CN113045392A

CN113045392A - Application of hierarchical pore molecular sieve in preparation of cyclopentadiene and JP-10 aviation fuel

Info

Publication number: CN113045392A
Application number: CN201911381164.2A
Authority: CN
Inventors: 李广亿; 李宁; 张涛; 王爱琴; 王晓东; 丛昱
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2019-12-27
Filing date: 2019-12-27
Publication date: 2021-06-29

Abstract

The invention relates to an application of a hierarchical pore molecular sieve in a process for preparing cyclopentadiene and JP-10 aviation fuel. The hierarchical pore molecular sieve is one or more than two of H-ZSM-5, H-beta, H-Y, H-USY and La-Y, H-MOR molecular sieves with hierarchical pore structures, sulfonated SBA-15, MCM-41, Ti-SBA-15, Ti-MCM-41, Zr-MCM-41 and Zr-SBA-15; the hierarchical pore structure includes micropores and mesopores. The catalyst and the raw materials used in the invention are cheap and easy to obtain, the preparation process is simple, and the catalyst has higher activity and selectivity for the rearrangement reaction of furfuryl alcohol, the hydrogenation reaction of hydroxyl cyclopentenone and the dehydration reaction. The invention provides a cheap and efficient synthesis method for synthesizing JP-10 aviation fuel by synthesizing a lignocellulose-based platform compound and furfuryl alcohol.

Description

Application of hierarchical pore molecular sieve in preparation of cyclopentadiene and JP-10 aviation fuel

Technical Field

The invention relates to the field of biomass catalytic conversion, in particular to application of a hierarchical pore molecular sieve in a process for preparing JP-10 aviation fuel.

Background

The environmental problems such as the decrease of fossil resources and the emission of greenhouse gases due to the combustion of fossil energy are becoming more prominent, and the social demand for energy is continuously increasing, so that the development of new energy capable of replacing fossil resources is imperative. The application of biomass as a renewable organic carbon source in the production of carbon materials, fuels and chemicals has become a current hot research.

Aviation fuel JP-10 is a high density aviation fuel commonly used internationally. The fuel had a density of 0.935g/cm according to U.S. military Specification MIL-P-87107C-1989³(16 ℃), the freezing point is-79 ℃, the heat value of combustion is 42.1MJ/Kg, and the fuel has higher energy density than the conventional hydrocarbon fuel and is an aviation fuel with excellent performance. The method is widely applied to supersonic fighters, cruise missiles, rockets and other aircrafts. JP-10 is a single-component fuel composed of exo-tetrahydrodicyclopentadiene, and the purity reaches 98.5%. The current synthetic route of JP-10 is as follows: bridge dicyclopentadiene is used as raw material, hydrogenated to be bridge tetrahydro dicyclopentadiene, and then added into AlCl₃、H₂SO₄Isomerizing into exo-tetrahydrodicyclopentadiene under the catalysis of catalysts. The method has more byproducts in each step, needs a complex separation process, and has serious environmental pollution and low yield in the acid catalytic isomerization step. There are also some other methods of synthesizing JP-10 aviation fuels, but they all use cyclopentadiene or dicyclopentadiene, which are derived from fossil energy, as a raw material, and are highly dependent on non-renewable fossil energy.

The subject group has long engaged in the work of preparing oils and chemicals by catalytic biomass conversion (Chinese patent ZL201110346501.1 and ChemSus chem.2012,5, 1958-. A series of routes for efficiently utilizing the biomass and the platform compounds thereof are developed. Furfuryl alcohol is one of important biomass platform compounds, and the synthesis of JP-10 aviation fuel by using renewable biomass and the platform compound furfuryl alcohol thereof as raw materials is also reported in earlier work of the subject group in Angew. chem. int. Ed.,2019,131, 12282-.

The synthetic routes disclosed above all report the steps for the synthesis of JP-10 from furfuryl alcohol via a six-step process. However, with H-USY as a catalyst, the yield of the target product cyclopentadiene was reduced from 58.4% to 40.9% after 24 hours of reaction (see Figure S1 in Angew. chem. int. Ed.,2019,131, 12282-12286).

Disclosure of Invention

Aiming at the technical problem that the yield of the target product is greatly reduced in the method for preparing JP-10 aviation fuel by furfuryl alcohol in the prior art, the inventor researches and discovers that the yield of the target product is influenced by the stability of the catalyst and is verified in a further catalyst stability test experiment, namely, in the dehydration reaction of 1, 3-cyclopentanediol, the conventional H-ZSM-5, H-USY, H-beta molecular sieve or amorphous SiO is adopted₂-Al₂O₃Or Amberlyst resin, Nafion resin, etc., may result in poor catalyst stability during the reaction in this step.

Therefore, the invention discloses a key step of a synthesis process for preparing JP-10 aviation fuel from furfuryl alcohol, which adopts hierarchical pore catalysts H-ZSM-5, H-beta, H-Y, H-USY and La-Y, H-MOR molecular sieves and sulfonated SBA-15, MCM-41, Ti-SBA-15, Ti-MCM-41, Zr-MCM-41 and Zr-SBA-15 catalysts with mesoporous structures, so that the activity of cyclopentadiene prepared by dehydrating 1, 3-cyclopentanediol is basically kept unchanged within the reaction time of 100 hours.

The preparation method for preparing the JP-10 aviation fuel from the furfuryl alcohol is simple and easy to obtain the used catalyst and low in cost; in the preparation process, other reagents with other stoichiometric ratios except hydrogen are not required to be consumed. The whole route is green and environment-friendly, and the JP-10 aviation fuel is efficiently prepared by using the renewable biomass platform compound furfuryl alcohol.

The invention aims to provide the application of the hierarchical pore molecular sieve in the process of preparing JP-10 aviation fuel by furfuryl alcohol;

the invention is realized by the following technical scheme:

on one hand, the invention provides the application of an acid catalyst in the preparation of cyclopentadiene by dehydrating 1, 3-cyclopentanediol, wherein the acid catalyst is a hierarchical pore molecular sieve; the hierarchical pore molecular sieve is one or more than two of H-ZSM-5, H-beta, H-Y, H-USY and La-Y, H-MOR molecular sieves with hierarchical pore structures, sulfonated SBA-15, MCM-41, Ti-SBA-15, Ti-MCM-41, Zr-MCM-41 and Zr-SBA-15; the hierarchical pore structure includes micropores and mesopores.

As a preferred technical solution, the hierarchical pore structure further comprises macropores.

