CN104130097B - The technique of a kind of liquid phase continuous production hanging type tetrahydrochysene dicyclopentadiene - Google Patents
The technique of a kind of liquid phase continuous production hanging type tetrahydrochysene dicyclopentadiene Download PDFInfo
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Abstract
The present invention discloses the technique of a kind of liquid phase continuous production hanging type tetrahydrochysene dicyclopentadiene, hydrogenation and different structure is effectively connected, saves catalyst separating operation, it is achieved the continuous high-efficient of hanging type tetrahydrochysene dicyclopentadiene is produced. Technique comprises: 1) adopt the circulation formula Continuous Flow bubbling hydrogenator with catalyzer self-separation function, 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 in autoclave isomerizing reactor, Lewis acid catalytic isomerization, through isomerizing reactor filtration unit suitable for reading, it is achieved the high efficiency separation of heterogeneous catalyst and product, and enter separation, the refining steps such as follow-up washing, rectifying, obtain hanging type tetrahydrochysene dicyclopentadiene. This technique is cleaning, low consumption, is a kind of high efficiency method preparing hanging type tetrahydrochysene dicyclopentadiene.
Description
(1) technical field
The present invention relates to the technique of a kind of liquid phase continuous production hanging type tetrahydrochysene dicyclopentadiene.
(2) background technology
Hanging type tetrahydrochysene dicyclopentadiene (exo-THDCPD), density is 0.934g/cm3Net heat of combustion is 39.6MJ/L, there is low freezing point (-79 DEG C), the advantages such as low flash-point (55 DEG C) are high density liquid hydrocarbon fuel and high viscosity fuel dilution agent (J.Org.Chem., 1986 of a kind of excellent property, 51:5410-5413), (J.Mol.Catal.A-Chem., 2005,231:161-167) such as the propelling agents being now widely used in high-performance cruise missile, supersonic plane and rocket. Hanging type tetrahydrochysene dicyclopentadiene is also a kind of fine-chemical intermediate, can be used for the synthesis (Appl.Catal.A., 2000,203:127-132) of diamantane.
The synthesis of hanging type tetrahydrochysene dicyclopentadiene generally includes two-step reaction (shown in formula one): namely dicyclopentadiene shortening obtains bridge-type tetrahydro-dicyclopentadiene (endo-THDCPD), endo-THDCPD obtains exo-THDCPD (EnergyFuel. through catalytic isomerization, 1999,13:641-649).
The hydrogenation process of hanging type tetrahydrochysene dicyclopentadiene has many catalyst system, and conventional has load-type nickel and other noble metal catalyst (the new section bar of chemical industry, 1995,9:20-24), and new catalyst then has ionic liquid etc. The problems such as the cost of load-type nickel catalyst system is low, technology maturation, but it is big to there is hydrogenation pressure, temperature of reaction height, reusability difference; Ionic liquid-catalyzed performance height, but preparation is complicated, preserves difficulty, industrialization difficulty big (petrochemical complex, 2002,31 (5): 345-348);Load gold catalyst also can be used for the hydrogenation process of hanging type tetrahydrochysene dicyclopentadiene, but catalyst preparation technology requires high, and hydrogenation process needs high pressure (GreenChem., 2012,14:976-983). Precious metal palladium, platinum catalyst activity height, selectivity are good, can hydrogenation at normal temperatures and pressures, and common coking or long-pending carbon under effectively avoiding high temperature, condition of high voltage are the effective catalysts of dicyclopentadiene Continuous Flow hydrogenation.
