阅读说明：本技术 四氢双环戊二烯的制备方法 (Preparation method of tetrahydrodicyclopentadiene ) 是由 闫瑞 陶志平 赵杰 于 2020-04-14 设计创作，主要内容包括：本发明提供一种四氢双环戊二烯的制备方法,包括：采用催化剂与双环戊二烯接触进行催化加氢反应,得到所述四氢双环戊二烯；其中催化剂通过下述方法获得：向镍源和硅源的混合物中加入水解剂和水,进行溶胶-凝胶反应；及溶胶-凝胶反应后的产物经还原处理,得到催化剂。该方法通过采用溶胶-凝胶法制备的晶态镍和无定形二氧化硅的复合物作为催化剂,使得整个反应过程副反应少,转化率和收率均较高,可实现四氢双环戊二烯稳定、连续地高效生产。(The invention provides a preparation method of tetrahydrodicyclopentadiene, which comprises the following steps: contacting a catalyst with dicyclopentadiene to perform a catalytic hydrogenation reaction to obtain the tetrahydrodicyclopentadiene; wherein the catalyst is obtained by the following method: adding a hydrolytic agent and water into a mixture of a nickel source and a silicon source to carry out sol-gel reaction; and reducing the product after the sol-gel reaction to obtain the catalyst. The method adopts the compound of crystalline nickel and amorphous silicon dioxide prepared by a sol-gel method as a catalyst, so that the side reaction is less in the whole reaction process, the conversion rate and the yield are higher, and the stable, continuous and efficient production of the tetrahydrodicyclopentadiene can be realized.)

1. A method for preparing tetrahydrodicyclopentadiene is characterized by comprising the following steps: contacting a catalyst with dicyclopentadiene to perform a catalytic hydrogenation reaction to obtain the tetrahydrodicyclopentadiene; wherein the catalyst is obtained by the following method:

adding a hydrolytic agent and water into a mixture of a nickel source and a silicon source to carry out sol-gel reaction; and

and reducing the product after the sol-gel reaction to obtain the catalyst.

2. The preparation method of claim 1, wherein the dicyclopentadiene is subjected to the catalytic hydrogenation reaction in a fixed bed reactor containing the catalyst, the reaction temperature is 10-200 ℃, the hydrogen pressure is 0.1-10 MPa, and the mass space velocity is 0.1h^-1～50h^-1The hydrogen-oil ratio is 50 to 2000.

3. The preparation method according to claim 1, wherein the dicyclopentadiene is subjected to the catalytic hydrogenation reaction in a high-pressure reaction kettle containing the catalyst, the reaction temperature is 10-200 ℃, the hydrogen pressure is 0.1-10 MPa, the reaction time is 0.1-10 h, the stirring speed is 400-1000 r/min, and the mass ratio of the catalyst to the dicyclopentadiene is 1: (1-50).

4. The method of preparing according to claim 1, wherein the method of obtaining a catalyst further comprises: before the reduction treatment, adding an auxiliary agent into the product after the sol-gel reaction, and carrying out forming treatment.

5. The method of claim 4, wherein the method of obtaining a catalyst further comprises: and roasting the product after the sol-gel reaction to obtain a nickel-silicon composite oxide, and adding the auxiliary agent into the nickel-silicon composite oxide to perform the forming treatment.

6. The method according to claim 1, wherein the nickel source is selected from one or more of basic nickel carbonate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetate; the silicon source is selected from one or more of water glass, silica sol and tetraethoxysilane; the molar ratio of the nickel source to the silicon source is 1 (0.1-40).

7. The preparation method according to claim 1, wherein the hydrolytic agent is an acid or a base, the hydrolytic agent has a concentration of 0.5mol/L to 2mol/L, the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, oxalic acid and citric acid, and the base is selected from one or more of ammonia water, triethylamine, ethylenediamine and tetramethylethylenediamine.

8. The method of claim 1, wherein the sol-gel reaction comprises:

adding the hydrolytic agent into the solution containing the nickel source and the silicon source, and stirring to generate sol; and

standing and aging the sol to obtain gel;

wherein the temperature of the standing and aging is 0-60 ℃, and the time is 0-24 h.

9. The preparation method according to claim 1, wherein the temperature of the reduction treatment is 400 to 600 ℃ and the time is 2 to 6 hours.

10. The method of claim 4, wherein the forming process is selected from one or more of extruding, rolling, tabletting and granulating.

11. The method for preparing the nano-particles according to claim 10, wherein the forming process is a tabletting process, the auxiliary agent comprises a binder, and the binder is one or more selected from sesbania powder, starch and graphite powder.

12. The method of manufacturing according to claim 11, wherein the tableting process comprises: mixing 1 part by mass of the product after the sol-gel reaction and 0.005-0.2 part by mass of the adhesive, tabletting by using a tabletting machine, and drying and roasting to obtain the material after tabletting.

13. The production method according to claim 12, wherein the mechanical strength of the tablet-shaped catalyst is 10 to 100N/pellet.

14. The preparation method according to claim 10, wherein the forming process is an extrusion process, and the auxiliary agent comprises a binder, a pore-forming agent and water, wherein the binder is selected from one or more of water glass, silica sol and tetraethoxysilane, and the pore-forming agent is selected from one or more of sesbania powder, graphite powder, starch and citric acid.

