CN107814676A - A kind of preparation method of decahydronaphthalene and naphthane - Google Patents
A kind of preparation method of decahydronaphthalene and naphthane Download PDFInfo
- Publication number
- CN107814676A CN107814676A CN201610822812.3A CN201610822812A CN107814676A CN 107814676 A CN107814676 A CN 107814676A CN 201610822812 A CN201610822812 A CN 201610822812A CN 107814676 A CN107814676 A CN 107814676A
- Authority
- CN
- China
- Prior art keywords
- reaction
- catalyst
- acid
- decahydronaphthalene
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C07C5/02—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- 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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/367—Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of by variation route that more cyclic ketones or more cyclic alcohol are Material synthesis decahydronaphthalene and naphthane.The decahydronaphthalene and naphthane obtained by the route can be directly used as the substitute of aviation kerosine and diesel oil or as the additive for improving fuel density and thermostability energy.The present invention is divided into four parts：1) for more cyclic ketones under metallic catalyst facilitation, hydrogenation obtains more cyclic alcohol；2) for more cyclic alcohol under acid catalysis, dehydration isomery obtains octahydro naphthalene；3) for octahydro naphthalene under metallic catalyst effect, hydrogenation obtains decahydronaphthalene；4) octahydro naphthalene dehydrogenation under metallic catalyst effect prepares naphthane.
Description
Technical field
The present invention relates to one kind using more cyclic ketones or more cyclic alcohol as raw material, the variation route of decahydronaphthalene is synthesized, particular content includes
Four parts：1) for more cyclic ketones under metallic catalyst effect, hydrogenation obtains more cyclic alcohol；2) more cyclic alcohol take off under acid catalyst effect
Water isomery obtains octahydro naphthalene；3) for octahydro naphthalene under metallic catalyst effect, hydrogenation obtains decahydronaphthalene；4) octahydro naphthalene is in metal catalytic
Under agent effect, dehydrogenation obtains naphthane.
Background technology
Aviation kerosine is as the liquid fuel being in great demand in the world at present, the usually mixing by carbon number between 8-16
Hydro carbons is formed.At present, aviation kerosine is mainly obtained with petroleum refining, yet with the non-renewable of fossil resource and
For people for the growing interest of environmental problem, finding reproducible organic carbon source to replace oil to prepare aviation kerosine becomes generation
The study hotspot of various countries of boundary.Compared with fossil energy, biomass fuel has the characteristics of recyclability and carbon dioxide neutrality.It is raw
The sulfur dioxide that thing boat coal gives off in burning is also well below mineral fuel oil.Therefore, research and development biology boat coal is to alleviating China
To the degree of dependence of imported crude oil, ensure that Chinese energy safety, acquirement green low-carbon competitive advantage have its own strategic significance.
The rise of biomass fuel experienced certain evolution.First generation biomass fuel is with corn and soybean etc.
Raw material prepares bio-ethanol and biodiesel by reactions such as fermentation, ester exchanges.This route using edible grain as raw material,
The national conditions that unsuitable China has a large population and a few land.Second generation biomass fuel is mainly given birth to using agriculture and forestry organic waste material as raw material by three kinds of approach
Into fuel：1) gasification of biomass processing generation synthesis gas, then produce alkane through F- T synthesis.The process comparative maturity, but
It is the condition for needing HTHP, energy consumption is huge；2) biomass high temperature pyrolysis generation bio-oil, then upgrade through deoxidation into liquid
Fuel.The process is complicated, and obtained bio-oil inferior quality, can not be directly used as engine fuel, need to further refine；
3) biomass obtains small molecule platform thing by chemistry and biological treatment (including hydrolyze, ferment, selective hydrogenation etc.), then with this
A little small molecule platform chemicals are that raw material has aviation kerosine chain length (C by C-C coupling reaction acquisition8-C16) oxygen-containing have
Machine compound.Finally, these oxygen-containing organic compounds are carried out with hydrogenation deoxidation reaction and liquid alkane is made.The process condition is relative
Compare gently, and synthetic route is versatile and flexible.
The method for synthesizing aviation kerosine by approach three has：
1st, hydroxyalkylation/alkylated reaction --- hydrogenation deoxidation reacts
2011, Corma et al. reported methylfuran and butyraldehyde, 5 methyl furfural, 5 hydroxymethyl furfural under acid catalysis
Between alkylated reaction and its own trimerization reaction be prepared for having the oxygen-containing organic of aviation kerosine or diesel oil chain length range
Compound, thereafter, they a series of have more subzero aviation coal further through being obtained to these compound hydrogenation deoxidations
Oily branched-chain hydrocarbons (Angew.Chem.Int.Ed.2011,50,1-5).But this method uses sulfuric acid and toluene sulfonic acide as catalyst
The corrosion to equipment and the pollution to environment can be caused.Then, the seminar reports 5 methyl furfural and 2- methylfurans again
Alkylated reaction, and use Pt/C, Pt/C-TiO2As hydrogenation deoxidation catalyst, higher liquid phase alkane yield is obtained.