Prepare in the process of exo-THDCPD in endo-THDCPD isomerization, dense H2SO4It it is the catalyzer used the earliest. But dense H2SO4Catalytic efficiency is low, easily cause coking, seriously corroded (US3381046). And Lewis acid AlCl3Catalytic activity height, the selectivity of catalyzer are good, progressively replace dense H at present2SO4Become the most widely used catalyzer of industrial production (US4086284, US4086286, US4270014). But AlCl3Also there is corrosion problems, some researchs adopt immobilized AlCl for this reason3. After it is immobilized, not only catalytic performance increases, and the sour water that its separation is simple, aftertreatment produces greatly reduces (CNl01130471). Acid mesoporous molecular sieve catalyst and ionic-liquid catalyst also endo-THDCPD isomerization prepare exo-THDCPD process in obtain application (GreenChem., 2007,9:589-593; Fuel, 2012:164-169). But the temperature of reaction height (180-200 DEG C) of catalysis that molecular sieve (comprises modified molecular screen), energy consumption height; The preparation cost height of ionic-liquid catalyst, not easily preserve. Therefore there is certain difficulty in this two classes catalyzer in the industrial application of isomerization reaction.
Conventional two-step synthetizing wall type tetrahydro-dicyclopentadiene adopts autoclave, periodical operation, and intermediate needs separation to purify, and causes throughput low, and catalyst attrition is big, and aftertreatment bothers, and production economy is poor. For solving rhythmic reaction Problems existing, by hydrogenation, isomerization reaction series connection, the method exploring continuous production hanging type tetrahydrochysene dicyclopentadiene is very necessary. A kind of method of gas phase continuous production hanging type tetrahydrochysene dicyclopentadiene disclosed in the recent studies of Xi'an, the method adopts fixed-bed tube reactor, reacted by gas-solid contact catalysis, realize hydrogenation and isomate process, continuous production hanging type tetrahydrochysene dicyclopentadiene (EnergyFuels., 2013,27 (11): 6339-6347). This technique achieves the continuous production of hanging type tetrahydrochysene dicyclopentadiene, but temperature of reaction height (160 DEG C), hydrogenation pressure big (needing 0.5��4Mpa), product selectivity general (70%), and, equipment requirements is strict, it is to increase production cost.
For Problems existing in the continuous flow procedure of hanging type tetrahydrochysene dicyclopentadiene. Providing a kind of method of liquid phase continuous production hanging type tetrahydrochysene dicyclopentadiene in the present invention, after steady running, product rate reaches more than 90%. Wherein, in hydrogenation reaction, devising the circulation formula Continuous Flow bubbling hydrogenator with catalyzer self-separation function, catalyzer is separated in reactor automatically with hydrogenation liquid, it is achieved that the serialization of hydrogenation process; Adopt supported palladium, the platinum group catalyst of high reactivity, Continuous Flow hydrogenation process is realized at normal temperatures and pressures. Isomerization process adopts Continuous Flow tank reactor, sour as catalyzer taking Lewis acid and load Lewis, is realized the high efficiency separation of catalyzer and solution by egress filtering device; Two processes effectively being connected, save catalyst separating operation, operating process is simple, and facility investment is low, it is achieved that the continuous high-efficient of hanging type tetrahydrochysene dicyclopentadiene is produced.
(3) summary of the invention
Technical problem to be solved by this invention overcomes in background the technical deficiency existed, disclose the technical process of a kind of liquid phase continuous production hanging type tetrahydrochysene dicyclopentadiene, hydrogenation and isomerization reaction are effectively connected, save catalyst separating operation, operating process is simple, facility investment is low, it is achieved that the continuous high-efficient of hanging type tetrahydrochysene dicyclopentadiene is produced. And devise the circulation formula Continuous Flow bubbling hydrogenator and Continuous Flow autoclave isomerizing reactor with catalyzer self-separation function.
The present invention provides the technical process that a kind of liquid phase produces hanging type tetrahydrochysene dicyclopentadiene continuously, and its synthesis step is:
1) the circulation formula bubbling Continuous Flow hydrogenator with catalyzer self-separation function is adopted, dicyclopentadiene solution and hydrogen continuously flow into through lower mouth, 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 in autoclave isomerizing reactor, under Lewis acid effect, and isoversion, and through filtration unit suitable for reading, with catalyst separating, enter separation, the refining steps such as follow-up washing, rectifying, obtain hanging type tetrahydrochysene dicyclopentadiene.
