CN104130097B - Process for continuously preparing exo-tetrahydrodicyclopentadiene in liquid phase - Google Patents

Abstract

The invention discloses a process for continuously preparing exo-tetrahydrodicyclopentadiene in a liquid phase, which effectively connects hydrogenation and isomerization in series, omits a catalyst separation process and realizes the continuous and efficient production of exo-tetrahydrodicyclopentadiene. The process comprises the following steps: 1) adopting a circulating continuous flow bubbling hydrogenation reactor with a catalyst self-separation function, wherein a dicyclopentadiene solution and hydrogen continuously flow in through a lower opening of the hydrogenation reactor and flow upwards in a parallel manner, a hydrogenation catalyst circularly flows along with the solution, the catalyst is separated from a hydrogenation liquid at an outlet, and the hydrogenation liquid enters the next working procedure through overflow; 2) the hydrogenation liquid continuously flows into a kettle type isomerization reactor, Lewis acid is used for catalyzing isomerization, the isomerization catalyst and the product are efficiently separated through a filtering device at the upper opening of the isomerization reactor, and the subsequent separation and refining procedures such as water washing, rectification and the like are carried out to obtain the hanging type tetrahydro dicyclopentadiene. The process is clean and low in consumption, and is an efficient method for preparing the exo-tetrahydrodicyclopentadiene.

Description

A kind of liquid-phase continuous preparation process of hanging tetrahydrodicyclopentadiene

(1) Technical field

The invention relates to a process for continuously preparing hanging tetrahydrodicyclopentadiene in liquid phase.

(2) Background technology

Hanging tetrahydrodicyclopentadiene (exo-THDCPD) has a density of 0.934g/cm ³ , a net heat of combustion of 39.6MJ/L, and has the advantages of low freezing point (-79°C) and low flash point (55°C), It is a high-density liquid hydrocarbon fuel and high-viscosity fuel diluent (J.Org.Chem., 1986, 51:5410-5413) with excellent performance, and has been widely used in high-performance cruise missiles, supersonic aircraft and rockets Propellants, etc. (J. Mol. Catal. A-Chem., 2005, 231:161-167). Hanging tetrahydrodicyclopentadiene is also a fine chemical intermediate, which can be used in the synthesis of adamantane (Appl.Catal.A., 2000, 203:127-132).

The synthesis of pendant tetrahydrodicyclopentadiene usually includes a two-step reaction (shown in formula 1): that is, catalytic hydrogenation of dicyclopentadiene to obtain bridged tetrahydrodicyclopentadiene (endo-THDCPD), endo-THDCPD Exo-THDCPD was obtained by catalytic isomerization (EnergyFuel., 1999, 13:641-649).

There are many catalytic systems for the hydrogenation process of hanging tetrahydrodicyclopentadiene. Conventional ones have supported nickel and other noble metal catalysts (Chemical New Materials, 1995, 9:20-24), and new catalysts include ionic liquids. The cost of the supported nickel catalyst system is low and the technology is mature, but there are problems such as high hydrogenation pressure, high reaction temperature, and poor reusability; the performance of ionic liquid catalysis is high, but the preparation is complicated, storage is difficult, and industrialization is difficult (petrochemical, 2002,31(5):345-348); Loaded gold catalysts can also be used for the hydrogenation process of hanging tetrahydrodicyclopentadiene, but the catalyst preparation technology requirements are high, and the hydrogenation process needs high pressure (GreenChem., 2012, 14:976-983). Noble metal palladium and platinum catalysts have high activity and good selectivity, can be hydrogenated at normal temperature and pressure, and can effectively avoid common coking or carbon deposition under high temperature and high pressure conditions, and are efficient for continuous flow hydrogenation of dicyclopentadiene catalyst.

During the isomerization of endo-THDCPD to prepare exo-THDCPD, concentrated H ₂ SO ₄ was the first catalyst used. However, the catalytic efficiency of concentrated H ₂ SO ₄ is low, and it is easy to cause coking and serious corrosion (US3381046). The Lewis acid AlCl ₃ catalyst has high catalytic activity and good selectivity, and has gradually replaced concentrated H ₂ SO ₄ to become the most widely used catalyst in industrial production (US4086284, US4086286, US4270014). However, AlCl ₃ also has corrosion problems, so some studies use solid-supported AlCl ₃ . After it is immobilized, not only the catalytic performance is improved, but also the separation is simple, and the acid water produced by post-treatment is greatly reduced (CN101130471). Acidic mesoporous molecular sieve catalysts and ionic liquid catalysts are also used in the process of isomerization of endo-THDCPD to prepare exo-THDCPD (GreenChem., 2007, 9:589-593; Fuel, 2012:164-169). However, the reaction temperature catalyzed by molecular sieves (including modified molecular sieves) is high (180-200° C.), and the energy consumption is high; the preparation cost of ionic liquid catalysts is high and storage is difficult. Therefore, these two types of catalysts have certain difficulties in the industrial application of isomerization reactions.

