CN1762927A - A kind of synthetic method of adamantane - Google Patents
A kind of synthetic method of adamantane Download PDFInfo
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- CN1762927A CN1762927A CN 200510100939 CN200510100939A CN1762927A CN 1762927 A CN1762927 A CN 1762927A CN 200510100939 CN200510100939 CN 200510100939 CN 200510100939 A CN200510100939 A CN 200510100939A CN 1762927 A CN1762927 A CN 1762927A
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000010189 synthetic method Methods 0.000 title claims description 8
- 239000002808 molecular sieve Substances 0.000 claims abstract description 40
- 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 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract 2
- 230000002194 synthesizing effect Effects 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 239000003930 superacid Substances 0.000 claims description 7
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910001573 adamantine Inorganic materials 0.000 abstract 3
- 239000011973 solid acid Substances 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 25
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 23
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000001020 rhythmical effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses the synthesis process of adamantine, which is synthesized with endo-TCD and through catalytic isomerization. The synthesis process has super strong solid acid ZrO2-SO42- or molecular sieve carried ZrO2-SO42- as catalyst, reaction temperature of 200-300 deg.c and reaction hydrogen pressure of 1.0-2.5 MPa. Supporting super strong solid acid with microporous or mesoporous molecular sieve can increase the dispersivity and surface utilization of the super strong solid acid greatly so as to raise the yield of adamantine. The present invention has yield of adamantine up to 20 %, and adopts no strong corrosive matter, resulting in no need of anticorrosive material and no environmental pollution.
Description
Technical field
The present invention relates to a kind of chemical synthesis process.Particularly, the present invention relates to a kind of synthetic method of diamantane.
Background technology
Diamantane (AdH) is a kind of cage shape hydrocarbon of being made up of 10 carbon atoms, can be used as various chemical substances such as lubricant and medicament intermediate.For synthesizing adamantane, usually the method that adopts is the isomerization of bridge-type tetrahydro-dicyclopentadiene reaction, and is catalyzer with the aluminum chloride, i.e. aluminum chloride isomerization method.
But there is distinct disadvantage in aluminum chloride isomerization method, particularly, when (1) adopts this method, must use a large amount of aluminum chlorides (its consumption almost equates with the raw material add-on); (2) during the isomerization reaction, aluminum chloride and heavy constituent form complex compound, therefore can not recycle, and therefore generate a large amount of aluminium wastes, and its serious problems are that the aluminium waste must handle, because its discharging can be polluted physical environment.Another problem of this method is that aluminum trichloride catalyst can make the diamantane that is synthesized painted, therefore also will make its decolouring with the product recrystallization or with gac after the reaction, but the last handling process more complicated.
In the another kind of diamantane synthetic method one Zeolite molecular sieve catalysis isomerization method, adopt impregnation steps, various transition metal such as platinum, rhenium, nickel or cobalt are loaded on the zeolite of rare earth or alkaline-earth metal metalloid cationic exchange, form certain solid catalyst, in order to carry out this isoversion reaction.If but do not feed hydrogen chloride gas and only use this catalyzer, then isomerization reaction synthetic diamantane productive rate is lower, and hydrogenchloride has severe corrosive, thereby must use the production unit of being made by the erosion resistance material of costliness, and this also is distinct disadvantage of this method.
Summary of the invention
Comprehensive above-mentioned two kinds of situations the purpose of this invention is to provide a kind of environment amenable solid catalyst, and in the production unit of making by common material synthesizing adamantane and can not pollute the method for physical environment optionally.
Through discovering: bridge-type tetrahydro-dicyclopentadiene is being carried out in the method for isoversion synthesizing adamantane, the molecular sieve that has a super acids performance in use can achieve the above object during as catalyzer.The present invention is accomplished on the basis of this discovery.
Embodiment of the present invention are described below:
Method of the present invention is that diamantane is formed by bridge-type tetrahydro-dicyclopentadiene (endo-TCD) isoversion; With solid super-strong acid or molecular sieve carried solid super-strong acid is catalyzer; Solid super-strong acid is 10～20% in molecular sieve area load amount.