Described technical process is hydrogenation and the series connection of isomerization operation, and this process unit comprises sampling pump, hydrogen formation apparatus, nitrogen gas generating device, circulation formula bubbling hydrogenator, Continuous Flow autoclave isomerizing reactor, it is possible to the tripping device such as washing, rectifying is accessed existing reaction flow process. 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, hydrogenation liquid enters subsequent processing by the two sections of overflows of clear liquid.
The solvent of described dicyclopentadiene solution is pentane, hexane, octane, and the mol ratio of hexanaphthene, chloroform, methylene dichloride or two or more mixed solutions, dicyclopentadiene and solvent is: 1:5��100.
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%.
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.
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; Loading type B acid: H3PO4/SiO2,H2SO4/SiO2��
Described step 2) in, Continuous Flow autoclave isomerizing reactor, temperature of reaction is 20 DEG C��120 DEG C, and mixing speed is 100rpm��1000rpm.
Described technical process is follow-up can connect washing except acid, standing separation, solvent distills, the separation such as rectifying, refining plant, obtain high purity hanging type tetrahydrochysene dicyclopentadiene, the bridge-type tetrahydro-dicyclopentadiene that rectifying obtains loops back Continuous Flow autoclave isomerization reactor to be continued to transform, and reaction solvent reclaims.
The advantage part of this technique is:
1. in the present invention, it is achieved that the liquid phase continuous high-efficient of hanging type tetrahydrochysene dicyclopentadiene is produced, compared to traditional still reaction, throughput is bigger, and efficiency is faster, and catalyst levels is less, and energy consumption is lower; Low compared to gas phase continuous processing temperature of reaction, pressure is little, product selectivity height.
2. in the present invention, the Continuous Flow bubbling style hydrogenator of design, catalyzer and hydrogenation liquid are circulated back to reactor through exit self-separation, and hydrogenation liquid enters subsequent processing by the two sections of overflows of clear liquid, has both achieved continuous use, turn avoid the loss of catalyzer;Hydrogenation conditions is gentle, is normal temperature and pressure reaction, effectively prevent long-pending carbon and coking, and catalyst life lengthens greatly.
3. in the present invention, hydrogenation liquid continuously flows in Continuous Flow autoclave isomerization reactor, decreases catalyst separating operation, and separated from solvent operation simplifies reaction process flow process, it is to increase efficiency, reduces costs.
4., in Continuous Flow autoclave isomerizing reactor, filter through exit, it is achieved that catalyzer is separated with reaction solution, different structure liquid enters separation, the refining steps such as follow-up washing, rectifying, obtaining hanging type tetrahydrochysene dicyclopentadiene, reduce the loss of catalyzer and the water consumption of washing step, flow process is environmental protection more.
5. in hydrogenation engineering, dicyclopentadiene transformation efficiency: 100%, bridge-type tetrahydro-dicyclopentadiene selectivity: 98.5%, hydrogenation catalyst steady running 200h.
6., in isomate process, the transformation efficiency of bridge-type tetrahydro-dicyclopentadiene: 98.5%, hanging type tetrahydrochysene dicyclopentadiene selectivity: 97.5%, catalyzer extends in time, and catalytic performance decreases, by adding catalyzer, it is achieved stable reaction carries out.
7., when a liang step carries out continuously, dicyclopentadiene transformation efficiency: 100%, the selectivity of hanging type tetrahydrochysene dicyclopentadiene is: 92%.