15. The method for preparing as claimed in claim 14, wherein the extruding process comprises: mixing 1 part by mass of a product obtained after sol-gel reaction, 0.02-50 parts by mass of the adhesive, 0-0.1 part by mass of the pore-forming agent and 0.05-0.4 part by mass of water, extruding the mixture into strips by a strip extruding machine, and then granulating, drying and roasting the strips to obtain the material after strip extruding treatment.

16. The production method according to claim 15, wherein the mechanical strength of the extruded catalyst is 10 to 30N/mm.

Technical Field

The invention relates to the technical field of petrochemical industry, in particular to a preparation method of tetrahydrodicyclopentadiene.

Background

The tetrahydrodicyclopentadiene is tricyclo [5,2,1,02,6] decane, is a fuel with high density, high stability and high combustion heat, and can be widely applied to military aviation fuels such as rockets and the like. Meanwhile, the tetrahydrodicyclopentadiene is an important intermediate for preparing the dicyclopentadiene derivative with the tricyclodecane structure; such as adamantane, exo-tetrahydrodicyclopentadiene, and the like. Therefore, the continuous and efficient production of the tetrahydrodicyclopentadiene has great significance in the fields of national defense and military industry, medicine and health and the like.

At present, tetrahydrodicyclopentadiene is mainly obtained by hydrogenation with a noble metal catalyst, as shown in formula I below. Patent CN10121521813 adopts Pd/C catalysis to prepare tetrahydrodicyclopentadiene, which has good catalytic activity; however, the use of noble metals has a problem of high cost. CN101406839 adopts Ni-Rh-Y/gamma-Al₂O₃The catalyst hydrogenation scheme solves the problem of high cost to a certain extent, but has the problem of harsh reaction conditions. Patent CN103877982A adopts cheap Ni-Cu/gamma-Al₂O₃The catalyst is used for preparing the tetrahydrodicyclopentadiene, but the stability of the catalyst is poor. Based on the background, the invention aims to realize the high-efficiency preparation of the tetrahydrodicyclopentadiene by adopting a novel catalyst.

It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.

Disclosure of Invention

The invention aims to overcome at least one defect of the prior art and provides a preparation method of tetrahydrodicyclopentadiene, which aims to solve the problems that the existing catalyst is high in cost, harsh in reaction conditions and difficult to realize stable and efficient catalytic hydrogenation reaction for preparing the tetrahydrodicyclopentadiene.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a preparation method of tetrahydrodicyclopentadiene, which comprises the following steps: contacting a catalyst with dicyclopentadiene to perform a catalytic hydrogenation reaction to obtain tetrahydrodicyclopentadiene; wherein the catalyst is obtained by the following method: adding a hydrolytic agent and water into a mixture of a nickel source and a silicon source to carry out sol-gel reaction; and reducing the product after the sol-gel reaction to obtain the catalyst.

According to one embodiment of the invention, dicyclopentadiene is subjected to catalytic hydrogenation reaction in a fixed bed reactor containing a catalyst, the reaction temperature is 10-200 ℃, the hydrogen pressure is 0.1-10 MPa, and the mass space velocity is 0.1h^-1～50h^-1The hydrogen-oil ratio is 50 to 2000.

According to one embodiment of the invention, dicyclopentadiene is subjected to catalytic hydrogenation reaction in a high-pressure reaction kettle containing a catalyst, the reaction temperature is 10-200 ℃, the hydrogen pressure is 0.1-10 MPa, the reaction time is 0.1-10 h, the stirring speed is 400-1000 r/min, and the mass ratio of the catalyst to the dicyclopentadiene is 1: (1-50).

According to an embodiment of the invention, the method of obtaining a catalyst further comprises: before reduction treatment, an auxiliary agent is added into a product after sol-gel reaction for molding treatment.

According to an embodiment of the invention, the method of obtaining a catalyst further comprises: roasting the product after the sol-gel reaction to obtain the nickel-silicon composite oxide, and adding an auxiliary agent into the nickel-silicon composite oxide for molding treatment.

According to one embodiment of the invention, the nickel source is selected from one or more of basic nickel carbonate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetate; the silicon source is selected from one or more of water glass, silica sol and tetraethoxysilane; the molar ratio of the nickel source to the silicon source is 1 (0.1-40).

According to one embodiment of the invention, the hydrolytic agent is acid or alkali, the concentration of the hydrolytic agent is 0.5 mol/L-2 mol/L, the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, oxalic acid and citric acid, and the alkali is selected from one or more of ammonia water, triethylamine, ethylenediamine and tetramethylethylenediamine.

According to one embodiment of the present invention, the sol-gel reaction comprises: adding a hydrolytic agent into a solution containing a nickel source and a silicon source, and stirring to generate sol; standing and aging the sol to obtain gel; wherein the temperature of the standing and aging is 0-60 ℃, and the time is 0-24 h.

According to one embodiment of the invention, the temperature of the reduction treatment is 400 ℃ to 600 ℃ and the time is 2h to 6 h.

According to one embodiment of the invention, the shaping process is selected from one or more of extrusion, rolling, tabletting and granulation.

According to one embodiment of the invention, the forming process is a tabletting process and the auxiliary agent comprises a binder selected from one or more of sesbania powder, starch and graphite powder.