The traditional two-step synthesis of hanging-type tetrahydrodicyclopentadiene adopts kettle type and batch operation, and the intermediate needs to be separated and purified, resulting in low production capacity, large catalyst loss, troublesome post-treatment, and poor production economy. In order to solve the problems existing in the batch reaction, it is necessary to explore the continuous preparation method of hanging tetrahydrodicyclopentadiene by connecting the hydrogenation and isomerization reactions in series. Xi'an Modern Research Institute discloses a method for continuously preparing hanging tetrahydrodicyclopentadiene in the gas phase. The method uses a fixed-bed tubular reactor to realize hydrogenation and isomerization through gas-solid contact catalytic reaction, and continuously prepares Hanging tetrahydrodicyclopentadiene (EnergyFuels., 2013, 27(11):6339-6347). This process has realized the continuous production of hanging tetrahydrodicyclopentadiene, but the reaction temperature is high (160°C), the hydrogenation pressure is high (0.5-4Mpa is required), the product selectivity is general (70%), and the equipment requirements Strict, increased production costs.

Problems in the continuous production process of hanging tetrahydrodicyclopentadiene. The present invention provides a liquid-phase continuous method for preparing pendant tetrahydrodicyclopentadiene. After stable operation, the yield reaches over 90%. Among them, in the hydrogenation reaction, a circulating continuous flow bubbling hydrogenation reactor with catalyst self-separation function is designed, and the catalyst and hydrogenation liquid are automatically separated in the reactor, realizing the continuous hydrogenation process; using high activity The supported palladium and platinum catalysts enable the continuous flow hydrogenation process to be realized at normal temperature and pressure. The isomerization process adopts a continuous flow tank reactor, using Lewis acid and loaded Lewis acid as catalysts, and the efficient separation of catalyst and solution is realized through the outlet filter device; the two processes are effectively connected in series, eliminating the catalyst separation process, and the operation process is simple , low equipment investment, and realizes the continuous and efficient production of hanging tetrahydrodicyclopentadiene.

(3) Contents of the invention

The technical problem to be solved by the present invention is to overcome the technical deficiencies in the background, and discloses a liquid-phase continuous preparation process for hanging tetrahydrodicyclopentadiene, which effectively connects hydrogenation and isomerization reactions in series, eliminating the need for catalyst separation The process and the operation process are simple, and the equipment investment is low, and the continuous and efficient production of hanging tetrahydrodicyclopentadiene is realized. And designed a circulating continuous flow bubbling hydrogenation reactor and a continuous flow tank isomerization reactor with the function of catalyst self-separation.

The invention provides a kind of technical process of liquid phase continuous production hanging type tetrahydrodicyclopentadiene, and its synthetic steps are:

1) A circulating bubbling continuous flow hydrogenation reactor with catalyst self-separation function is adopted. The dicyclopentadiene solution and hydrogen flow continuously through the lower port and flow upwards. The hydrogenation catalyst circulates with the solution. At the outlet, the catalyst Separated from the hydrogenation liquid, the hydrogenation liquid enters the next process through overflow;

2) The hydrogenation liquid continuously flows into the kettle-type isomerization reactor, under the action of Lewis acid, catalyzes isomerization, and is separated from the catalyst through an upper filter device, and enters subsequent separation and refining processes such as water washing and rectification to obtain Hanging tetrahydrodicyclopentadiene.

The described process flow is a series connection of hydrogenation and isomerization processes, and the process device includes a sampling pump, a hydrogen generating device, a nitrogen generating device, a circulating bubbling hydrogenation reactor, a continuous flow tank type isomerization reactor, and Separation devices such as water washing and rectification can be connected to the existing reaction process. Among them, the hydrogenation and isomerization reactor is a jacketed reactor, which adopts an external circulation heating method to make the heating uniform. The top expansion structure of the bubbling hydrogenation reactor design reduces the gas velocity, which is conducive to the static precipitation of the catalyst and realizes self-separation. The hydrogenation liquid enters the next process through the two-stage overflow of the clear liquid.

The solvent of described dicyclopentadiene solution is pentane, hexane, octane, hexanaphthene, chloroform, methylene chloride or two or more mixed solutions, and the mol ratio of dicyclopentadiene to solvent is: 1 : 5-100.

The hydrogenation catalyst is a supported Pd, Pt catalyst or Pd-Cu, Pd-Ni bimetallic catalyst supported by C, Al ₂ O ₃ , SiO ₂ , Al ₂ O ₃ -SiO ₂ , wherein Pd or Pt accounts for The mass percent content of the hydrogenation catalyst is 0.5%-10%.

In the step 1), the hydrogen pressure in the bubbling hydrogenator is normal pressure to 0.5MPa, the temperature is 20°C to 80°C, the hydrogen flow rate is 50ml/min to 500ml/min, and the liquid injection rate is 0.2m1 /min～15ml/min.