On this basis, we organize by a series of solid acid catalysts be catalyzed methylfuran and furfural, butyraldehyde, acetone, hydroxypropanone-,
A series of oxygen-containing organic compounds with aviation kerosine or diesel oil chain length range of levulic acid Lipase absobed, then by this
A little compound hydrogenation deoxidations, which obtain, a series of has more subzero aviation kerosine branched-chain hydrocarbons.Because this method is with furfural
Selection hydrogenation products methylfuran be the relatively high (Chinese Patent Application No. of cost of material：201110346501.1；China
Patent 201210169817.2).
2nd, aldol reaction --- hydrogenation deoxidation reacts
2005, Dumesic, Huber et al. [Science, 2005,308,1446-1450] and patent [US7,671,
246] report using hydroxymethylfurfural or furfural and acetone as raw material, by the aldol reaction and hydrogenation of base catalysis and add
Hydrogen deoxygenation has produced C8To C15The liquid alkane of scope.Author is with Pt/SiO2-Al2O3For hydrogenation deoxidation catalyst, use
The phase flow reactor of fixed bed four, need to be passed through organic solvent (such as hexadecane) to prevent catalyst inactivation, technique ratio in course of reaction
It is more complicated.2008, the seminar made carrier using the niobium oxide of phosphorylation instead of sial composite oxides.It was found that using new
Organic solvent need not be passed through after carrier in reaction system can also obtain good effect, so as to simplify technique
(ChemSusChem,2008,1,417-424).But because the alkane of process synthesis is linear paraffin, these hydro carbons
Very high (the n-pentadecane of freezing point：8.5-10 DEG C, n-tridecane：- 5.5 DEG C, n-dodecane:- 12 DEG C), do not meet aviation kerosine
It is required that (fusing point is less than -40 DEG C).It need to be handled by further hydroisomerizing and just can serve as aviation kerosine.On this basis, we
It is carried out aldol condensation with propione, hexone respectively under condition of no solvent and added by group using furfural as substrate
Hydrogen deoxygenation, obtains C9-C10The liquid alkane of scope, the liquid alkane of this method synthesis is branched paraffin, and product need not
Isomery can be used in aviation kerosine.
3rd, deoxygenation --- olefinic polyreaction --- hydrogenation reaction
2010, Dumesic et al. reported on [Science, 2010,327,1110-1114] using gamma-valerolactone as
Raw material, C is produced by open loop decarboxylic reaction and olefinic polyreaction8To C16The liquefied olefines of scope.Author is with SiO2/
Al2O3For decarboxylation catalyst, Amberlyst-70 is polymerization catalyst, and the increasing of carbochain is realized in continuous fixed bed reactors
Long and oxygen atom removing.Thereafter, the group explores the new route using gamma-valerolactone as Material synthesis diesel oil:Gamma-valerolactone passes through
Pd/Nb2O5After open loop hydrogenation, valeric acid is obtained；Again through Ce0.5Zr0.5O2Catalysis is lower to occur the obtained butyl ketone of ketonization reaction；5- nonyls
Ketone obtains C after being hydrogenated with, being dehydrated successively again9Alkene mixture；Again C is obtained under Amberlyst-70 catalysis9-C18Alkene
Hydrocarbon, after the alkene is hydrogenated, you can as diesel oil.
In summary, the aviation kerosine synthesized at present by biomass is mainly chain alkane.With traditional aviation kerosine (ring
The mixture of hydrocarbon and chain hydrocarbon) compare with density and the shortcomings that relatively low volume calorific value and the problem of sealing is poor.In reality
Need to be used in mixed way the technical indicator that can reach current aviation kerosine with traditional aviation kerosine in.And decahydronaphthalene has because of it
There are higher volume calorific value and thermostability energy, there is addition, even certain model special type aviation fuel in a variety of Aviation Fuels
Important composition composition；Naphthane has higher density, its density and sealing can be improved in aviation kerosine with addition
Performance.So exploitation is synthesized decahydronaphthalene and naphthane tool with higher density and thermostability energy by biomass platform chemicals
There is important application value, also would be even more beneficial to the industrialization of biomass aviation kerosine technology.Ring pentylidene cyclopentanone can be by giving birth to
Acquisition of the aqueous phase selective hydrogenation product cyclopentanone of material platform chemicals furfural through itself aldol reaction in high yield；And
Cyclopenta ring pentanone, ring pentylidene cyclopentanol or cyclopenta ring amylalcohol can be hydrogenated with by ring pentylidene cyclopentanone and obtained or by biomass
Platform chemicals cyclopentanol reacts through Guerbet to be obtained.