The hierarchical pore structure comprises micropores and mesopores, and the pore diameter of each micropore is less than 2 nm; the aperture of the mesopores is 2nm-50 nm; the pore diameter of the macropores is larger than 50 nm.

As a preferred technical scheme, the ratio of the mass of the acid catalyst to the mass of the substrate solution for the dehydration reaction is between 0.01 and 20 percent.

As a preferable technical scheme, the molecular sieve with the hierarchical pore structure is obtained by carrying out post-treatment on a bulk molecular sieve.

The post-treatment method includes at least one of acid treatment, alkali treatment, hydrothermal treatment, and fluoride treatment.

The acid treatment preferably comprises the steps of: adding a molecular sieve into 0.001-0.2mol/L acid solution, stirring for 0.1-10 hours at the temperature of 20-100 ℃, and washing, filtering, drying and roasting to prepare an acid-treated hierarchical pore molecular sieve; wherein the mass ratio of the molecular sieve to the alkali solution is between 0.001 and 1; the acid is one or more of nitric acid, hydrochloric acid, oxalic acid, acetic acid, succinic acid, and citric acid; the drying temperature is between 60 and 120 ℃, and the roasting temperature is between 200 and 700 ℃.

The alkali treatment preferably comprises the steps of: adding a molecular sieve into 0.001-0.2mol/L alkali solution, stirring for 0.1-10 hours at 0-90 ℃, and washing, filtering, drying and roasting to prepare an alkali-treated hierarchical-pore molecular sieve; wherein the mass ratio of the molecular sieve to the alkali solution is between 0.001 and 1; the alkali is selected from ammonia water, NaOH, KOH, and Na₂CO₃、(NH₄)₂CO₃One or a mixture of two or more of them; the drying temperature is between 60 and 120 ℃, and the roasting temperature is between 200 and 700 ℃.

The hydrothermal treatment preferably comprises the steps of: mixing the molecular sieve with 0.01-2.0mol/L NH₄ ⁺Ion exchange is carried out on the salt solution to form the ammonium type molecular sieve(ii) a Then, under the temperature of 400 ℃ and 900 ℃, introducing steam for treatment for 0.1-10 hours, thus preparing the hydrothermal treatment hierarchical pore molecular sieve; wherein the molecular sieve is mixed with NH₄ ⁺The mass ratio of the salt solution is between 0.001 and 1; NH (NH)₄ ⁺The salt solution is one or a mixture of more than two of ammonium chloride, ammonium sulfate and ammonium nitrate;

the fluoride treatment preferably comprises the steps of: adding a molecular sieve into 0.001-0.2mol/L fluoride solution, stirring for 0.1-10 hours at 0-100 ℃, and washing, filtering, drying and roasting to prepare a multi-stage pore molecular sieve for fluorination treatment; wherein the mass ratio of the molecular sieve to the alkali solution is between 0.001 and 1; the fluoride is HF and NH⁴One or a mixture of more than two of F; the drying temperature is between 60 and 120 ℃, and the roasting temperature is between 200 and 700 ℃.

In another aspect, the invention provides the use of an acid catalyst in a process for the preparation of JP-10 aviation fuel from furfuryl alcohol, the acid catalyst being a hierarchical pore molecular sieve as described above.

The JP-10 aviation fuel prepared by taking furfuryl alcohol as a raw material is divided into six reactions:

reaction route for preparing JP-10 from furfuryl alcohol

In another aspect, the invention provides a process for preparing JP-10 aviation fuel from furfuryl alcohol, which comprises six reaction steps:

firstly, preparing hydroxyl cyclopentenone by furfuryl alcohol solution through rearrangement reaction under the condition of alkali catalyst or without catalyst;

the second reaction is that the hydroxyl cyclopentenone reacts with hydrogen under the catalysis of a hydrogenation catalyst to prepare 1, 3-cyclopentanediol;

the third reaction is to prepare cyclopentadiene by catalyzing 1, 3-cyclopentanediol to dehydrate by using an acid catalyst;

reacting the cyclopentadiene through D-A to generate dicyclopentadiene;

fifthly, hydrogenating the dicyclopentadiene to generate bridge type tetrahydro dicyclopentadiene;

sixthly, isomerizing bridge type tetrahydro dicyclopentadiene to generate hanging type tetrahydro dicyclopentadiene;

in the sixth reaction, the catalyst for the isomerization reaction of the bridged tetrahydrodicyclopentadiene is any one of the hierarchical pore molecular sieves, and the ratio of the mass of the catalyst to the mass of the reaction substrate solution is 0.01-50%.

Preferably, in the third reaction, the acid catalyst for catalyzing the dehydration reaction of 1, 3-cyclopentanediol is one or a mixture of two or more of the following catalysts.

Preferably, in the sixth reaction, the ratio of the mass of the catalyst to the mass of the reaction substrate solution is 0.01-50% of the hierarchical pore molecular sieve mentioned above as the catalyst for the isomerization reaction of the bridged tetrahydrodicyclopentadiene.

Preferably, in the first reaction, the alkali catalyst is one or more of the following catalysts: NaOH, KOH, Na₂CO₃、NaHCO ₃25% by mass of ammonia water, Ca (OH)₂、Mg(OH)₂CaO, MgO, Mg-Al hydrotalcite, Ni-Al hydrotalcite, CeO₂(ii) a Wherein the ratio of the mass of the base catalyst to the mass of the reaction substrate solution for the rearrangement reaction is between 0 and 1000 ppm;

preferably, in the second reaction, the hydrogenation catalyst is one or a mixture of two or more of the following catalysts: supported metal catalyst, transition metal carbide and/or nitride catalyst, Raney nickel catalyst, amorphous alloy catalyst; wherein, the supported metal catalyst takes one or a mixture of more than two of active carbon, mesoporous carbon, silicon oxide, aluminum oxide, cerium oxide and titanium oxide as a carrier, and loads one or more than two of metals of Pt, Pd, Ru, Ir, Ni, Co and Cu; the mass content of metal in the hydrogenation catalyst is 0.01-30%; the ratio of the mass of the hydrogenation catalyst to the mass of the hydrogenated reaction substrate solution is between 0.01 and 20 percent;

preferably, in the fourth reaction, the cyclopentadiene produced by the D-A reaction is one or more of the following mixed or no catalyst: quality ofHydrochloric acid with concentration of 36%, sulfuric acid, Nafion resin, Amberlyst resin, ZnCl₂、AlCl₃(ii) a The ratio of the mass of the catalyst to the mass of the reaction substrate solution is between 0.01 and 20 percent;

preferably, in the fifth reaction, the catalyst for the hydrogenation reaction is one or more than two of the following catalysts: supported metal catalyst, transition metal carbide and/or nitride catalyst, Raney nickel catalyst, amorphous alloy catalyst; wherein, the supported metal catalyst takes one or a mixture of more than two of active carbon, mesoporous carbon, silicon oxide, aluminum oxide, cerium oxide and titanium oxide as a carrier, and loads one or more than two of metals of Pt, Pd, Ru, Ir, Ni, Co and Cu; wherein the metal content in the supported catalyst is between 0.1 and 30 percent; the ratio of the mass of the catalyst for the hydrogenation reaction to the mass of the reaction substrate solution is between 0.1 and 20 percent.