The isomerization catalyst is Lewis acid: AlCl ₃ , ZnCl ₂ ; supported Lewis acid: AlCl ₃ /SiO ₂ , AlCl ₃ /γ-Al ₂ O ₃ , AlCl ₃ /Al ₂ O ₃ -SiO ₂ , ZnCl ₂ /γ -Al ₂ O ₃ , ZnCl ₂ /SiO ₂ , ZnCl ₂ /Al ₂ O ₃ -SiO ₂ ; supported B acid: H ₃ PO ₄ /SiO ₂ , H ₂ SO ₄ /SiO ₂ .

In the step 2), the continuous flow tank type isomerization reactor has a reaction temperature of 20° C. to 120° C. and a stirring speed of 100 rpm to 1000 rpm.

The process flow can be followed by connecting water washing to remove acid, static separation, solvent distillation, rectification and other separation and refining devices to obtain high-purity hanging tetrahydrodicyclopentadiene, and bridge tetrahydrodicyclopentadiene obtained by rectification Circulate back to the continuous flow tank type isomerization reactor to continue conversion, and recover the reaction solvent.

The advantages of this process are:

1. In the present invention, the liquid-phase continuous and efficient production of hanging tetrahydrodicyclopentadiene is realized. Compared with the traditional tank reaction, the production capacity is larger, the efficiency is faster, the catalyst consumption is less, and the energy consumption is lower. ; Compared with the gas phase continuous process, the reaction temperature is low, the pressure is small, and the product selectivity is high.

2. In the present invention, in the designed continuous flow bubbling hydrogenation reactor, the catalyst and the hydrogenation liquid are self-separated and circulated back to the reactor through the outlet, and the hydrogenation liquid enters the next process through the two-stage overflow of the clear liquid. The continuous use is realized, and the loss of the catalyst is avoided; the hydrogenation reaction conditions are mild, and the reaction is normal temperature and pressure, which effectively avoids carbon deposition and coking, and greatly prolongs the life of the catalyst.

3. In the present invention, the hydrogenation liquid continuously flows into the continuous flow tank type isomerization reactor, which reduces the catalyst separation process and solvent separation process, simplifies the reaction process, improves efficiency and reduces cost.

4. In the continuous-flow still-type isomerization reactor, the separation of the catalyst and the reaction liquid is realized through filtration at the outlet, and the isomerization liquid enters subsequent separation and refining processes such as water washing and rectification to obtain hanging tetrahydrodicyclopentadiene. The loss of catalyst and the water consumption in the washing process are reduced, and the process is more environmentally friendly.

5. In the hydrogenation project, the conversion rate of dicyclopentadiene: 100%, the selectivity of bridged tetrahydrodicyclopentadiene: 98.5%, and the hydrogenation catalyst runs stably for 200 hours.

6. During the isomerization process, the conversion rate of bridged tetrahydrodicyclopentadiene: 98.5%, and the selectivity of hanging tetrahydrodicyclopentadiene: 97.5%. The catalytic performance of the catalyst decreases with time. By adding Catalyst to achieve stable reaction.

7. When the two steps are carried out continuously, the conversion rate of dicyclopentadiene is 100%, and the selectivity of hanging tetrahydrodicyclopentadiene is 92%.

(4) Description of drawings:

Fig. 1 is the technological process schematic diagram of continuous preparation of hanging type tetrahydrodicyclopentadiene of the present invention, among the figure:

1-hydrogen generator, 2, 7-gas regulator valve, 3, 8-gas temperature flow valve, 4-hydrogen flow meter, 5, 10-one-way valve, 6-nitrogen cylinder, 11, 13-three-way valve , 12-convection pump, 14-liquid flow meter, 15-one-way valve, 16-drainage port, 17, 20-injection port, 18-air inlet, 19-hydrogenation liquid outlet, 21-isomerization product Outlet (built-in filter sand core device), 22, 23, 24, 25-insulation water inlet and outlet, 26-continuous flow bubbling hydrogenation reactor, 27-continuous flow kettle type isomerization reactor.

The reaction product can be purified through the post-processing device in the virtual frame: 28-washing acid removal device, 29-static separation device, 30-distillation device, 31-rectification device, 32-water inlet, 33-drain outlet, 34, 37 - condenser, 35, 38 - condensate storage tank, 36 - solvent recovery outlet, 39 - hanging tetrahydrodicyclopentadiene collection outlet, 40, 41 - tower kettle reboiler.

(5) Specific implementation methods:

The present invention will be described in further detail below in conjunction with accompanying drawing 1 and implementation examples, but these implementation examples do not limit the protection scope of the present invention.

Implementation case one:

(1) Add 150ml of dicyclopentadiene solution (0.25mol/L) to the bubble reactor 26, hydrogenation catalyst Pd/C1.0g, temperature 30°C, after being replaced by nitrogen, hydrogen is introduced at normal pressure , flow rate 60ml/min, reaction 4h, by gas chromatography analysis, the conversion rate of dicyclopentadiene reaches 100%, and the yield of bridged tetrahydrodicyclopentadiene reaches 99.5%;

(2) Convection pump 12 adds dicyclopentadiene solution in the bubble reactor 26 with a flow rate of 0.625ml/min, and feeds hydrogen to make dicyclopentadiene stay in the bubble reactor 26 on average Time is 4h, continuous flow reaction, after stabilization, through gas chromatography analysis, the productive rate of bridged tetrahydrodicyclopentadiene reaches 98.5%, reacts 200h, the conversion rate of raw material is stable at 100%, the productive rate of product is stable at 98.5% %.

