CN101130471A - Novel method for producing hanging type tetrahydrochysene dicyclopentadiene on solid acid catalyst - Google Patents
Novel method for producing hanging type tetrahydrochysene dicyclopentadiene on solid acid catalyst Download PDFInfo
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- CN101130471A CN101130471A CNA2007100125914A CN200710012591A CN101130471A CN 101130471 A CN101130471 A CN 101130471A CN A2007100125914 A CNA2007100125914 A CN A2007100125914A CN 200710012591 A CN200710012591 A CN 200710012591A CN 101130471 A CN101130471 A CN 101130471A
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- dicyclopentadiene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 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 18
- 239000011973 solid acid Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 4
- 239000012188 paraffin wax Substances 0.000 claims abstract description 3
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical class C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- 229910002796 Si–Al Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 5
- 239000000377 silicon dioxide Substances 0.000 abstract 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 description 7
- 230000009466 transformation Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- GUOAPVPPPVLIQQ-UHFFFAOYSA-N dimethyldicyclopentadiene Chemical compound C1=CC2CC1C1C2C(C)C(C)=C1 GUOAPVPPPVLIQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003407 synthetizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a new making method of hung tetrahydrochysene dicyclopentadiene on the solid acid catalyst, which comprises the following steps: making AlCl3 fixed on the dielectric or large-hole Al2O3, Al2O3-SiO2, alumina silica molecular sieve or SiO2 carrier to form the solid acid catalyst; reacting bridge tetrahydrochysene dicyclopentadiene as raw material as hydrogenation product of cyclopentadiene dipolymer as raw material to synthesize tetrahydrochysene dicyclopentadiene through isomerization reaction; adopting liquid-solid multi-phased stirring reaction pattern or fixed bed reaction pattern and C6-C10 straight-line paraffin or naphthene as solvent for isomerization reaction under 0. 1Mpa-1. 0Mpa in the N2 or H2 atmosphere at 0-100 deg. c; obtaining the hung tetrahydrochysene dicyclopentadiene with receiving rate over 99%. The invention doesn't request the reacting device with strong anti-corrosion ability, which needn't separating course of catalyst and product in the environment friendly catalyzing course.
Description
Technical field
The present invention relates to a kind of method of producing hanging type tetrahydrochysene dicyclopentadiene, more particularly, is a kind of method that adopts liquid-solid heterogeneous stirring reaction or fixed bed reaction mode to produce hanging type tetrahydrochysene dicyclopentadiene on solid acid catalyst.
Background technology
Hanging type tetrahydrochysene dicyclopentadiene (exo-TCD) is that a kind of important high-density can storage type hydrocarbon fuel, has density big (0.94g/ml), zero pour low (79 ℃) and combustion heat height (39.6GJm
-3) characteristics, compare with kerosene stock at present commonly used, exo-TCD can make the voyage of aircraft increase by 15%, is the ideal fuels (being JP-10 fuel) of modern novel hypersonic vehicle.Synthetic exo-TCD need realize by two step chemical reactions: the dimer of (1) cyclopentadiene complete hydrogenation under metal catalyst (as Raney Ni, Pt/C, Rh/C etc.) catalysis generates bridge-type tetrahydro-dicyclopentadiene (endo-TCD); (2) endo-TCD generates exo-TCD by isomerization reaction under the effect of Lewis acid catalyst.The catalyzer that uses in the second step isomerization reaction mainly is AlCl
3But this catalyzer can form complex compound with heavy constituent in isomerization reaction, can not recycle.Will correspondingly produce problems such as catalyzer and product separation difficulty and aftertreatment technology complexity like this.Adopt solid acid catalyst to replace traditional AlCl
3It is the effective way that addresses the above problem.
Zhang Xiangwen etc. (Journal of Molecular Catalysis A:Chemical 231 (2005) 161) have reported NH
4Y, NaY, ReY, NH
4-USY, NH
4-SSY, H-beta, HZSM-5 equimolecular sieve prepares catalytic activity in the exo-TCD reaction in the endo-TCD isomerization, wherein the H-USY effect is best, under 195 ℃ temperature of reaction, the endo-TCD transformation efficiency is 94.93%, the yield of exo-TCD is 89.69%, the yield of by product diamantane is 3.03%, and the investigator finds the aperture and the acid feed stock conversion and the product yield of influencing of molecular sieve.
