CN117342921A - Method for preparing adamantane from dicyclopentadiene - Google Patents
Method for preparing adamantane from dicyclopentadiene Download PDFInfo
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 36
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 33
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 13
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 20
- 229910000510 noble metal Inorganic materials 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- -1 preferably HY Chemical compound 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000006004 Quartz sand Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00539—Pressure
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing adamantane from dicyclopentadiene, which comprises the following steps: firstly, dicyclopentadiene and a reaction solvent are uniformly mixed and then flow in from the upper end of a fixed bed reactor, and the lower end of the fixed bed reactor flows out; in a fixed bed reactor, the upper section is filled with a hydrogenation catalyst, the middle is separated by an inert material, the lower section is filled with an isomerization catalyst, the hydrogenation conversion of dicyclopentadiene into bridge-type tetrahydrodicyclopentadiene is completed through the hydrogenation catalyst of the upper section, and the bridge-type tetrahydrodicyclopentadiene can be converted into adamantane through the isomerization catalyst of the lower section. The method can be implemented in one reactor to directly convert dicyclopentadiene into adamantane, and the hydrogenation process and the isomerization process are coupled, so that the process flow is simplified, and the device investment is reduced.
Description
Technical Field
The invention relates to a preparation method of hydrocarbon fine chemicals, in particular to a preparation method of adamantane.
Background
Adamantane (ADH) is a highly symmetrical polycyclic cage hydrocarbon compound of formula C 10 H 16 The catalyst has the characteristics of high density, good thermal stability, fat solubility and the like, and hydrogen atoms on the ring can undergo substitution reaction and oxidation reaction such as halogenation reaction, nitration reaction, sulfonation reaction and the like, so that the catalyst has very wide application in the fields of drug intermediate synthesis, novel material development, preparation of lubricating oil and high-density liquid fuel and the like.
At present, raw materials for synthesizing adamantane are dicyclopentadiene (DCPD), and the synthesis process mainly comprises two parts, wherein the two parts comprise that the dicyclopentadiene is hydrogenated to prepare bridge-type tetrahydrodicyclopentadiene (Endo-THDCPD), then the bridge-type tetrahydrodicyclopentadiene is subjected to deep isomerization to prepare the adamantane, and a shallow isomerization product of the bridge-type tetrahydrodicyclopentadiene (Exo-THDCPD) is also generated in the process.
These two processes are often carried out separately, the former using hydrogenation catalysts such as Raney nickel and the like and are typically carried out in batch reaction units; the latter is carried out with isomerisation catalysts such as aluminium trichloride or the like and is generally also carried out in batch reaction units. The isomerization process using aluminum trichloride as a catalyst also has the problems of heavy pollution, more post-treatment steps, incapability of recycling the catalyst and large tar generation amount, so that the whole process is complex in process, long in flow and high in production cost, and the development trend of green and low-carbon chemical industry in the future cannot be met.
The reaction mechanism for preparing adamantane is acid-catalyzed carbonium ion reaction, acid is needed as a catalyst, olefin intermediates are also generated in the reaction process, and the olefin intermediates easily generate excessive tar byproducts under the action of stronger acid catalysis and form competition reaction with the generation of adamantane, so that the adamantane has low selectivity and serious material loss; when the acid strength is insufficient or the reaction conditions are too mild, the generation of adamantane can not be promoted, so that the product mainly comprises a shallow isomerism product of hanging tetrahydrodicyclopentadiene, and the selectivity of adamantane is also lower.
The article "synthesis of adamantane on PW/USY composite catalyst, higher chemical engineering report, 2007,127-132." the PW/USY catalyst loaded with 10% phosphotungstic acid is used for isomerization of Endo-THDCPD into adamantane, 28.3% yield is obtained, but the reaction is carried out in a reaction kettle, carbon deposition is on the surface of PW/USY catalyst after each reaction, high-temperature roasting regeneration is needed, regeneration is frequent, and continuous production capability is not needed, so that a proper catalyst and a matched process are needed to be developed for the molecular sieve isomerization process.