Implementation case two:

(1) Add 150ml of dicyclopentadiene solution (1mol/L) in the bubble reactor 26, hydrogenation catalyst Pd/C1.0g, temperature 30°C, after nitrogen replacement, normal pressure feed hydrogen, The flow rate is 60ml/min, and the reaction is 4 hours. According to gas chromatography analysis, the conversion rate of dicyclopentadiene reaches 100%, and the yield of bridged tetrahydrodicyclopentadiene reaches 99.5%;

(2) Convection pump 12 adds dicyclopentadiene solution in the bubble reactor 26 with a flow rate of 0.625ml/min, and feeds hydrogen to make dicyclopentadiene stay in the bubble reactor 26 on average Time is 4h, continuous flow reaction, after stabilization, through gas chromatography analysis, the productive rate of bridged tetrahydrodicyclopentadiene reaches 98.2%, reacts 200h, the conversion rate of raw material is stable at 100%, the productive rate of product is stable at 98.2% %.

Implementation case three:

(1) Add 75ml of bridged tetrahydrodicyclopentadiene solution (0.25mol/L) to continuous flow tank reactor 27, 1.0g of isomerization catalyst AlCl ₃ , react at 70°C for 2h, analyze by gas chromatography, bridged The conversion rate of tetrahydrodicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98%;

(2) Advection pump 12 adds the bridged tetrahydrodicyclopentadiene solution into the tank reactor 27 with a flow rate of 0.625ml/min, so that the bridged tetrahydrodicyclopentadiene has an average residence time of 2h in 27 and flows continuously Reaction, after stabilization, gas chromatographic analysis, the conversion rate of bridge type tetrahydrodicyclopentadiene reaches 98%, the productive rate of hanging type tetrahydrodicyclopentadiene reaches 98%, and catalyst prolongs with time, and catalytic performance reduces to some extent, By adding the catalyst, the reaction proceeds stably, the conversion rate of the bridged tetrahydrodicyclopentadiene is stable at 98%, and the yield of the hanging tetrahydrodicyclopentadiene is stable at 98%.

Implementation case four:

(1) Add 75ml bridged tetrahydrodicyclopentadiene solution (1mol/L) into the continuous flow tank reactor 27, isomerization catalyst AlCl ₃ 1.0g, temperature 70°C, react for 2h, analyze by gas chromatography, bridged The conversion rate of tetrahydrodicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98%;

(2) Advection pump 12 adds the bridged tetrahydrodicyclopentadiene solution into the tank reactor 27 with a flow rate of 0.625ml/min, so that the bridged tetrahydrodicyclopentadiene has an average residence time of 2h in 27 and flows continuously Reaction, after stabilization, gas chromatographic analysis, the conversion rate of bridge type tetrahydrodicyclopentadiene reaches 97.3%, the productive rate of hanging type tetrahydrodicyclopentadiene reaches 96%, and catalyst prolongs with time, and catalytic performance reduces to some extent, By adding the catalyst, the reaction proceeds stably, the conversion rate of the bridged tetrahydrodicyclopentadiene is stable at 97.3%, and the yield of the hanging tetrahydrodicyclopentadiene is stable at 96%.

Implementation case five:

(1) Add 150ml of dicyclopentadiene solution (0.25mol/L) into the bubble reactor 26, hydrogenation catalyst Pd/C1.0g, normal pressure, temperature 30°C, after nitrogen replacement, feed hydrogen The flow rate is 60ml/min, the reaction is 4h, the composition is analyzed by gas chromatography, the conversion rate of dicyclopentadiene reaches 100%, and the yield of bridged tetrahydrodicyclopentadiene reaches 99.5%;

(2) Add 75ml bridged tetrahydrodicyclopentadiene solution (0.25mol/L) to the reactor of continuous flow tank type 27, AlCl ₃ 1.0g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridged tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 to 1.8ml/min, and injected into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The average residence time of dicyclopentadiene in 26 is 4h, the hydrogenation liquid flows out through the product outlet 19, enters the continuous flow isomerization kettle 27 through the inlet 20, and the hanging tetrahydrodicyclopentadiene product solution passes through the outlet 21 The outflow is analyzed regularly by gas chromatography. When the yield of hanging tetrahydrodicyclopentadiene decreases, an appropriate amount of AlCl ₃ is added. After stabilization, the yield of hanging tetrahydrodicyclopentadiene is 96%.