Preferably, the solvent for the first reaction, the reaction for preparing the hydroxycyclopentenone from the furfuryl alcohol solution is water or a mixture of water and one or more of the following solvents: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide; the reaction for preparing the hydroxy cyclopentenone from the furfuryl alcohol solution is carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 160 and 250 ℃; the mass concentration of the furfuryl alcohol is 0.1-10%; when a kettle type reactor is adopted, the reaction time is between 0.01h and 0.5 h; when a fixed bed reactor is adopted, the mass space velocity is 1h^-1-100h^-1To (c) to (d);

preferably, in the second reaction, the hydroxy cyclopentenone hydrogenation reaction adopts one or more of the following solvents: water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide; the hydrogenation reaction of the hydroxyl cyclopentenone can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 0 and 160 ℃; the hydrogen pressure is between 1MPa and 5 MPa; wherein the mass concentration of the hydroxy cyclopentenone is 5-50%; when a kettle type reactor is adopted, the reaction time is between 0.1h and 2 h; when using fixed bed reactorsThe mass space velocity is 1h^-1-10h^-1To (c) to (d); the molar ratio of the hydrogen to the reaction raw material is 2-1500;

preferably, the third reaction, namely the catalytic dehydration reaction of the 1, 3-cyclopentanediol, adopts one or more of the following solvents: water, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, cyclohexane and tridecane; the catalytic dehydration reaction of the 1, 3-cyclopentanediol can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 180 and 350 ℃; wherein the mass concentration of the 1, 3-cyclopentanediol is 0.1-10%; when a kettle type reactor is adopted, the reaction time is between 0.1h and 12 h; when a fixed bed reactor is adopted, the mass space velocity is 0.1h^-1-10h^-1To (c) to (d);

preferably, the reaction of the fourth step, cyclopentadiene D-A, can be carried out without a solvent, or with a mixture of one or more of the following solvents: water, benzene, toluene, benzyl alcohol, decalin, cyclohexane, n-heptane, n-hexane; wherein the mass concentration of the cyclopentadiene is 10-100 percent; the reaction temperature is between 0 and 170 ℃; the cyclopentadiene D-A reaction can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 0 and 170 ℃; when a kettle type reactor is adopted, the reaction time is between 0.1h and 10 h; when a fixed bed reactor is adopted, the mass space velocity is 0.2h^-1-10h^-1To (c) to (d);

preferably, in the reaction of five, the hydrogenation reaction of dicyclopentadiene does not use a solvent, or one or more than two of the following solvents are mixed: water, dichloromethane, dichloroethane, chloroform, benzene, toluene, benzyl alcohol, decalin, cyclohexane, n-heptane, n-hexane; the hydrogenation reaction of dicyclopentadiene can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 0 and 160 ℃; the hydrogen pressure is between 0.1MPa and 4 MPa; wherein the mass concentration of the bridge dicyclopentadiene is 10-90%; when a kettle type reactor is adopted, the reaction time is between 1h and 12 h; when a fixed bed reactor is adopted, the volume space velocity is 1h^-1-10h^-1The molar ratio of the hydrogen to the reaction raw material is 2-150;

preferably, the reaction is six, the isomerization reaction of the bridged tetrahydrodicyclopentadiene can be carried out without a solvent, or by using one or more of the following solvents: water, dichloromethane, dichloroethane, chloroform, benzene, toluene, benzyl alcohol, decalin, cyclohexane, n-heptane, n-hexane; the isomerization reaction of the bridge type tetrahydro dicyclopentadiene can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 100 and 220 ℃; wherein the mass concentration of the bridge type tetrahydro dicyclopentadiene is 20-100 percent; when a kettle type reactor is adopted, the reaction time is between 2h and 24 h; when a fixed bed reactor is adopted, the volume space velocity is 0.1h^-1-10h^-1To (c) to (d);

preferably, each of the first to sixth reactions may be carried out in a single reactor or fixed bed reactor, or two or more of them may be carried out simultaneously in a single reactor or fixed bed reactor. For example, in the fourth reaction, because the reaction is carried out at normal temperature and normal pressure, a high conversion rate can be obtained without a catalyst, and the reaction is generally not required to be carried out as one-step reaction; reaction five and reaction six are also carried out in one step.

Advantageous effects

The invention provides a cheap and efficient synthesis method for synthesizing JP-10 aviation fuel by synthesizing a lignocellulose-based platform compound and furfuryl alcohol, wherein the raw material is renewable lignocellulose-based platform compound furfuryl alcohol. The rearrangement reaction, the hydrogenation reaction, the dehydration reaction and the isomerization reaction all adopt common alkali catalysts, hydrogenation catalysts and acid catalysts, are simple and easy to obtain, have lower catalyst cost and get rid of the dependence on the traditional fossil energy.

Compared with the technical scheme disclosed in the invention patent application CN108117474A, the invention adopts H-ZSM-5, H-beta, H-Y, H-USY and La-Y, H-MOR molecular sieves with hierarchical pore structures, sulfonated SBA-15, MCM-41, Ti-SBA-15, Ti-MCM-41, Zr-MCM-41 and Zr-SBA-15; greatly prolongs the service life of the catalyst in the third step of the dehydration reaction of the 1, 3-cyclopentanediol, thereby being capable of reducing the whole process cost for preparing the JP-10 aviation fuel by the furfuryl alcohol.

The process of this patent is therefore a very practical method for the synthesis of JP-10 aviation fuel from renewable biomass platform compounds.

