CN102408297B - Method for preparing cyclohexane by hydrogenating benzene - Google Patents
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- CN102408297B CN102408297B CN201010291922.4A CN201010291922A CN102408297B CN 102408297 B CN102408297 B CN 102408297B CN 201010291922 A CN201010291922 A CN 201010291922A CN 102408297 B CN102408297 B CN 102408297B
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Abstract
The invention relates to a method for preparing cyclohexane by hydrogenating benzene. According to the requirements of adaptability to water content fluctuation of a reaction system and inhibition of carbon deposit in the process of hydrogenating the benzene at present, hydrogen/benzene mixed gas in a certain molar ratio is introduced into a reactor and contacted with a benzene hydrogenation catalyst to prepare the cyclohexane at the inlet temperature of between 100 and 320 DEG C under the reaction pressure of 0.1 to 4.0MPa, wherein the hydrogenation catalyst comprises a carrier, metal active ingredients and a silane group which is grafted by silylation and accounts for 0.1 to 15 weight percent of the catalyst. Compared with the prior art, the method has the advantages that: the method is high in raw material applicability on the premise of ensuring that the benzene hydrogenation catalyst has high activity and selectivity, and the catalytic performance of the benzene hydrogenation catalyst is almost not influenced by trace water; meanwhile, the carbon deposit on the surface of the catalyst can be obviously inhibited, the service life of the catalyst is prolonged, and the catalyst has a long stable operation period.
Description
Technical field
The present invention relates to a kind of method of hydrotreating, more particularly, the present invention relates to a kind of method of preparing cyclohexane by hydrogenating benzene.
Background technology
Hexanaphthene is a kind of important Organic Chemicals.Its colourless, easy mobile, irritant smell, mainly for the production of products such as hexalin, pimelinketone, hexanolactam, hexanediamine and hexanedioyls, and can dissolve gas chromatography, toxicity is less than benzene, it is the fine solvent of ether of cellulose, resin, wax, grease, pitch and rubber.More than 90% hexanaphthene is standby by prepared from benzene and hydrogen, its production technology comparative maturity, conventional catalyzer has nickel system, platinum group and palladium system etc., and wherein nickel aluminium System Catalyst is because there being good activity to be widely used on existing full scale plant with relative cheap price.As patent US 4490480 introduces.But the active temperature scope of the nickel aluminium System Catalyst of current industrial use is narrower, because benzene hydrogenation is thermopositive reaction, when heat can not be removed and just easily cause overtemperature from beds in time, be prone to " temperature runaway " phenomenon, cause by product to increase, in operation, be difficult to control, also poor to the poison resistance of sulfide, these shortcomings it is generally acknowledged it is because Nickel Content In Catalyst is higher to a great extent, nickel is piled up at carrier surface, dispersity is not high, the effective rate of utilization of nickel is low, and at high temperature nickel and alumina catalyst support interact and form nickel aluminate, make catalyzer be difficult to reduce and lose catalytic activity, so effectively improve nickle atom utilization ratio and reduce the loss of nickel active ingredient and just seem particularly important.
Chinese patent CN1546230 has introduced a kind of method that adopts coprecipitation method to prepare the mixture benzene hydrogenating catalyst of nickel oxide and rare earth oxide.Chinese patent CN1210759A has introduced a kind of sol-gel method that adopts and has prepared the method that nickel is benzene hydrogenating catalyst.The Deng Jing of Fudan University the people such as sends out and adopts quenching legal system for Ni-Al-P amorphous alloy catalyst, and experimental result shows, this catalyst performance is obviously due to conventional Raney Ni catalyzer, and better heat stability.The nano metal nickel cerium ion hydrogenation catalyst that Qingtao Chemical Engineering College's nanometer material science is prepared, because of its superior performance, is also expected to be called a kind of new and effective benzene hydrogenating catalyst.Although the benzene hydrogenating catalyst of preparing of introducing in above-mentioned document has certain benzene hydrogenation effect, the equal more complicated of preparation process of each method, is difficult to suitability for industrialized production catalyzer.