Implementation case six:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pd/C1.0g, normal pressure, temperature 30°C, after nitrogen replacement, feed hydrogen The flow rate is 60ml/min, the reaction is 4h, the composition is analyzed by gas chromatography, the conversion rate of dicyclopentadiene reaches 100%, and the yield of bridged tetrahydrodicyclopentadiene reaches 99.5%;

(2) Add 75ml bridged tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow tank reactor 27, AlCl ₃ 2.0g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridged tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98.3%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the advection pump 12 controls the flow rate of the above-mentioned dicyclopentadiene solution to 0.6ml/min, and injects it into the bubbling hydrogenation reactor 26 through the raw material inlet 17, The average residence time of dicyclopentadiene in the hydrogenation reactor 26 is 4 hours, and the hydrogenation product bridging tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and continuously enters the tank type isomerization reaction through the raw material inlet 20 Device 27, the hanging tetrahydrodicyclopentadiene product solution flows out through the discharge port 21, and the gas chromatography detects regularly. When the hanging tetrahydrodicyclopentadiene production rate decreases, add an appropriate amount of AlCl ₃ . The yield of hydrogen dicyclopentadiene was 94.7%.

Implementation case seven:

(1) Add 150ml of dicyclopentadiene solution (1.25mol/L) into the bubble reactor 26, hydrogenation catalyst Pd/C1.0g, normal pressure, temperature 30°C, after nitrogen replacement, feed hydrogen The flow rate is 60ml/min, the reaction is 6h, the composition is analyzed by gas chromatography, the conversion rate of dicyclopentadiene reaches 100%, and the yield of bridged tetrahydrodicyclopentadiene reaches 99.5%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (1.25mol/L) into the continuous flow tank type 27 reactor, AlCl ₃ 2.0g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridging tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and 12 advection pumps control the flow rate of the above-mentioned dicyclopentadiene solution at 0.36ml/min, and inject it into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The average residence time of dicyclopentadiene in 26 is 6h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow isomerization kettle 27 through the feed port 20, and the hanging tetrahydro The dicyclopentadiene product solution flows out through the outlet 21, and is regularly detected by gas chromatography. When the productive rate of the hanging tetrahydrodicyclopentadiene decreases, an appropriate amount _of AlCl is added. After stabilization, the productive rate of the hanging tetrahydrodicyclopentadiene 93.8%.

Implementation case eight:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pd/C1.0g, normal pressure, temperature 70°C, after nitrogen replacement, feed hydrogen The flow rate is 60ml/min, the reaction is 4h, the composition is analyzed by gas chromatography, the conversion rate of dicyclopentadiene reaches 100%, and the yield of bridged tetrahydrodicyclopentadiene reaches 99.5%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow tank type 27 reactor, AlCl ₃ 1.0g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridging tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The average residence time of dicyclopentadiene in 26 is 4h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor 27 through the inlet 20, and the hanging type Tetrahydrodicyclopentadiene product solution flows out through outlet 21, and gas chromatography detects regularly, and when hanging type tetrahydrodicyclopentadiene productive rate reduces, add appropriate amount of AlCl ₃ , after stabilization, the production rate of hanging type tetrahydrodicyclopentadiene The rate is 96.1%.

Implementation Case Nine:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pd/C1.0g, normal pressure, temperature 70°C, after nitrogen replacement, feed hydrogen The flow rate is 60ml/min, the reaction is 4h, the composition is analyzed by gas chromatography, the conversion rate of dicyclopentadiene reaches 100%, and the yield of bridged tetrahydrodicyclopentadiene reaches 99.5%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow tank type 27 reactor, AlCl ₃ 1.0g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridging tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and 12 advection pumps control the flow rate of the above-mentioned dicyclopentadiene solution at 0.6ml/min, and inject it into the bubbling hydrogenation reactor 26 through 17 raw material inlets, so that The average residence time of dicyclopentadiene in 26 is 4h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor 27 through the inlet 20, and the hanging type Tetrahydrodicyclopentadiene product solution flows out through outlet 21, detects regularly through gas chromatography, when hanging type tetrahydrodicyclopentadiene productive rate reduces, add appropriate amount of AlCl ₃ , after stabilization, the hanging type tetrahydrodicyclopentadiene Yield 95.4%.

Implementation Case Ten:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pd/Al ₂ O ₃ 1.0g, normal pressure, temperature 70°C, after nitrogen replacement, The flow rate of hydrogen was 60ml/min, the reaction was 4h, the composition was analyzed by gas chromatography, the conversion rate of dicyclopentadiene reached 100%, and the yield of bridged tetrahydrodicyclopentadiene reached 99.5%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow tank type 27 reactor, AlCl ₃ 1.0g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridging tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the 17 raw material inlet, so that The average residence time of dicyclopentadiene in 26 is 4h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor 27 through the inlet 20, and the hanging type Tetrahydrodicyclopentadiene product solution flows out through outlet 21, detects regularly through gas chromatography, when hanging type tetrahydrodicyclopentadiene productive rate reduces, add appropriate amount of AlCl ₃ , after stabilization, the hanging type tetrahydrodicyclopentadiene Yield 95.7%.