According to one embodiment of the invention, the tableting process comprises: mixing 1 part by mass of a product obtained after sol-gel reaction and 0.005-0.2 part by mass of an adhesive, tabletting by using a tabletting machine, and drying and roasting to obtain a material subjected to tabletting treatment.

According to one embodiment of the present invention, the mechanical strength of the catalyst subjected to tableting is 10 to 100N/pellet.

According to one embodiment of the invention, the forming treatment is an extrusion treatment, and the auxiliary agent comprises a binder, a pore-forming agent and water, wherein the binder is selected from one or more of water glass, silica sol and tetraethoxysilane, and the pore-forming agent is selected from one or more of sesbania powder, graphite powder, starch and citric acid.

According to one embodiment of the present invention, the extrusion process includes: mixing 1 part by mass of a product obtained after sol-gel reaction, 0.02-50 parts by mass of an adhesive, 0-0.1 part by mass of a pore-forming agent and 0.05-0.4 part by mass of water, extruding the mixture into strips by a strip extruding machine, and then granulating, drying and roasting the strips to obtain the material subjected to strip extruding treatment.

According to one embodiment of the present invention, the mechanical strength of the extruded catalyst is 10N/mm to 30N/mm.

According to the technical scheme, the invention has the beneficial effects that:

according to the preparation method of the tetrahydrodicyclopentadiene, the dicyclopentadiene is subjected to hydrogenation treatment by using the hydrogenation catalyst prepared by a specific sol-gel method, so that the side reaction in the whole reaction process is less, the conversion rate and the yield are higher, the tetrahydrodicyclopentadiene is stably, continuously and efficiently produced, and the preparation method has important significance in the fields of national defense and military industry, medicine and health and the like.

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 shows XRD spectra of the nickel silicon composite oxide and the catalyst in example 1, respectively.

Detailed Description

The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application 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 ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.

The invention provides a preparation method of tetrahydrodicyclopentadiene, which comprises the following steps: contacting a catalyst with dicyclopentadiene to perform a catalytic hydrogenation reaction to obtain tetrahydrodicyclopentadiene; wherein the catalyst is obtained by the following method: adding a hydrolytic agent and water into a mixture of a nickel source and a silicon source to carry out sol-gel reaction; and reducing the product after the sol-gel reaction to obtain the catalyst.

According to the invention, the tetrahydrodicyclopentadiene is a fuel with high density, high stability and high combustion heat, can be widely applied to military aviation fuels such as rockets, and is prepared by hydrogenation reaction of dicyclopentadiene catalyzed by noble metal catalysts and the like at present, but the catalysts have the problems of high cost, harsh reaction conditions and the like. The inventor finds that the nickel-silicon dioxide composite prepared by the sol-gel method can be used as a catalyst for catalyzing dicyclopentadiene to carry out hydrogenation reaction, has the characteristics of high activity and stability and easiness in separation, and has a good application prospect.

In some embodiments, dicyclopentadiene is subjected to catalytic hydrogenation in a fixed bed reactor containing the aforementioned catalyst, specifically, dicyclopentadiene is dissolved in an organic solvent, such as methylcyclohexane, etc., and then contacted with the catalyst in the fixed bed reactor to perform the reaction under the action of hydrogen. The reaction temperature is 10 ℃ to 200 ℃, for example, 20 ℃, 40 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, 100 ℃, 103 ℃, 110 ℃, 116 ℃, 124 ℃, 136 ℃, 141 ℃, 159 ℃, 168 ℃, 180 ℃, 190 ℃ and the like. Optionally, the reaction temperature is from 40 ℃ to 160 ℃. The hydrogen pressure is from 0.1MPa to 10MPa, such as from 0.2MPa, 0.7MPa, 1MPa, 2MPa, 3.5MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, and the like, optionally from 2MPa to 7 MPa. The mass space velocity is 0.1h^-1～50h^-1For example, 0.1h^-1、0.5h^-1、1h^-1、2h^-1、4h^-1、10h^-1、25h^-1、37h^-1、45h^-1、50h^-1And the hydrogen-oil ratio is 50 to 2000, such as 100, 220, 350, 490, 550, 760, 880, 1000, 1600, 2000, and the like.

In some embodiments, dicyclopentadiene is subjected to catalytic hydrogenation in an autoclave containing the aforementioned catalyst, specifically, dicyclopentadiene is dissolved in an organic solvent such as methylcyclohexane, etc., and then placed in the autoclave, and a catalyst is added to the autoclave, and the catalyst is contacted with dicyclopentadiene and stirred to perform a reaction under the action of hydrogen. The reaction temperature is 10 ℃ to 200 ℃, for example, 20 ℃, 40 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, 100 ℃, 103 ℃, 110 ℃, 116 ℃, 124 ℃, 136 ℃, 141 ℃, 159 ℃, 168 ℃, 180 ℃, 190 ℃ and the like. Optionally, the reaction temperature is from 40 ℃ to 160 ℃. The hydrogen pressure is 0.1MPa to 10MPa, for example, 0.2MPa, 0.7MPa, 1MPa, 2MPa, 3.5MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, etc., preferably 2MPa to 7 MPa. The reaction time is 0.1h to 10h, e.g., 0.1h, 0.5h, 1h, 2h, 4h, 10h, etc., alternatively, 0.5h to 4 h. The stirring speed is 400 r/min-1000 r/min, such as 400r/min, 500r/min, 670r/min, 800r/min, 950r/min, 1000r/min and the like; the mass ratio of the catalyst to the dicyclopentadiene is 1: (1 to 50), for example, 1:10, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, etc.