The content of the invention
It is an object of the invention to provide one from platform chemicals derived from lignocellulosic, prepare decahydronaphthalene and
The variation route of naphthane.
The present invention is achieved through the following technical solutions：
The first step, more cyclic ketones hydrogenation under metallic catalyst effect obtain more cyclic alcohol；Raw material is one or both of table 1
Mixture；
Table cyclic ketones concrete structure formula more than 1
Metallic catalyst includes Raney Ni, Raney Co, Raney Cu, nickel aluminum hydrotalcite, cobalt aluminum hydrotalcite and born
Load type Pt, Pd, Ru, Rh, Ir, Ni, Co, Cu catalyst, wherein for loaded catalyst, carrier include cerium oxide, aluminum oxide,
Mixture more than one or both of magnesia, activated carbon, silica and molecular sieve etc.；
Formaldehyde reducing process is respectively adopted in load type metal catalyst and prepared by equi-volume impregnating.Wherein formaldehyde reducing process is grasped
It is as follows to make method：With water ultrasonic disperse carrier, the metal front liquid solution that percentage by weight is 2%-40% is added dropwise at room temperature, stirs
Mix 1h；After left undisturbed overnight, NaOH solution is added in 45 DEG C and adjusts pH value to 9-10；The lower formalin for adding excess of stirring, and in
85 DEG C of stirring 1h-2h；Cooling washing is to without Cl-After 80 DEG C of oven drying 4h-10h；Thus the catalyst mark that method obtains
For M-CR；
The operating method of incipient impregnation is as follows：By 2%-40% metal front liquid solution, phase is added to by metering ratio
The medium volume impregnation of carrier answered, 6h-12h is dried after 4h-12h is stood, is finally reduced under 100 DEG C of -600 DEG C of hydrogen atmospheres
1h-4h；The catalyst obtained by this method is labeled as M-IP.
Reaction is directly carried out under the conditions of liquid solvent-free；Reaction temperature is between 20 DEG C -300 DEG C, preferably 20 DEG C -150 DEG C；
Reaction pressure is between 0.1MPa-10.0MPa, preferably 1MPa-4MPa；When from tank reactor, reaction time 0.5h-
12h, catalyst amount are the 0.1%-50%, preferably 1%-10% of reaction raw materials quality；When from fixed bed reactors, instead
Feed/catalyst mass space velocity is answered in 0.1h-1-10.0h-1, H2Mol ratio with substrate is 8-1500, preferably 8-100.
Second step, more cyclic alcohol obtain octahydro naphthalene through dehydration, isomerization reaction under acid catalysis；
Raw material is mixture more than one or both of table 2, can directly commercially available or by step 1 hydrogenation production
Used after thing purification；
Table cyclic alcohol concrete structure formula more than 2
The acid catalyst includes liquid acid and solid acid, wherein, liquid acid is included in sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid
One or more kinds of mixtures；Solid acid include acidic molecular sieve, acidic metal oxide, phosphotungstic acid, phosphomolybdic acid, to first
Mixtures more than one or both of base benzene sulfonic acid, sulfonation carbon, acidic resins；Molecular sieve has H-Y, HZSM-5 etc., metal
Oxide has niobium oxide, tantalum oxide etc., and acidic resins have Amberlyst catalyst series, Nafion resins etc..
The reaction temperature of the reaction is between 20 DEG C -300 DEG C, preferably 50 DEG C -140 DEG C；Reaction pressure is in 0.1MPa-
10.0MPa, preferably 0.1MPa-1MPa；Reaction can be carried out under condition of no solvent；When using tank reactor, the reaction time
For 4h-12h, the acid catalyst levels are the 0.1%-50%, preferably 5%-20% of reaction raw materials quality；When using fixed bed
During reactor, reaction raw materials/catalyst quality air speed is in 0.1h-1-10.0h-1, N2Mol ratio with substrate is 8-1500.When adopting
During with water segregator, reaction time 12h-24h, the acid catalyst levels are the 1%-50% of reaction raw materials quality, excellent
Select 5%-20%；
3rd step, the hydrogenated reaction of polycyclic dehydration of alcohols-isomerized products octahydro naphthalene is produced by decahydronaphthalene by metallic catalyst；
Metallic catalyst includes Raney Ni, Raney Co, Raney Cu, nickel aluminum hydrotalcite, cobalt aluminum hydrotalcite and born
Load type Pt, Pd, Ru, Rh, Ir, Ni, Co, Cu catalyst, wherein for loaded catalyst, carrier include cerium oxide, aluminum oxide,
Mixture more than one or both of magnesia, activated carbon, silica and molecular sieve etc.；
The same step 1 of preparation method of loaded catalyst, including formaldehyde reducing process and equi-volume impregnating；
Reaction is directly carried out under the conditions of liquid solvent-free；Reaction temperature is between 20 DEG C -200 DEG C, preferably 20-150 DEG C；Instead
Pressure is answered between 0.1MPa-10.0MPa, preferably 0.1MPa-3.0MPa；When from tank reactor, the reaction time is
0.5h-12h, catalyst amount are the 0.1%-50%, preferably 1%-5% of reaction raw materials quality；When from fixed bed reactors
When, reaction raw materials/catalyst quality air speed is in 0.1h-1-10.0h-1, H2Mol ratio with substrate is 8-1500, preferably 8-100.
