at room temperature for 8 h to obtain solution A. 3g of PMMA colloidal template (formed by self-assembly of monodisperse PMMA microspheres with a particle size of 200 nm) was added to 30mL of solution A and soaked for 5h. The solution was then vacuum filtered to obtain the filter residue. The residue was vacuum dried at 40℃ for 24h and then calcined in a tube furnace. The calcination process was as follows: the temperature was increased to 310℃ at a rate of 1℃ / min under N2 atmosphere and held for 3h, then allowed to cool naturally to room temperature. The temperature was then increased to 310℃ at a rate of 1℃ / min under air atmosphere and held for 2h, followed by an increase to 700℃ at a rate of 1℃ / min and held for 4h. Finally, the temperature was allowed to cool naturally to room temperature to obtain the precursor LaAl. 0.8 Co 0.1 Ni 0.1 O3.

[0042] 2) Preparation of Co-Ni / La2O3-LaAlO3 bimetallic supported perovskite catalyst: The precursor was placed in a tube furnace and heated to 730℃ at a rate of 1℃ / min under a 20% H2 / Ar atmosphere and held for 2h. After cooling to room temperature, Co-Ni / La2O3-LaAlO3 (denoted as Co0.1Ni0.1 / LAO-730) was obtained.

[0043] 3) Industrial dipentene gaseous hydrogenation at normal pressure to prepare p-menthane: 10 g of Co-Ni / La2O3-LaAlO3 catalyst was loaded into a hydrogenation reactor, and the vaporizer and hydrogenation reactor connected in series vertically were purged with H2for 12 min to remove air. H2was continuously introduced, and the temperature of the vaporizer and hydrogenation reactor was increased to 220°C and 200°C, respectively. When the temperature was stable at the specified temperature, industrial dipentene was added into the vaporizer at a flow rate of 0.5 ml / min, and the generated gaseous dipentene was introduced into the hydrogenation reactor to perform hydrogenation reaction at normal pressure. A small amount of gas phase product was introduced into a gas chromatograph-mass spectrometer for online analysis, and the rest was condensed to obtain product bio-jet fuel p-menthane. The results are shown in Table 1.

[0044] As shown in Table 1, under the catalytic hydrogenation of Co0.1Ni0.1 / LaO-730 catalyst, the conversion rate of dipentene reached 100%, the selectivity of p-menthane reached 100%, and the content of p-menthane in the product was 97.2%.

[0045] By the preparation method of this embodiment, the product was taken once every 1 h for online analysis by gas chromatograph-mass spectrometer under the same reaction conditions while the catalyst remained unchanged, and a total of 10 times were taken. The test results are shown in Table 2. The conversion rate of dipentene was 100%, the selectivity of p-menthane was above 99.8%, and the yield of p-menthane in the product was above 97.0%. By this method, p-menthane can be continuously prepared without changing the catalyst, and the stability is good.

[0046] The above Co-Ni / La2O3-LaAlO3 catalyst can be used stably and continuously for several months without obvious carbon deposition. After the catalyst is deactivated, it can be regenerated by the following method: heating to 700°C at a rate of 1°C / min under air and maintaining for 2 h, naturally cooling to room temperature, then reducing at a rate of 1°C / min to 730°C under an atmosphere of 20% H2 / Ar for 2 h, and then naturally cooling to room temperature to complete the regeneration. After regeneration, the catalyst is reused for the preparation of p-menthane by gaseous hydrogenation of industrial dipentene. After 5 cycles, the conversion rate of dipentene can still reach 100%, and the selectivity can still reach above 99.5% without obvious attenuation.

[0047] Example 2

[0048] The difference between this embodiment and Example 1 is that the hydrogenation reactor temperature in step 3) is changed to 210°C, and the rest refers to Example 1. The results of online analysis of the product by gas chromatograph-mass spectrometer are shown in Table 1.

[0049] As shown in Table 1, under the catalytic hydrogenation of Co0.1Ni0.1 / LaO-730 catalyst, the conversion rate of dipentene reached 100%, the selectivity of p-menthane reached 100%, and the content of p-menthane in the product was 97.2%.

[0050] Example 3

[0051] The difference between this embodiment and Example 1 is that the temperature of the hydrogenation reactor is changed to 230°C in step 3), while the rest is the same as in Example 1. The results of online gas chromatography-mass spectrometry analysis of the product are shown in Table 1.

[0052] As shown in Table 1, under the catalytic hydrogenation of Co0.1Ni0.1 / LAO-730 catalyst, the conversion rate of dipentene reached 100%, the selectivity for menthol reached 96.3%, and the content of menthol in the product was 93.6%.