Implementation Case Eleven:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pt/Al ₂ O ₃ 1.0g, normal pressure, temperature 70°C, after nitrogen replacement, The flow rate of hydrogen was 60ml/min, the reaction was 4h, the composition was analyzed by gas chromatography, the conversion rate of dicyclopentadiene reached 100%, and the yield of bridged tetrahydrodicyclopentadiene reached 99.5%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow tank type 27 reactor, AlCl ₃ 1g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridging tetrahydro The conversion rate of dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98.3%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The average residence time of dicyclopentadiene in 26 is 4h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor 27 through the inlet 20, and the hanging type Tetrahydrodicyclopentadiene product solution flows out through outlet 21, detects regularly through gas chromatography, when hanging type tetrahydrodicyclopentadiene productive rate reduces, add appropriate amount of AlCl ₃ , after stabilization, the hanging type tetrahydrodicyclopentadiene Yield 96.1%.

Implementation Case Twelve:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pd/Al ₂ O ₃ 1.0g, normal pressure, temperature 70°C, after nitrogen replacement, The flow rate of hydrogen was 120ml/min, the reaction was 4h, the composition was analyzed by gas chromatography, the conversion rate of dicyclopentadiene reached 100%, and the yield of bridged tetrahydrodicyclopentadiene reached 99.5%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow tank type 27 reactor, AlCl ₃ 1.0g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridging tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98.2%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The average residence time of dicyclopentadiene in 26 is 4h, and the hydrogenation product bridge tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor through the inlet 20, and the hanging type four The hydrogen dicyclopentadiene product solution flows out through the outlet 21, and is regularly detected by gas chromatography. When the hanging tetrahydrodicyclopentadiene production rate decreases, an appropriate amount _of AlCl is added. After stabilization, the production of the hanging tetrahydrodicyclopentadiene The rate is 95.9%.

Implementation Case Thirteen:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pd/Al ₂ O ₃ 1.0g, normal pressure, temperature 70°C, after nitrogen replacement, The flow rate of hydrogen was 240ml/min, the reaction was 4h, and the composition was analyzed by gas chromatography, the conversion rate of dicyclopentadiene reached 100%, and the yield of bridged tetrahydrodicyclopentadiene reached 99.5%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow tank type 27 reactor, AlCl ₃ 1g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridging tetrahydro The conversion rate of dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The residence time of dicyclopentadiene in 26 is 4h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor 27 through the inlet 20, and the hanging type four The hydrogen dicyclopentadiene product solution flows out through the outlet 21, and is regularly detected by gas chromatography. When the hanging tetrahydrodicyclopentadiene production rate decreases, an appropriate amount _of AlCl is added. After stabilization, the production of the hanging tetrahydrodicyclopentadiene The rate is 95.5%.

Implementation Case Fourteen:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pd/Al ₂ O ₃ 1.0g, normal pressure, temperature 70°C, after nitrogen replacement, The flow rate of hydrogen was 60ml/min, the reaction was 4h, the composition was analyzed by gas chromatography, the conversion rate of dicyclopentadiene reached 100%, and the yield of bridged tetrahydrodicyclopentadiene reached 99.5%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow tank type 27 reactor, AlCl ₃ 1.0g, temperature 50°C, react for 2h, analyze the composition by gas chromatography, bridging tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 80.2%, and the yield of hanging tetrahydrodicyclopentadiene reaches 71.3%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The residence time of dicyclopentadiene in 26 is 4h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor 27 through the inlet 20, and the hanging type four The hydrogen dicyclopentadiene product solution flows out through the outlet 21, and is regularly detected by gas chromatography. When the hanging tetrahydrodicyclopentadiene production rate decreases, an appropriate amount _of AlCl is added. After stabilization, the production of the hanging tetrahydrodicyclopentadiene rate of 68%.

Implementation Case 15:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pd/Al ₂ O ₃ 1.0g, normal pressure, temperature 70°C, after nitrogen replacement, The flow rate of hydrogen was 60ml/min, the reaction was 4h, the composition was analyzed by gas chromatography, the conversion rate of dicyclopentadiene reached 100%, and the yield of bridged tetrahydrodicyclopentadiene reached 99.5%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L), AlCl ₃ /Al ₂ O ₃ 1.0g to the continuous flow tank type 27 reactor, react for 2h at a temperature of 20°C, and analyze by gas chromatography Composition, the conversion rate of bridged tetrahydrodicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98.4%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The residence time of dicyclopentadiene in 26 is 4h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor 27 through the inlet 20, and the hanging type four The hydrogen dicyclopentadiene product solution flows out through the outlet 21, and is regularly detected by gas chromatography. When the yield of the hanging tetrahydrodicyclopentadiene decreases, an appropriate amount of AlCl ₃ /Al ₂ O ₃ is added. After stabilization, the hanging tetrahydrobicyclopentadiene The yield of pentadiene was 96.9%.