Domestic hexanaphthene manufacturer, as Ba Ling petrochemical industry and Yanshan Petrochemical, catalyzer used is traditional nickel aluminium system, as serial in the NCG that former southization catalyst plant is produced, it has good activity and good selectivity, but because Ni content in this class catalyzer is generally up to 30～50% (production application be often 40% left and right), because nickel content is high, during reduction, catalyzer must reduction for a long time under 400～500 ℃, hydrogen atmosphere, and NiO just can be reduced into metal state nickel.So not only in reduction process, consume mass energy, facility investment is increased, and after catalyzer high temperature reduction, also will be reduced to low temperature use, to industrial production, make troubles.
In sum, catalyzer in existing benzene hydrogenation technology mostly is Ni, Pt and Rh etc. for active ingredient, take aluminum oxide, silicon oxide, silico-aluminate or clay etc. is carrier, the preparations such as multiplex coprecipitation method, sol-gel method, though the catalyzer obtaining with this has certain hydrogenation effect to benzene hydrogenation, but for this type of catalyzer, in raw material, the existence of water will significantly reduce its hydrogenation activity, even can significantly reduce its work-ing life.In benzene hydrogenation process, in the existence of many Water Unders, be inevitable.This makes many catalyzer in industrial operation, and reactive behavior declines, and the life-span reduces.It needs to be noted, in industrial actual moving process, in reactor, water-content changes erraticly often, and unexpected variation will produce larger fluctuation to benzene hydrogenation hydrogenation effect, cause the unstable of catalyzer operation.In addition,, because benzene hydrogenation generally all carries out in High Temperature High Pressure, the coking precursors such as polymerization generation colloid easily occur benzene self causes catalyst carbon deposition and affects Hydrogenation.
Yet in existing benzene hydrogenation process, all fail to consider water and the impact of area carbon on benzene hydrogenating catalyst activity and stability in reaction system.For this reason, for preparing cyclohexane by hydrogenating benzene, develop a kind of method and overcome moisture in reaction system or the impact of water-content fluctuation on benzene hydrogenating catalyst catalytic performance, reduce the generation of catalyzer agent area carbon simultaneously the factory application to benzene hydrogenating catalyst is had important practical significance.
Summary of the invention
For the adaptability that at present in preparing cyclohexane by hydrogenating benzene process, reaction system is contained to water or water-content fluctuation and to requirement aspect suppress that carbon distribution generates two, contriver proposes a kind of method for preparing cyclohexane by hydrogenating benzene, guaranteeing that benzene hydrogenating catalyst has under the prerequisite of better activity and selectivity, can effectively solve problem moisture in reaction system or that water-content fluctuation impacts benzene hydrogenating catalyst hydrogenation effect, can effectively suppress the generation of catalyst surface carbon distribution again simultaneously.
The present invention relates to a kind of method of preparing cyclohexane by hydrogenating benzene, concrete grammar is: 100 ℃～320 ℃ of the temperature ins of benzene hydrogenation device, reaction pressure 0.1MPa～4.0MPa, passes into reactor and benzene hydrogenating catalyst bed contact preparation hexanaphthene by the hydrogen/benzene gas mixture that contains certain mole of proportioning; Described benzene hydrogenating catalyst contains carrier, metal active constituent and silane group, and silane group is processed grafting through silylanizing.Compare with existing hydrogenation process for preparing cyclohexane method, the inventive method has following two aspect advantages: the one, and benzene hydrogenating catalyst Hydrogenation is subject to the impact of water-content and water-content fluctuation in reaction system less; The 2nd, benzene hydrogenating catalyst area carbon growing amount is little, long service life.
Contriver studies and finds by utilizing the silane group of grafting can change water at adsorptive capacity and the adsorption strength of catalyst surface on the carrier supported catalyst of hydroxyl containing, also find that having very close relationship with area carbon is the surface hydroxyl quantity of catalyzer, and the reactive hydrogen quantity on methyl-monosilaneization processing rear catalyst surface significantly reduces simultaneously.The present invention completes based on above discovery.
The concrete technical scheme of the inventive method is as follows:
A kind of method of preparing cyclohexane by hydrogenating benzene, 100 ℃～320 ℃ of the temperature ins of benzene hydrogenation device, reaction pressure 0.1MPa～4.0MPa, passes into reactor and benzene hydrogenating catalyst bed contact preparation hexanaphthene by the hydrogen/benzene gas mixture that contains certain mole of proportioning; Described benzene hydrogenating catalyst contains carrier, metal active constituent and silane group, and silane group is processed grafting through silylanizing.