[0053] Example 4

[0054] The difference between this embodiment and Example 1 is that the temperature of the hydrogenation reactor is changed to 190°C in step 3), while the rest is the same as in Example 1. The results of online gas chromatography-mass spectrometry analysis of the product are shown in Table 1.

[0055] As shown in Table 1, under the catalytic hydrogenation of Co0.1Ni0.1 / LAO-730 catalyst, the conversion rate of dipentene reached 100%, the selectivity for menthol reached 99.8%, and the content of menthol in the product was 97.0%.

[0056] Example 5

[0057] The difference between this embodiment and Example 1 is that the catalyst loading amount is changed to 15 g in step 3), while the rest is the same as in Example 1. The results of online gas chromatography-mass spectrometry analysis of the product are shown in Table 1.

[0058] As shown in Table 1, under the catalytic hydrogenation of Co0.1Ni0.1 / LAO-730 catalyst, the conversion rate of dipentene reached 100%, the selectivity for menthol reached 97.8%, and the content of menthol in the product was 95.1%.

[0059] Example 6

[0060] The difference between this embodiment and Example 1 is that the precursor reduction temperature in step 2) is changed to 800℃, while the rest is the same as in Example 1. The catalyst prepared in this case is Co-Ni / La2O3-LaAlO3 (denoted as Co0.1Ni0.1 / LAO-800). The results of online analysis of the product by gas chromatography-mass spectrometry are shown in Table 1.

[0061] As shown in Table 1, under the catalytic hydrogenation of Co0.1Ni0.1 / LAO-800 catalyst, the conversion rate of dipentene reached 99.4%, the selectivity for menthol reached 97.1%, and the content of menthol in the product was 93.8%.

[0062] Example 7

[0063] The difference between this embodiment and embodiment 1 is that the precursor reduction temperature in step 2) is changed to 650 DEG C, and the rest is referred to embodiment 1, at this time, the prepared catalyst is Co-Ni / La2O3-LaAlO3 (marked as Co0.1Ni0.1 / LAO-650). The product is analyzed by gas chromatography-mass spectrometer on-line, and the results are shown in table 1.

[0064] From table 1, under the catalytic hydrogenation of Co0.1Ni0.1 / LAO-650 catalyst, the conversion rate of dipentene reaches 100%, the selectivity of p-menthane reaches 97.4%, and the content of p-menthane in the product is 94.7%.

[0065] Embodiment 8

[0066] The difference between this embodiment and embodiment 1 is that the molar ratio of metal nitrate in step 1) is changed to lanthanum nitrate: aluminum nitrate: cobalt nitrate: nickel nitrate: citric acid = 1:0.7:0.15:0.15:0.4, and the rest is referred to embodiment 1, at this time, the prepared catalyst is Co-Ni / La2O3-LaAlO3 (marked as Co0.15Ni0.15 / LAO-730). The product is analyzed by gas chromatography-mass spectrometer on-line, and the results are shown in table 1.

[0067] From table 1, under the catalytic hydrogenation of Co0.15Ni0.15 / LAO-730 catalyst, the conversion rate of dipentene reaches 100%, the selectivity of p-menthane reaches 96.7%, and the content of p-menthane in the product is 94.0%.

[0068] Embodiment 9

[0069] The difference between this embodiment and embodiment 1 is that the aluminum nitrate is changed to chromium nitrate in step 1), and the rest is referred to embodiment 1, at this time, the prepared catalyst is Co-Ni / La2O3-LaCrO3 (marked as Co0.1Ni0.1 / LCO-730). The product is analyzed by gas chromatography-mass spectrometer on-line, and the results are shown in table 1.

[0070] From table 1, under the catalytic hydrogenation of Co0.1Ni0.1 / LCO-730 catalyst, the conversion rate of dipentene reaches 100%, the selectivity of p-menthane reaches 97.2%, and the content of p-menthane in the product is 94.5%.

[0071] Embodiment 10

[0072] The difference between this embodiment and embodiment 9 is that the precursor reduction temperature in step 2) is changed to 770 DEG C, and the rest is referred to embodiment 9, at this time, the prepared catalyst is Co-Ni / La2O3-LaCrO3 (marked as Co0.1Ni0.1 / LCO-770). The product is analyzed by gas chromatography-mass spectrometer on-line, and the results are shown in table 1.