4th step, polycyclic dehydration of alcohols-isomerized products octahydro naphthalene is produced by naphthane through dehydrogenation reaction by metallic catalyst；
The same step 3 of type and preparation method of metallic catalyst.
Reaction is directly carried out under the conditions of liquid solvent-free；Reaction temperature is between 20 DEG C -200 DEG C, preferably 50-170 DEG C；Instead
Pressure is answered between 0.1MPa-10.0MPa, preferably 0.1MPa-3.0MPa；When from tank reactor, the reaction time is
0.5h-12h, catalyst amount are the 0.1%-50%, preferably 1%-5% of reaction raw materials quality；When from fixed bed reactors
When, reaction raw materials/catalyst quality air speed is in 0.1h-1-10.0h-1, N2Mol ratio with substrate is 8-1500, preferably 8-100.
By above technical scheme, decahydronaphthalene or naphthane can be obtained in high yield, realizes and is derived with lignocellulosic
Thing is the cheap easy novel synthetic that raw material prepares decahydronaphthalene and naphthane.
Decahydronaphthalene and naphthane are synthesized by biomass route first, compared with existing coal decahydronaphthalene route, conversion ratio
Height, selectivity are good.
Brief description of the drawings
The GC-MS spectrograms of the more cyclic ketones hydrogenation reactions of Fig. 1；
The GC-MS spectrograms of the polycyclic dehydration of alcohols isomerization reactions of Fig. 2；
The GC-MS spectrograms of Fig. 3 octahydro naphthalene hydrogenation reactions；
The GC-MS spectrograms of Fig. 4 octahydro naphthalene dehydrogenation reactions；
The conversion ratio and time history of more cyclic alcohol under the effect of Fig. 5 different catalysts；
The lower octahydro naphthalene yield of Fig. 6 different catalysts effect and time history.
Embodiment
Embodiment 1-20
1. the preparation of catalyst：
1) preparation of metallic catalyst：
Raney Ni, Raney Co, Raney Cu are the commercial catalysts product directly bought；Nickel aluminum hydrotalcite (NiAl-
HT) be by mol ratio be 3:1 Ni (NO3)2·6H2O and Al (NO3)3·9H2O mixed solutions with 3mL/min be added dropwise to NaOH and
NaCO3Mixed solution in, dropwise addition process is carried out under 65 DEG C of water-bath strong agitations.Continue to stir aging 18h after completion of dropwise addition,
Then filtration washing, it is dried overnight in 80 DEG C, need to be in 500 DEG C of reductase 12 h before use.
Catalyst Step prepared by formaldehyde liquid phase reduction is as follows：With water ultrasonic disperse carrier, weight hundred is added dropwise at room temperature
Divide than the metal front liquid solution for 2%-40%, stir 1h；After left undisturbed overnight, NaOH solution is added in 45 DEG C and adjusts pH value to 9-
10；Stirring is lower to add excessive formalin, and stirs 1h-2h in 85 DEG C；Cooling washing is to without Cl-After 80 DEG C of oven dryings
4h-10h；Thus the catalyst that method obtains is labeled as M-CR；
Catalyst Step prepared by equi-volume impregnating is as follows：By certain density precursor solution, added by metering ratio
It is last before use, need to be in 120 DEG C of oven drying 6h-12h after 4h-12h is stood to the medium volume impregnation of corresponding carrier
1h-4h is reduced under 500 DEG C of hydrogen atmospheres.The catalyst obtained by this method is labeled as M-IP.Carrier bag used in the present invention
It is commercially available to include cerium oxide, aluminum oxide, magnesia, silica, activated carbon, niobium oxide and molecular sieve (HZSM-5, H β)
Product；Metal precursor used includes palladium bichloride, chloroplatinic acid, chloro-iridic acid, radium chloride, ruthenic chloride, nickel nitrate, copper nitrate, nitre
Sour cobalt etc.；Obtained catalyst is shown in Table 3.