Described metal active constituent is at least one of nickel, palladium, platinum and ruthenium, and its content accounts for the 1.0wt%～25.0wt% of catalyzer overall weight.Preferably, described metal active constituent is at least one of nickel, platinum and ruthenium, and its content accounts for the 5.0wt%～20.0wt% of catalyzer overall weight.
For improving the hydrogenation effect of benzene hydrogenating catalyst, benzene hydrogenating catalyst also contains metal promoter a, at least one metallic element in described metal promoter a ShiIAZu, IIAZu, IIIA Zu,IVAHe VA family, its content is the 0.01wt%～10.0wt% of catalyzer overall weight.Preferably, metal promoter a comprises at least one of sodium, potassium, caesium, calcium, magnesium, barium, gallium, indium, lead and bismuth, and its content is the 0.01wt%～6.0wt% of catalyzer overall weight.
For further improving the hydrogenation effect of benzene hydrogenating catalyst, at benzene hydrogenating catalyst, contain or do not contain in the various schemes of metal promoter a, benzene hydrogenating catalyst also contains metal promoter b, at least one in described metal promoter b Shi IBZu, IIBZu, IIIB family, group vib and VIIB, its content is the 0.01wt%～10.0wt% of catalyzer overall weight.Preferably, metal promoter b comprises at least one in copper, zinc, mercury, lanthanum, thorium, cerium, chromium, molybdenum, manganese, rhenium and tungsten, and its content is the 0.05wt%～6.0wt% of catalyzer overall weight.
Preferably, the carrier of benzene hydrogenating catalyst is selected from Al
2o
3, Fe
2o
3, V
2o
5, ZnO, SnO
2, ZrO
2, a kind of in MgO, SiC, gac, kaolin, sepiolite and diatomite or two or more mixture in them, or carrier is by Al
2o
3, V
2o
5, ZnO, SnO
2be carried on at least one in MgO the complex carrier forming on inertial base, described inertial base comprises metal base and pottery.Preferred support of the catalyst is Al
2o
3, ZrO
2, a kind of in ZnO, SiC, gac, sepiolite and diatomite or two or more mixture in them.
Preferably, the silane group in benzene hydrogenating catalyst be take silicomethane base as raw material passes through silylation reactive grafting, accounts for the 0.05wt%～25.0wt% of catalyzer overall weight.Preferred silane group accounts for the 0.1wt%～15wt% of catalyzer overall weight.
Preferably, above-mentioned silicomethane base is a kind of in organosilane, organo-siloxane, organosilazanes and organic oxosilane or two or more mixture in them.More preferably the silicomethane base using is a kind of in organo-siloxane and organosilazanes or their mixture.
Preferably, the reaction conditions of preparing cyclohexane by hydrogenating benzene is: 130 ℃～280 ℃ of reactor inlet temperatures, and reaction pressure 0.2MPa～3.0MPa, hydrogen/benzene mole is than 2.0～15.0: 1, volume space velocity 0.5～10.0h during the liquid of benzene
-1.
Although silane group still imperfectly understands in the surperficial grafting form of catalyzer,, according to the principle of the molecular structure of silylating reagent and Silanization reaction, can make rational supposition to the form of silane group.Existence form after the grafting of several silane groups of below giving an example wherein on catalyzer:
Described silane group can be expressed as with following general formula (1):
Wherein, R1, R2 and R3 are identical or different alkyl independently of one another, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or cyclohexyl etc., simultaneously according to the option demand reacting, alkyl can also be aromatic, another covalent linkage of the Sauerstoffatom of the upper connection of Si is connected on catalyzer, the covalent linkage by this Sauerstoffatom by silane group grafting on catalyzer.
Described silane group can also be expressed as with following general formula (2):
Wherein R1, R2, R4 and R5 are identical or different alkyl independently of one another, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, cyclohexyl etc., simultaneously according to the option demand reacting, alkyl can also be aromatic, R3 is a kind of in chlorine, nitrogen and oxygen, another covalent linkage of the Sauerstoffatom of the upper connection of Si is connected on catalyzer, the covalent linkage by this Sauerstoffatom by silane group grafting on catalyzer.
