CN102838441A - Method for producing trans-decahydronaphthalene through naphthalene hydrogenation - Google Patents
Method for producing trans-decahydronaphthalene through naphthalene hydrogenation Download PDFInfo
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Abstract
The present invention discloses a method for producing trans-decahydronaphthalene through naphthalene hydrogenation. According to the method, a fixed bed reactor is adopted; naphthalene and hydrogen are subjected to a reverse contact in the reactor; in the presence of a hydrogenation catalyst, a hydrogenation reaction is performed under a hydrogenation reaction condition to obtain the trans-decahydronaphthalene, wherein the hydrogenation catalyst comprises a ZSM-5 molecular sieve, an alkali metal, a VIII group metal, an auxiliary agent and silicon dioxide. With the method of the present invention, the naphthalene and the hydrogen are subjected to counterflow contact, such that the content of the trans-decahydronaphthalene produced through naphthalene hydrogenation under the suitable reaction condition can be more than 80 wt%, separation purification efficiency can be significantly improved, and target product production cost can be reduced.
Description
Technical field
The present invention relates to a kind of method of naphthalene hydrogenation, particularly a kind of naphthalene hydrogenation is produced the method for trans-decalin.
Background technology
Perhydronaphthalene belongs to the condensed ring hydrocarbon polymer, has trans and two kinds of configuration bodies of cis.Perhydronaphthalene all has very extensively and important use in chemical industry, electronic industry (for example the decahydro naphthalene derivatives is good liquid crystal raw material) and pharmaceutical industries; For example perhydronaphthalene can be used as the solvent of ultra high molecular weight polyethylene, also can be used as the hydrogen storage material etc. of solvent, varnish remover and the decentralized fuel cell of lubricant, fat extraction agent, coating, grease, resin, rubber etc.Trans, cis-decaline also respectively has its purposes: the thermostability of trans-decalin is superior to long chain alkane, is to improve the requisite interpolation component of aviation kerosene thermostability; Cis-decaline is mainly used in produces sebacic acid and then produces nylon 6, nylon 10 and softening agent.The production of perhydronaphthalene in the market mainly is the hydrogenation that comes from naphthalene, has stronger practicality and considerable economic value so investigate naphthalene hydrogenation production perhydronaphthalene.
The existing some correlative study reports of the hydrogenation reaction of naphthalene (for example: Gyorgy G; Akos R; Gyongyi H. Hydrogenation activity of reduced and sulfided catalysts:Hydrogenation of naphthalene by nickel-molybdenum/alumina catalyst. [J]. Magy Kem Lapja; 1992.47 (6-7): 259 ~ 263. with Koki I; Yoshifumi K, Hideki K. Preliminary study on mechanism of naphthalene hydrogenation to form decalins via tetralin over Pt/TiO
2[J] .Ind Eng Chem Res; 1995.34 (4): 1140 ~ 1148.); Also there is a small amount of document that the selectivity generation of anti-in the reaction/suitable perhydronaphthalene (for example: Huang T C, Kang B C, Naphthalene hydrogenation over Pt/Al has been carried out inquiring in recent years
2O
3Catalyst in a trickle bed reactor [J]. Ind Eng Chem.Res.1995,34 (7): 2349 ~ 2357).Someone is showing the result of study on the molecular sieve carried noble metal catalyst; Catalyzer is formed and processing condition can influence anti-in the naphthalene hydrogenation products/suitable isomer proportion (Huang T C, Kang B C. The hydrogenation of naphthalene with Pt/Al to a certain extent
2O
3Phosphate catalysts. [J]. Ind Eng Chem. Res, 1995,34 (9): 2955 ~ 2963.).The more hydrogenation reaction that is used for naphthalene such as precious metals pt, Pd; Yet cost an arm and a leg; Easy inactivation under the harsh reaction conditions of HTHP has the catalyst based investigation of carrying out the naphthalene hydrogenation of the cheap Ni of human, (for example: Monica M has also obtained ideal results; Angelo V. Vapors phase hydrogenation of naphthalene on a novel Ni-containing mesoporous aluminosilicate catalyst. [J]. applied catalysis; A:general, 2002,231 (1 ~ 2): 263 ~ 268.).