Therefore, the catalyst of the invention is adopted to catalyze and prepare the tetrahydrodicyclopentadiene, the reaction condition is mild, and the cost is low. The method is suitable for both fixed bed reactors and high-pressure reaction kettle reactors.

The method for producing the catalyst will be specifically described below.

First, a hydrolysis agent and water are added to a mixture of a nickel source and a silicon source to perform a sol-gel reaction. The nickel source is a soluble nickel source, including but not limited to one or more of basic nickel carbonate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetate; the silicon source is a soluble silicon source, and includes but is not limited to one or more of water glass, silica sol and tetraethoxysilane; the molar ratio of the nickel source to the silicon source is 1 (0.1-40), for example, 1:3, 1:4.5, 1:5, 1:7, 1:10, 1:11, 1:14, etc. In one embodiment, the molar ratio of the nickel source to the silicon source is 1 (2-15).

In the sol-gel reaction process, firstly mixing a nickel source, a silicon source and water to prepare a mixed solution, then adding a hydrolytic agent into the mixed solution, and stirring to generate sol; and standing and aging the obtained sol to obtain gel. In the sol-gel reaction process, the temperature of the standing and aging is generally 0 to 60 ℃, preferably 10 to 30 ℃, and the time of the standing and aging is 0 to 24 hours, preferably 2 to 12 hours.

The hydrolytic agent is generally an acid or an alkali, and the concentration of the hydrolytic agent is 0.5mol/L to 2mol/L, such as 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L and the like. The acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, oxalic acid and citric acid, and the base is selected from one or more of ammonia water, triethylamine, ethylenediamine and tetramethylethylenediamine.

In some embodiments, the present invention further comprises drying and calcining the sol-gel reaction product, and shaping the calcined product. The drying temperature is 60-120 ℃, preferably 100-120 ℃, the roasting temperature is 300-700 ℃, the roasting time is 2-6 h, the obtained product is nickel-silicon composite oxide, the structure of the nickel-silicon composite oxide is a porous structure formed by aggregating silicon oxide with an amorphous structure and nickel oxide particles with a crystal structure, the size of nickel oxide crystal grains in the nickel-silicon composite oxide is approximately equivalent to that of nickel metal crystal grains in the finally reduced catalyst, and the nickel-silicon composite oxide has a similar structure and approximately equivalent pore structure parameters.

The specific molding process will be described below as if the gel which had not been dried and then calcined was directly subjected to the molding treatment. Of course, the invention can also carry out the molding treatment on the nickel-silicon composite oxide after the gel is roasted, and the invention is not limited to the method. The forming process of the present invention includes, but is not limited to, one or more of extruding, rolling, tabletting, and pelletizing.

In some embodiments, the aforementioned molding process is an extrusion process. In the strip extrusion treatment process, the auxiliary agent comprises an adhesive, a pore-forming agent and water, wherein the adhesive is selected from one or more of water glass, silica sol and tetraethoxysilane, and the pore-forming agent is selected from one or more of sesbania powder, graphite powder, starch and citric acid. Specifically, the process of the extrusion treatment comprises the following steps: mixing 1 part by mass of a product obtained after sol-gel reaction, 0.02-50 parts by mass of an adhesive, 0-0.1 part by mass of a pore-forming agent and 0.05-0.4 part by mass of water, extruding the mixture into strips by a strip extruding machine, and then granulating, drying and roasting the strips to obtain the material subjected to strip extruding treatment. Wherein, the mass of the product after the sol-gel reaction, the adhesive and the pore-foaming agent is calculated by dry basis. In some embodiments, the drying temperature in the extrusion treatment process is 100-130 ℃ for 2-24 h, and the roasting temperature is 300-700 ℃ for 2-6 h. And further reducing the material after the extrusion treatment after roasting, wherein the reduction temperature is 400-600 ℃ and the time is 2-6 h. And reducing to obtain a composite formed by crystalline nickel and amorphous silicon dioxide, namely the catalyst.

The catalyst obtained after the strip extrusion treatment is a strip catalyst, and specifically comprises a cylinder, a cloverleaf shape or a butterfly shape. The section size of the strip catalyst can be 0.5 mm-3 mm, such as 1mm, 1.5mm, 2mm, 2.5mm and the like, and the section size refers to the size of the cross section of the strip catalyst in each direction within the range of 0.5-3 mm; in addition, the length of the strip catalyst can be 0.2 cm-0.8 cm. Generally, the mechanical strength of the resulting catalyst in the form of a strip after the aforementioned treatment is 10N/mm to 30N/mm, for example, 10N/mm, 12N/mm, 15N/mm, 22N/mm, 24N/mm, 25N/mm, 30N/mm, etc.