Patent US4288644 discloses the method that a kind of solid acid catalysis bridge-type tetrahydro dimethyl dicyclopentadiene isomerization reaction generates hanging tetrahydrochysene dimethyl dicyclopentadiene.Solid acid catalyst is acidic alumina, activated carbon or the sial composite oxides of load Ni or Pd, the optimum load amount of Ni is 40wt%～90wt%, the optimum load amount of Pd is 0.25wt%～20wt%, and 125 ℃～350 ℃ of temperature of reaction are filled H in the reactive system
2Can suppress the generation of carbon distribution and polymkeric substance, improve catalyzer work-ing life.
Summary of the invention
The purpose of this invention is to provide a kind of novel method of on solid acid catalyst, making hanging type tetrahydrochysene dicyclopentadiene, with solid acid---immobilized AlCl
3Be catalyzer, the new technology of isoversion synthetizing wall type tetrahydro-dicyclopentadiene (exo-TCD), (endo-TCD) is raw material with bridge-type tetrahydro-dicyclopentadiene, adopts liquid-solid heterogeneous stirring reaction mode or fixed bed reaction mode to carry out.Product postprocessing is simple, and environment is not had negative impact.
Technical scheme of the present invention is, a kind of novel method of on solid acid catalyst, making hanging type tetrahydrochysene dicyclopentadiene, and this method is by the cycle pentadiene dimer hydrogenation products---the isomerization of bridge-type tetrahydro-dicyclopentadiene reaction, with immobilized AlCl
3As isomerization catalyst, isomerization reaction is carried out in liquid-solid heterogeneous stirred reactor or fixed-bed reactor, and temperature of reaction is 0 ℃～100 ℃, and reaction pressure is 0.1MPa～1.0MPa, N
2Or H
2Make protection gas, catalyst levels (in muriatic weight on the catalyzer) is 2～20% of a raw material bridge-type tetrahydro-dicyclopentadiene weight, and the optimum solvent consumption is 20～100 times of raw material bridge-type tetrahydro-dicyclopentadiene weight.Described immobilized AlCl
3Catalyzer is AlCl
3Realize supportedly by reacting with the carrier surface hydroxyl, charge capacity is the 3-30% of catalyst weight.Described immobilized AlCl
3Carrier in the catalyzer is the Al with mesoporous or macroporous structure
2O
3, Al
2O
3-SiO
2, Si-Al molecular sieve or SiO
2, solvent is with C
6～C
10Straight-chain paraffin or naphthenic hydrocarbon nonpolar organic matter.
The invention has the beneficial effects as follows that the yield of hanging type tetrahydrochysene dicyclopentadiene product is more than 99%.Therefore the catalyzer non-corrosiveness does not require that reaction unit possesses strong resistance to corrosion.Need not catalyzer and product sepn process after the reaction, environmentally safe, facility investment is few, and economy belongs to the environmental friendliness catalytic process.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
(1) Preparation of Catalyst
Fixed bed AlCl
3The 20mL high purity of packing in producer γ-Al
2O
3(spherical d=1.8-2.0mm) is heated to 500 ℃, feeds N respectively with the flow velocity of 40ml/min and 0.8-2.0mL/h
2And CCl
4, produce AlCl
3Steam; Fixed bed AlCl
3Pack in the immobilized reactor and have the γ-Al of meso-hole structure
2O
3(60-100 order) 5mL (3.08g) carries out dehydration fever at 500 ℃ earlier and handles 2h; At 40mL/min N
2The AlCl that produces of following of carrier band
3Add AlCl
3In the immobilized reactor, under 300 ℃, carry out AlCl
3Immobilized reaction, reaction times 3.0h uses N then under 400 ℃
2Purge 1h, it is standby after this to reduce to room temperature.Chloride content is 9.86% of a catalyst weight on the catalyzer.
(2) hanging type tetrahydrochysene dicyclopentadiene is synthetic
The isomerization reaction of synthetizing wall type tetrahydro-dicyclopentadiene (exo-TCD) is carried out in the intermittent type suspended-bed reactor, with the immobilized AlCl of 1mL (0.62g)
3Catalyzer, 20mL hexanaphthene and 0.5g bridge-type tetrahydro-dicyclopentadiene (endo-TCD) join in the there-necked flask that volume is 100mL successively, N
2Make protection gas.Adopt the water-bath control reaction temperature.Reaction times 10min.After reaction finishes,, adopt gc analysis with suction pipe sucking-off reaction solution.Endo-TCD transformation efficiency and exo-TCD yield the results are shown in Table 1 under the differential responses temperature.
AlCl under table 1 differing temps
3/ γ-Al
2O
3The exo-TCD reaction result is synthesized in catalysis
| Temperature of reaction ℃ | Endo-TCD transformation efficiency % | Exo-TCD yield % |
| 25 40 50 60 | 100 100 100 100 | 100 100 99.19 99.01 |
Comparative example 1
Prepare catalyzer by the method among the embodiment 1 (1), difference is to select mesoporous SiO
2As support of the catalyst.Chloride content is 14.75% of a catalyst weight on this catalyzer.With the synthetic exo-TCD of the method in the example 1 (2), difference is that temperature of reaction is 25 ℃ again, and the reaction times is respectively 10min, 20min, 30min, 50min, the results are shown in Table 2.
AlCl under the table 2 differential responses time
3/ SiO
2The exo-TCD reaction result is synthesized in catalysis
| Reaction times min | Endo-TCD transformation efficiency % | Exo-TCD yield % |
| 10 20 30 50 | 53.02 64.35 70.74 76.03 | 100 100 100 100 |
Comparative example 2
Prepare catalyzer by the method among the embodiment 1 (1), difference is to select mesoporous Al
2O
3-SiO
2As support of the catalyst.Chloride content is 11.26% of a catalyst weight on this catalyzer.With the synthetic exo-TCD of the method in the example 1 (2), difference is that temperature of reaction is 25 ℃ again, and the reaction times is respectively 5min, 8min, 10min, 20min, the results are shown in Table 3.
A1Cl under the table 3 differential responses time
3/ Al
2O
3-SiO
2The exo-TCD reaction result is synthesized in catalysis
| Reaction times min | Endo-TCD transformation efficiency % | Exo-TCD yield % |
| 5 8 10 20 | 82.61 95.88 98.46 100 | 100 100 100 100 |
Embodiment 2
(1) Preparation of Catalyst
In high-purity N
2Under the protection, with the mesoporous γ-Al of 5mL 60 ~ 100 orders
2O
3Carrier granule is put into the round-bottomed flask that magneton is housed handle 3h under 400 ℃ in retort furnace after, adds the CCl that handled through 5 molecular sieve dehydrations then
4Solution, 80 ℃ are heated up in a steamer 2h next time, add anhydrous AlCl again in flask
3, continue to heat up in a steamer 48h next time at 80 ℃.Steam remaining CCl
4Use new CCl again
4The washing solid sample repeatedly till no chlorion is detected in washings, at this moment promptly gets immobilized AlCl
3Catalyst precursor.The catalyst precursor of gained is used N at 400 ℃
21h is swept in air-blowing, then at N
2Purge and be cooled to room temperature under the protection.Chloride content is 10.75% of a catalyst weight on the catalyzer.
(2) hanging type tetrahydrochysene dicyclopentadiene (exo-TCD) is synthetic
1mL catalyzer (0.62g), 20mL hexanaphthene and the 0.5g bridge-type tetrahydro-dicyclopentadiene (endo-TCD) of preparation among the embodiment 2 (1) are joined in the there-necked flask that volume is 100mL N successively
2Make protection gas, 25 ℃ of temperature of reaction, reaction times 10min.Post-reaction treatment and analytical procedure are with embodiment 1 (2).Experimental result shows that the endo-TCD transformation efficiency is 100%, and the exo-TCD yield is 99.75%.
Claims (4)
1. novel method of making hanging type tetrahydrochysene dicyclopentadiene on solid acid catalyst is characterized in that this method is by the cycle pentadiene dimer hydrogenation products---the isomerization of bridge-type tetrahydro-dicyclopentadiene reaction, and with immobilized AlCl
3As isomerization catalyst, Gu isomerization reaction is carried out in liquid-heterogeneous stirred reactor or fixed-bed reactor, temperature of reaction is 0 ℃～100 ℃, and reaction pressure is 0.1MPa～1.0MPa, N
2Or H
2Make protection gas, catalyst levels (in muriatic weight on the catalyzer) is 2～20% of a raw material bridge-type tetrahydro-dicyclopentadiene weight, and the optimum solvent consumption is 20～100 times of raw material bridge-type tetrahydro-dicyclopentadiene weight.
2. a kind of novel method of making hanging type tetrahydrochysene dicyclopentadiene on solid acid catalyst according to claim 1 is characterized in that described immobilized AlCl
3Be AlCl
3Realize supportedly by reacting with the carrier surface hydroxyl, charge capacity is the 3-30% of catalyst weight.
3. a kind of novel method of making hanging type tetrahydrochysene dicyclopentadiene on solid acid catalyst according to claim 1 and 2 is characterized in that described immobilized AlCl
3Carrier be Al with mesoporous or macroporous structure
2O
3, Al
2O
3-SiO
2, Si-Al molecular sieve or SiO
2
4. according to claim 1 or 3 described a kind of novel methods of on solid acid catalyst, making hanging type tetrahydrochysene dicyclopentadiene, it is characterized in that described solvent is with C
6～C
10Straight-chain paraffin or naphthenic hydrocarbon nonpolar organic matter.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100125914A CN101130471A (en) | 2007-08-24 | 2007-08-24 | Novel method for producing hanging type tetrahydrochysene dicyclopentadiene on solid acid catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100125914A CN101130471A (en) | 2007-08-24 | 2007-08-24 | Novel method for producing hanging type tetrahydrochysene dicyclopentadiene on solid acid catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101130471A true CN101130471A (en) | 2008-02-27 |
Family
ID=39127903
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260018B (en) * | 2008-04-24 | 2010-10-20 | 西安近代化学研究所 | Method for synthesizing exo-tetrahydrocyclopentadiene |
| CN102924216A (en) * | 2012-11-02 | 2013-02-13 | 中科合成油技术有限公司 | Synthetic method for exo-tetrahydrodicyclopentadiene (THDCPD) |
| CN103706382A (en) * | 2013-12-12 | 2014-04-09 | 华东理工大学 | Aluminium chloride catalyst with high load capacity, preparation method and applications thereof |
| KR101622660B1 (en) | 2014-08-14 | 2016-05-19 | 국방과학연구소 | Continuous manufacturing methods of dicyclopentadiene-cyclopentadiene oligomer using fixed-bed reactor |
| CN106699499A (en) * | 2016-12-27 | 2017-05-24 | 中央军委后勤保障部油料研究所 | Method for improving isomeric selectivity of endo-tetrahydrodicyclotadiene |
| CN114751804A (en) * | 2022-03-07 | 2022-07-15 | 肯特催化材料股份有限公司 | Preparation method of adamantane |
-
2007
- 2007-08-24 CN CNA2007100125914A patent/CN101130471A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260018B (en) * | 2008-04-24 | 2010-10-20 | 西安近代化学研究所 | Method for synthesizing exo-tetrahydrocyclopentadiene |
| CN102924216A (en) * | 2012-11-02 | 2013-02-13 | 中科合成油技术有限公司 | Synthetic method for exo-tetrahydrodicyclopentadiene (THDCPD) |
| CN102924216B (en) * | 2012-11-02 | 2014-12-24 | 中科合成油技术有限公司 | Synthetic method for exo-tetrahydrodicyclopentadiene (THDCPD) |
| CN103706382A (en) * | 2013-12-12 | 2014-04-09 | 华东理工大学 | Aluminium chloride catalyst with high load capacity, preparation method and applications thereof |
| CN103706382B (en) * | 2013-12-12 | 2015-11-18 | 华东理工大学 | A kind of high capacity amount aluminum chloride catalyst and its preparation method and application |
| KR101622660B1 (en) | 2014-08-14 | 2016-05-19 | 국방과학연구소 | Continuous manufacturing methods of dicyclopentadiene-cyclopentadiene oligomer using fixed-bed reactor |
| CN106699499A (en) * | 2016-12-27 | 2017-05-24 | 中央军委后勤保障部油料研究所 | Method for improving isomeric selectivity of endo-tetrahydrodicyclotadiene |
| CN106699499B (en) * | 2016-12-27 | 2019-05-24 | 中央军委后勤保障部油料研究所 | A method of improving isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity |
| CN114751804A (en) * | 2022-03-07 | 2022-07-15 | 肯特催化材料股份有限公司 | Preparation method of adamantane |
| CN114751804B (en) * | 2022-03-07 | 2023-09-12 | 肯特催化材料股份有限公司 | Preparation method of adamantane |
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