[0073] As shown in Table 1, under the catalytic hydrogenation of the Co0.1Ni0.1 / LCO-770 catalyst, the conversion rate of dipentene reached 100%, the selectivity of p-menthane reached 97.5%, and the content of p-menthane in the product was 94.8%.

[0074] Comparative Example 1

[0075] In order to highlight the effective synergistic effect of Co-Ni bimetal on the catalytic reaction, the difference between this example and Example 1 is that no nickel nitrate is added in step 1), and the molar ratio of metal nitrate is changed to lanthanum nitrate: aluminum nitrate: cobalt nitrate: citric acid = 1:0.8:0.2:0.4, and the rest is the same as Example 1. At this time, the prepared catalyst is Co / La2O3-LaAlO3 (marked as Co0.2 / LAO-730). The results of online analysis of the product by gas chromatography-mass spectrometer are shown in Table 1.

[0076] As shown in Table 1, under the catalytic hydrogenation of the Co0.2 / LAO-730 catalyst, the conversion rate of dipentene reached 84.5%, the selectivity of p-menthane reached 99.3%, and the content of p-menthane in the product was 81.6%.

[0077] Comparative Example 2

[0078] In order to highlight the effective synergistic effect of Co-Ni bimetal on the catalytic reaction, the difference between this example and Example 1 is that no cobalt nitrate is added in step 1), and the molar ratio of metal nitrate is changed to lanthanum nitrate: aluminum nitrate: nickel nitrate: citric acid = 1:0.8:0.2:0.4, and the rest is the same as Example 1. At this time, the prepared catalyst is Ni / La2O3-LaAlO3 (marked as Ni0.2 / LAO-730). The results of online analysis of the product by gas chromatography-mass spectrometer are shown in Table 1.

[0079] As shown in Table 1, under the catalytic hydrogenation of the Ni0.2 / LAO-730 catalyst, the conversion rate of dipentene reached 93.3%, the selectivity of p-menthane reached 91.7%, and the content of p-menthane in the product was 83.2%.

[0080] Comparative Example 3

[0081] In order to highlight the effective mass transfer effect of three-dimensional ordered macroporous, the difference between this example and Example 1 is that no PMMA colloidal template is added in step 1), and a small amount of solution A is placed into a vacuum oven to continue the steps of Example 1. At this time, the prepared catalyst is Co-Ni / La2O3-LaAlO3 (marked as Co0.1Ni0.1 / LAO-730-no template). The results of online analysis of the product by gas chromatography-mass spectrometer are shown in Table 1.

[0082] As shown in Table 1, under the catalytic hydrogenation of Co0.1Ni0.1 / LAO-730-template-free catalyst, the conversion rate of dipentene reached 73.6%, the selectivity of p-menthane reached 94.5%, and the content of p-menthane in the product was 67.6%.

[0083] Comparative Example 4

[0084] To highlight the effective role of the carrier La2O3-LaAlO3, in this example, the difference from Example 1 is that no aluminum nitrate is added in step 1), and the molar ratio of metal nitrate is changed to lanthanum nitrate: cobalt nitrate: nickel nitrate: citric acid = 1:0.5:0.5:0.4, and the rest is the same as Example 1. At this time, the prepared catalyst is Co-Ni / La2O3 (denoted as Co0.5Ni0.5 / LO-730). The results of online analysis of the product by gas chromatography-mass spectrometer are shown in Table 1.

[0085] As shown in Table 1, under the catalytic hydrogenation of Co0.5Ni0.5 / LO-730 catalyst, the conversion rate of dipentene reached 87.3%, the selectivity of p-menthane reached 90.7%, and the content of p-menthane in the product was 77.0%.

[0086] Table 1 Experimental results of Examples 1-10 and Comparative Examples 1-4