In some embodiments, the aforementioned molding process comprises a tableting process. In the tabletting process, the auxiliary agent comprises a binder, the binder is selected from one or more of sesbania powder, starch and graphite powder, and preferably, the binder is graphite powder. Specifically, the tabletting process comprises the following steps: mixing 1 part by mass of a product obtained after sol-gel reaction and 0.005-0.2 part by mass of an adhesive, tabletting by using a tabletting machine, and drying and roasting to obtain a material subjected to tabletting treatment. Wherein, the mass of the gel and the adhesive is calculated on a dry basis. The mass ratio of the product after the sol-gel reaction to the binder may be 1:0.00625, 1:0.008, 1:0.01, 1:0.03, 1:0.05, 1:0.08, 1:0.1, 1:0.12, 1:0.15, 1:0.18, or the like. In some embodiments, the drying temperature during the tableting process is 110 ℃ to 130 ℃,2 hours to 24 hours, and the firing temperature is 400 ℃ to 600 ℃, e.g., 450 ℃, 500 ℃, 550 ℃; the time is 2-6 h.

The roasted material after tabletting is further reduced at 400-600 deg.c, e.g. 450 deg.c, 500 deg.c and 550 deg.c for 2-6 hr, and the reducing agent may be hydrogen. The catalyst of the invention is obtained by reduction treatment. The catalyst comprises a composite of nickel and silica, wherein the nickel is in a crystalline structure and the silica is in an amorphous structure. After the series of treatments, the catalyst obtained after tabletting is granular or flaky, the section size of the catalyst is 1 mm-5 mm, and generally, the larger the size is, the larger the tolerance is; the mechanical strength is 10N/pellet to 100N/pellet, and further 20 to 60N/pellet, for example, 12N/pellet, 15N/pellet, 20N/pellet, 25N/pellet, 27.3N/pellet, 30N/pellet, 35N/pellet, 38.9N/pellet, 40N/pellet, 45N/pellet, 45.7N/pellet, 50N/pellet, 55N/pellet, 60N/pellet, 62.4N/pellet, 65N/pellet, 70N/pellet, 80N/pellet, 90N/pellet, 95N/pellet, and the like.

The aforementioned compound of nickel and silica has a chemical formula of Ni- (SiO)₂)_aAnd a has a value of 0.1 to 40, for example, 2.1, 3, 3.2, 4.5, 5, 6.7, 6.8, 6.9, 7, 7.1, 10, 10.8, 11, 13.9, 14, etc. In some embodiments, a is preferably 2.9-11.1. The structure of the composite is a porous structure formed by gathering nickel crystal grains and silicon dioxide oxide particle clusters, the particle clusters are distributed irregularly, the cluster size is 200 nm-1500 nm, and the nickel crystal grain size is 0.5 nm-10 nm. The specific surface area of the catalyst is 200m²/g～500m²A/g, preferably of 200m²/g～380m²G, e.g. 220m²/g、240m²/g、300m²/g、320m²(iv)/g, etc.; the pore volume is 0.2cc/g to 0.7cc/g, preferably 0.3cc/g to 0.7cc/g, for example, 0.37cc/g, 0.40cc/g, 0.42cc/g, 0.44cc/g, 0.45cc/g, etc. From the foregoing, it can be seen that the catalyst has a specific porous cluster aggregation structure, which is beneficial to increasing the specific surface area of the catalyst in contact with reactants, and further improving the catalytic activity.

In some embodiments, the nickel is present in the catalyst in an amount of 1 wt% to 60 wt%, e.g., 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, etc.; the content of silica is 40 to 99 wt%, for example, 42, 45, 48, 50, 52, 55, 60, 65, 70, 75, 80, 85, etc. Preferably, the nickel content is 5 wt% to 40 wt%, and the silica content is 60 wt% to 95 wt%.

The invention obtains the compound of nickel and silicon dioxide by adopting a sol-gel method, the method is simple and easy to implement, has low cost, basically does not use organic solvent in the process, and is environment-friendly. In addition, the mechanical strength of the compound is further improved through molding treatment, and the compound is applied to hydrogenation reaction of a fixed bed reactor, so that the phenomenon of bed layer blockage caused by catalyst crushing can be effectively avoided, the reaction can be continuously operated, and the production cost and the operation difficulty are reduced. The obtained catalyst has the characteristics of higher activity and stability, easy separation and good reusability. The catalyst is applied to preparing the tetrahydrodicyclopentadiene, has the characteristics of low cost, mild reaction conditions, high raw material conversion rate, high yield of the tetrahydrodicyclopentadiene and the like, and has good industrial application prospect.

The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. All the starting materials used are commercially available, unless otherwise specified.

The XRD characterization of the present invention was measured using X-ray diffractometer model D max-2600PC, manufactured by Nippon Denshi electric machinery industries, under the following test conditions: the scanning speed of the Cu target Kalpha ray is 5 degrees/min, the scanning range is 10 degrees to 80 degrees, the step length is 0.02 degree, the tube current is 100mA, and the tube voltage is 40 kV;

the SEM characterization of the invention adopts a scan electron microscope of a Quan TA-400F type of FEI company, and the selected scan voltage is 20 kV;

the TEM representation of the invention adopts a transmission electron microscope of Tecnai G2F 20S-TWIN of FEI company, and the accelerating voltage is selected to be 200 kV;

the qualitative and quantitative analysis of the material adopts a mass spectrum detector and a hydrogen flame ion detector of an Agilent 5977A-7890B gas chromatograph-mass spectrometer.