Described silane group can also be expressed as with following general formula (3):
Wherein R1 and R2 are identical or different alkyl independently of one another, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, cyclohexyl etc., simultaneously according to the option demand reacting, alkyl can also be aromatic, another covalent linkage of the Sauerstoffatom of the upper connection of Si is connected on catalyzer, the covalent linkage by this Sauerstoffatom by silane group grafting on catalyzer.
Active constituent loading can be multiple to the mode on carrier, for example, by the salt of active metal element or the solution of oxide compound or suspension, flood, then dry.Dry post-heating to 300 ℃-500 ℃ of roastings are metal oxide, and the atmosphere of roasting can be a kind of in air, nitrogen, oxygen and argon gas or their mixture.In addition, also can to load to carrier by the mode of spraying, metal or metallorganics evaporation, uniform deposition first-class for active ingredient.To the carrying method example of active ingredient, be just active ingredient on explanation catalyzer above, those skilled in the art can be easily by conversion step to realize the load of active ingredient and adding of auxiliary agent, these do not affect essence of the present invention.
Auxiliary agent can be realized and improve catalyst performance with same the loading on carrier of active ingredient by above-mentioned.The joining day of auxiliary agent can be before active constituent loading, add afterwards or together with active ingredient.Adding of auxiliary agent can also be in the moulding process of carrier.In the moulding process of carrier, the salt of auxiliary agent or oxide compound can add, and are dispersed on catalyzer.
Grafting after the complete active ingredient of silane group load on carrier and each auxiliary agent.Silane group is that after the hydroxyl on silicomethane base and catalyst surface being carried out to condensation reaction by silylation reactive, catalyst surface is arrived in grafting.The principle that the organo-siloxane of take is silicomethane base raw material is exemplified below:
Grafting process can be carried out in liquid phase solvent, and effectively solvent can be a kind of in ketone, ether, hydrocarbon and ester, preferably ether and hydro carbons.Particularly, a kind of or mixed solvent in toluene, benzene, dimethylbenzene, hexanaphthene, normal hexane, heptane, ether, methyl-phenoxide, tetrahydrofuran (THF), whiteruss, the saturated gasoline of hydrogenation, the saturated diesel oil of hydrogenation and sherwood oil.Grafting process generally need to be controlled temperature at 30 ℃～320 ℃, is preferably 50 ℃～180 ℃.
The grafting of silane group can be by another kind of way also: silicomethane base form with gas or fine droplet under the carrying of carrier gas is contacted with catalyzer, thereby complete, the silylation of catalyzer is processed.The carrier gas of using can be a kind of in nitrogen, air, oxygen, carbonic acid gas and argon gas or their mixture.In the limited Catalyst Production factory of some conditions, in absence lower time of carrier gas, contacts the grafting of carrying out silane group after also silicomethane base can being heated to be to steam with catalyzer.Temperature is controlled at 60 ℃～450 ℃ during grafting by this method, and preferably temperature is 85 ℃～280 ℃.
Silicomethane base can be selected from organosilane, organo-siloxane, at least one in organosilazanes and organic oxosilane, for example, Union carbide A-162 for example, dimethyldiethoxysilane, trimethylammonium diethoxy silane, ethyl triethoxysilane, diethyl diethoxy silane, triethyl-ethoxy-silicane alkane, ethyl trimethoxy silane, butyl triethoxyl silane, dimethyl one ethyl methoxy silane, dimethyl one phenyl ethoxy silane, tripropyl methoxy silane, trimethylchlorosilane, dimethyldichlorosilane(DMCS), dimethyl one propyl chloride silane, dimethylbutyl chlorosilane, dimethyl isopropyl chloride silane, tributyl chlorosilane, hexamethyldisilazane, heptamethyldisilazane, tetramethyl-disilazane, 1, 3-dimethyl diethyl disilazane and 1, 3-phenylbenzene tetramethyl-disilazane etc.
Silane group is larger to catalyzer water resisting property of the present invention and anti-carbon performance impact in the coverage of catalyst surface.When coverage is lower, water resisting property and anti-carbon performance can not be brought into play completely, and when coverage is too high, thereby may cause the Adsorption of polymerization covering catalyst between silane, reduce the activity of catalyzer, therefore the content of silane group in catalyzer needs to control, and accounts for the 0.05wt%～25wt% of catalyzer overall weight, is preferably 0.1wt%～15wt%.The coverage of silane group can be by regulating the methods such as silicomethane base raw material, silylanizing treatment time, silylanizing treatment temp, carrier gas kind and flow velocity (vapor phase process) and solvent (liquid phase method) to realize point-device control.
On catalyzer of the present invention, the coverage of the silane group of grafting can be analyzed by use x-ray photoelectron power spectrum (XPS), thereby confirms the surperficial amount of carbon atom gauging surface coverage of catalyzer; Also can use infrared instrument (IR) to observe the functional group of catalyst surface, as pass through-CH
3characteristic peak (～2970cm
-1) gauging surface silane level of coverage, by the characteristic peak (～3750cm of-OH
-1) calculate catalyst surface hydroxyl residual content.Can be by organic carbon/elemental carbon (OC/EC) thus the quantitative organic carbon content of analyser accurately obtains the silylation quality on catalyzer.
Benzene hydrogenating catalyst of the present invention, in preparing the process of hexanaphthene, is limited to 15wt% in the water content in permission raw material.
With existing hydrogenation process for preparing cyclohexane technology Comparatively speaking, the method for preparing cyclohexane by hydrogenating benzene of the present invention has the following advantages:
1. in method of the present invention, benzene hydrogenating catalyst is after silylation is processed, and it has good physical strength, is difficult for efflorescence and loss active ingredient in reaction;
2. method of the present invention has obvious reaction system suitability.The in the situation that in reaction system, water-content changing, the performance of catalyzer is almost constant; The in the situation that in reaction system, water-content fluctuation being larger especially, can there are not big ups and downs in the performance of catalyzer.This safe and stable operation to ensuring equipment has larger help.
3. method of the present invention can suppress the generation of colloid on catalyzer significantly, thereby reduces the growing amount of area carbon, the work-ing life of significantly improving catalyzer;
4. the Catalyst Production method that method of the present invention is used can make full use of prior art and equipment, easily industrialization.
Embodiment
Below by embodiment, describe further the present invention, the present invention is more in depth understood promoting.But the present invention is also confined to not be subject to following examples.
Embodiment 1
This embodiment illustrates the preparation process of the hydrogenation catalyst in the inventive method.
1) take alumina supporter 50.0g, with the 35ml aqueous solution containing 0.90g saltpetre, adopt equi-volume impregnating dipping 0.5h, 120 ℃ of dry 4h, 550 ℃ of roasting 6h;
2) then with the aqueous solution containing 50.1g nickelous nitrate, adopt in two steps equi-volume impregnating dipping, 120 ℃ of dry 4h, 450 ℃ of roasting 6h, and at hydrogen atmosphere, 400 ℃ reductase 12 0h;
3) by Union carbide A-162 silylanizing at 120 ℃, process 1.5h, obtain catalyst A-1, catalyzer forms in Table 1.
Embodiment 2
This embodiment illustrates the preparation process of the hydrogenation catalyst in the inventive method.
1) take alumina supporter 50g, with the 35ml aqueous solution containing 2.43g magnesium nitrate, adopt equi-volume impregnating dipping 0.5h, 120 ℃ of dry 4h, 550 ℃ of roasting 6h;
2) then with the aqueous solution containing 120.4g nickelous nitrate, adopt in two steps equi-volume impregnating dipping 0.5h, 120 ℃ of dry 4h, 450 ℃ of roasting 6h, and at hydrogen atmosphere, 400 ℃ reductase 12 0h;
3) by Union carbide A-162 silylanizing at 120 ℃, process 1.5h, obtain catalyst A-2, catalyzer forms in Table 1.
Embodiment 3
This embodiment illustrates the preparation process of the hydrogenation catalyst in the inventive method.
1) take alumina supporter 50.0g, with the 35ml aqueous solution containing 1.82g cerous nitrate, adopt equi-volume impregnating dipping 0.5h, 120 ℃ of dry 4h, 550 ℃ of roasting 6h;
2) then with the aqueous solution containing 50.0g nickelous nitrate, adopt in two steps equi-volume impregnating dipping 0.5h, 120 ℃ of dry 4h, 450 ℃ of roasting 6h, and at hydrogen atmosphere, 400 ℃ reductase 12 0h;
3) by Union carbide A-162 silylanizing at 120 ℃, process 1.5h, obtain catalyst A-3, catalyzer forms in Table 1.
Embodiment 4
This embodiment illustrates the preparation process of the hydrogenation catalyst in the inventive method.
1) take alumina supporter 50.0g, with the 35ml aqueous solution containing 1.09g lanthanum nitrate, adopt equi-volume impregnating dipping 0.5h, 120 ℃ of dry 4h, 550 ℃ of roasting 6h;
2) then with the aqueous solution containing 50g nickelous nitrate, adopt in two steps equi-volume impregnating dipping 0.5h, 120 ℃ of dry 4h, 450 ℃ of roasting 6h, and at hydrogen atmosphere, 400 ℃ reductase 12 0h;
3) by Union carbide A-162 silylanizing at 120 ℃, process 1.5h, obtain catalyst A-4, catalyzer forms in Table 1.
Embodiment 5
This embodiment illustrates the preparation process of the hydrogenation catalyst in the inventive method.
1) take above-mentioned carrier 50.0g, with the 75ml aqueous solution containing 1.09g lanthanum nitrate, adopt equi-volume impregnating dipping 0.5h, 120 ℃ of dry 4h, 550 ℃ of roasting 6h;
2) then with the 72ml aqueous solution containing Palladous nitrate 2.80g, spray above-mentioned carrier, 100 ℃ of dry 4h, 450 ℃ of roasting 6h, and at hydrogen atmosphere, 300 ℃ reductase 12 0h;
3) by Union carbide A-162 silylanizing at 120 ℃, process 1.5h, obtain catalyst A-5, catalyzer forms in Table 1.
Embodiment 6
This embodiment illustrates the preparation process of the hydrogenation catalyst in the inventive method.
With reference to the preparation process Kaolinite Preparation of Catalyst A-6 of embodiment 1, what difference was that silylanizing process to be used is trimethylchlorosilane.Catalyzer forms in Table 1.
Comparative example 1
With reference to the preparation process Kaolinite Preparation of Catalyst B-1 of embodiment 1, difference is that catalyzer does not carry out silylanizing processing.Catalyzer forms in Table 1.
Comparative example 2
With reference to the preparation process Kaolinite Preparation of Catalyst B-2 of embodiment 5, difference is that catalyzer does not carry out silylanizing processing.Catalyzer forms in Table 1.
Each catalyst component of table 1 and content
Embodiment 7～12 and comparative example 3～4
Embodiment 7～12 and embodiment 3～4 illustrate respectively reactivity worth, hydrothermal stability and the anti-carbon performance of catalyzer provided by the invention.
Catalyzer need be at prereduction 2h under 250 ℃, hydrogen atmosphere before evaluating.Reaction conditions is: temperature of reaction is that 220 ℃, reaction pressure are that 1.0MPa, liquid benzene air speed are 2.0h
-1, hydrogen/phenylacetylene mol ratio 8: 1, on fixed-bed reactor, evaluated respectively catalyst A-1～6 and B-1～2, after stable reaction, carry out again benzene transformation efficiency and hexanaphthene and optionally investigate.In reaction process, at 100h clock pulse, rush in the water resisting property of investigating catalyzer into 0.5ml water vapour.After finishing, reaction 1000h passes through the carbon deposition quantity of TG-MS (simultaneous thermal analysis instrument and mass spectrometer coupling, simultaneous thermal analysis instrument: NETZSCH, STA 449 C Jupiter, mass spectrograph: NETZSCH, QMS 403 C Aolos) each catalyzer of analytical calculation.Reaction result data are in Table 2.
From table 2, data can be found out, compare with existing benzene hydrogenating catalyst, and it is high that catalyzer of the present invention has hydrogenation activity, and hexanaphthene selectivity is good, and move continuously 1000h catalytic activity and exist fluctuation range less to water.This shows that catalyzer of the present invention has good hydrothermal stability, and has the longer cycle of operation.In addition, in table 2, area carbon amount data can be found out, catalyzer of the present invention has very strong carbon accumulation resisting ability, and then increase the work-ing life of catalyzer.
Claims (14)
1. the method for a preparing cyclohexane by hydrogenating benzene, it is characterized in that, 100 ℃～320 ℃ of the temperature ins of benzene hydrogenation device, reaction pressure 0.1MPa～4.0MPa, passes into reactor and benzene hydrogenating catalyst contact preparation hexanaphthene by the hydrogen/benzene gas mixture that contains certain mole of proportioning; Described benzene hydrogenating catalyst contains carrier, metal active constituent and silane group, and silane group is processed grafting through silylanizing, the grafting after carrier loaded complete metal active constituent and auxiliary agent of described silane group, and in described benzene hydrogenating catalyst, silane group accounts for the 0.05wt%～25wt% of catalyzer overall weight.
2. the method for claim 1, is characterized in that, described metal active constituent is at least one of nickel, palladium, platinum and ruthenium, and its content accounts for the 1.0wt%～25.0wt% of catalyzer overall weight.
3. method as claimed in claim 2, is characterized in that, described metal active constituent is at least one of nickel, platinum and ruthenium, and its content accounts for the 5.0wt%～20.0wt% of catalyzer overall weight.
4. the method for claim 1, it is characterized in that, described benzene hydrogenating catalyst also contains metal promoter a, at least one metallic element in described metal promoter a ShiIAZu, IIAZu, IIIA Zu,IVAHe VA family, and its content is the 0.01wt%～10.0wt% of catalyzer overall weight.
5. method as claimed in claim 4, is characterized in that, described metal promoter a is at least one of sodium, potassium, caesium, calcium, magnesium, barium, gallium, indium, lead and bismuth, and its content is the 0.01wt%～6.0wt% of catalyzer overall weight.
6. the method as described in claim 1 or 4, it is characterized in that, described benzene hydrogenating catalyst also contains metal promoter b, at least one in described metal promoter b Shi IBZu, IIBZu, IIIB family, group vib and VIIB, and its content is the 0.01wt%～10.0wt% of catalyzer overall weight.
7. method as claimed in claim 6, is characterized in that, described metal promoter b is at least one in copper, zinc, mercury, lanthanum, thorium, cerium, chromium, molybdenum, manganese, rhenium and tungsten, and its content is the 0.05wt%～6.0wt% of catalyzer overall weight.
8. the method for claim 1, is characterized in that, described carrier is selected from Al
2o
3, Fe
2o
3, V
2o
5, ZnO, SnO
2, ZrO
2, a kind of in MgO, SiC, gac, kaolin, sepiolite and diatomite or two or more mixture in them, or carrier is by Al
2o
3, V
2o
5, ZnO, SnO
2be carried on at least one in MgO the complex carrier forming on inertial base, described inertial base comprises metal base and pottery.
9. method as claimed in claim 8, is characterized in that, described carrier is preferably Al
2o
3, ZrO
2, a kind of in ZnO, SiC, gac, sepiolite and diatomite or two or more mixture in them.
10. the method for claim 1, is characterized in that, described silane group be take silicomethane base and passed through silylation reactive grafting as raw material.
11. methods as described in claim 1 or 10, is characterized in that, described silane group accounts for the 0.1wt%～15wt% of catalyzer overall weight.
12. methods as claimed in claim 10, is characterized in that, the silicomethane base of use is a kind of in organosilane, organo-siloxane, organosilazanes and organic oxosilane or two or more mixture in them.
13. methods as claimed in claim 12, is characterized in that, the silicomethane base of use is a kind of in organo-siloxane and organosilazanes or two or more mixture in them.
14. the method for claim 1, it is characterized in that, the reaction conditions of described preparing cyclohexane by hydrogenating benzene is: 130 ℃～280 ℃ of reaction temperature ins, reaction pressure 0.2MPa～3.0MPa, hydrogen/benzene mole is than 2.0～20:1, benzene liquid hourly space velocity 0.5～10.0h
-1.
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| CN103483123B (en) * | 2012-06-08 | 2015-05-13 | 中国石油化工股份有限公司 | Method of preparing butadiene from normal alkane |
| CN102921414B (en) * | 2012-10-17 | 2015-01-21 | 江苏景宏新材料科技有限公司 | Benzene ring alkyl ester hydrogenation catalyst and preparation method thereof |
| CN104513121B (en) * | 2013-09-30 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of method of preparing cyclohexane by hydrogenating benzene |
| CN106925264A (en) * | 2017-03-17 | 2017-07-07 | 钦州学院 | A kind of catalyst and preparation method for producing cyclohexane by adding hydrogen in benzene |
| CN106925309A (en) * | 2017-03-17 | 2017-07-07 | 钦州学院 | A kind of catalyst for gasoline hydrodesulfurizationmethod and preparation method thereof |
| CN106881127A (en) * | 2017-03-17 | 2017-06-23 | 钦州学院 | A kind of catalyst and preparation method for gasoline desulfurization modification |
| CN106927996A (en) * | 2017-03-17 | 2017-07-07 | 钦州学院 | A kind of method of producing cyclohexane by adding hydrogen in benzene |
| CN107417483A (en) * | 2017-06-02 | 2017-12-01 | 钦州学院 | A kind of method of benzene hydrogenation |
| CN117358235A (en) * | 2023-08-01 | 2024-01-09 | 江苏清泉化学股份有限公司 | Catalyst for preparing MACM by continuous hydrogenation and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1355160A (en) * | 2000-11-29 | 2002-06-26 | 三星电子株式会社 | Method for preparation of 1,3-alkamediol by 3-carboxy ester |
| CN1457923A (en) * | 2002-12-25 | 2003-11-26 | 南化集团研究院 | Platinum catalyst for preparing cyclohexane by hydrogenating benzene and its preparing process |
| CN1830927A (en) * | 2006-04-13 | 2006-09-13 | 中国科学院大连化学物理研究所 | Method for on-line modification of catalyst for methylating toluene to produce paraxylene |
| CN101757917A (en) * | 2008-12-25 | 2010-06-30 | 南化集团研究院 | Low nickel-content benzene hydrogenation catalyst and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2778341B1 (en) * | 1998-05-07 | 2000-06-09 | Inst Francais Du Petrole | CATALYST BASED ON NOBLE GROUP VIII METAL CONTAINING BORON AND / OR SILICON AND ITS USE IN HYDROCARBON CHARGE HYDROTREATMENT |
-
2010
- 2010-09-21 CN CN201010291922.4A patent/CN102408297B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1355160A (en) * | 2000-11-29 | 2002-06-26 | 三星电子株式会社 | Method for preparation of 1,3-alkamediol by 3-carboxy ester |
| CN1457923A (en) * | 2002-12-25 | 2003-11-26 | 南化集团研究院 | Platinum catalyst for preparing cyclohexane by hydrogenating benzene and its preparing process |
| CN1830927A (en) * | 2006-04-13 | 2006-09-13 | 中国科学院大连化学物理研究所 | Method for on-line modification of catalyst for methylating toluene to produce paraxylene |
| CN101757917A (en) * | 2008-12-25 | 2010-06-30 | 南化集团研究院 | Low nickel-content benzene hydrogenation catalyst and preparation method thereof |
Non-Patent Citations (9)
| Title |
|---|
| A. Quintanilla等.Tuning the support adsorption properties of Pd/SiO2 by silylation to improve the selective hydrogenation of aromatic ketones.《Journal of Catalysis》.2008,第257卷 |
| Alkylation of isobutane/1-butene on methyl-modified Nafion/SBA-15 materials;Wei Shen等;《Applied Catalysis A:General》;20100207;第377卷;第1-8页 * |
| M.C. Capel-Sanchez等.Silylation and surface properties of chemically grafted hydrophobic silica.《Journal of Colloid and Interface Science》.2004,第277卷 |
| Silylation and surface properties of chemically grafted hydrophobic silica;M.C. Capel-Sanchez等;《Journal of Colloid and Interface Science》;20040607;第277卷;第146-153页 * |
| Ti-HMS分子筛的合成和气相硅烷化;李学峰等;《石油化工》;20071231;第36卷(第5期);第441-446页 * |
| Tuning the support adsorption properties of Pd/SiO2 by silylation to improve the selective hydrogenation of aromatic ketones;A. Quintanilla等;《Journal of Catalysis》;20080521;第257卷;第55-63页 * |
| Wei Shen等.Alkylation of isobutane/1-butene on methyl-modified Nafion/SBA-15 materials.《Applied Catalysis A:General》.2010,第377卷 |
| 李学峰等.Ti-HMS分子筛的合成和气相硅烷化.《石油化工》.2007,第36卷(第5期), |
| 李武客等.硅对γ-Al2O3载体表面酸性及催化剂催化性能的影响.《华中师范大学学报（自然科学版）》.2004,第38卷(第2期), * |
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