The load type metal catalyst of table 3
| Embodiment | Catalyst |
| Embodiment 1 | Ru/C-CR |
| Embodiment 2 | Pd/C-CR |
| Embodiment 3 | Pt/C-CR |
| Embodiment 4 | Rh/C-CR |
| Embodiment 5 | Ir/C-CR |
| Embodiment 6 | Ru/C-IP |
| Embodiment 7 | Ni/C-IP |
| Embodiment 8 | Cu/C-IP |
| Embodiment 9 | Co/C-IP |
| Embodiment 10 | Ni/MgO-IP |
| Embodiment 11 | Ni/SiO2-IP |
| Embodiment 12 | Ni/CeO2-IP |
| Embodiment 13 | Ni/Hβ-IP |
| Embodiment 14 | Ni/HZSM-5-IP |
| Embodiment 15 | Ni/γ-Al2O3-IP |
| Embodiment 16 | Ni/Nb2O5-IP |
| Embodiment 17 | NiAl-HT |
| Embodiment 18 | Raney Ni |
| Embodiment 19 | Raney Co |
| Embodiment 20 | Raney Cu |
2) preparation of acid catalyst：
HY, HZSM-5, Amberlyst catalyst series, Nafion resins etc. are commercially available product；ZrP be by
ZrCl2O·8H2O (1.0M, 31.9mL) and NH4H2PO4After (1.0M, 63.8mL) mixed precipitation, filtered, washing, 100 DEG C it is dry
It is dry, then be calcined 3h at 400 DEG C and be made.Sulfonation C catalyst is that sulfonation is handled under concentrated sulfuric acid effect by commercially available coconut carbon
Obtain.
12h need to be dried before all catalyst uses in 120 DEG C of baking ovens.
Cyclic ketones hydrogenation reaction more than 2.
Embodiment 21-66
1) tank reactor is used:More cyclic ketones a1,0.5g catalyst of 10g are added in 100mL reactor, at 120 DEG C,
H2Pressure is to stir 3h under 3MPa.Detailed reaction the results are shown in Table 4.
The table hydrogenation reaction of cyclic ketones more than 4 and its result
As can be seen from Table 4, the acid-base property of catalyst has a great impact to the selectivity of product, and strong acid and strong basicity carry
Body is all unfavorable for the generation of more cyclic alcohol products.In numerous catalyst, the activity of Ru/C catalyst and the selection to target product
Property it is optimal, and its preparation method on reaction do not influence.There is commercially produced product in view of Ru/C-CR catalyst, we select
The catalyst is furtherd investigate.Investigate the shadow of reaction temperature, reaction pressure, reaction time and catalyst amount to reaction
Ring, the results are shown in Table 5.
The influence of the temperature of table 5., pressure, time and catalyst amount to more cyclic ketones hydrogenation reactions
From table 5, when temperature is higher than 120 DEG C, pressure is higher than 3MPa, reaction time 3h, catalyst amount/raw material matter
When amount is more than 5%, you can obtain optimal target product yield, high income is up to 99%.
2) fixed bed reactors are used：It is anti-that more cyclic ketones a1 are pumped into fixed bed with certain speed with efficient liquid-phase chromatographic pump
Answer in device, using Ru/C-CR as catalyst, investigate the influence of temperature, pressure and air speed to reaction.It the results are shown in Table 6.
The influence of the temperature of table 6, pressure, mass space velocity to more cyclic ketones hydrogenation reactions
From table 6, using fixed bed reactors, when reaction condition is:T=120 DEG C, mass space velocity 1h-1, pressure is
3MPa, hydrogen flowing quantity 200mL*min-1When, the yield of required target product is up to 97%.
3. polycyclic dehydration of alcohols isomerization reaction：After previous step hydrogenation products are purified, its in the more cyclic alcohol or table 2 of acquisition
Mixture more than one or both of its alcohol compound is used in the reaction as raw material.
Embodiment 67-101
1) fixed bed reactors are used：1.0g catalyst is fitted into reaction tube, it is 0.1MPa to keep pressure in reactor,
120 DEG C, nitrogen flow rate 150mL/min of temperature, by raw material b1It is pumped into efficient liquid-phase chromatographic pump with 0.04mL/min in reactor.
Reaction result is shown in Table 7.
The polycyclic dehydration of alcohols isomerization reaction of table 7 and its result
As can be seen from Table 7, different metallic catalysts has certain activity to the reaction of polycyclic dehydration of alcohols.Wherein with
Amberlyst-15 is best to the selectivity of octahydro naphthalene.Still using Amberlyst-15 as catalyst, in fixed bed reactors
In, the mass space velocity of different Hydrogen Vapor Pressures, reaction temperature, reaction raw materials and catalyst, nitrogen flow are investigated to dehydration
Influence, the results are shown in Table 8.