The molar ratio and the mass content of the composite material are calculated according to an XRF characterization method, and the total pore volume and the specific surface area are measured by nitrogen adsorption and desorption characterization.

The catalyst strength of the strip catalyst in the invention refers to the radial strength (i.e. the direction passing through the axis in the radial plane) of the strip catalyst; the strength was measured using a mechanical strength meter.

According to the invention, the dicyclopentadiene conversion rate is obtained by quantitative calculation through liquid chromatography, and the yield of the tetrahydrodicyclopentadiene is obtained by calculation through gas chromatography by adopting a peak area normalization method.

Example 1

290g of Ni (NO) are weighed₃)₂·6H₂O and 2960g of tetraethyl orthosilicate (TEOS) were dissolved in deionized water to prepare a solution of 1.0mol/L in terms of Ni ions, and the solution was stirred for 1 hour to obtain a solution a. And adding citric acid (the weight ratio of citric acid to silicon source is 0.2:1) and deionized water into the solution a, stirring until sol is formed, continuing stirring to form gel, aging for 2 hours, finally putting the obtained material into a forced air drying oven, drying for 12 hours at 100 ℃, and roasting for 5 hours in a muffle furnace at 500 ℃ to obtain a black solid, namely the nickel-silicon composite oxide.

Putting 6.0g of nickel-silicon composite oxide into a tube furnace, and reducing for 3 hours at 500 ℃ with the hydrogen flow rate of 30mL/min to obtain Ni/SiO₂A catalyst.

Fig. 1 shows XRD spectra of the nickel silicon composite oxide and the catalyst in example 1, respectively. As seen from fig. 1: the nickel-silicon composite oxide and the catalyst have no obvious SiO₂Diffraction characteristic peak, indicating SiO₂Exist in an amorphous structure. In addition, NiO diffraction characteristic peaks exist in the nickel-silicon composite oxide, which indicates that NiO exists in a crystal structure; catalyst Presence of example 1Characteristic peaks of Ni diffraction indicate that Ni also exists in a crystal structure.

Taking part of the above Ni/SiO₂The catalyst is subjected to hydrogenation reaction of dicyclopentadiene in a high-pressure reaction kettle, methylcyclohexane is used as a solvent, and the mass fraction of dicyclopentadiene is 30%; the mass ratio of the catalyst to the dicyclopentadiene is 1: 20; the reaction temperature is 80 ℃, the stirring speed is 600r/min, the pressure is 3MPa, and the reaction time is 1 h. Finally, the dicyclopentadiene conversion was 99.9% and the tetrahydrodicyclopentadiene yield was 99.2%.

The catalyst after the reaction was recovered by centrifugation and repeatedly used for the hydrogenation test 8 times. The specific test results are shown in table 1. As can be seen from Table 1, after the catalyst is repeatedly used for reaction, a sample is a transparent liquid after each reaction, and through GC-MS analysis, the conversion rate of the raw material is more than 99%, and the molar yield of the tetrahydrodicyclopentadiene is more than 97%.

TABLE 1

Example 2

290g of Ni (NO) are weighed₃)₂·6H₂O and 2960g of tetraethyl orthosilicate (TEOS) were dissolved in deionized water to prepare a solution of 1.0mol/L in terms of Ni ions, and the solution was stirred for 1 hour to obtain a solution a. And adding citric acid (the weight ratio of citric acid to silicon source is 0.2:1) and deionized water into the solution a, stirring until sol is formed, continuing stirring to form gel, aging for 2 hours, finally putting the obtained material into a forced air drying oven, drying for 12 hours at 100 ℃, and roasting for 5 hours in a muffle furnace at 500 ℃ to obtain a black solid, namely the nickel-silicon composite oxide.

Putting 6.0g of nickel-silicon composite oxide into a tube furnace, and reducing for 3 hours at 500 ℃ with the hydrogen flow rate of 30mL/min to obtain Ni/SiO₂A catalyst.

Taking part of the above Ni/SiO₂Catalyst is reacted at high pressurePerforming hydrogenation reaction of dicyclopentadiene in a reactor, wherein the mass fraction of the dicyclopentadiene is 70% by taking methylcyclohexane as a solvent; the mass ratio of the catalyst to the dicyclopentadiene is 1: 10; the reaction temperature is 120 ℃, the stirring speed is 620r/min, the pressure is 3MPa, and the reaction time is 4 h. Finally, the dicyclopentadiene conversion was 99.9% and the tetrahydrodicyclopentadiene yield was 99.6%.

The catalyst after the reaction was recovered by centrifugation and repeatedly used for the hydrogenation test 8 times. The specific test results are shown in Table 2. As can be seen from Table 2, after the catalyst is repeatedly used for reaction, a sample is a transparent liquid after each reaction, and through GC-MS analysis, the conversion rate of the raw material is more than 99%, and the molar yield of the tetrahydrodicyclopentadiene is more than 97%.