CN200310106565 discloses a kind of compound method of perhydronaphthalene; Be to be raw material with the naphthalene; Adopt naphthane as the solvent of solid raw naphthalene material, the nickel catalyst Technology of one-step synthesis perhydronaphthalene in the reaction kettle under lower pressure and temperature, its reaction pressure is that 6～12MPa, temperature of reaction are 180 ℃～220 ℃, volume space velocity (LHSV) is 0.5～1.0 h during liquid
-1, the transformation efficiency of naphthalene reaches more than 98%, and the productive rate of perhydronaphthalene reaches 98%, and the side reaction thing is less than 1%.Though this method has obtained result preferably,,, be difficult to satisfy the large-scale market requirement, and the ratio of the perhydronaphthalene of the not isomorphism type in the product can not be controlled so production efficiency is very low owing to be the batch operation that in reaction kettle, carries out.
CN200510041404.6 discloses a kind of continuous hydrogenation synthesis method of perhydronaphthalene, and this method is the working method of the synthetic perhydronaphthalene of naphthalene continuous hydrogenation in stable state trickle bed catalyticreactor, under certain pressure and temperature condition.Adopt perhydronaphthalene or naphthane as the solvent of solid raw naphthalene material, adopt catalyzer such as platinum aluminium or nickel aluminium, 2～15MPa, 120～280 ℃, volume space velocity (LHSV) is 0.1～5.0h during liquid
-1, the synthetic perhydronaphthalene of continuous hydrogenation under hydrogen-oil ratio 1～3000NL/L condition, the transformation efficiency of its naphthalene is 70%～99%, the side reaction thing is less than 1%.Though this technology can realize quantity-produced, because poor stability, the process cost of this Technology aspect control transformation efficiency higher, naphthalene also awaits further raising, and the ratio of the perhydronaphthalene of the not isomorphism type in the product can not be controlled.
Because there is the product (cis-decaline and trans-decalin) of two kinds of configurations in perhydronaphthalene, there is evident difference in the perhydronaphthalene of these two kinds of configurations in nature, also be used in different aspects; For example high-performance plasticizer just must use highly purified cis-decaline, and trans-decalin is an important added ingredients in the boat coal; Medicine synthetic with liquid crystal aspect all use the perhydronaphthalene of highly purified not isomorphism type, and these two kinds of configuration perhydronaphthalenes are because thermodynamic (al) stability difference, so in general technology; The aromatic ring of naphthalene is in saturation history; Because catalyzer or reaction conditions are different, possibly cause the product of certain configuration preferentially to generate, and the product of other a kind of configuration are relatively low; But the perhydronaphthalene of these two kinds of configurations is under hydro condition; On catalyzer, can transform mutually rapidly, be easy to reach near equilibrated and be about 1:2 (cis-product about 33%) along reverse proportionality, the content of trans product is no more than 70wt% in the product.Such mixture is difficult to meet the demands in some application facet, obtain pure product, must increase the production cost of purpose product widely through complex separation process.
Summary of the invention
For overcoming weak point of the prior art; The invention provides a kind of naphthalene hydrogenation and produce the method for trans-decalin; This method can make the content of the trans-decalin that the naphthalene hydrogenation generates more than 80wt%, can improve significantly and separate purification efficiency and reduce the purpose production cost of products.