(4) accompanying drawing illustrates:
Fig. 1 is the process flow diagram of continuous production hanging type tetrahydrochysene dicyclopentadiene of the present invention, in figure:
1-hydrogen generator, 2,7-gas pressure maintaining valve, 3,8-gas temperature stream valve, 4-hydrogen stream gauge, 5,10-one-way valve, 6-nitrogengas cylinder, 11,13-T-valve, 12-constant-flux pump, 14-liquid meter, 15-one-way valve, 16-discharge opeing mouth, 17,20-injection port, 18-inlet mouth, 19-hydrogenation liquid exports, 21-isomerized products outlet (built-in filtration core device), 22,23,24,25-is incubated water entrance, 26-Continuous Flow bubbling hydrogenator, 27-Continuous Flow autoclave isomerizing reactor.
Reaction product can be passed through in empty frame after-treatment device and purifies: 28-washes deacidification device, 29-standing separation device, 30-water distilling apparatus, 31-rectifier unit, 32-water-in, 33-water port, 34,37-condenser, 35, the cool lime set storage tank of 38-, 36-solvent recuperation exports, 39-hanging type tetrahydrochysene dicyclopentadiene collects outlet, and 40,41-tower reactor reboiler.
(5) embodiment:
Below in conjunction with accompanying drawing 1 and case study on implementation, the present invention is described in further details, but these case study on implementation do not limit the scope of the invention.
Case study on implementation one:
(1) bubbling style reactor 26 adds the dicyclopentadiene solution (0.25mol/L) of 150ml, hydrogenation catalyst Pd/C1.0g, temperature 30 DEG C, after nitrogen is replaced, normal pressure leads to into hydrogen, flow velocity 60ml/min, reaction 4h, through gas chromatographic analysis, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) dicyclopentadiene solution is added in bubbling style reactor 26 with 0.625ml/min flow by constant-flux pump 12, lead to into hydrogen, dicyclopentadiene mean residence time in bubbling style reactor 26 is made to be 4h, continuous flow is reacted, after stable, through gas chromatographic analysis, the product rate of bridge-type tetrahydro-dicyclopentadiene reaches 98.5%, reaction 200h, the transformation efficiency of raw material is stabilized in 100%, and the product rate of product is stabilized in 98.5%.
Case study on implementation two:
(1) bubbling style reactor 26 adds the dicyclopentadiene solution (1mol/L) of 150ml, hydrogenation catalyst Pd/C1.0g, temperature 30 DEG C, after nitrogen is replaced, normal pressure leads to into hydrogen, flow velocity 60ml/min, reaction 4h, through gas chromatographic analysis, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) dicyclopentadiene solution is added in bubbling style reactor 26 with 0.625ml/min flow by constant-flux pump 12, lead to into hydrogen, dicyclopentadiene mean residence time in bubbling style reactor 26 is made to be 4h, continuous flow is reacted, after stable, through gas chromatographic analysis, the product rate of bridge-type tetrahydro-dicyclopentadiene reaches 98.2%, reaction 200h, the transformation efficiency of raw material is stabilized in 100%, and the product rate of product is stabilized in 98.2%.
Case study on implementation three:
(1) Continuous Flow tank reactor 27 adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.25mol/L), heterogeneous catalyst AlCl31.0g, temperature 70 DEG C, reaction 2h, gas chromatographic analysis, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98%;
(2) bridge-type tetrahydro-dicyclopentadiene solution is added in tank reactor 27 with 0.625ml/min flow by constant-flux pump 12, bridge-type tetrahydro-dicyclopentadiene mean residence time in 27 is made to be 2h, continuous flow is reacted, after stable, gas chromatographic analysis, the transformation efficiency of bridge-type tetrahydro-dicyclopentadiene reaches 98%, the product rate of hanging type tetrahydrochysene dicyclopentadiene reaches 98%, catalyzer extends in time, catalytic performance decreases, by adding catalyzer, stable reaction carries out, the transformation efficiency of bridge-type tetrahydro-dicyclopentadiene is stabilized in 98%, the product rate of hanging type tetrahydrochysene dicyclopentadiene is stabilized in 98%.
Case study on implementation four:
(1) Continuous Flow tank reactor 27 adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (1mol/L), heterogeneous catalyst AlCl31.0g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98%;
(2) bridge-type tetrahydro-dicyclopentadiene solution is added in tank reactor 27 with 0.625ml/min flow by constant-flux pump 12, bridge-type tetrahydro-dicyclopentadiene mean residence time in 27 is made to be 2h, continuous flow is reacted, after stable, gas chromatographic analysis, the transformation efficiency of bridge-type tetrahydro-dicyclopentadiene reaches 97.3%, the product rate of hanging type tetrahydrochysene dicyclopentadiene reaches 96%, catalyzer extends in time, catalytic performance decreases, by adding catalyzer, stable reaction carries out, the transformation efficiency of bridge-type tetrahydro-dicyclopentadiene is stabilized in 97.3%, the product rate of hanging type tetrahydrochysene dicyclopentadiene is stabilized in 96%.
Case study on implementation five:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.25mol/L), hydrogenation catalyst Pd/C1.0g, normal pressure, temperature 30 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 4h, through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.25mol/L), AlCl31.0g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 1.8ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene mean residence time in 26 is made to be 4h, hydrogenation liquid exports 19 outflows through product, the different structure still 27 of Continuous Flow is entered through injection port 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, gas-chromatography periodic analysis forms, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 96% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation six:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pd/C1.0g, normal pressure, temperature 30 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 4h, through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow tank reactor 27 adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl32.0g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98.3%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, , bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene mean residence time in hydrogenator 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, autoclave isomerization reactor 27 is entered continuously through feed(raw material)inlet 20, hanging type tetrahydrochysene dicyclopentadiene product solution flows out through discharge port 21, gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 94.7% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation seven:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (1.25mol/L), hydrogenation catalyst Pd/C1.0g, normal pressure, temperature 30 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 6h, gas chromatographic analysis forms, and dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (1.25mol/L), AlCl32.0g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98%;
(3) after above-mentioned two-step reaction balances, connect two reactors, 12 constant-flux pumps control above-mentioned dicyclopentadiene solution flow rate 0.36ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene mean residence time in 26 is made to be 6h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, the different structure still 27 of Continuous Flow is entered through opening for feed 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, adopt gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 93.8% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation eight:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pd/C1.0g, normal pressure, temperature 70 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 4h, through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl31.0g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene mean residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor 27 is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 96.1% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation nine:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pd/C1.0g, normal pressure, temperature 70 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 4h, through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl31.0g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98%;
(3) after above-mentioned two-step reaction balances, connect two reactors, 12 constant-flux pumps control above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through 17 feed(raw material)inlets, dicyclopentadiene mean residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor 27 is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 95.4% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation ten:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pd/Al2O31.0g, normal pressure, temperature 70 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 4h, and through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl31.0g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through 17 feed(raw material)inlets, dicyclopentadiene mean residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor 27 is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 95.7% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation 11:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pt/Al2O31.0g, normal pressure, temperature 70 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 4h, and through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl31g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98.3%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene mean residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor 27 is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 96.1% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation 12:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pd/Al2O31.0g, normal pressure, temperature 70 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 120ml/min, reaction 4h, and through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl31.0g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98.2%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene mean residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 95.9% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation 13:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pd/Al2O31.0g, normal pressure, temperature 70 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 240ml/min, reaction 4h, and through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl31g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor 27 is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 95.5% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation 14:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pd/Al2O31.0g, normal pressure, temperature 70 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 4h, and through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl31.0g, temperature 50 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 80.2%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 71.3%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor 27 is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 68% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation 15:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pd/Al2O31.0g, normal pressure, temperature 70 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 4h, and through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl3/Al2O31.0g, temperature 20 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98.4%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor 27 is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3/Al2O3, after stable, the product rate 96.9% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation 16:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pd/Al2O31.0g, normal pressure, temperature 70 DEG C, nitrogen leads to into hydrogen flow rate 60ml/min after replacing, reaction 4h, and through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.5%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl3/Al2O31.0g, temperature 50 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 90%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor 27 is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3/Al2O3, after stable, the product rate 88.4% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation 17:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pt/Al2O31.5g, normal pressure, temperature 70 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 4h, and through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.3%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl31.5g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through 17 feed(raw material)inlets, dicyclopentadiene residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor 27 is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 96.5% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation 18:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pt/Al2O31.5g, normal pressure, temperature 70 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 4h, and through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.3%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl31.5g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98.1%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor 27 is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 94.6% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation 19:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pt/C1.5g, normal pressure, temperature 70 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 300ml/min, reaction 3.5h, through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.6%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl31.5g, temperature 70 DEG C, reaction 4h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98.1%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene residence time in 26 is made to be 4h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 94.5% of hanging type tetrahydrochysene dicyclopentadiene.