The influence of the temperature of table 8., pressure, mass space velocity to polycyclic dehydration of alcohols isomerization reaction
2) tank reactor is used:45g raw materials, 4.5g acid catalysts are added in 100mL reactor, at 120 DEG C, often
Pressure stirring 6h.Detailed reaction the results are shown in Table 9.
The influence of the temperature of table 9., pressure, time and catalyst amount to polycyclic dehydration of alcohols isomerization reaction
From table 9, for liquid acid, including：Hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid, because it contains water so that octahydro
The selectivity of naphthalene product is very poor.Meanwhile fixed bed is not so good as the selectivity of octahydro naphthalene using same catalyst, tank reactor
Reactor.
3) water knockout drum reaction unit is used：38g raw materials, 7.6g catalyst, 120 are added in 100mL round-bottomed flask
Stir, sample at regular intervals, the conversion ratio of raw material and yield result such as Fig. 5 and Fig. 6 of product octahydro naphthalene under DEG C normal pressure
It is shown.
It can be seen from upper figure in the case where three kinds of resin catalysts act on, 8h is reacted, more cyclic alcohol can convert completely；And prolong
In the long reaction time, under Nafion catalyst actions, the yield of octahydro naphthalene gradually steps up, and during 24h, yield is up to 91%.
4. octahydro naphthalene hydrogenation reaction：
Embodiment 102-134
1) tank reactor is used:10g raw materials, 0.5g catalyst are added in 100mL reactor, at 120 DEG C, H2Pressure
Power is to stir 3h under 3MPa.Detailed reaction the results are shown in Table 10.
The octahydro naphthalene hydrogenation reaction of table 10 and its product yield result
As can be seen from Table 10, octahydro naphthalene Hydrogenation is easier for decahydronaphthalene, and different catalyst has to the reaction
Certain activity.The catalyst decahydronaphthalene high income that wherein noble metal supports is up to 100%, and Ni bases are urged in non-precious metal catalyst
Agent all shows excellent catalytic activity, and acid carrier is more beneficial for the generation of decahydronaphthalene.
2) fixed bed reactors are used：Octahydro naphthalene is pumped into fixed bed reaction with certain speed with efficient liquid-phase chromatographic pump
In device, using Pd/C-CR as catalyst, the influence of temperature, pressure and air speed to reaction is investigated.It the results are shown in Table 11.
The temperature of table 11, the influence of pressure and air speed to octahydro naphthalene hydrogenation reaction
As can be seen from Table 11, at 120 DEG C, air speed 3h-1, pressure is under 0.5MPa, using Pd/C-CR as catalyst
High yield obtains decahydronaphthalene.
5. octahydro naphthalene dehydrogenation reaction：
Embodiment 135-161
1) tank reactor is used:10g raw materials, 0.5g catalyst are added in 100mL reactor, in 170 DEG C of stirrings
3h.Detailed reaction the results are shown in Table 12.
The octahydro naphthalene dehydrogenation reaction of table 12 and its product yield result
As can be seen from Table 12, different catalyst has certain activity to the reaction, but naphthane yield is very low, this
It is that the hydrogen in-situ of generation, which is hydrogenated with, causes octahydro naphthalene hydrogenation in part to obtain decahydronaphthalene because being reacted in tank reactor.
2) fixed bed reactors are used：Octahydro naphthalene is pumped into fixed bed reaction with certain speed with efficient liquid-phase chromatographic pump
In device, using Pd/C-CR as catalyst, in a nitrogen atmosphere, the influence of temperature, pressure and air speed to reaction is investigated.It the results are shown in Table
13.
The temperature of table 13, the influence of pressure and air speed to octahydro naphthalene dehydrogenation reaction
As can be seen from Table 13, at 170 DEG C, air speed 1h-1, pressure is under 0.1MPa, using Pd/C-CR as catalyst
High yield (85%) obtains naphthane.
Claims (6)
- A kind of 1. preparation method of decahydronaphthalene and naphthane, it is characterised in that：The preparation of decahydronaphthalene：1) under metallic catalyst effect, more cyclic ketones hydrogenation obtain more cyclic alcohol；2) under acid catalyst effect, more cyclic alcohol obtain octahydro naphthalene by being dehydrated isomery；3) under metallic catalyst effect, octahydro naphthalene hydrogenation obtains decahydronaphthalene；And/or the preparation of naphthane：1) under metallic catalyst effect, more cyclic ketones hydrogenation obtain more cyclic alcohol；2) under acid catalyst effect, more cyclic alcohol obtain octahydro naphthalene by being dehydrated isomery；3) under metallic catalyst effect, the dehydrogenation of octahydro naphthalene obtains naphthane.