[0087] Catalyst abbreviation Catalyst amount / g Metal nitrate and its molar ratio Reduction temperature / ℃ Hydrogenation temperature / ℃ Dipentene conversion / % P-Menthanes selectivity / % P-Menthanes content in product / % Example 1 Co0.1Ni0.1 / LAO-730 10 Lanthanum salt: aluminum salt: cobalt salt: nickel salt = 1:0.8:0.1:0.1 730 200 100 100 97.2 Example 2 Co0.1Ni0.1 / LAO-730 10 Lanthanum salt: aluminum salt: cobalt salt: nickel salt = 1:0.8:0.1:0.1 730 210 100 100 97.2 Example 3 Co0.1Ni0.1 / LAO-730 10 Lanthanum salt: aluminum salt: cobalt salt: nickel salt = 1:0.8:0.1:0.1 730 230 100 96.3 93.6 Example 4 Co0.1Ni0.1 / LAO-730 10 Lanthanum salt: aluminum salt: cobalt salt: nickel salt = 1:0.8:0.1:0.1 730 190 100 99.8 97.0 Example 5 Co0.1Ni0.1 / LAO-730 15 Lanthanum salt: aluminum salt: cobalt salt: nickel salt = 1:0.8:0.1:0.1 730 200 100 97.8 95.1 Example 6 Co0.1Ni0.1 / LAO-800 10 Lanthanum salt: aluminum salt: cobalt salt: nickel salt = 1:0.8:0.1:0.1 800 200 99.4 97.1 93.8 Example 7 Co0.1Ni0.1 / LAO-650 10 Lanthanum salt: aluminum salt: cobalt salt: nickel salt = 1:0.8:0.1:0.1 650 200 100 97.4 94.7 Example 8 Co0.15Ni0.15 / LAO-730 10 Lanthanum salt: aluminum salt: cobalt salt: nickel salt = 1:0.7:0.15:0.15 730 200 100 96.7 94.0 Example 9 Co0.1Ni0.1 / LCO-730 10 Lanthanum salt: chromium salt: cobalt salt: nickel salt = 1:0.8:0.1:0.1 730 200 100 97.2 94.5 Example 10 Co0.1Ni0.1 / LCO-770 10 Lanthanum salt: chromium salt: cobalt salt: nickel salt = 1:0.8:0.1:0.1 770 200 100 97.5 94.8 Comparative Example 1 Co0.2 / LAO-730 10 Lanthanum salt: aluminum salt: cobalt salt = 1:0.8:0.2 730 200 84.5 99.3 81.6 Comparative Example 2 Ni0.2 / LAO-730 10 Lanthanum salt: aluminum salt: nickel salt = 1:0.8:0.2 730 200 93.3 91.7 83.2 Comparative Example 3 Co0.1Ni0.1 / LAO-730-no template 10 Lanthanum salt: aluminum salt: cobalt salt: nickel salt = 1:0.8:0.1:0.1 730 200 73.6 94.5 67.6 Comparative Example 4 Co0.5Ni0.5 / LO-730 10 Lanthanum salt: cobalt salt: nickel salt = 1:0.5:0.5 730 200 87.3 90.7 77.0

[0088] Table 2 Repeated use results of catalysts

[0089] Repeated sampling time / h 1 2 3 4 5 6 7 8 9 10 Dipentene conversion / % 100 100 100 100 100 100 100 100 100 100 P-Menthanes selectivity / % 100 100 100 99.9 100 99.8 99.9 99.8 99.8 99.9 P-Menthanes content in product / % 97.2 97.2 97.2 97.1 97.2 97.0 97.1 97.0 97.0 97.1

[0090] Table 3 Gas chromatography-mass spectrometer analysis results of dipentene raw materials used in each example

[0091] No. Retention time / min Content / % Molecular formula Relative molecular mass, Mr Compound (Chinese name) Compound (English name) 1 9.659 0.3 C 10 H 16 ]]> 136 Camphene Camphene 2 10.297 0.5 C 10 H 16 ]]> 136 3-Carene α-Terpinene 3 10.503 23.9 C 10 H 16 ]]> 136 D-Limonene γ-Terpinene 4 10.711 32.5 C 10 H 16 ]]> 136 Terpinolene ​ 5 11.001 8.0 [C 10 H 16 ]]> 136 ​ ​ 6 11.464 32.8 [C 10 H 16 ]]> 136 ​ ​

[0092] Note: Another 2% of the components were not detected for specific components

[0093] Table 3 is the gas chromatography-mass spectrometer analysis results of industrial dipentene raw materials used in each example. The sum of the mass fractions of the four components belonging to the dipentene series in the industrial dipentene raw material, i.e., α-terpinene, limonene, γ-terpinene and isopinocamphone, is 97.2%, and other impurities mainly include a small amount of camphene, carene, etc.