Case study on implementation 20:
(1) bubbling style reactor 26 adds 150ml dicyclopentadiene solution (0.75mol/L), hydrogenation catalyst Pt/Al2O30.5g, normal pressure, temperature 40 DEG C, after nitrogen is replaced, leads to into hydrogen flow rate 60ml/min, reaction 4h, and through gas chromatographic analysis composition, dicyclopentadiene transformation efficiency reaches 100%, and bridge-type tetrahydro-dicyclopentadiene product rate reaches 99.2%;
(2) Continuous Flow autoclave 27 reactor adds 75ml bridge-type tetrahydro-dicyclopentadiene solution (0.75mol/L), AlCl31.5g, temperature 70 DEG C, reaction 2h, through gas chromatographic analysis composition, bridge-type tetrahydro-dicyclopentadiene transformation efficiency reaches 100%, and hanging type tetrahydrochysene dicyclopentadiene product rate reaches 98%;
(3) after above-mentioned two-step reaction balances, connect two reactors, constant-flux pump 12 controls above-mentioned dicyclopentadiene solution flow rate 0.6ml/min, bubbling style hydrogenator 26 is injected through feed(raw material)inlet 17, dicyclopentadiene residence time in 26 is made to be 6h, hydrogenation products bridge-type tetrahydro-dicyclopentadiene solution exports 19 outflows through product, Continuous Flow autoclave isomerization reactor 27 is entered through entrance 20, hanging type tetrahydrochysene dicyclopentadiene product solution is through exporting 21 outflows, through gas-chromatography periodic detection, when hanging type tetrahydrochysene dicyclopentadiene product rate reduces, add appropriate AlCl3, after stable, the product rate 94.5% of hanging type tetrahydrochysene dicyclopentadiene.
The above case study on implementation, hydrogenation catalyst can operate more than 500h continuously and activity remains unchanged, and isomerization catalyst activity slowly reduces, and by regularly adding, activity can be recovered. Bubbling style hydrogenator can be adopted separately, continuous production bridge-type tetrahydro-dicyclopentadiene; Or adopt separately Continuous Flow autoclave isomerizing reactor, continuously bridge-type tetrahydro-dicyclopentadiene is converted into hanging type tetrahydrochysene dicyclopentadiene; Hydrogenator and isomerization reactor can effectively be connected use, it is achieved liquid phase continuous production hanging type tetrahydrochysene dicyclopentadiene. Follow-up also can the increasing in empty frame of technique that Continuous Flow prepares hanging type tetrahydrochysene dicyclopentadiene is washed, and distillation, rectifier unit, completes product purification, and solvent recuperation and unconverted feedstock circulation utilize.
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.
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| CN107417485B (en) * | 2017-08-21 | 2020-08-21 | 大连理工大学 | Method for directly preparing exo-tetrahydrodicyclopentadiene from dicyclopentadiene |
| CN111662149B (en) * | 2019-03-07 | 2023-03-14 | 中国石油化工股份有限公司 | Method and device for continuously preparing bridge type dihydrodicyclopentadiene |
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