Naphthalene hydrogenation of the present invention is produced the method for trans-decalin, adopts fixed-bed reactor, and naphthalene and hydrogen reverse contact in reactor drum are in the presence of hydrogenation catalyst; Under hydrogenation conditions, carry out hydrogenation reaction, obtain trans-decalin, wherein said hydrogenation catalyst is a benchmark with the weight of catalyzer; The content of ZSM-5 molecular sieve is 10.0% ~ 80.0%, is preferably 20% ~ 70%, more preferably 30% ~ 60%, and alkali-metal content is 0.1% ~ 10.0%; Be preferably 0.5% ~ 8%, more preferably 1% ~ 5%, the content of group VIII metal is 0.01% ~ 5.0%, is preferably 0.1% ~ 3.0%; More preferably 0.2% ~ 2.0%, the content of auxiliary agent is preferably 0.5% ~ 5.0% in element 0.1% ~ 5.0%; More preferably 0.5% ~ 3% with the silicon-dioxide of surplus, described auxiliary agent is one or more in tin, lead, the rhenium, is preferably tin.Described hydrogenation conditions is following: the hydrogen dividing potential drop is 0.1MPa ~ 10.0MPa, and temperature is 100 ℃ ~ 500 ℃, and volume space velocity is 0.1 h
-1~ 10.0h
-1, hydrogen to oil volume ratio is 100 ~ 1000.
In the used naphthalene hydrogenation catalyst of the present invention, the SO of described ZSM-5 molecular sieve
2/ Al
2O
3Mol ratio is preferably more than 500 greater than 200, more preferably the pure silicon molecular sieve.Described basic metal is selected from one or more in lithium, sodium, potassium, rubidium, caesium and the francium, is preferably sodium or/and potassium, more preferably potassium.Described group VIII metal is selected from one or more in nickel, palladium, platinum, ruthenium, cobalt, rhodium and the iridium, is preferably palladium or and platinum, more preferably platinum.
The naphthalene hydrogenization catalyst preparation method that the present invention is used, but be not limited thereto method, comprising:
(1), ZSM-5 molecular sieve, alkali metal cpd, silicon-dioxide, extrusion aid and water fully mixed pinches into plastic paste, extruded moulding through super-dry and roasting, obtains support of the catalyst;
(2), group VIII metal and auxiliary agent are loaded on the support of the catalyst that step (1) makes, through super-dry and roasting, obtain naphthalene hydrogenation catalyst of the present invention.
Described silicon-dioxide surpasses 99% powdery substance for silica weight content, and the weight content of silicon-dioxide in catalyzer is 5% ~ 80%.Described silicon-dioxide is selected from one or more in WHITE CARBON BLACK, silica gel and the colloid silica.Described molybdic oxide be purity greater than 99.5wt%, granularity be 300 mesh sieve percent of pass greater than 95%, be preferably more than 98%.Described extrusion aid is the material that helps extruded moulding, can be selected from graphite, starch, Mierocrystalline cellulose and the sesbania powder one or more, is preferably the sesbania powder, and its add-on is 0.5% ~ 10% of a carrier butt weight, is preferably 1% ~ 5%.
Described group VIII metal of step (2) and auxiliary agent load on the support of the catalyst that step (1) makes, and mode of loading can adopt ion exchange method or pickling process.Group VIII metal and auxiliary agent can step load on support of the catalyst, also can load on the support of the catalyst simultaneously.Group VIII metal and auxiliary agent load can be adopted conventional water-soluble cpds to process the aqueous solution to be used for IX or dipping; Can adopt in muriate, nitrate salt, vitriol and the carbonate one or more such as containing the group VIII metallic compound, such as in Platinic chloride, the Palladous chloride etc. one or more.Contain auxiliary compound and can adopt in muriate, nitrate salt, vitriol and the carbonate one or more, such as tin chloride, nitric acid tin, stannous octoate.When adopting ion exchange method or pickling process, the volume of preparing nickeliferous solution is 1 times of catalyst volume ~ 10 times, and nickeliferous solution contacts certain hour with support of the catalyst.When adopting saturated pickling process, the solution containing nickel volume of preparation is the support of the catalyst s-adsorption, directly mixes or sprays on the support of the catalyst.
Drying conditions described in step (1) and (2) is normal temperature ~ 300 ℃ maintenance 1h ~ 48h, and step (1) can be identical with (2) described drying conditions, also can be different.The roasting condition of step (1) and (2) is 400 ℃ ~ 900 ℃ and keeps 0.5h ~ 10.0h that step (1) can be identical with (2) described roasting condition, also can be different.