Drawings

FIG. 1 of furfuryl alcohol rearrangement reaction product hydroxycyclopentenone¹H-NMR spectrum;

FIG. 2 of furfuryl alcohol rearrangement reaction product hydroxycyclopentenone¹³A C-NMR spectrum;

FIG. 3 Process for the hydrogenation of the Hydroxycyclopentenone product 1, 3-cyclopentanediol¹H-NMR spectrum;

FIG. 4 production of 1, 3-cyclopentanediol as a product of hydrogenation of hydroxycyclopentenone¹³A C-NMR spectrum;

FIG. 5(a) GC-MS spectrum of dicyclopentadiene-total ion flow diagram-1;

FIG. 5(b) GC-MS spectrum-1 of dicyclopentadiene;

FIG. 5(c) GC-MS spectrum of dicyclopentadiene-total ion flow diagram-2;

FIG. 5(d) GC-MS spectrum-2 of dicyclopentadiene;

FIG. 6(a) total ion flow diagram of tetrahydrodicyclopentadiene;

FIG. 6(b) GC-MS diagram-1 of tetrahydrodicyclopentadiene;

FIG. 6(c) GC-MS diagram-2 of tetrahydrodicyclopentadiene;

FIG. 7(a) the nitrogen physisorption of an acid treated ZSM-5 molecular sieve;

FIG. 7(b) pore distribution of acid treated ZSM-5 molecular sieves;

FIG. 8(a) the nitrogen physisorption of alkali treated beta molecular sieve;

FIG. 8(b) pore distribution of base treated beta molecular sieve;

FIG. 9(a) nitrogen physisorption of hydrothermally treated USY molecular sieves;

FIG. 9(b) pore distribution of hydrothermally treated USY molecular sieves;

FIG. 10(a) nitrogen physisorption of fluoride treated MOR molecular sieves;

FIG. 10(b) pore distribution of fluoride treated MOR molecular sieves.

Detailed Description

The invention will now be illustrated by means of specific examples, without restricting its scope to these examples.

1. Experiment on the preparation of hydroxycyclopentenone from furfuryl alcohol (influence of catalyst, kettle reactor)

Adding 50mL of furfuryl alcohol aqueous solution with the mass concentration of 2% into a 100mL reaction kettle, adding a certain amount of alkali catalyst, and reacting for a specific time at a certain temperature.

TABLE 1 rearrangement reactivity of different base catalysts

As can be seen from the results in Table 1, different base catalysts can effectively catalyze the furfuryl alcohol rearrangement reaction to obtain high-yield hydroxycyclopentenone in which the weak-base CeO₂The effect is slightly poor. However, even without any catalyst, a yield of 60% of hydroxycyclopentenone can still be obtained under the preferred reaction conditions. The influence of the catalyst amount on the reaction activity is obvious, wherein about 5mg of NaOH can obtain better yield, and the yield of the hydroxycyclopentenone is reduced when the NaOH content is more than or less than the value. The influence of the reaction time is similar to the amount of the catalyst, the optimal yield is obtained in 0.02h, and the target product is further subjected to side reaction due to too long time, so that the product yield is reduced; if the reaction time is too short, a part of the raw materials is not completely converted, resulting in a low yield. The reaction temperature also has an optimal value, the yield of the hydroxycyclopentenone is maximized at 240 ℃, and the yield is reduced slightly due to the excessively high or excessively low temperature.

2. Experiment on the preparation of hydroxycyclopentenone from furfuryl alcohol (influence of solvent, kettle reactor)

50mL of furfuryl alcohol water solution with certain concentration or a mixed solution of water and other solvents is added into a 100mL reaction kettle, NaOH is used as a catalyst, and the reaction is carried out for 0.02h at 240 ℃.

TABLE 2 Effect of different solvents on the rearrangement reactivity

As can be seen from the results in Table 2, the yield of hydroxycyclopentenone decreases significantly as the furfuryl alcohol concentration of the reaction substrate increases, but remains at a higher level. This requires a combination of yield and energy efficiency to achieve the optimum concentration in the actual production process. The mixed solvent has little influence on the yield of the target product, and higher yield of the hydroxycyclopentenone can be obtained even if the ratio of the mixed solvent to the water is floated in a larger range.

3. Experiment on the preparation of hydroxycyclopentenone from furfuryl alcohol (fixed bed reactor)

In a fixed bed reactor, furfuryl alcohol aqueous solutions with different concentrations are pumped into the fixed bed reactor at a certain speed by a liquid chromatography pump, and the reaction is carried out at different temperatures by taking magnesium-aluminum hydrotalcite as a catalyst.

TABLE 3 furfuryl alcohol rearrangement reactivity in fixed bed reactor

As can be seen from Table 3, higher yields of hydroxycyclopentenones can be obtained at the same furfuryl alcohol concentration in the fixed bed reactor than in the kettle reactor. Too large or too small a space velocity in the fixed bed leads to a reduction in the yield of hydroxycyclopentenones, which is similar to the reason why the reaction time in the tank reactor influences the yield. The temperature has a great influence on the formation of the hydroxycyclopentenone, the formation of the target product is not favored by too low a temperature, and the optimal reaction temperature is 240 ℃.

4. Experiment on Hydroxycyclopentenone hydrogenation (influence of catalyst, kettle reactor)

50mL of 20% hydroxycyclopentenone solution with THF as a solvent is added into a 100mL reaction kettle, 0.1g of hydrogenation catalyst is added, and the reaction is carried out for a specific time at a certain temperature.

TABLE 4 hydrogenation reactivity of different catalysts

As can be seen from the data in table 4, almost all the common hydrogenation catalysts have good effect on the hydrogenation of hydroxycyclopentenones, with the activities expressed by the metals Ni and Ru being the best. The metal loading and reaction time had a slight, but not significant, effect on the yield of 1, 3-cyclopentanediol. The reaction temperature is relatively much affected, and 160 ℃ is the optimum reaction temperature.

5. Experiment on Hydroxycyclopentenone hydrogenation (influence of solvent, kettle reactor)

50mL of hydroxycyclopentenone solution with a certain concentration is added into a 100mL reaction kettle, 5% Ru/AC or Raney Ni is used as a catalyst, the adding amount of the catalyst is 0.1g, and the reaction is carried out for 1h at 160 ℃.

TABLE 5 Effect of different solvents on hydrogenation reactivity

As can be seen from the data in Table 5, the solvent has a great influence on the hydrogenation reaction, and a high yield of 1, 3-cyclopentanediol can be obtained in aprotic solvents such as THF, DMF, DMSO, etc. While the yield of 1, 3-cyclopentanediol in systems such as water and alcohol is relatively low. The mixed solvent effect is between the two. The substrate concentration has a greater influence on the yield of 1, 3-cyclopentanediol, the lower the concentration, the higher the yield.

6. Experiment of Hydroxycyclopentenone hydrogenation (fixed bed reactor)

In a fixed bed reactor, liquid chromatographic pump is used to pump THF solutions of hydroxycyclopentenone in different concentrations into the fixed bed reactor at certain rate, Ru/AC is used as catalyst, and the reaction is carried out at different temperatures.

TABLE 6 hydrogenation activity in fixed bed reactor

As can be seen from the data in Table 6, the substrate concentration has a great influence on the hydrogenation reaction, and an excessively high substrate concentration leads to a significant decrease in the yield of 1, 3-cyclopentanediol. The space velocity has a relatively small effect on the yield of 1, 3-cyclopentanediol. The reaction temperature has little influence on the yield of the 1, 3-cyclopentanediol at a high temperature of 160-300 ℃, and when the temperature is lower than 100 ℃, the yield of the 1, 3-cyclopentanediol is obviously reduced.

7.1, 3-Cyclopentylene glycol dehydration to cyclopentadiene experiment (kettle reactor)

In a 100mL reaction vessel, 5mL of 1, 3-cyclopentanediol and 45mL of tridecane were added, and 2g of an acid catalyst was added, followed by reaction at a certain temperature for a certain period of time.

TABLE 7 dehydration reactivity of different catalysts

Wherein, the specific preparation method of the hierarchical pore molecule is shown in example 253-256. As can be seen from the data in Table 7, all the hierarchical pore molecular sieves and the sulfonated mesoporous material catalysts have good effect on the dehydration reaction of 1, 3-cyclopentanediol, wherein Zr-MCM-41-SO is used₃H and multi-well HUSY-255 showed the best activity. When the reaction temperature is higher than 180 ℃, the reaction time is more than one hour, and the influence on the yield of the product is not great.

Experiment (fixed bed reactor) for preparing cyclopentadiene by dehydrating 1, 3-cyclopentanediol

In a fixed bed reactor, 1, 3-cyclopentanediol tetrahydrofuran solutions with different concentrations are pumped into the fixed bed reactor at a certain rate by a liquid chromatography pump, and reaction is carried out at different temperatures by taking a hierarchical porous H beta-254 molecular sieve as a catalyst.

TABLE 8 dehydration reactivity in fixed bed reactor

As can be seen from the data in Table 8, the substrate concentration had little effect on the dehydration reaction, and increasing the substrate concentration resulted in a slight decrease in the cyclopentadiene yield. The space velocity has a relatively small effect on the cyclopentadiene yield. The reaction temperature in the high temperature section of 180-350 ℃ has little influence on the yield of cyclopentene.

Experiment stability experiment for preparing cyclopentadiene by dehydrating 9.1, 3-cyclopentanediol

Pumping 1, 3-cyclopentanediol tetrahydrofuran solution with a mass concentration of 10% into the fixed bed reactor at a certain rate by using a liquid chromatography pump in the fixed bed reactor, and controlling the mass space velocity of the reaction to be 1h^-1The reaction temperature was 250 ℃, samples were taken at different reaction times, and the stability of the catalyst was examined.

TABLE 9 dehydration reactivity in fixed bed reactor

Wherein, the preparation of the hierarchical pore molecular sieve is detailed in example 253-256. It can be seen from the data in table 9 that all the hierarchical pore molecular sieves and the sulfonated mesoporous material catalysts have good stability for the dehydration reaction of 1, 3-cyclopentanediol, and the activity remains almost unchanged after the reaction is performed for 100 hours, while the activity of the conventional HUSY molecular sieve is significantly reduced after the reaction is performed for 10 hours, and the activity is reduced to less than half of the initial activity after the reaction is performed for 40 hours. The superiority of the medium-grade molecular sieve and the sulfonated mesoporous material catalyst of the invention is fully proved.

10. Cyclopentadiene D-A reaction for producing dicyclopentadiene (kettle type reactor)

50mL of cyclopentadiene (by mass) was added to a 100mL reaction vessel, and reacted at a constant temperature for a specific time without adding a catalyst or with 1% of a catalyst.

TABLE 10 DA reactivity of different catalysts

As can be seen from the data in Table 10, cyclopentadiene can be easily produced into dicyclopentadiene by the D-A reaction without the need for a catalyst; even at normal temperature, the yield of dicyclopentadiene is still considerable given a sufficiently long reaction time. The reaction rate can be increased by adding a small amount of acid as a catalyst.

Thus, in practice, the preparation of dicyclopentadiene from cyclopentadiene does not require a special one-step reaction to operate, and usually it is carried out in one step in combination with other reactions.

11. Experiment of hydrogenation of Dicyclopentadiene to produce bridge-type tetrahydro-Dicyclopentadiene (different catalysts, kettle type reactor)

50mL of 50% dicyclopentadiene-cyclohexane solution was added to a 100mL reaction vessel, 1.0g of catalyst was added, the reaction vessel was replaced with hydrogen, and then the pressure of 4MPa was applied, and the reaction was carried out at a constant temperature for a predetermined time.

TABLE 11 dicyclopentadiene hydrogenation reactivity of different catalysts

As can be seen from the data in Table 11, the catalysts listed in the table all have a good effect on the hydrogenation of dicyclopentadiene. Pd/MC can be efficiently hydrogenated to produce the bridge type tetrahydro dicyclopentadiene at normal temperature.

12. Experiment on bridge type tetrahydro dicyclopentadiene preparation by hydrogenation of dicyclopentadiene (different solvents, kettle type reactor)

50mL of a 50% by mass solution of dicyclopentadiene was added to a 100mL reaction vessel, and 1.0g of 5% Pd/AC was added to the reaction vessel to conduct a reaction at 140 ℃ for 5 hours.

TABLE 12 Effect of different solvents on the hydrogenation reactivity of Dicyclopentadiene

As can be seen from the data in Table 12, the solvents listed in the table all have good effect on the hydrogenation of dicyclopentadiene and are also better obtained without the addition of solvent. The hydrogen pressure has little influence on the reaction, and when the pressure is more than 1MPa, the bridge type tetrahydrodicyclopentadiene yield with high yield can be obtained.

13. Experiment (fixed bed reactor) for preparing bridge type tetrahydro dicyclopentadiene by hydrogenation of dicyclopentadiene

In a fixed bed reactor, a liquid chromatographic pump is used for pumping cyclohexane solutions of dicyclopentadiene with different concentrations into the fixed bed reactor at a certain speed, 5 percent Pd/AC is used as a catalyst, and the reaction is carried out at different temperatures.