Implementation Case Sixteen:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pd/Al ₂ O ₃ 1.0g, normal pressure, temperature 70°C, nitrogen replacement, pass The hydrogen flow rate was 60ml/min, the reaction was 4h, and the composition was analyzed by gas chromatography. The conversion rate of dicyclopentadiene reached 100%, and the yield of bridged tetrahydrodicyclopentadiene reached 99.5%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L), 1.0g of AlCl ₃ /Al ₂ O ₃ , and react for 2 hours at a temperature of 50°C, and analyze by gas chromatography Composition, the conversion rate of bridged tetrahydrodicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 90%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The residence time of dicyclopentadiene in 26 is 4h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor 27 through the inlet 20, and the hanging type four The hydrogen dicyclopentadiene product solution flows out through the outlet 21, and is regularly detected by gas chromatography. When the yield of the hanging tetrahydrodicyclopentadiene decreases, an appropriate amount of AlCl ₃ /Al ₂ O ₃ is added. After stabilization, the hanging tetrahydrobicyclopentadiene The yield of pentadiene was 88.4%.

Implementation Case Seventeen:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pt/Al ₂ O ₃ 1.5g, normal pressure, temperature 70°C, after nitrogen replacement, The flow rate of hydrogen was 60ml/min, the reaction was 4h, the composition was analyzed by gas chromatography, the conversion rate of dicyclopentadiene reached 100%, and the yield of bridged tetrahydrodicyclopentadiene reached 99.3%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow kettle type 27 reactor, AlCl ₃ 1.5g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridging tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the 17 raw material inlet, so that The residence time of dicyclopentadiene in 26 is 4h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor 27 through the inlet 20, and the hanging type four The hydrogen dicyclopentadiene product solution flows out through the outlet 21, and is regularly detected by gas chromatography. When the hanging tetrahydrodicyclopentadiene production rate decreases, an appropriate amount _of AlCl is added. After stabilization, the production of the hanging tetrahydrodicyclopentadiene The rate is 96.5%.

Implementation Case Eighteen:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pt/Al ₂ O ₃ 1.5g, normal pressure, temperature 70°C, after nitrogen replacement, The flow rate of hydrogen was 60ml/min, the reaction was 4h, the composition was analyzed by gas chromatography, the conversion rate of dicyclopentadiene reached 100%, and the yield of bridged tetrahydrodicyclopentadiene reached 99.3%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow kettle type 27 reactor, AlCl ₃ 1.5g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridging tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98.1%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The residence time of dicyclopentadiene in 26 is 4h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor 27 through the inlet 20, and the hanging type four The hydrogen dicyclopentadiene product solution flows out through the outlet 21, and is regularly detected by gas chromatography. When the hanging tetrahydrodicyclopentadiene production rate decreases, an appropriate amount _of AlCl is added. After stabilization, the production of the hanging tetrahydrodicyclopentadiene The rate is 94.6%.

Implementation Case Nineteen:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) to the bubble reactor 26, hydrogenation catalyst Pt/C1.5g, normal pressure, temperature 70°C, after nitrogen replacement, feed hydrogen The flow rate is 300ml/min, the reaction is 3.5h, the composition is analyzed by gas chromatography, the conversion rate of dicyclopentadiene reaches 100%, and the yield of bridged tetrahydrodicyclopentadiene reaches 99.6%;

(2) Add 75ml of bridged tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow tank type 27 reactor, AlCl ₃ 1.5g, temperature 70°C, react for 4h, analyze the composition by gas chromatography, bridged tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98.1%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The residence time of dicyclopentadiene in 26 is 4h, and the hydrogenated product bridging tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor through the inlet 20, and the hanging tetrahydro The dicyclopentadiene product solution flows out through the outlet 21, and is regularly detected by gas chromatography. When the productive rate of the hanging tetrahydrodicyclopentadiene decreases, an appropriate amount _of AlCl is added. After stabilization, the productive rate of the hanging tetrahydrodicyclopentadiene 94.5%.

Implementation case twenty:

(1) Add 150ml of dicyclopentadiene solution (0.75mol/L) into the bubble reactor 26, hydrogenation catalyst Pt/Al ₂ O ₃ 0.5g, normal pressure, temperature 40°C, after nitrogen replacement, The flow rate of hydrogen was 60ml/min, the reaction was 4h, the composition was analyzed by gas chromatography, the conversion rate of dicyclopentadiene reached 100%, and the yield of bridged tetrahydrodicyclopentadiene reached 99.2%;

(2) Add 75ml of bridging tetrahydrodicyclopentadiene solution (0.75mol/L) to the continuous flow kettle type 27 reactor, AlCl ₃ 1.5g, temperature 70°C, react for 2h, analyze the composition by gas chromatography, bridging tetrahydrodicyclopentadiene The conversion rate of hydrogen dicyclopentadiene reaches 100%, and the yield of hanging tetrahydrodicyclopentadiene reaches 98%;

(3) After the above-mentioned two-step reaction is balanced, two reactors are connected in series, and the flow rate of the above-mentioned dicyclopentadiene solution is controlled by the advection pump 12 at 0.6ml/min, and injected into the bubbling hydrogenation reactor 26 through the raw material inlet 17, so that The residence time of dicyclopentadiene in 26 is 6h, and the hydrogenation product bridged tetrahydrodicyclopentadiene solution flows out through the product outlet 19, and enters the continuous flow tank type isomerization reactor 27 through the inlet 20, and the hanging type four The hydrogen dicyclopentadiene product solution flows out through the outlet 21, and is regularly detected by gas chromatography. When the hanging tetrahydrodicyclopentadiene production rate decreases, an appropriate amount _of AlCl is added. After stabilization, the production of the hanging tetrahydrodicyclopentadiene The rate is 94.5%.

In the above-mentioned implementation cases, the hydrogenation catalyst can be continuously operated for more than 500 hours without changing the activity, and the activity of the isomerization catalyst is gradually reduced, and the activity can be recovered through regular supplementation. The bubbling hydrogenation reactor can be used alone to continuously prepare bridged tetrahydrodicyclopentadiene; or the continuous flow tank isomerization reactor can be used alone to continuously convert bridged tetrahydrodicyclopentadiene into hanging tetrahydro Dicyclopentadiene; the hydrogenation reactor and the isomerization reactor can be effectively used in series to realize the continuous preparation of hanging tetrahydrodicyclopentadiene in liquid phase. The process of continuous flow preparation of hanging tetrahydrodicyclopentadiene can also be followed by adding water washing, distillation and rectification devices in the virtual frame to complete product refining, solvent recovery and recycling of unconverted raw materials.

Claims (4)

1. a liquid phase produces the method for hanging type tetrahydrochysene dicyclopentadiene continuously, it is characterised in that hydrogenation and isomerization reaction is effectively connected, saves catalyst separating operation, it is achieved the high-efficiency and continuous of hanging type tetrahydrochysene dicyclopentadiene is produced, and comprises the following steps:

1) the circulation formula Continuous Flow bubbling hydrogenator with catalyzer self-separation function is adopted, dicyclopentadiene solution and hydrogen mouth under hydrogenator continuously flows into, upwards and flow, hydrogenation catalyst flows with solution circulated, in exit, catalyzer is separated with hydrogenation liquid, and hydrogenation liquid enters subsequent processing by overflow;

2) hydrogenation liquid continuously flows into, under Lewis acid effect, and isoversion, and through isomerizing reactor filtration unit suitable for reading, with catalyst separating, enter follow-up washing, rectifying separation, refining step, obtain hanging type tetrahydrochysene dicyclopentadiene;

Wherein, technical process is hydrogenation and the series connection of different structure operation, this process unit comprises sampling pump, hydrogen formation apparatus, nitrogen gas generating device, circulation formula bubbling hydrogenator, Continuous Flow autoclave isomerizing reactor, also comprises and is linked in reaction flow process by washing, the separation of rectifying, refining plant; Wherein, hydrogenation and isomerizing reactor are chuck type reactor, adopt external circulation heating mode, make homogeneous heating; Structure is expanded at the top of bubbling hydrogenator design, gas speed is reduced, is conducive to catalyzer to leave standstill precipitation, it is achieved self-separation, and hydrogenation liquid enters subsequent processing by the two sections of overflows of clear liquid; Described step 1) in, in bubbling style hydrotreater, hydrogen pressure is normal pressure��0.5MPa, and temperature is 20 DEG C��80 DEG C, and hydrogen flow rate is 50ml/min��500ml/min, and Liquid sample introduction speed is 0.2m1/min��15ml/min; Described step 2) in, in autoclave isomerizing reactor, temperature of reaction is 20 DEG C��120 DEG C, and mixing speed is 100rpm��1000rpm, and isomerization catalyst is Lewis acid: AlCl3, ZnCl2; Loading type Lewis acid: AlCl3/SiO2, AlCl3/ ��-Al2O3, AlCl3/Al2O3-SiO2, ZnCl2/ ��-Al2O3, ZnCl2/SiO2, ZnCl2/Al2O3-SiO2.

2. method according to claim 1, it is characterized in that: the solvent of described dicyclopentadiene solution is pentane, hexane, octane, one or more mixed solution in hexanaphthene, chloroform, methylene dichloride, the mol ratio of dicyclopentadiene and solvent is: 1:2��100.

3. method according to claim 1, it is characterised in that: described hydrogenation catalyst is with C, Al₂O₃��SiO₂��Al₂O₃-SiO₂For the loading type Pd of carrier, Pt catalyzer or Pd-Cu, Pd-Ni bimetallic catalyst, wherein Pd or Pt accounts for the mass percentage of described hydrogenation catalyst is 0.5%��10%.

4. method according to claim 1, it is characterized in that: technical process is follow-up also comprises washing except acid, standing separation, solvent distills, rectifying is at interior separation, refining plant, obtaining high purity hanging type tetrahydrochysene dicyclopentadiene, the bridge-type tetrahydro-dicyclopentadiene that rectifying obtains loops back Continuous Flow autoclave isomerizing reactor to be continued to transform.