Disclosure of Invention
The invention aims at solving the problems of complex whole process, long process and high investment caused by the fact that the prior industrial production of adamantane by dicyclopentadiene mainly consists of two independent processes of hydrogenation and isomerization, and AlCl is adopted in the isomerization process 3 The method for directly preparing adamantane by dicyclopentadiene in a fixed bed reactor is provided for the problems of incapability of continuous production, serious pollution and complex post-treatment caused by the catalyst.
The invention provides a method for preparing adamantane from dicyclopentadiene, which comprises the following steps: after evenly mixing dicyclopentadiene and a reaction solvent, flowing in from the upper end of a fixed bed reactor, carrying out hydrogenation and isomerization serial reaction, and flowing out a product from the lower end to obtain adamantane; in a fixed bed reactor, the upper section is filled with a hydrogenation catalyst, and the lower section is filled with an isomerization catalyst, wherein the upper reaction temperature is 60-180 ℃, preferably 80-160 ℃, more preferably 100-140 ℃; the lower reaction temperature is 181-300 deg.c, preferably 200-260 deg.c.
The reacted material is further separated into hanging tetrahydrodicyclopentadiene and a reaction solvent, adamantane concentrated solution can be obtained, adamantane crude product can be obtained by cooling and crystallization, adamantane product with higher purity can be obtained by recrystallization, and the separated hanging tetrahydrodicyclopentadiene and reaction solvent can be recycled, so that the atom utilization rate is high.
The dicyclopentadiene may be prepared in various ways as disclosed in the prior art, and is also commercially available.
Wherein the reaction pressure of the whole fixed bed is 0.5MPa-5MPa, preferably 1.0MPa-3.0MPa; the mass space velocity is 0.2h -1 -5h -1 Preferably 0.5h -1 -2h -1 The hydrogen-hydrocarbon volume ratio is 200-3200, preferably 600-1200.
The hydrogenation catalyst is a traditional supported metal hydrogenation catalyst, the active metal is one or more of noble metal Pt, pd, rh, ru, non-noble metal Ni and the like, and the carrier is non-acidic carrier, such as Al 2 O 3 、 SiO 2 、TiO 2 、ZrO 2 、CeO 2 Activated carbon. Based on the total mass of the hydrogenation catalyst, the loading of the non-noble metal is 1% -40%, preferably 5% -30%, and the loading of the noble metal is 0.1% -10%, preferably 0.3% -3%.
The isomerization catalyst is a molecular sieve supported metal catalyst, and the active metal is one or more of noble metal Pd, pt, ru, rh and non-noble metal Ni, preferably Pt and Pd; the molecular sieve is a Y-type molecular sieve, such as HY, USY, REHY, NEY, SSY, etc., preferably HY, USY, REHY. Based on the total mass of the isomerization catalyst, the loading of the non-noble metal is 1% -15%, preferably 3% -10%; the loading of noble metal is 0.05% -5%, preferably 0.1% -1%.
The molecular sieve supported metal catalyst may be prepared according to conventional methods, such as an isovolumetric impregnation method, an excess volumetric impregnation method, etc. During the specific preparation, a certain amount of metal precursor solution is prepared according to the metal loading amount, then is immersed on a molecular sieve, is kept stand for more than 6 hours at normal temperature, is accompanied by intermittent stirring in the process, is dried for more than 12 hours at 80-120 ℃, and is calcined for 2-5 hours at 450-550 ℃ in air atmosphere. And (3) reducing the calcined catalyst in a reducing atmosphere such as hydrogen at 400-550 ℃ for 2-5 h to obtain the activated catalyst.
The reaction solvent is a solvent with a boiling point of 40-300 ℃, such as cyclohexane, methylcyclohexane, methylene dichloride and the like, preferably C6-C10 hydrocarbons, such as cyclohexane and methylcyclohexane; after the dicyclopentadiene is mixed with the reaction solvent, the mass concentration of the dicyclopentadiene is 10% -50%, preferably 10% -30%.
According to the method, the traditional process of preparing adamantane by hydrogenation and isomerism of dicyclopentadiene is integrated in a fixed bed reactor, and the two sections of reaction conditions are identical except for different reaction temperatures, so that the adamantane is continuously prepared in the fixed bed reactor, the whole process flow is simplified, the conversion rate can reach 100%, the adamantane selectivity can reach 16%, and the system can stably operate for a long period.
Detailed Description
The invention provides a continuous method for preparing adamantane, which comprises the following steps: in a fixed bed reactor, the upper section is filled with a traditional hydrogenation catalyst, the middle is separated by inert material quartz sand, the lower section is filled with an isomerization catalyst, dicyclopentadiene and a reaction solvent are uniformly mixed and then are added into the fixed bed reactor, and the dicyclopentadiene is continuously converted into adamantane through hydrogenation of the upper section and isomerization of the lower section.
Wherein the upper reaction temperature is 60-180 ℃, the lower reaction temperature is 181-300 ℃, the reaction pressure of the whole fixed bed is 0.5-5 MPa, and the mass airspeed is 0.2h -1 -5h -1 The hydrogen-hydrocarbon volume ratio is 200-3200.
The inert material may be selected from SiO 2 、Al 2 O 3 Carbon material, quartz sand, etc., preferably quartz sand.
According to the invention, dicyclopentadiene and reaction solvent are premixed uniformly in a feed tank and pumped to the top of a fixed bed reactor, and then reaction products flow out from the lower end of the fixed bed. After the system was stable for 20h, the samples were collected for gas chromatography to calculate the reactant conversion and product selectivity.
Specific embodiments of the present invention are further described below with reference to examples.
In the following examples, dicyclopentadiene is purchased from Beijing enoki technologies Co.
In the following examples, quartz sand was filled between the hydrogenation section and the isomerization section as an inert material.
Examples 1 to 7 (influence of different isomerization catalysts)
Taking methylcyclohexane solution containing 20wt% of dicyclopentadiene as a raw material; in 20wt% Ni/SiO 2 The catalyst is a hydrogenation catalyst, and the reaction temperature of a hydrogenation section is 100 ℃; the reaction temperature of the isomerism section is 220 ℃, the reaction pressure of the whole fixed bed is 1MPa, and the mass airspeed is 1h -1 The hydrogen to hydrocarbon volume ratio was 1000 and the effect of different isomerization catalysts was examined. The results are shown in Table 1.
TABLE 1
Examples 8 to 13 (influence of different reaction temperatures)
Taking methylcyclohexane solution containing 20wt% of dicyclopentadiene as a raw material; in 20wt% Ni/SiO 2 As hydrogenation catalyst, 0.3% Pt/REHY is used as isomerization catalyst; the reaction pressure of the whole fixed bed is 1MPa, and the mass airspeed is 1h -1 The hydrogen-hydrocarbon volume ratio was 1000, and the effect of the reaction temperature was examined. The results are shown in Table 2.
TABLE 2
Examples 14 to 17 (influence of different reaction pressures)
Taking methylcyclohexane solution containing 20wt% of dicyclopentadiene as a raw material; in 20wt% Ni/SiO 2 As hydrogenation catalyst, 0.3% PtREHY is an isomerization catalyst; the temperature of the hydrogenation section is 100 ℃, the temperature of the isomerization section is 220 ℃, and the mass airspeed is 1h -1 The hydrogen-hydrocarbon volume ratio was 1000, and the effect of the reaction pressure was examined. The results are shown in Table 3.
TABLE 3 Table 3
Examples 18 to 21 (Effect of different mass space velocities)
Taking methylcyclohexane solution containing 20wt% of dicyclopentadiene as a raw material; in 3wt% Pd/SiO 2 As hydrogenation catalyst, 0.3% Pt/REHY is used as isomerization catalyst; the hydrogenation section temperature is 100 ℃, the isomerization section temperature is 220 ℃, the reaction pressure of the whole fixed bed is 1MPa, the hydrogen-hydrocarbon volume ratio is 1000, and the influence of mass airspeed is examined. The results are shown in Table 4.
TABLE 4 Table 4
Examples 22 to 24 (influence of different hydrogen-hydrocarbon volume ratios)
Taking methylcyclohexane solution containing 20wt% of dicyclopentadiene as a raw material; in 0.5wt% Pd/SiO 2 As hydrogenation catalyst, 0.3% Pt/REHY is used as isomerization catalyst; the hydrogenation section temperature is 100 ℃, the isomerization section temperature is 220 ℃, the reaction pressure of the whole fixed bed is 1MPa, and the mass airspeed is 1h -1 The effect of the hydrogen to hydrocarbon volume ratio was examined. The results are shown in Table 5.
TABLE 5
Examples 25 to 29 (influence of different solvents and solvent ratios)
Preparing a 20wt% dicyclopentadiene reaction solution by taking methylcyclohexane, cyclohexane, dichloromethane and isopropanol as reaction solvents; then methyl cyclohexane is used as a reaction solvent to prepareDicyclopentadiene reaction solutions of different concentrations; in 10wt% Ni/SiO 2 As hydrogenation catalyst, 0.3% Pt/REHY is used as isomerization catalyst; the hydrogenation section temperature is 100 ℃, the isomerization section temperature is 220 ℃, the reaction pressure of the whole fixed bed is 1MPa, and the mass airspeed is 1h -1 The hydrogen-hydrocarbon volume ratio was 1000, and the influence of different solvents and solvent ratios was examined. The results are shown in Table 6.
TABLE 6
Example 30
Example 1 was run for a period of 100 hours and sampled every 20 hours for analysis to investigate the stability of the system and the life of the catalyst. The results are shown in Table 7.
TABLE 7
Claims (11)
1. A process for preparing adamantane from dicyclopentadiene comprising: after evenly mixing dicyclopentadiene and a reaction solvent, flowing in from the upper end of a fixed bed reactor, carrying out hydrogenation and isomerization serial reaction, and flowing out a product from the lower end to obtain adamantane; in the fixed bed reactor, the upper section is filled with hydrogenation catalyst, the lower section is filled with isomerization catalyst, wherein the upper section reaction temperature is 60-180 ℃, and the lower section reaction temperature is 181-300 ℃.
2. The process according to claim 1, wherein the upper reaction temperature is from 100 ℃ to 160 ℃; the reaction temperature of the lower section is 200-260 ℃.
3. The process according to claim 1, wherein the fixed bed reaction pressure is from 0.5MPa to 5MPa, preferably from 1.0MPa to 3.0MPa.
4. The method according to claim 1Wherein, in the fixed bed reactor, the mass space velocity is 0.2h -1 -5h -1 Preferably 0.5h -1 -2h -1 。
5. The process according to claim 1, wherein the hydrogen-hydrocarbon volume ratio in the fixed bed reactor is from 200 to 3200, preferably from 600 to 1200.
6. The process according to claim 1, wherein the active metal of the hydrogenation catalyst is one or more selected from noble metal Pt, pd, rh, ru and non-noble metal Ni, and the carrier is a non-acidic carrier, preferably Al 2 O 3 、SiO 2 、TiO 2 、ZrO 2 、CeO 2 Activated carbon.
7. The process according to claim 1, wherein the loading of non-noble metal is from 1% to 40%, preferably from 5% to 30% based on the total mass of the hydrogenation catalyst; the loading of noble metal is 0.1% -10%, preferably 0.3% -3%.
8. The method of claim 1, wherein the active metal of the isomerization catalyst is selected from one or more of noble metal Pd, pt, ru, rh and non-noble metal Ni; the molecular sieve is a Y-type molecular sieve, preferably HY, USY, REHY.
9. The process according to claim 8, wherein the loading of non-noble metal is from 1% to 15%, preferably from 3% to 10% based on the total mass of isomerisation catalyst; the loading of noble metal is 0.05% -5%, preferably 0.1% -1%.
10. The process according to claim 1, wherein the reaction solvent is a solvent having a boiling point of 40 ℃ to 300 ℃, preferably a C6-C10 hydrocarbon such as cyclohexane, methylcyclohexane.
11. The process according to claim 1, wherein the concentration of dicyclopentadiene after mixing with the reaction solvent is from 10% to 50% by mass, preferably from 10% to 30% by mass.
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