TABLE 13 Dicyclopentadiene hydrogenation reactivity in fixed bed reactor

As can be seen from the data in Table 13, under the conditions we used, the substrate concentration had little effect on the hydrogenation reaction, and even without the use of a solvent, i.e., with a feed concentration of 100%, higher yields of bridged tetrahydrodicyclopentadiene could be obtained. The lower the space velocity, the higher the yield of the bridge tetrahydrodicyclopentadiene, and the yield of the target product is obviously reduced at a particularly high space velocity. The reaction temperature is 100-200 ℃ in a high temperature section, the influence on the yield of the bridge type tetrahydrodicyclopentene is small, and when the temperature is lower than 50 ℃, the yield of the bridge type tetrahydrodicyclopentadiene is obviously reduced.

14. Experiment of bridge type tetrahydro dicyclopentadiene isomerization to produce hanging tetrahydro dicyclopentadiene (different solvents, kettle type reactor)

50mL of bridged tetrahydrodicyclopentadiene solution with a certain mass concentration is added into a 100mL reaction kettle, 5.0g of catalyst is added, and the reaction is carried out for 2h at a certain temperature.

TABLE 14 Effect of different solvents on the isomerization reactivity

Wherein, the preparation of the hierarchical pore molecular sieve is detailed in example 253-256. As can be seen from the data in Table 14, the solvents listed in the table all work well for the isomerization of bridged tetrahydrodicyclopentadiene. The concentration of the substrate has a great influence on the reaction, and the high concentration of the substrate is beneficial to the isomerization reaction. The hierarchical porous La-Y-254 molecular sieve can obtain high isomerization yield, the temperature is higher than 100 ℃, and the influence of good isomerization reaction activity exists.

15. Bridge type tetrahydro dicyclopentadiene isomerization preparation hanging type tetrahydro dicyclopentadiene experiment (fixed bed reactor)

In a fixed bed reactor, pumping cyclohexane solutions of bridge tetrahydrodicyclopentadiene with different concentrations into the fixed bed reactor at a certain speed by a liquid chromatography pump, wherein a catalyst is a hierarchical porous HUSY-255 molecular sieve, and reacting at different temperatures.

TABLE 15 isomerization reactivity in fixed bed reactor

As can be seen from the data in Table 15, the influence of the substrate concentration on the isomerization reaction is large, and the yield of exo-tetrahydrodicyclopentadiene can be increased by increasing the substrate concentration. The smaller the space velocity, the less the influence on the yield of the exo-tetrahydrodicyclopentadiene. The reaction temperature is 160-220 ℃ in the high temperature section, the influence on the yield of the exo-dicyclopentene is small, and when the temperature is as low as 130 ℃, the yield of the exo-tetrahydrodicyclopentadiene is obviously reduced.

As can be seen from the above examples, the exo-tetrahydrodicyclopentadiene can be prepared from furfuryl alcohol in high yield by six reactions, and the obtained exo-tetrahydrodicyclopentadiene has a purity of more than 98.5% and can be directly used as JP-10 aviation fuel. And the catalyst adopted in the process is common and cheap alkali catalyst, hydrogenation catalyst and acid catalyst. In the process, except hydrogen, other extra consumables are not required to be added, the whole process is green and environment-friendly, and the method is a very efficient method for synthesizing the JP-10 aviation fuel from the renewable biomass platform compound furfuryl alcohol.

Examples 113 and 114

In the inventive examples 113 and 114, Amberlyst-36 was used as a catalyst, and the reaction was carried out at the same temperature (140 ℃) for 8 hours, whereby the cyclopentadiene yield was 90%. But the second recycle of the resin reduced the cyclopentadiene yield to 13%. It can be seen that this catalyst cannot be recycled in the dehydration reaction of cyclopentanediol.

Comparative example 1

ACS Sustainable chem. Eng.2016,4, 6160-. Through condition optimization (140 ℃), the yield of cyclopentene can reach 84.0%, and Amberlyst-36 resin can be recycled for 7 times without obvious reduction of activity.

As can be seen from comparison of comparative example 1 with examples 113 and 114, the dehydration reaction of cyclopentanol is much more difficult than that of cyclopentanol, the catalyst for dehydration of cyclopentanol is not suitable for dehydration reaction of cyclopentanol, and Amberlyst-36 is not the catalyst protected in this patent.

Example 168-

In the embodiment 168-170 of the invention, the multi-stage pore SAPO-34 molecular sieve catalyst is adopted, and the yield of the initial cyclopentadiene is 63 percent, which is basically equivalent to the reaction activity of other multi-stage pore molecular sieves. But the cyclopentadiene yield after 40 hours of reaction had dropped to 33%; after 100 hours of reaction, the cyclopentadiene yield was only 13%. Therefore, the multistage pore SAPO-34 molecular sieve cannot effectively improve the dehydration stability of the cyclopentanediol. The multi-stage pore SAPO-34 molecular sieve is also not a catalyst as claimed in this patent.

Comparative example 2

The synthesis of the hierarchical pore molecular sieve SAPO-34 and the application thereof in the reaction of preparing olefin from methanol are reported in the synthesis and catalytic performance of the hierarchical pore SAPO-34 molecular sieve in volume 25 of 2017 in industrial catalysis. In FIG. 5, it can be seen that the multi-stage pore SAPO-34 has no obvious deactivation phenomenon within the reaction time of 400 min.

Comparison of comparative example 2 with example 168-170 shows that not the conventional hierarchical pore molecular sieve catalyst can improve the stability of dehydration of cyclopentanediol.

Example 253 acid treatment preparation of a hierarchical pore molecular sieve

Adding 2g of ZSM-5 or 2gY type molecular sieve into 100mL of 0.05mol/L oxalic acid solution, stirring for 2 hours at 90 ℃, washing for three times, filtering, drying for 6 hours at 120 ℃, and roasting for 2 hours at 550 ℃ to prepare the acid-treated hierarchical pore ZSM-5 molecular sieve. The nitrogen physical adsorption of the multi-stage hole ZSM-5 is shown in figure 7(a), and the obvious hysteresis ring characteristic curve of the mesoporous material is shown. The thus calculated pore size distribution of the hierarchical pore ZSM-5 is shown in FIG. 7(b), and the pore size thereof is in the range of 5 to 30 nm. The prepared catalyst is marked as hierarchical pore HZSM-5-253 and hierarchical pore HY-253.