Above-mentioned catalyzer is ZrO
2-SO
4 2-The type solid super-strong acid.
Above-mentioned catalyzer is area load ZrO
2-SO
4 2-The molecular sieve type solid super-strong acid.
Above-mentioned molecular sieve as support of the catalyst can be micro porous molecular sieve REY, and USY also can be mesopore molecular sieve MCM-41.
Above-mentioned temperature of reaction is 200～300 ℃.
Above-mentioned reaction is to carry out in pressure is the hydrogen atmosphere of 1.0～2.5MPa.
The present invention is a kind of by having in the presence of the functional molecular sieve solid catalyst of superpower acidity, bridge-type tetrahydro-dicyclopentadiene is carried out the method for isoversion reaction synthesizing adamantane.
Tetrahydro-dicyclopentadiene is the parent material among the present invention.
The catalyzer that the present invention adopts is the acid catalyzer of solid super strong, and it contains or do not contain molecular sieve carrier.When containing molecular sieve carrier, load SO in the above
4 2-/ ZrO
2(being abbreviated as SZ) makes catalyzer, changes the SZ charge capacity, and making with the same molecular sieve is the catalyzer of same a series of different SZ charge capacity of carrier; When not containing molecular sieve carrier, directly with pure solid super-strong acid SO
4 2-/ ZrO
2As catalyzer.
Aspect these a few class catalyzer of preparation, for the catalyzer that contains molecular sieve carrier, adopt impregnation steps, molecular sieve is put into certain zirconium salt solution, make metal load on the molecular sieve effectively, through oversulfated processing (at certain density ammoniumsulphate soln dipping), prepare by dry, roasting more then; For the catalyzer that does not contain molecular sieve carrier, then save adding molecular sieve step.
In the method that the present invention relates to, isomerization reaction is in the presence of above-mentioned catalyzer, and temperature of reaction is 230～290 ℃; Reaction atmosphere is H
2Required hydrogen pressure 1.0～2.5MPa.Intermittently form is taked in reaction, carries out in the stainless steel autoclave that a volume is 100ml.Product is formed the employing gc analysis, and chromatographic column is the OV-101 capillary column, column length 50m, internal diameter 0.25mm.
Embodiment
According to embodiment and comparative example the present invention is further elaborated below, the present invention is not limited to these embodiment.
Embodiment 1
(1) preparation of catalyst S Z (10%)/REY
Get 0.346 times Zr (NO of REY molecular sieve quality
3)
45H
2O is dissolved in appropriate amount of deionized water, adds aequum REY dipping.110 ℃ of oven dry, 300 ℃ of roastings 3 hours grind to form less than 120 purpose fine powders.In " 15ml ammonium sulfate/g molecular sieve " ratio, be 0.5mol/L ammoniumsulphate soln dipping fine powder 24 hours with concentration, suction filtration, filter cake be 110 ℃ of dryings, 650 ℃ of roastings 3 hours.Obtain containing ZrO
210% SZ/REY (is designated as SZ (10%)/REY) catalyzer.
(2) diamantane is synthetic
Adopt the 110ml stainless steel autoclave as rhythmic reaction equipment.2.4g reactant endo-TCD and 1.5g catalyzer 10%SZ/REY are put into autoclave.N with 1.0MPa
2Replace air in the still, use the H of 1.0MPa again
2N in the displacement still
2, keep hydrogen pressure 1.5MPa in the still.250 ℃ were stirred 3 hours.Cool to room temperature is drained gas reactor, adds the 21ml cyclohexane, removes by filter catalyzer.Reaction result sees Table 1, table 3.
Endo-TCD, diamantane yield and diamantane selectivity are calculated according to following formula respectively.
Endo-TCD transformation efficiency=(endo-TCD add-on-endo-TCD residual content)/endo-TCD add-on * 100%
Diamantane yield=(diamantane growing amount/endo-TCD add-on) * 100%
Diamantane selectivity=(diamantane yield/endo-TCD transformation efficiency) * 100%
Comparative example 1-1
Prepare SZ (10)/REY with same way as among the embodiment 1 (1), again with same way as synthesizing adamantane among the embodiment 1 (2), but temperature of reaction changes 230 ℃ respectively into, 270 ℃, 290 ℃, the results are shown in Table 1.
Table 1 temperature of reaction is to the influence of reaction conversion ratio and diamantane yield
| Catalyzer | Temperature of reaction/℃ | Hydrogen pressure/MPa | Transformation efficiency/% | Diamantane yield/% | |
| Comparative example 1-1 embodiment 1 comparative example 1-1 comparative example 1-1 | SZ (10%)/REY is the same the same | 230 250 270 290 | 1.5 1.5 1.5 1.5 | 49.86 91.75 95.54 97.66 | 3.92 11.95 8.25 2.25 |
Comparative example 1-2
Prepare SZ (10)/REY with same way as among the embodiment 1 (1), again with same way as synthesizing adamantane among the embodiment 1 (2), but hydrogen pressure changes 1.0,2.0 respectively into, and 2.5MPa the results are shown in Table 2.
Table 2 hydrogen pressure is to the influence of reaction conversion ratio and diamantane yield
| Catalyzer | Temperature of reaction/℃ | Hydrogen pressure/MPa | Transformation efficiency/% | Diamantane yield/% | |
| Embodiment 4 comparative example 1-2 comparative example 1-2 comparative example 1-2 | SZ (10%)/REY is the same the same | 250 250 250 250 | 1.0 1.5 2.0 2.5 | 82.35 91.75 85.92 85.74 | 4.85 11.95 7.62 8.90 |
Comparative example 1-3
Prepare SZ/REY with same way as among the embodiment 1 (1), but Zr (NO
3)
45H
2The O quality changes 0.519 times of REY molecular sieve quality into, obtains containing ZrO
215% SZ/REY (is designated as SZ (15%)/REY).Again with same way as synthesizing adamantane among the embodiment 1 (2), but catalyzer changes SZ (15%)/REY into.Reaction result sees Table 3
Comparative example 1-4
Prepare SZ/REY with same way as among the embodiment 1 (1), but Zr (NO
3)
45H
2The O quality changes 0.692 times of REY molecular sieve quality into, obtains containing ZrO
220% SZ/REY (is designated as SZ (20%)/REY).Again with same way as synthesizing adamantane among the embodiment 1 (2), but catalyzer changes SZ (20%)/REY into.Reaction result sees Table 3.
Embodiment 2
Prepare catalyzer with same way as among the embodiment 1 (1), but support of the catalyst changes the USY molecular sieve into, obtains SZ (10%)/USY.Again with same way as synthesizing adamantane among the embodiment 1 (2), but catalyzer changes SZ (10%)/USY into.Reaction result sees Table 3.
Comparative example 2-1
Same way as prepares catalyzer among the comparative example 1-3, but support of the catalyst changes the USY molecular sieve into, obtains SZ (15%)/USY.Again with same way as synthesizing adamantane among the embodiment 2, but catalyzer changes SZ (15%)/USY into.Reaction result sees Table 3.
Comparative example 2-2
Prepare catalyzer with same way as among the comparative example 1-4, but support of the catalyst changes the USY molecular sieve into, obtain SZ (20%)/USY.Again with same way as synthesizing adamantane among the embodiment 2, but catalyzer changes SZ (20%)/USY into.Reaction result sees Table 3.
Embodiment 3
Prepare catalyzer with same way as among the embodiment 2, but molecular sieve carrier changes MCM-41 into, obtain SZ (10%)/MCM-41.Again with same way as synthesizing adamantane among the embodiment 2, but catalyzer changes SZ (10%)/MCM-41 into.Reaction result sees Table 3.