- 2. according to the preparation method described in claim 1, it is characterised in that：More cyclic ketones are one or both of following a1, a2, a3 thing mixed above：More cyclic alcohol are one or both of following b1, b2, b3 thing mixed above：
- 3. according to the preparation method described in claim 1, it is characterised in that：Step 1), step 1 '), step 3) and step 3 ') in, the metallic catalyst include Raney Ni, Raney Co, One in Raney Cu, nickel aluminum hydrotalcite, cobalt aluminum hydrotalcite and support type Pt, Pd, Ru, Rh, Ir, Ni, Co, Cu catalyst Kind is two or more, wherein for loaded catalyst, carrier includes cerium oxide, aluminum oxide, magnesia, activated carbon, silica And mixture more than one or both of molecular sieve etc.；Step 2) and step 2 ') in, the acid catalyst is included more than one or both of liquid acid and solid acid, wherein, Liquid acid includes mixture more than one or both of sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid；Solid acid include acidic molecular sieve, More than one or both of acidic metal oxide, phosphotungstic acid, phosphomolybdic acid, p-methyl benzenesulfonic acid, sulfonation carbon, acidic resins Mixture；Acidic molecular sieve has more than one or both of H-Y, HZSM-5 etc., and acidic metal oxide has niobium oxide, oxidation More than one or both of tantalum etc., acidic resins have one kind or two in Amberlyst catalyst series, Nafion resins etc. More than kind.
- 4. according to the preparation method described in claim 1, it is characterised in that：Step 1), step 2), step 3), step 1 '), step 2 ') and step 3 ') reaction can enter under condition of no solvent OK, reaction temperature is at 20 DEG C -300 DEG C；Reactor uses tank reactor, fixed bed reactors or water knockout drum reaction unit；The condition of tank reactor is：Catalyst amount is the 0.1%-50% of reaction raw materials quality；Reaction time is 0.5h- 48h；Reaction pressure is 0.1MPa-10.0MPa；The condition of fixed bed reactors is：Reaction pressure is between 0.1MPa-10.0MPa, reaction raw materials/catalyst quality air speed In 0.1h-1-10.0h-1；N2Or H2Mol ratio with reaction raw materials is 8-1500；The reaction condition of water knockout drum reaction unit is：Catalyst amount is the 0.1%-50% of reaction raw materials quality；Reaction time For 0.5h-48h.
- 5. decahydronaphthalene and/or Tetrahydronaphthalencompounds compounds made from a kind of any preparation methods of claim 1-4.
- 6. according to decahydronaphthalene and Tetrahydronaphthalencompounds compounds described in claim 5, it is characterised in that：Can directly as aviation kerosine or As additives for jet fuel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610822812.3A CN107814676B (en) | 2016-09-14 | 2016-09-14 | Preparation method of decahydronaphthalene and tetrahydronaphthalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610822812.3A CN107814676B (en) | 2016-09-14 | 2016-09-14 | Preparation method of decahydronaphthalene and tetrahydronaphthalene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107814676A true CN107814676A (en) | 2018-03-20 |
| CN107814676B CN107814676B (en) | 2021-12-28 |
Family
ID=61601077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610822812.3A Active CN107814676B (en) | 2016-09-14 | 2016-09-14 | Preparation method of decahydronaphthalene and tetrahydronaphthalene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107814676B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114436208A (en) * | 2022-01-30 | 2022-05-06 | 北京东方红升新能源应用技术研究院有限公司 | Catalytic hydrogen supply system based on organic liquid and hydrogen supply method thereof |
| CN115746923A (en) * | 2022-10-21 | 2023-03-07 | 中国科学院广州能源研究所 | Method for preparing aviation fuel from lignin derivatives |
| WO2023245790A1 (en) * | 2022-06-21 | 2023-12-28 | 中节能万润股份有限公司 | Method for preparing cycloalkane from cyclic alcohol in one step by means of molecular sieve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009046398A (en) * | 2007-08-13 | 2009-03-05 | National Institute Of Advanced Industrial & Technology | Naphthalenes hydrogenation catalyst |
| CN102227261A (en) * | 2008-11-28 | 2011-10-26 | 弗门尼舍有限公司 | Hydrogenation of ester, ketone or aldehyde groups with ruthenium complexes having di-amine and phosphorous-nitrogen bidentate ligand |
| CN105838410A (en) * | 2016-06-07 | 2016-08-10 | 浙江工业大学 | Method for preparing aviation fuels by non-hydrogen conversion of high-water-content oils/greases |
-
2016