EXAMPLE 254 base treatment preparation of a hierarchical pore molecular sieve

Adding 2g of beta or LaY molecular sieve into 100mL of 0.05mol/L ammonia water solution, stirring for 2 hours at 30 ℃, washing for three times, filtering, drying for 6 hours at 120 ℃, and roasting for 2 hours at 550 ℃ to prepare the alkali-treated hierarchical pore beta molecular sieve. The nitrogen physical adsorption of the multi-level pore beta molecular sieve is shown in figure 8(a), and the hysteresis loop characteristic curve of the mesoporous material is obvious. The pore size distribution of the hierarchical pore beta molecular sieve thus calculated is shown in FIG. 8(b), and the pore size is in the range of 5 to 30 nm. The prepared catalyst is marked as multi-stage hole H beta-254 and multi-stage hole LaY-254.

EXAMPLE 255 hydrothermal treatment preparation of a hierarchical pore molecular sieve

Adding 2g of USY or 2g of SAPO-34 molecular sieve into 100mL of 0.2mol/L ammonium chloride solution for ion exchange to form an ammonium type molecular sieve; and then introducing water vapor at 600 ℃ for treatment for 2 hours to obtain the hydrothermal-treated hierarchical porous USY molecular sieve. The nitrogen physical adsorption of the hierarchical pore USY molecular sieve is shown in figure 9(a), and the hysteresis ring characteristic curve of the mesoporous material is obvious. The pore size distribution of the hierarchical pore USY molecular sieve thus calculated is shown in FIG. 9(b), and the pore size is in the range of 5-30 nm. The prepared catalyst is marked as multi-stage pore HUSY-255 and multi-stage pore SAPO-34-255.

EXAMPLE 256 preparation of a hierarchical pore molecular sieve by fluorination treatment

Adding 2g of MOR molecular sieve into 100mL of 0.1mol/L ammonium fluoride solution, stirring for 2 hours at 20 ℃, washing for three times, filtering, drying for 6 hours at 120 ℃, and roasting for 2 hours at 550 ℃ to prepare the fluoride-treated hierarchical-pore MOR molecular sieve. The nitrogen physical adsorption of the hierarchical-pore MOR molecular sieve is shown in figure 10(a), and the hysteresis loop characteristic curve of the mesoporous material is obvious. The distribution of the pore sizes of the hierarchical pore MOR molecular sieve thus calculated is shown in FIG. 10(b), and the pore sizes thereof are in the range of 5 to 50 nm. The catalyst prepared is marked as hierarchical pore HMOR-256.

Claims

1. The application of the acid catalyst in the preparation of cyclopentadiene by dehydrating 1, 3-cyclopentanediol is characterized in that the acid catalyst is a hierarchical pore molecular sieve;

the hierarchical pore molecular sieve is one or more than two of H-ZSM-5, H-beta, H-Y, H-USY and La-Y, H-MOR molecular sieves with hierarchical pore structures, sulfonated SBA-15, MCM-41, Ti-SBA-15, Ti-MCM-41, Zr-MCM-41 and Zr-SBA-15;

the hierarchical pore structure includes micropores and mesopores.

2. Use according to claim 1, characterized in that: the hierarchical pore structure also includes macropores.

3. Use according to claim 1, characterized in that:

the ratio of the mass of the acid catalyst to the mass of the substrate solution for the dehydration reaction is between 0.01% and 20%.

4. Use according to claim 1, characterized in that:

the molecular sieve with the hierarchical pore structure is obtained by post-treating a bulk molecular sieve;

the post-processing method comprises the following steps: at least one of acid treatment, alkali treatment, hydrothermal treatment, and fluoride treatment.

5. Use according to claim 4, characterized in that:

the acid treatment comprises the following steps:

adding a molecular sieve into 0.001-0.2mol/L acid solution, stirring for 0.1-10 hours at the temperature of 20-100 ℃, and washing, filtering, drying and roasting to prepare an acid-treated hierarchical pore molecular sieve;

wherein the mass ratio of the molecular sieve to the acid solution is between 0.001 and 1; the acid is one or more of nitric acid, hydrochloric acid, oxalic acid, acetic acid, succinic acid, and citric acid; the drying temperature is between 60 and 120 ℃, and the roasting temperature is between 200 and 700 ℃;

the alkali treatment comprises the following steps:

adding a molecular sieve into 0.001-0.2mol/L alkali solution, stirring for 0.1-10 hours at 0-90 ℃, and washing, filtering, drying and roasting to prepare an alkali-treated hierarchical-pore molecular sieve;

wherein the mass ratio of the molecular sieve to the alkali solution is between 0.001 and 1; the alkali is selected from ammonia water, NaOH, KOH, and Na₂CO₃、(NH₄)₂CO₃One or a mixture of two or more of them; the drying temperature is between 60 and 120 ℃, and the roasting temperature is between 200 and 700 ℃;

the hydrothermal treatment comprises the following steps:

mixing the molecular sieve with 0.01-2.0mol/L NH₄ ⁺Carrying out ion exchange on the salt solution to form an ammonium type molecular sieve; then, under the temperature of 400 ℃ and 900 ℃, introducing steam for treatment for 0.1-10 hours, thus preparing the hydrothermal treatment hierarchical pore molecular sieve;

wherein the molecular sieve is mixed with NH₄ ⁺The mass ratio of the salt solution is between 0.001 and 1; NH (NH)₄ ⁺The salt solution is one or a mixture of more than two of ammonium chloride, ammonium sulfate and ammonium nitrate;

the fluoride treatment comprises the following steps:

adding a molecular sieve into 0.001-0.2mol/L fluoride solution, stirring for 0.1-10 hours at 0-100 ℃, and washing, filtering, drying and roasting to prepare a multi-stage pore molecular sieve for fluorination treatment;

wherein the mass ratio of the molecular sieve to the alkali solution is between 0.001 and 1; the fluoride is HF and NH₄One or a mixture of more than two of F; the drying temperature is between 60 and 120 ℃, and the roasting temperature is between 200 and 700 DEG C。

6. Use of an acid catalyst in a process for the preparation of JP-10 aviation fuel from furfuryl alcohol, wherein the acid catalyst is a hierarchical pore molecular sieve according to any one of claims 1 to 6.

7. The process method for preparing the JP-10 aviation fuel by the furfuryl alcohol is characterized by comprising six reaction steps:

reacting the cyclopentadiene through D-A to generate dicyclopentadiene;

in the sixth reaction, the catalyst for the isomerization reaction of bridged tetrahydrodicyclopentadiene is the hierarchical pore molecular sieve of any one of claims 1 to 6, and the ratio of the mass of the catalyst to the mass of the reaction substrate solution is 0.01 to 50%.