Naphthalene hydrogenation catalyst of the present invention need carry out prereduction before use, and purpose is that the group VIII metal component on the catalyzer is converted into the simple substance state.Described prereduction condition: hydrogen partial pressure is 0.1MPa ~ 20.0MPa, is preferably 0.2MPa ~ 10.0MPa; Temperature is 100 ℃ ~ 600 ℃, is preferably 200 ℃ ~ 500 ℃; Gas agent volume ratio is 100 ~ 2000, is preferably 300 ~ 1500; The prereduction time is 0.1h ~ 24h, is preferably 1h ~ 12h; Reaction gas is preferably pure hydrogen for containing hydrogen.
In the inventive method; Naphthalene is that naphthalene gets into reactor drum as raw material from reactor drum top with hydrogen reverse contact in reactor drum; Hydrogen gets into reactor drum in reactor lower part, the hydrogenation conditions that adopts following: hydrogen partial pressure 0.1MPa ~ 10.0MPa is preferably 0.5MPa ~ 5.0MPa; Temperature of reaction is 100 ℃ ~ 500 ℃, is preferably 200 ℃ ~ 400 ℃; Volume space velocity 0.1 h
-1~ 10.0h
-1, be preferably 0.2 h
-1~ 5.0h
-1Hydrogen to oil volume ratio is 100 ~ 1000, is preferably 150 ~ 500.Used hydrogen feed preferably adopts pure hydrogen.
The inventive method adopts specific catalyst and suitable reaction conditions, and the content that can make the trans-decalin that the naphthalene hydrogenation generates can improve significantly and separate purification efficiency and reduce the purpose production cost of products more than 80wt%, is in particular in:
(1) adopted the ZSM-5 molecular sieve in the used hydrogenation catalyst, the pore passage structure regular, homogeneous of this molecular sieve provides suitable reaction environment for the naphthalene hydrogenation;
(2) utilize contacting of naphthalene raw material and hydrogen countercurrent direction; Avoided reactant in bigger duct, to pass beds fast; Guarantee that raw material fully contacts with active site on the catalyzer; And significantly increase the residence time of reactant (or product) on catalyzer, and promote the perhydronaphthalene of cis-structure to be converted into the more stable trans-decalin of structure fully, improve the transconfiguration product selectivity;
(3) because the naphthalene raw material is reverse the contact with hydrogen; Highly purified hydrogen (such as: temperature of reaction is high, the reactant quality is good, hydrogen purity is high) under better reaction environment reacts with reactant; Make the hydrogenation of naphthalene more complete, improve the transformation efficiency of naphthalene.
Embodiment
Further specify Preparation of catalysts process of the present invention through embodiment below, but invention should not be deemed limited among the following embodiment.Among the present invention, wt% is a massfraction, and mol% is an x.
Catalyzer of the present invention is to adopt the medium-sized fixed-bed reactor of 100ml to estimate, and loaded catalyst is 100ml, before the charging, carry out prereduction to hydrogenation catalyst, and condition is seen table 1.Appreciation condition is seen embodiment; Charging is that (for example raw naphthalene material gets into reactor drum from the reactor drum upper end to reverse the contact in reactor drum with hydrogen; Hydrogen gets into reactor drum in the reactor drum lower end); Reaction is carried out after 4 hours product being carried out composition analysis, calculate naphthalene transformation efficiency and the selectivity of trans-decalin, concrete method of calculation are following:
Naphthalene transformation efficiency=[(advance the weight of naphthalene in the reactor feedstocks-go out the weight of naphthalene in the reactor stream)/advance the weight of naphthalene in the reactor feedstocks] * 100%
Trans-decalin selectivity=(going out the mole number of mole number/naphthalene conversion of trans-decalin in the reactor stream) * 100%.