Claims

1. The use of a bimetallic supported perovskite catalyst in the industrial atmospheric pressure gaseous hydrogenation of dipentene to produce biofuel, characterized in that: The bimetallic supported perovskite catalyst has the composition Co-Ni / La2O3-LaMO3, where M is Al or Cr; gaseous dipentene undergoes atmospheric pressure hydrogenation under the catalysis of the bimetallic supported perovskite catalyst to produce biofuel. The preparation method of bimetallic supported perovskite catalyst includes the following steps: 1) Lanthanum nitrate, metal M nitrate, cobalt nitrate, nickel nitrate, and citric acid were added to a methanol-ethylene glycol solution in a molar ratio of lanthanum nitrate: metal M nitrate: cobalt nitrate: nickel nitrate: citric acid = 1:(0.7-0.9):(0.05-0.15):(0.05-0.15):0.4 to maintain the total metal ion concentration at 2 mol / L. The solution was stirred at room temperature for 6-8 h to obtain solution A. The sum of the molar amounts of metal M nitrate, cobalt nitrate, and nickel nitrate was equal to the molar amount of lanthanum nitrate. 2) Add the PMMA colloidal template to solution A, soak for 4-5 hours, and then filter under vacuum to obtain the filter residue; wherein, the PMMA colloidal template is formed by the self-assembly of monodisperse PMMA microspheres with a particle size of 80-500 nm, and 28-32 mL of solution A is required for every 3g of PMMA colloidal template; 3) After vacuum drying the filter residue at 35-40℃ for 20-24 hours, it is placed in a tube furnace for calcination. The calcination process is as follows: under N2 atmosphere, the temperature is increased to 310℃ at a rate of 1℃ / min and held for 3 hours, then cooled to room temperature, and then under air atmosphere, the temperature is increased to 310℃ at a rate of 1℃ / min and held for 2 hours, then increased to 700℃ at a rate of 1℃ / min and held for 4 hours. Finally, it is naturally cooled to room temperature to obtain the precursor LaM. 1-x-y Co x Ni y O3, where x ranges from 0.05 to 0.15 and y ranges from 0.05 to 0.15; 4) Place the precursor in a tube furnace and heat it to the reduction temperature at a rate of 1℃ / min under a 20% H2 / Ar atmosphere and hold it for 1.5~2h. After naturally cooling to room temperature, Co-Ni / La2O3-LaMO3 is obtained. In the 20% H2 / Ar, 20% refers to the volume percentage of H2 being 20%.

2. The use of the bimetallic supported perovskite catalyst as described in claim 1 in the industrial atmospheric pressure gaseous hydrogenation of dipentene to produce biofuel, characterized in that: The temperature for hydrogenation reaction is 170-230℃.

3. The use of the bimetallic supported perovskite catalyst as described in claim 2 in the industrial atmospheric pressure gaseous hydrogenation of dipentene to produce biofuel, characterized in that: The temperature for hydrogenation reaction is 190-210℃.

4. The use of the bimetallic supported perovskite catalyst according to any one of claims 1-3 in the industrial atmospheric pressure gaseous hydrogenation of dipentene to produce biofuel, characterized in that: The hydrogenation reaction includes the following steps: 1) Load the bimetallic supported perovskite catalyst into the hydrogenation reactor, and purge the vertically connected vaporizer and hydrogenation reactor with H2 for 10-15 minutes to remove all air; 2) Continue to introduce H2 and raise the temperature of the vaporizer to 200-230℃ and the temperature of the hydrogenation reactor to 170-230℃; 3) Industrial dipentene is continuously added to the vaporizer at a flow rate of 0.5 ml / min per 10-15 g of bimetallic supported perovskite catalyst. The resulting gaseous dipentene then enters the hydrogenation reactor for hydrogenation under atmospheric pressure. The obtained gaseous product is condensed to obtain biofuel.

5. The use of the bimetallic supported perovskite catalyst according to any one of claims 1-3 in the industrial atmospheric pressure gaseous hydrogenation of dipentene to produce biofuel, characterized in that: The precursor for the bimetallic supported perovskite catalyst is LaAl 0.8 Co 0.1 Ni 0.1 O3.

6. The use of the bimetallic supported perovskite catalyst according to any one of claims 1-3 in the industrial atmospheric pressure gaseous hydrogenation of dipentene to produce biofuel, characterized in that: When M is Al, the reduction temperature is 650-800℃; when M is Cr, the reduction temperature is 700-830℃.

7. The use of the bimetallic supported perovskite catalyst as described in claim 6 in the industrial atmospheric pressure gaseous hydrogenation of dipentene to produce biofuel, characterized in that: When M is Al, the reduction temperature is 730℃; when M is Cr, the reduction temperature is 770℃.

8. The use of the bimetallic supported perovskite catalyst according to any one of claims 1-3 in the industrial atmospheric pressure gaseous hydrogenation of dipentene to produce biofuel, characterized in that: Industrial dipentenes also include one or more of the following: limonene, α-terpinene, limonene, γ-terpinene, isoterpinene, α-phellandrene, β-phellandrene, and p-cymene.