- 2016-09-14 CN CN201610822812.3A patent/CN107814676B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009046398A (en) * | 2007-08-13 | 2009-03-05 | National Institute Of Advanced Industrial & Technology | Naphthalenes hydrogenation catalyst |
| CN102227261A (en) * | 2008-11-28 | 2011-10-26 | 弗门尼舍有限公司 | Hydrogenation of ester, ketone or aldehyde groups with ruthenium complexes having di-amine and phosphorous-nitrogen bidentate ligand |
| CN105838410A (en) * | 2016-06-07 | 2016-08-10 | 浙江工业大学 | Method for preparing aviation fuels by non-hydrogen conversion of high-water-content oils/greases |
Non-Patent Citations (4)
| Title |
|---|
| M. B. TUROVA-POLLAK等: "Isomerization of polymethylene hydrocarbons under the influence of aluminum chloride. XVIII. Isomerization of dicyclopentyl", 《ZHURNAL OBSHCHEI KHIMII》 * |
| NORIHITO HIYOSHI等: "Hydrogenation of benzothiophene-free naphthalene over charcoal-supported metal catalysts in supercritical carbon dioxide solvent", 《APPLIED CATALYSIS A: GENERAL》 * |
| RAN WANG等: "Synthesis of Decaline-Type Thermal-Stable Jet Fuel Additives with Cycloketones", 《ACS SUSTAINABLE CHEM. ENG.》 * |
| XUERU SHENG等: "Synthesis of high density aviation fuel with cyclopentanol derived from lignocellulose", 《SCIENTIFIC REPORTS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114436208A (en) * | 2022-01-30 | 2022-05-06 | 北京东方红升新能源应用技术研究院有限公司 | Catalytic hydrogen supply system based on organic liquid and hydrogen supply method thereof |
| CN114436208B (en) * | 2022-01-30 | 2023-12-05 | 北京东方红升新能源应用技术研究院有限公司 | Catalytic hydrogen supply system based on organic liquid and hydrogen supply method thereof |
| WO2023245790A1 (en) * | 2022-06-21 | 2023-12-28 | 中节能万润股份有限公司 | Method for preparing cycloalkane from cyclic alcohol in one step by means of molecular sieve |
| CN115746923A (en) * | 2022-10-21 | 2023-03-07 | 中国科学院广州能源研究所 | Method for preparing aviation fuel from lignin derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107814676B (en) | 2021-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103087748B (en) | Preparation method of aviation kerosene or diesel | |
| Shylesh et al. | Novel strategies for the production of fuels, lubricants, and chemicals from biomass | |
| CN104711021B (en) | Method for preparing cycloparaffin as aviation kerosene or diesel oil by biomass route | |
| Pourzolfaghar et al. | Atmospheric hydrodeoxygenation of bio-oil oxygenated model compounds: A review | |
| CN103805224B (en) | A kind of preparation method of aerial kerosene | |
| CN103450940B (en) | A kind of method being prepared aviation kerosene and diesel oil by biomass derivatives | |
| CN104119943B (en) | A kind of method that furyl oxygen-containing organic compound hydrogenation deoxidation prepares aerial kerosene | |
| CN105273739B (en) | Preparation method for aviation kerosene | |
| CN108130112B (en) | The method that one kettle way or one-step method prepare diesel oil or aviation kerosine | |
| Ma et al. | Alumina supported molybdenum catalyst for lignin valorization: effect of reduction temperature | |
| CN104711007A (en) | Preparation method of aviation kerosene or diesel oil scope liquid alkane | |
| CN102850157B (en) | Novel technique for preparing long-chain alkane efficiently through multifunctional catalyst in one-step method | |
| CN105713642B (en) | Method for synthesizing high density aviation fuel from lignocellulose | |
| Palankoev et al. | Promising processes for producing drop-in biofuels and petrochemicals from renewable feedstock | |
| Kong et al. | Production of liquid fuel intermediates from furfural via aldol condensation over La2O2CO3-ZnO-Al2O3 catalyst | |
| CN107987868B (en) | Method for preparing liquid fuel by stepwise deoxygenation of grease | |
| CN107814676A (en) | A kind of preparation method of decahydronaphthalene and naphthane | |
| CN104711012A (en) | Applications of hydrodeoxygenation catalyst in synthesis of renewable diesel fuel or aviation kerosene | |
| CN101428229B (en) | Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof | |
| Yu et al. | Recent applications of nickel and nickel-based bimetallic catalysts for hydrodeoxygenation of biomass-derived oxygenates to fuels | |
| CN107446611B (en) | A kind of preparation method of aviation kerosine cycloalkane and aromatic hydrocarbons | |
| KR101670515B1 (en) | A method for preparing paraffin from ketone | |
| CN109718850B (en) | Method for preparing aviation kerosene precursor | |
| WO2020051956A1 (en) | Method for producing methylbenzyl alcohol by catalytic conversion of ethanol and catalyst therefor | |
| WO2022156342A1 (en) | Method for preparing fuel from light bio-oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |