CN102838441B - 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 condensed ring hydrocarbon polymer, has trans and two kinds of configuration bodies of cis.Perhydronaphthalene for example, all has very extensive and important application in chemical industry, electronic industry (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 of solvent, varnish remover and the decentralized fuel cell of lubricant, fat extraction agent, coating, grease, resin, rubber etc. etc.Trans, cis-decaline also respectively has its purposes: the thermostability of trans-decalin is better than long chain alkane, is to improve the requisite interpolation component of aviation kerosene thermostability; Cis-decaline is mainly for the production of sebacic acid and then produce nylon 6, nylon 10 and softening agent.The production of perhydronaphthalene is in the market mainly the hydrogenation that comes from naphthalene, has stronger practicality and considerable economic worth so investigate naphthalene hydrogenation production perhydronaphthalene.
The existing some correlative studys of hydrogenation reaction of naphthalene (for example: Gyorgy G are reported, 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. and 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 in recent years a small amount of document to generate and (for example: Huang T C, Kang B C, Naphthalene hydrogenation over Pt/Al carried out inquiring into the selectivity of anti-in reaction/suitable perhydronaphthalene
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 molecular sieve carried noble metal catalyst, catalyzer composition and processing condition can affect anti-in 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.).Precious metals pt, Pd etc. are used for the hydrogenation reaction of naphthalene, but expensive, easy inactivation under the harsh reaction conditions of High Temperature High Pressure, someone is with the catalyst based investigation of carrying out naphthalene hydrogenation of cheap Ni, also (for example: Monica M obtained desirable result, 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 synthetic method of perhydronaphthalene, taking naphthalene as raw material, adopt naphthane as the solvent of solid raw naphthalene material, the nickel catalyst Technology of one-step synthesis perhydronaphthalene in reactor under lower pressure and temperature, its reaction pressure is that 6～12MPa, temperature of reaction are 180 DEG C～220 DEG C, volume space velocity (LHSV) is 0.5～1.0 h when liquid
-1, the transformation efficiency of naphthalene reaches more than 98%, and the productive rate of perhydronaphthalene reaches 98%, and side reaction thing is less than 1%.Although the method has obtained good result, owing to being the batch operation carrying out in reactor, so production efficiency is very low, be difficult to meet the large-scale market requirement, and the ratio of the perhydronaphthalene of not isomorphism type in product can not be controlled.
CN200510041404.6 discloses a kind of continuous hydrogenation synthesis method of perhydronaphthalene, and the method is the production 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 the catalyzer such as platinum aluminium or nickel aluminium, 2～15MPa, 120～280 DEG C, volume space velocity (LHSV) is 0.1～5.0h when 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%, side reaction thing is less than 1%.Although this technology can realize quantity-produced, because this Technology also awaits further raising at the poor stability aspect control, process cost transformation efficiency higher, naphthalene, and the ratio of the perhydronaphthalene of not isomorphism type in product can not be controlled.
Due to the product (cis-decaline and trans-decalin) of two kinds of configurations of perhydronaphthalene existence, there is obvious difference in nature in the perhydronaphthalene of these two kinds of configurations, also be used in different aspects, for example high-performance plasticizer, just must use highly purified cis-decaline, trans-decalin is important added ingredients in boat coal, aspect synthetic and liquid crystal, all use the perhydronaphthalene of highly purified not isomorphism type at medicine, and these two kinds of configuration perhydronaphthalenes are due to thermodynamic (al) stability difference, so in general technique, the aromatic ring of naphthalene is in saturation history, due to catalyzer or reaction conditions difference, may cause the product of certain configuration preferentially to generate, and the product of another configuration is 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 the suitable reverse proportionality that approaches balance and be about 1:2(cis-product approximately 33%), in product, the content of trans product is no more than 70wt%.Such mixture is difficult to meet the demands in some application aspect, obtain pure product, must, through complicated sepn process, increase widely the production cost of object product.
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, the method can make the content of trans-decalin that naphthalene hydrogenation generates more than 80wt%, can improve significantly separating-purifying efficiency and reduce the production cost of object product.
Naphthalene hydrogenation of the present invention is produced the method for trans-decalin, adopt fixed-bed reactor, naphthalene and hydrogen reverse contact in reactor, under hydrogenation catalyst exists, under hydrogenation conditions, carry out hydrogenation reaction, obtain trans-decalin, wherein said hydrogenation catalyst, taking the weight of catalyzer as benchmark, the content of ZSM-5 molecular sieve is 10.0% ~ 80.0%, be preferably 20% ~ 70%, more preferably 30% ~ 60%, 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%, be preferably 0.1% ~ 3.0%, more preferably 0.2% ~ 2.0%, the content of auxiliary agent is in element 0.1% ~ 5.0%, be preferably 0.5% ~ 5.0%, more preferably 0.5% ~ 3% and the silicon-dioxide of surplus, described auxiliary agent is tin, plumbous, one or more in rhenium, be preferably tin.Described hydrogenation conditions is as follows: hydrogen dividing potential drop is 0.1MPa ~ 10.0MPa, and temperature is 100 DEG C ~ 500 DEG C, and volume space velocity is 0.1 h
-1~ 10.0h
-1, hydrogen to oil volume ratio is 100 ~ 1000.
In the present invention's naphthalene hydrogenation catalyst used, the SO of described ZSM-5 molecular sieve
2/ Al
2o
3mol ratio is greater than 200, is preferably more than 500, more preferably pure silicon molecular sieve.Described basic metal is selected from one or more in lithium, sodium, potassium, rubidium, caesium and 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 iridium, is preferably palladium or and platinum, more preferably platinum.
The preparation method of the present invention's naphthalene hydrogenation catalyst used, but be not limited to this method, comprising:
(1), abundant to ZSM-5 molecular sieve, alkali metal compound, silicon-dioxide, extrusion aid and water kneading is become to plastic paste, extruded moulding, through super-dry and roasting, obtains support of the catalyst;
(2), group VIII metal and auxiliary agent are loaded in 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 is that silica weight content exceedes 99% powdery substance, 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 colloid silica.Described molybdic oxide is that purity is greater than 99.5wt%, granularity is that 300 mesh sieve percent of pass are greater than 95%, is preferably more than 98%.Described extrusion aid is the material that is conducive to extruded moulding, can be selected from one or more in graphite, starch, Mierocrystalline cellulose and sesbania powder, is preferably sesbania powder, and its add-on is 0.5% ~ 10% of carrier butt weight, is preferably 1% ~ 5%.
The group VIII metal that step (2) is described and auxiliary agent load in 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 in support of the catalyst simultaneously.Group VIII metal and auxiliary agent load can adopt conventional water-soluble cpds to make the aqueous solution for ion-exchange or dipping, such as can adopt one or more in muriate, nitrate, vitriol and carbonate containing group VIII metallic compound, such as one or more in Platinic chloride, Palladous chloride etc.Can adopt one or more in muriate, nitrate, vitriol and carbonate containing auxiliary compound, such as tin chloride, nitric acid tin, stannous octoate.In the time adopting ion exchange method or pickling process, the volume of preparing nickeliferous solution is catalyst volume 1 times ~ 10 times, nickeliferous solution contacts certain hour with support of the catalyst.In the time adopting saturated pickling process, the solution containing nickel volume of preparation is support of the catalyst saturated extent of adsorption, directly mixes or sprays in support of the catalyst.
Drying conditions described in step (1) and (2) is that normal temperature ~ 300 DEG C keep 1h ~ 48h, and the described drying conditions in step (1) and (2) can be identical, also can be different.The roasting condition of step (1) and (2) is 400 DEG C ~ 900 DEG C maintenance 0.5h ~ 10.0h, and the described roasting condition in step (1) and (2) can be identical, also can be different.
Naphthalene hydrogenation catalyst of the present invention needs to carry out prereduction before use, and object is that the group VIII metal component on catalyzer is converted into simple substance state.Described prereduction condition: hydrogen partial pressure is 0.1MPa ~ 20.0MPa, is preferably 0.2MPa ~ 10.0MPa; Temperature is 100 DEG C ~ 600 DEG C, is preferably 200 DEG C ~ 500 DEG C; Gas agent volume ratio is 100 ~ 2000, is preferably 300 ~ 1500; The prereduction time is 0.1h ~ 24h, is preferably 1h ~ 12h; Reaction gas, for containing hydrogen, is preferably pure hydrogen.
In the inventive method, naphthalene is that naphthalene enters reactor as raw material from reactor top with hydrogen reverse contact in reactor, hydrogen enters reactor in reactor lower part, the hydrogenation conditions that adopts as follows: hydrogen partial pressure 0.1MPa ~ 10.0MPa, is preferably 0.5MPa ~ 5.0MPa; Temperature of reaction is 100 DEG C ~ 500 DEG C, is preferably 200 DEG C ~ 400 DEG C; Volume space velocity 0.1 h
-1~ 10.0h
-1, be preferably 0.2 h
-1~ 5.0h
-1; Hydrogen to oil volume ratio is 100 ~ 1000, is preferably 150 ~ 500.Hydrogen feed used preferably adopts pure hydrogen.
The inventive method adopts specific catalyzer and suitable reaction conditions, can make the content of trans-decalin that naphthalene hydrogenation generates more than 80wt%, can improve significantly separating-purifying efficiency and reduce the production cost of object product, is in particular in:
(1) in hydrogenation catalyst used, adopted ZSM-5 molecular sieve, the pore passage structure of regular, the homogeneous of this molecular sieve provides suitable reaction environment for naphthalene hydrogenation;
(2) utilize contacting of naphthalene raw material and hydrogen countercurrent direction, avoid reactant in larger duct, to pass fast beds, ensure that raw material fully contacts with the active centre on catalyzer, and significantly increase the residence time of reactant (or product) on catalyzer, promote the perhydronaphthalene of cis-structure to be converted into fully the trans-decalin that structure is more stable, improve the selectivity of transconfiguration product;
(3) because naphthalene raw material and hydrogen are reverse contacts, highly purified hydrogen under better reaction environment (such as: temperature of reaction is high, reactant quality is good, hydrogen purity is high) react with reactant, make the hydrogenation of naphthalene more complete, improve the transformation efficiency of naphthalene.
Embodiment
Further illustrate the preparation process of catalyzer of the present invention below by embodiment, but invention should not be deemed limited in following embodiment.In the present invention, wt% is massfraction, and mol% is molar fraction.
Catalyzer of the present invention is to adopt the medium-sized fixed-bed reactor of 100ml to evaluate, and loaded catalyst is 100ml, before charging, carry out prereduction to hydrogenation catalyst, and condition is in table 1.Appreciation condition is shown in embodiment, charging is that (for example raw naphthalene material enters reactor from reactor upper end to reverse contact with hydrogen in reactor, hydrogen enters reactor in reactor lower end), reaction is carried out, after 4 hours, product is carried out to composition analysis, calculate naphthalene transformation efficiency and the selectivity of trans-decalin, concrete method of calculation are as follows:
Naphthalene transformation efficiency=[(enter the weight of naphthalene in reactor feedstocks-go out the weight of naphthalene in reactor stream)/enter the weight of naphthalene in reactor feedstocks] × 100%
Trans-decalin selectivity=(going out the mole number of mole number/naphthalene conversion of trans-decalin in reactor stream) × 100%.