TABLE 2

Example 3

Weighing 238g of Ni (NO)₃)₂·6H₂O and 2960g of tetraethyl orthosilicate (TEOS) were dissolved in deionized water to prepare a solution of 1.0mol/L in terms of Ni ions, and the solution was stirred for 1 hour to obtain a solution a. And adding citric acid (the weight ratio of citric acid to silicon source is 0.2:1) and deionized water into the solution a, stirring until sol is formed, continuing stirring to form gel, aging for 2 hours, finally putting the obtained material into a forced air drying oven, drying for 12 hours at 100 ℃, and roasting for 5 hours in a muffle furnace at 500 ℃ to obtain a black solid, namely the nickel-silicon composite oxide.

Putting 6.0g of nickel-silicon composite oxide into a tube furnace, and reducing for 3 hours at 400 ℃ with the hydrogen flow rate of 50mL/min to obtain Ni/SiO₂A catalyst.

Taking part of the above Ni/SiO₂The catalyst is subjected to hydrogenation reaction of dicyclopentadiene in a high-pressure reaction kettle, methylcyclohexane is used as a solvent, and the mass fraction of dicyclopentadiene is 50%; catalyst and dicyclopentadienylThe mass ratio of the alkene is 1: 30; the reaction temperature is 80 ℃, the stirring speed is 700r/min, the pressure is 3MPa, and the reaction time is 1 h. Finally, the dicyclopentadiene conversion was 99.9% and the tetrahydrodicyclopentadiene yield was 98.4%.

The catalyst after the reaction was recovered by centrifugation and repeatedly used for the hydrogenation test 8 times. The specific test results are shown in Table 3. As can be seen from Table 3, after the catalyst is repeatedly used for reaction, a sample is a transparent liquid after each reaction, and the GC-MS analysis shows that the conversion rate of the raw material is more than 99 percent, and the molar yield of the tetrahydrodicyclopentadiene is more than 97 percent.

TABLE 3

Example 4

290g of Ni (NO) are weighed₃)₂·6H₂O and 1460g of Tetraethylorthosilicate (TEOS) were dissolved in deionized water to prepare a solution of 1.0mol/L in terms of Ni ions, and the solution was stirred for 1 hour to obtain a solution a. And adding citric acid (the weight ratio of citric acid to silicon source is 0.2:1) and deionized water into the solution a, stirring until sol is formed, continuing stirring to form gel, aging for 2 hours, finally putting the obtained material into a forced air drying oven, drying for 12 hours at 100 ℃, and roasting for 5 hours in a muffle furnace at 500 ℃ to obtain a black solid, namely the nickel-silicon composite oxide.

6.0g of the nickel-silicon composite oxide is placed in a tube furnace, and reduction is carried out for 3 hours at 400 ℃ under the condition of keeping the hydrogen flow rate of 50mL/min to obtain Ni/SiO₂A catalyst.

Taking part of the above Ni/SiO₂The catalyst is subjected to hydrogenation reaction of dicyclopentadiene in a high-pressure reaction kettle, methylcyclohexane is used as a solvent, and the mass fraction of dicyclopentadiene is 30%; the mass ratio of the catalyst to the dicyclopentadiene is 1: 20; the reaction temperature is 80 ℃, the stirring speed is 800r/min, the pressure is 3MPa, and the reaction time is 1 h. Finally, dicyclopentadiene conversionThe yield was 99.9%, and the yield of tetrahydrodicyclopentadiene was 99.3%.

The catalyst after the reaction was recovered by centrifugation and repeatedly used for the hydrogenation test 8 times. The specific test results are shown in Table 4. As can be seen from Table 4, after the catalyst is repeatedly used for reaction, a sample is a transparent liquid after each reaction, and the GC-MS analysis shows that the conversion rate of the raw material is more than 99 percent, and the molar yield of the tetrahydrodicyclopentadiene is more than 97 percent.

TABLE 4

Example 5

580g of Ni (NO) are weighed₃)₂·6H₂O and 1460g of Tetraethylorthosilicate (TEOS) were dissolved in deionized water to prepare a solution of 1.0mol/L in terms of Ni ions, and the solution was stirred for 1 hour to obtain a solution a. And adding citric acid (the weight ratio of citric acid to silicon source is 0.2:1) and deionized water into the solution a, stirring until sol is formed, continuing stirring to form gel, aging for 2 hours, finally putting the obtained material into a forced air drying oven, drying for 12 hours at 100 ℃, and roasting for 5 hours in a muffle furnace at 500 ℃ to obtain a black solid, namely the nickel-silicon composite oxide.

6.0g of the nickel-silicon composite oxide is placed in a tube furnace, and reduction is carried out for 3 hours at 400 ℃ under the condition of keeping the hydrogen flow rate of 50mL/min to obtain Ni/SiO₂A catalyst.

Taking part of the above Ni/SiO₂The catalyst is subjected to hydrogenation reaction of dicyclopentadiene in a high-pressure reaction kettle, methylcyclohexane is used as a solvent, and the mass fraction of dicyclopentadiene is 30%; the mass ratio of the catalyst to the dicyclopentadiene is 1: 10; the reaction temperature is 60 ℃, the stirring speed is 700r/min, the pressure is 3MPa, and the reaction time is 1 h. Finally, the dicyclopentadiene conversion was 99.7% and the tetrahydrodicyclopentadiene yield was 99.0%.