Embodiment 1
The concrete embodiment of present embodiment comprises following steps:
(1) Preparation of Catalyst: get 60 gram pure silicon ZSM-5 molecular sieves, 7.2 gram Pottasium Hydroxide, 35 gram WHITE CARBON BLACKs; 6 gram sesbania powder fully mix with an amount of water and pinch into plastic paste; Extruded moulding (1.5 millimeters of diameters) through 120 ℃ of dryings 8 hours and 550 ℃ of roastings 3 hours, obtains carrier; Get 3.2 gram tin chloride (SnCl
22H
2O) and 0.8 gram Platinic chloride be dissolved into and be configured to 200 ml solns in an amount of water; Carrier thorough mixing with this solution and above-mentioned preparation is evaporated to no open fire, and 8 hours, 500 ℃ roastings of 130 ℃ of dryings are after 4 hours; Make catalyzer of the present invention, its weight consists of: Pt/Sn/ZSM-5/K/SiO
2=0.3/1.7/60/5/33;
(2) catalyzer is carried out prereduction and handle, reductive condition is seen table 1;
(3) the naphthalene hydrogenation is estimated; Charging is that (raw material gets into reactor drum from the reactor drum upper end to reverse the contact in reactor drum with hydrogen; New hydrogen gets into reactor drum in the reactor drum lower end), processing condition are: hydrogen dividing potential drop 1.5MPa, temperature are that 320 ℃, volume space velocity are 1.0h
-1Hydrogen to oil volume ratio is 200.4 hours sampling analysis of catalyst runs are numbered E-1, and evaluation result is seen table 2.
Embodiment 2
The present embodiment scheme is with embodiment 1, and difference is that employed catalyzer consists of: Rh/Sn/ZSM-5/K/SiO
2=0.3/1.7/60/5/33, in step (3) processing condition, the hydrogen dividing potential drop is 0.5MPa, temperature is that 380 ℃, volume space velocity are 0.3h
-1Hydrogen to oil volume ratio is 150.Be numbered E-2, the catalyst reduction condition is seen table 1, and evaluation result is seen table 2.
Embodiment 3
The present embodiment scheme is with embodiment 1, and difference is that employed catalyzer consists of: Pt/Sn/ZSM-5/K/SiO
2=0.3/1.7/60/5/33, in step (3) processing condition, the hydrogen dividing potential drop is 1.0MPa, temperature is that 360 ℃, volume space velocity are 0.5h
-1Hydrogen to oil volume ratio is 150.Be numbered E-3, the catalyst reduction condition is seen table 1, and evaluation result is seen table 2.
Embodiment 4
The present embodiment scheme is with embodiment 1, and difference is that employed catalyzer consists of: Pt/Sn/ZSM-5/K/SiO
2=0.5/2.5/60/7/30, in step (3) processing condition, the hydrogen dividing potential drop is 2.0MPa, temperature is that 340 ℃, volume space velocity are 0.8h
-1Hydrogen to oil volume ratio is 200.Be numbered E-4, the catalyst reduction condition is seen table 1, and evaluation result is seen table 2.
Embodiment 5
Present embodiment is with embodiment 1, and difference is that employed catalyzer consists of: Pt/Sn/ZSM-5/K/SiO
2=0.5/2.5/60/7/30, in step (3) processing condition, the hydrogen dividing potential drop is 3.0MPa, temperature is that 300 ℃, volume space velocity are 0.5h
-1Hydrogen to oil volume ratio is 250, is numbered E-5, and the catalyst reduction condition is seen table 1, and evaluation result is seen table 2.
Embodiment 6
Present embodiment is with embodiment 1, and difference is that employed catalyzer consists of: Pt/Sn/ZSM-5/K/SiO
2=0.5/2.5/60/7/30, in step (3) processing condition, temperature of reaction is that 280 ℃, volume space velocity are 0.5h
-1, hydrogen to oil volume ratio is 300, is numbered E-6, the catalyst reduction condition is seen table 1, evaluation result is seen table 2.