8. The process of claim 7,

in the first reaction, the alkali catalyst is one or more than two of the following catalysts: NaOH, KOH, Na₂CO₃、NaHCO₃25% by mass of ammonia water, Ca (OH)₂、Mg(OH)₂CaO, MgO, Mg-Al hydrotalcite, Ni-Al hydrotalcite, CeO₂(ii) a Wherein the ratio of the mass of the base catalyst to the mass of the reaction substrate solution for the rearrangement reaction is between 0 and 1000 ppm;

in the second reaction, the hydrogenation catalyst is one or a mixture of more than two of the following catalysts: supported metal catalyst, transition metal carbide and/or nitride catalyst, Raney nickel catalyst, amorphous alloy catalyst; wherein, the supported metal catalyst takes one or a mixture of more than two of active carbon, mesoporous carbon, silicon oxide, aluminum oxide, cerium oxide and titanium oxide as a carrier, and loads one or more than two of metals of Pt, Pd, Ru, Ir, Ni, Co and Cu; the mass content of metal in the hydrogenation catalyst is 0.01-30%; the ratio of the mass of the hydrogenation catalyst to the mass of the hydrogenated reaction substrate solution is between 0.01 and 20 percent;

in the fourth reaction, the cyclopentadiene is reacted by the D-A to generate the dicyclopentadiene, which is one or more than two of the following mixed or not using the catalyst: hydrochloric acid with mass concentration of 36%, sulfuric acid, Nafion resin, Amberlyst resin and ZnCl₂、AlCl₃(ii) a The ratio of the mass of the catalyst to the mass of the reaction substrate solution is between 0.01 and 20 percent;

in the fifth reaction, the catalyst for the hydrogenation reaction is one or more than two of the following catalysts: supported metal catalyst, transition metal carbide and/or nitride catalyst, Raney nickel catalyst, amorphous alloy catalyst; wherein, the supported metal catalyst takes one or a mixture of more than two of active carbon, mesoporous carbon, silicon oxide, aluminum oxide, cerium oxide and titanium oxide as a carrier, and loads one or more than two of metals of Pt, Pd, Ru, Ir, Ni, Co and Cu; wherein the metal content in the supported catalyst is between 0.1 and 30 percent; the ratio of the mass of the catalyst for the hydrogenation reaction to the mass of the reaction substrate solution is between 0.1 and 20 percent.

9. The method of claim 8, wherein:

firstly, the solvent for the reaction of preparing the hydroxycyclopentenone from the furfuryl alcohol solution is water or the mixture of water and one or more than two of the following solvents: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide; the reaction for preparing the hydroxy cyclopentenone from the furfuryl alcohol solution is carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is highThe temperature is between 160 ℃ and 250 ℃; the mass concentration of the furfuryl alcohol is 0.1-10%; when a kettle type reactor is adopted, the reaction time is between 0.01h and 0.5 h; when a fixed bed reactor is adopted, the mass space velocity is 1h^-1-100h^-1To (c) to (d);

in the second reaction, the hydrogenation reaction of the hydroxy cyclopentenone adopts one or more than two of the following solvents: water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide; the hydrogenation reaction of the hydroxyl cyclopentenone can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 0 and 160 ℃; the hydrogen pressure is between 1MPa and 5 MPa; wherein the mass concentration of the hydroxy cyclopentenone is 5-50%; when a kettle type reactor is adopted, the reaction time is between 0.1h and 2 h; when a fixed bed reactor is adopted, the mass space velocity is 1h^-1-10h^-1To (c) to (d); the molar ratio of the hydrogen to the reaction raw material is 2-1500;

and step three, catalyzing the dehydration reaction of the 1, 3-cyclopentanediol by adopting one or more of the following solvents: water, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, cyclohexane and tridecane; the catalytic dehydration reaction of the 1, 3-cyclopentanediol can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 180 and 350 ℃; wherein the mass concentration of the 1, 3-cyclopentanediol is 0.1-10%; when a kettle type reactor is adopted, the reaction time is between 0.1h and 12 h; when a fixed bed reactor is adopted, the mass space velocity is 0.1h^-1-10h^-1To (c) to (d);

reaction IV, cyclopentadiene D-A reaction can be carried out without solvent or by adopting one or more of the following solvents: water, benzene, toluene, benzyl alcohol, decalin, cyclohexane, n-heptane, n-hexane; wherein the mass concentration of the cyclopentadiene is 10-100 percent; the reaction temperature is between 0 and 170 ℃; the cyclopentadiene D-A reaction can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 0 and 170 ℃; when a kettle type reactor is adopted, the reaction time is between 0.1h and 10 h; when a fixed bed reactor is adopted, the mass space velocity is 0.2h^-1-10h^-1To (c) to (d);

in the reaction V, the hydrogenation reaction of the dicyclopentadiene does not need a solvent, or one or more than two of the following solvents are mixed: water, dichloromethane, dichloroethane, chloroform, benzene, toluene, benzyl alcohol, decalin, cyclohexane, n-heptane, n-hexane; the hydrogenation reaction of dicyclopentadiene can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 0 and 160 ℃; the hydrogen pressure is between 0.1MPa and 4 MPa; wherein the mass concentration of the bridge dicyclopentadiene is 10-90%; when a kettle type reactor is adopted, the reaction time is between 1h and 12 h; when a fixed bed reactor is adopted, the volume space velocity is 1h^-1-10h^-1The molar ratio of the hydrogen to the reaction raw material is 2-150;

reaction VI, the isomerization reaction of the bridged tetrahydrodicyclopentadiene can be carried out without a solvent or by adopting one or more than two of the following solvents: water, dichloromethane, dichloroethane, chloroform, benzene, toluene, benzyl alcohol, decalin, cyclohexane, n-heptane, n-hexane; the isomerization reaction of the bridge type tetrahydro dicyclopentadiene can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 100 and 220 ℃; wherein the mass concentration of the bridge type tetrahydro dicyclopentadiene is 20-100 percent; when a kettle type reactor is adopted, the reaction time is between 2h and 24 h; when a fixed bed reactor is adopted, the volume space velocity is 0.1h^-1-10h^-1To (c) to (d);

each of the first to sixth reactions is carried out in a reaction vessel or a fixed bed reactor separately, or two or more of them are carried out simultaneously in a reaction vessel or a fixed bed reactor.