Comparative example 3-1
Prepare catalyzer with same way as among the comparative example 1-4, but support of the catalyst changes the MCM-41 mesopore molecular sieve into, obtain SZ (15%)/MCM-41.Again with same way as synthesizing adamantane among the embodiment 3, but catalyzer changes SZ (15%)/MCM-41 into.Reaction result sees Table 3.
Comparative example 3-2
Prepare catalyzer with same way as among the comparative example 1-4, but support of the catalyst changes the MCM-41 mesopore molecular sieve into, obtain SZ (20%)/MCM-41.Again with same way as synthesizing adamantane among the embodiment 3, but catalyzer changes SZ (20%)/MCM-41 into.Reaction result sees Table 3.
Embodiment 4
(1) preparation of catalyst S Z
10 gram Zr (NO
3)
45H
2O is dissolved in the 110ml deionized water.Dripping concentration under the vigorous stirring is 28% ammoniacal liquor, and leave standstill regulator solution pH value to 9 ~ 10.Suction filtration, filter cake grinds to form less than 120 purpose fine powders 110 ℃ of dryings 4 hours.In " 15ml sulfuric acid/g molecular sieve " ratio, 0.5mol/L sulfuric acid was flooded fine powder 24 hours, suction filtration, filter cake is 110 ℃ of dryings.Desciccate was 550 ℃ of roastings 3 hours.Obtain SZ.
(2) diamantane is synthetic
With same way as synthesizing adamantane among the embodiment 3, but catalyzer changes SZ into.Reaction result sees Table 3.
Table 3 differing molecular sieve is to the influence of reaction conversion ratio and diamantane yield
| Catalyzer | Temperature of reaction/℃ | Hydrogen pressure/MPa | Transformation efficiency/% | Diamantane yield/% | |
| Embodiment 1 comparative example 1-3 comparative example 1-4 embodiment 2 comparative example 2-1 comparative example 2-2 embodiment 3 comparative example 3-1 comparative example 3-2 embodiment 4 | SZ(10％)/REY SZ(15％)/REY SZ(20％)/REY SZ(10％)/USY SZ(15％)/USY SZ(20％)/USY SZ(10％)/MCM-41 SZ(15％)/MCM-41 SZ(20％)/MCM-41 SZ | 250 250 250 250 250 250 250 250 250 250 | 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 | 91.75 90.83 88.56 86.56 80.00 70.46 89.08 89.44 90.70 89.03 | 11.95 17.33 22.77 13.44 18.45 23.38 12.96 18.26 27.06 5.27 |
According to the present invention, under solid super-strong acid or molecular sieve carried solid super acid catalyst effect, endo-TCD can be converted into diamantane by isomerization reaction.Adopt micropore or mesoporous molecular sieve carried solid super-strong acid, the dispersity of solid super-strong acid, surperficial utilization ratio are enlarged markedly, thereby help to improve the diamantane yield, and reduce the catalyzer cost.In the synthesizing adamantane process, owing to do not use strong corrosive material such as hydrogenchloride, so reaction unit do not need to use the erosion resistance material, and can not pollute physical environment, effectively synthesizing adamantane.
Claims (6)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140352A (en) * | 2013-05-06 | 2014-11-12 | 中国科学院大连化学物理研究所 | A method for preparing adamantane compounds from alcohol raw materials |
| CN114425401A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Solid super acidic catalyst and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140352A (en) * | 2013-05-06 | 2014-11-12 | 中国科学院大连化学物理研究所 | A method for preparing adamantane compounds from alcohol raw materials |
| CN104140352B (en) * | 2013-05-06 | 2016-07-06 | 中国科学院大连化学物理研究所 | A kind of method being prepared adamantane compound by alcohols feedstock |
| CN114425401A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Solid super acidic catalyst and preparation method and application thereof |
| CN114425401B (en) * | 2020-10-15 | 2024-02-02 | 中国石油化工股份有限公司 | Solid super acidic catalyst and preparation method and application thereof |
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