Embodiment 7
Present embodiment is with embodiment 1, Pt/Pd/Sn/ZSM-5/K/SiO
2=0.1/0.2/1.7/60/5/33, in step (3) processing condition, temperature of reaction is that 240 ℃, volume space velocity are 0.2h
-1, hydrogen to oil volume ratio is 200, is numbered E-7, the catalyst reduction condition is seen table 1, evaluation result is seen table 2.
Embodiment 8
Present embodiment is with embodiment 1, and difference is that employed catalyzer consists of: Ru/Sn/ZSM-5/K/SiO
2=0.3/1.7/60/5/33 is numbered E-8, and the catalyst reduction condition is seen table 1, and evaluation result is seen table 2.
Comparative Examples 1
This Comparative Examples is with embodiment 1, and difference is that employed catalyzer consists of: Pt/ZSM-5/Al
2O
3=0.3/60/39.7, in step (3) processing condition, charging and hydrogen is and flows into reactor drum, and be numbered C-1, the catalyst reduction condition is seen table 1, and evaluation result is seen table 2.
Comparative Examples 2
This Comparative Examples is with Comparative Examples 1, and difference is that employed catalyzer consists of: Pt/Pd/ZSM-5/Al
2O
3=0.1/0.2/60/39.7, in step (3) processing condition, charging and hydrogen is and flows into reactor drum, and be numbered C-2, the catalyst reduction condition is seen table 1, and evaluation result is seen table 2.
The reductive condition of each embodiment of table 1 and Comparative Examples
| Catalyzer | E-1~E-3 | E-4~ E-6 | E-7~ E-8 | C-1~C-2 |
| Reductive condition: | ? | ? | ? | ? |
| The hydrogen dividing potential drop, MPa | 1.0 | 0.5 | 5.0 | 1.0 |
| Temperature, ℃ | 320 | 380 | 480 | 320 |
| Volume space velocity, h -1 | 1.0 | 0.5 | 2.0 | 1.0 |
| Gas agent volume ratio | 400 | 600 | 800 | 400 |
| Recovery time, hour | 8 | 12 | 3 | 8 |
The evaluation result of each embodiment of table 2 and Comparative Examples
| ? | The catalyzer numbering | The naphthalene transformation efficiency, wt% | The trans-decalin selectivity, mol% |
| Embodiment 1 | E-1 | 99.5 | 86.5 |
| Embodiment 2 | E-2 | 99.1 | 82.8 |
| Embodiment 3 | E-3 | 99.1 | 84.2 |
| Embodiment 4 | E-4 | 99.4 | 88.5 |
| Embodiment 5 | E-5 | 99.0 | 90.4 |
| Embodiment 6 | E-6 | 99.4 | 91.7 |
| Embodiment 7 | E-7 | 99.3 | 85.3 |
| Embodiment 8 | E-8 | 99.7 | 86.2 |
| Comparative Examples 1 | C-1 | 98.8 | 67.2 |
| Comparative Examples 2 | C-2 | 99.0 | 66.7 |
Annotate: 4 hours sampling analysis of catalyst runs.
Can find out that from the result of table 1 the present invention produces in the reaction of perhydronaphthalene at the naphthalene hydrogenation, compare that when the naphthalene transformation efficiency was suitable, the trans-decalin selectivity was high more than 15% in the product that the present invention's technology is produced with Comparative Examples.The result shows that the inventive method has remarkable advantages in the reaction of naphthalene hydrogenation production trans-decalin.
Claims (14)
1. the method that the naphthalene hydrogenation is produced trans-decalin adopts fixed-bed reactor, naphthalene and hydrogen reverse contact in reactor drum; In the presence of hydrogenation catalyst, under hydrogenation conditions, carry out hydrogenation reaction, obtain trans-decalin; Wherein said naphthalene hydrogenation catalyst is a benchmark with the weight of catalyzer, and the content of ZSM-5 molecular sieve is 10.0% ~ 80.0%; Alkali-metal content is 0.1% ~ 10.0%; The content of group VIII metal is 0.01% ~ 5.0%, and the content of auxiliary agent is the silicon-dioxide in element 0.1% ~ 5.0% and surplus, and described auxiliary agent is one or more in tin, lead, the rhenium; Described hydrogenation conditions is following: the hydrogen dividing potential drop is 0.1MPa ~ 10.0MPa, and temperature is 100 ℃ ~ 500 ℃, and volume space velocity is 0.1 h
-1~ 10.0h
-1, hydrogen to oil volume ratio is 100 ~ 1000.