embodiment 1
The present embodiment specific embodiment comprises following steps:
(1) catalyzer preparation: get 60 grams of pure silicon ZSM-5 molecular sieves, 7.2 grams of potassium hydroxide, 35 grams of white carbon blacks, 6 grams of sesbania powder become plastic paste with the appropriate abundant kneading of water, extruded moulding (1.5 millimeters of diameters), through 120 DEG C of dry 8 hours and 550 DEG C of roastings 3 hours, obtains carrier; Get 3.2 grams of tin chloride (SnCl
22H
2o) and 0.8 gram of Platinic chloride is dissolved into and in appropriate water, is configured to 200 ml solns, this solution is fully mixed with the carrier of above-mentioned preparation, be evaporated to without open fire, 130 DEG C of dry 8 hours, 500 DEG C roastings 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 to prereduction processing, reductive condition is in table 1;
(3) naphthalene hydrogenation is evaluated, charging is that (raw material enters reactor from reactor upper end to reverse contact with hydrogen in reactor, new hydrogen enters reactor in reactor lower end), processing condition are: hydrogen dividing potential drop 1.5MPa, temperature are that 320 DEG C, volume space velocity are 1.0h
-1; Hydrogen to oil volume ratio is 200.4 hours sampling analysis of catalyst runs, are numbered E-1, and evaluation result is in table 2.
embodiment 2
The present embodiment scheme is with embodiment 1, and difference is that used catalyzer consists of: Rh/Sn/ZSM-5/K/SiO
2=0.3/1.7/60/5/33, in step (3) processing condition, hydrogen dividing potential drop is 0.5MPa, temperature is that 380 DEG C, volume space velocity are 0.3h
-1; Hydrogen to oil volume ratio is 150.Be numbered E-2, catalyst reduction condition is in table 1, and evaluation result is in table 2.
embodiment 3
The present embodiment scheme is with embodiment 1, and difference is that used catalyzer consists of: Pt/Sn/ZSM-5/K/SiO
2=0.3/1.7/60/5/33, in step (3) processing condition, hydrogen dividing potential drop is 1.0MPa, temperature is that 360 DEG C, volume space velocity are 0.5h
-1; Hydrogen to oil volume ratio is 150.Be numbered E-3, catalyst reduction condition is in table 1, and evaluation result is in table 2.
embodiment 4
The present embodiment scheme is with embodiment 1, and difference is that used catalyzer consists of: Pt/Sn/ZSM-5/K/SiO
2=0.5/2.5/60/7/30, in step (3) processing condition, hydrogen dividing potential drop is 2.0MPa, temperature is that 340 DEG C, volume space velocity are 0.8h
-1; Hydrogen to oil volume ratio is 200.Be numbered E-4, catalyst reduction condition is in table 1, and evaluation result is in table 2.
embodiment 5
The present embodiment is with embodiment 1, and difference is that used catalyzer consists of: Pt/Sn/ZSM-5/K/SiO
2=0.5/2.5/60/7/30, in step (3) processing condition, hydrogen dividing potential drop is 3.0MPa, temperature is that 300 DEG C, volume space velocity are 0.5h
-1; Hydrogen to oil volume ratio is 250, is numbered E-5, and catalyst reduction condition is in table 1, and evaluation result is in table 2.
embodiment 6
The present embodiment is with embodiment 1, and difference is that used 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 DEG C, volume space velocity are 0.5h
-1, hydrogen to oil volume ratio is 300, is numbered E-6, catalyst reduction condition is in table 1, evaluation result is in table 2.
embodiment 7
The 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 DEG C, volume space velocity are 0.2h
-1, hydrogen to oil volume ratio is 200, is numbered E-7, catalyst reduction condition is in table 1, evaluation result is in table 2.
embodiment 8
The present embodiment is with embodiment 1, and difference is that used catalyzer consists of: Ru/Sn/ZSM-5/K/SiO
2=0.3/1.7/60/5/33, is numbered E-8, and catalyst reduction condition is in table 1, and evaluation result is in table 2.
comparative example 1
This comparative example is with embodiment 1, and difference is that used 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 to into reactor, and be numbered C-1, catalyst reduction condition is in table 1, and evaluation result is in table 2.
comparative example 2
This comparative example is with comparative example 1, and difference is that used 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 to into reactor, and be numbered C-2, catalyst reduction condition is in table 1, and evaluation result is in table 2.
the reductive condition of the each embodiment of table 1 and comparative example
| Catalyzer | E-1~E-3 | E-4~ E-6 | E-7~ E-8 | C-1~C-2 |
| Reductive condition: | ? | ? | ? | ? |
| Hydrogen dividing potential drop, MPa | 1.0 | 0.5 | 5.0 | 1.0 |
| Temperature, DEG C | 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 the each embodiment of table 2 and comparative example
| ? | Catalyzer numbering | Naphthalene transformation efficiency, wt% | 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 example 1 | C-1 | 98.8 | 67.2 |
| Comparative example 2 | C-2 | 99.0 | 66.7 |
Note: 4 hours sampling analysis of catalyst runs.
From the results shown in Table 1, the present invention produces in the reaction of perhydronaphthalene at naphthalene hydrogenation, and compared with comparative example, in the time that naphthalene transformation efficiency is suitable, in the product that the technology of the present invention is produced, trans-decalin selectivity is high more than 15%.Result shows that the inventive method has obvious advantage in the reaction of naphthalene hydrogenation production trans-decalin.
Claims (10)
1. the method that naphthalene hydrogenation is produced trans-decalin, adopt fixed-bed reactor, naphthalene and hydrogen reverse contact in reactor, under hydrogenation catalyst exists, under hydrogenation conditions, carry out hydrogenation reaction, obtain trans-decalin, wherein said naphthalene hydrogenation catalyst, taking the weight of catalyzer as benchmark, the content of ZSM-5 molecular sieve is 10.0%～70.0%, alkali-metal content is 0.1%～10.0%, the content of group VIII metal is 0.01%～5.0%, the content of auxiliary agent is the silicon-dioxide in element 0.1%～5.0% and surplus, described auxiliary agent is tin, one or more in lead, described ZSM-5 molecular sieve is pure silicon molecular sieve, described group VIII metal is selected from one or more in palladium, platinum, ruthenium, rhodium and iridium, described hydrogenation conditions is as follows: hydrogen dividing potential drop is 0.1MPa～10.0MPa, and temperature is 100 DEG C～500 DEG C, and volume space velocity is 0.1h
-1～10.0h
-1, hydrogen to oil volume ratio is 100～1000, hydrogen feed used adopts pure hydrogen.
2. in accordance with the method for claim 1, it is characterized in that described naphthalene hydrogenation catalyst, taking the weight of catalyzer as benchmark, the content of ZSM-5 molecular sieve is 20%～70%, 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. in accordance with the method for claim 1, it is characterized in that described naphthalene hydrogenation catalyst, taking the weight of catalyzer as benchmark, the content of ZSM-5 molecular sieve is 30%～60%, 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. in accordance with the method for claim 1, it is characterized in that adopted hydrogenation conditions is as follows: hydrogen partial pressure 0.5MPa～5.0MPa, temperature of reaction is 200 DEG C～400 DEG C, volume space velocity is 0.2h
-1～5.0h
-1, hydrogen to oil volume ratio is 150～500.
5. in accordance with the method for claim 1, it is characterized in that described basic metal is selected from one or more in lithium, sodium, potassium, rubidium, caesium and francium.
6. in accordance with the method for claim 1, it is characterized in that described basic metal is selected from sodium or/and potassium.
7. in accordance with the method for claim 1, it is characterized in that described group VIII metal is platinum and/or palladium.
8. in accordance with the method for claim 1, it is characterized in that described auxiliary agent is tin.
9. in accordance with the method for claim 1, it is characterized in that described naphthalene hydrogenation catalyst needs to carry out prereduction before use, described prereduction condition is as follows: hydrogen partial pressure is 0.1MPa～20.0MPa, temperature is 100 DEG C～600 DEG C, gas agent volume ratio is 100～2000, the prereduction time is 0.1h～24h, and reaction gas is hydrogen-containing gas.
10. in accordance with the method for claim 9, it is characterized in that described prereduction condition is as follows: hydrogen partial pressure is 0.2MPa～10.0MPa, and temperature is 200 DEG C～500 DEG C, and gas agent volume ratio is 300～1500; The prereduction time is 1h～12h; Reaction gas is pure hydrogen.
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| CN102838441A (en) | 2012-12-26 |
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