The catalyst after the reaction was recovered by centrifugation and repeatedly used for the hydrogenation test 8 times. The specific test results are shown in Table 5. As can be seen from Table 5, after the catalyst is repeatedly used for reaction, a sample is a transparent liquid after each reaction, and the GC-MS analysis shows that the conversion rate of the raw material is more than 99 percent, and the molar yield of the tetrahydrodicyclopentadiene is more than 97 percent.

TABLE 5

Example 6

290g of Ni (NO) are weighed₃)₂·6H₂O and 2960g of tetraethyl orthosilicate (TEOS) were dissolved in deionized water to prepare a solution of 1.0mol/L in terms of Ni ions, and the solution was stirred for 1 hour to obtain a solution a. And adding citric acid (the weight ratio of citric acid to silicon source is 0.2:1) and deionized water into the solution a, stirring until sol is formed, continuing stirring to form gel, aging for 2 hours, finally putting the obtained material into a forced air drying oven, drying for 12 hours at 100 ℃, and roasting for 5 hours in a muffle furnace at 500 ℃ to obtain a black solid, namely the nickel-silicon composite oxide.

Uniformly mixing 160.0g of nickel-silicon composite oxide, 140.0g of silica sol (with the solid content of 30 percent), 1.0g of citric acid, 10.0g of sesbania powder and 40.0g of water, repeatedly kneading, extruding into cylindrical thin strips with the diameter of 1.8mm by using a strip extruding machine, cutting into strips with the length of 3-5 mm, drying at 120 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours; finally, hydrogen reduction was carried out at 400 ℃ for 3 hours to obtain a catalyst in the form of a strip having a mechanical strength of 19.3N/mm.

Taking 3g of the catalyst to carry out hydrogenation saturation reaction of dicyclopentadiene in a fixed bed reactor, taking methylcyclohexane as a solvent, wherein the mass fraction of the dicyclopentadiene is 30%; the reaction temperature is 80 ℃, the pressure is 3MPa, and the reaction mass space velocity is 2h^-1Hydrogen to oil volume ratio 500. Finally, the catalyst is continuously operated for 800h, the catalytic activity is not obviously reduced, the average conversion rate of dicyclopentadiene is 99.8 percent, and the average yield of tetrahydrodicyclopentadiene is reducedThe ratio was 99.1%.

Comparative example 1

290g of Ni (NO) are weighed₃)₂·6H₂Dissolving O in deionized water to prepare a solution a of 2.0mol/L calculated by Ni ions; 8.6mL of solution a were measured and slowly added to 14g of γ -Al₂O₃The powder was stirred continuously and a small amount of deionized water was added to the powder to bring it to an incipient wetness state. After the dropwise addition, the stirring is stopped, and the mixture is kept stand and aged for 8 hours. Drying the obtained product in a blast drying oven at 120 ℃ for 12h, and roasting in a muffle furnace at 500 ℃ for 3 h; finally, the catalyst is obtained by reducing the mixture for 3 hours in a tubular furnace at 500 ℃.

Taking part of the catalyst to perform a hydrogenation reaction of dicyclopentadiene in a high-pressure reaction kettle, taking methylcyclohexane as a solvent, wherein the mass fraction of the dicyclopentadiene is 30%; the mass ratio of the catalyst to the dicyclopentadiene is 1: 20; the reaction temperature is 80 ℃, the pressure is 3MPa, and the reaction time is 1 h. Finally, the dicyclopentadiene conversion was 85.9% and the tetrahydrodicyclopentadiene yield was 69.1%.

Comparative example 2

290g of Ni (NO) are weighed₃)₂·6H₂Dissolving O in deionized water to prepare a solution a of 2.0mol/L calculated by Ni ions; 8.6mL of solution a were measured and slowly added to 14g of SiO₂The powder was stirred continuously and a small amount of deionized water was added to the powder to bring it to an incipient wetness state. After the dropwise addition, the stirring is stopped, and the mixture is kept stand and aged for 8 hours. Drying the obtained product in a blast drying oven at 120 ℃ for 12h, and roasting in a muffle furnace at 500 ℃ for 3 h; finally, the catalyst is obtained by reducing the mixture for 3 hours in a tubular furnace at 500 ℃.

Taking part of the catalyst to perform a hydrogenation reaction of dicyclopentadiene in a high-pressure reaction kettle, taking methylcyclohexane as a solvent, wherein the mass fraction of the dicyclopentadiene is 30%; the mass ratio of the catalyst to the dicyclopentadiene is 1: 20; the reaction temperature is 80 ℃, the pressure is 3MPa, and the reaction time is 1 h. Finally, the dicyclopentadiene conversion was 72.3% and the tetrahydrodicyclopentadiene yield was 58.6%.

Table 6 shows the relevant parameters of the catalysts obtained in examples 1 to 6 and comparative examples 1 and 2, respectively.

TABLE 6

As can be seen from Table 6, the specific porous cluster aggregation structure of the catalyst prepared by the sol-gel method is beneficial to improving the specific surface area of the catalyst in contact with reactants, so that the catalytic activity of the catalyst is improved. When the catalyst is applied to preparing the tetrahydrodicyclopentadiene, the catalyst embodies higher catalytic activity and stability, the yield of the tetrahydrodicyclopentadiene can basically reach more than 98 percent, and the catalyst has good application prospect.

It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.