2. according to the described method of claim 1; It is characterized in that described naphthalene hydrogenation catalyst; Weight with catalyzer is benchmark, and the content of ZSM-5 molecular sieve is 20% ~ 70%, and alkali-metal content is 0.5% ~ 8%; The content of group VIII metal is 0.1% ~ 3.0%, and the content of auxiliary agent is the silicon-dioxide in element 0.5% ~ 5.0% and surplus.
3. according to the described method of claim 1; It is characterized in that described naphthalene hydrogenation catalyst; Weight with catalyzer is benchmark, and the content of ZSM-5 molecular sieve is 30% ~ 60%, and alkali-metal content is 1% ~ 5%; The content of group VIII metal is 0.2% ~ 2.0%, and the content of auxiliary agent is the silicon-dioxide in element 0.5% ~ 3% and surplus.
4. according to the described method of claim 1, it is characterized in that the hydrogenation conditions that adopts following: hydrogen partial pressure 0.5MPa ~ 5.0MPa, temperature of reaction is 200 ℃ ~ 400 ℃, volume space velocity is 0.2 h
-1~ 5.0h
-1, hydrogen to oil volume ratio is 150 ~ 500.
5. according to the described method of claim 1, it is characterized in that used hydrogen feed adopts pure hydrogen.
6. according to the described method of claim 1, it is characterized in that the SO of described ZSM-5 molecular sieve
2/ Al
2O
3Mol ratio is greater than 200.
7. according to the described method of claim 1, it is characterized in that described ZSM-5 molecular sieve is the pure silicon molecular sieve.
8. according to the described method of claim 1, it is characterized in that described basic metal is selected from one or more in lithium, sodium, potassium, rubidium, caesium and the francium.
9. according to the described method of claim 1, it is characterized in that described basic metal is selected from sodium or/and potassium.
10. according to the described method catalyzer of claim 1, it is characterized in that described group VIII metal is selected from one or more in nickel, palladium, platinum, ruthenium, cobalt, rhodium and the iridium.
11., it is characterized in that described group VIII metal is platinum and/or palladium according to the described method of claim 1.
12., it is characterized in that described auxiliary agent is a tin according to the described method of claim 1.
13. according to the described method of claim 1; It is characterized in that described naphthalene hydrogenation catalyst need carry out prereduction before use; Described prereduction condition is following: hydrogen partial pressure is 0.1MPa ~ 20.0MPa, and temperature is 100 ℃ ~ 600 ℃, and gas agent volume ratio is 100 ~ 2000; The prereduction time is 0.1h ~ 24h, and reaction gas is a hydrogen-containing gas.
14. according to the described method of claim 13, it is characterized in that described prereduction condition is following: hydrogen partial pressure is 0.2MPa ~ 10.0MPa, temperature is 200 ℃ ~ 500 ℃, and gas agent volume ratio is 300 ~ 1500; The prereduction time is 1h ~ 12h; Reaction gas is pure hydrogen.
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| CN104130095A (en) * | 2014-08-04 | 2014-11-05 | 西安近代化学研究所 | Cis-decahydronaphthalene and trans-decahydronaphthalene separating method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130095A (en) * | 2014-08-04 | 2014-11-05 | 西安近代化学研究所 | Cis-decahydronaphthalene and trans-decahydronaphthalene separating method |
| CN104130095B (en) * | 2014-08-04 | 2015-10-28 | 西安近代化学研究所 | A kind of method being separated cis-decaline and trans-decalin |
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