CN103962153B - Producing cyclohexene with benzene selective hydrogenation Ru-YNi catalyst, its preparation method and application thereof - Google Patents
Producing cyclohexene with benzene selective hydrogenation Ru-YNi catalyst, its preparation method and application thereof Download PDFInfo
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- CN103962153B CN103962153B CN201410204672.4A CN201410204672A CN103962153B CN 103962153 B CN103962153 B CN 103962153B CN 201410204672 A CN201410204672 A CN 201410204672A CN 103962153 B CN103962153 B CN 103962153B
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Abstract
The invention discloses a kind of cheap efficient producing cyclohexene with benzene selective hydrogenation Ru-YNi catalyst, its preparation method and application thereof, described catalyst has shell stratum nucleare structure, and central core layer is W metal, and shell is by metal Ru and Y
2o
3composition.Catalyst of the present invention compensate for industrial non-loaded Ru-Zn catalyst due to the high shortcoming of noble metal dosage high cost, at ZnSO
4there is under existence higher activity and cyclohexene selective.The activated Ni of apparatus of the present invention makes carrier, instead of indifferent oxide and make carrier, realize the combination with high hydrogenation active metals Ni catalyst and the selective Ru-Y catalyst of high cyclohexene, Ru-YNi catalyst shows high activity and high cyclohexene is selective.
Description
Technical field
The invention belongs to chemical field, in particular to a kind of producing cyclohexene with benzene selective hydrogenation Ru-YNi catalyst, its preparation method and application thereof.
Background technology
Along with building, decoration, automobile, the developing rapidly of national defense industry, the chemical products demands such as cyclohexanone, adipic acid, nylon-6, nylon-66 grow with each passing day.Most enterprise of the current China of the said goods adopts traditional benzene complete hydrogenation route to produce, and there is potential safety hazard, the wasting of resources and environmental pollution.By comparison, benzene selective hydrogenation route consumes the hydrogen of 1/3rd less, carbon atom utilization rate 100%, environmental friendliness.Benzene selective hydrogenation catalysis technique only has Japan to achieve industrialization in the world so far, the patent that Asahi Kasei Corporation applies in China is as CN1159269C etc., method for preparing catalyst is coprecipitation, catalyst consists of Ru-Zn system, the key technical indexes is benzene when transforming 40%, and the selective and yield of cyclohexene is respectively 80% and about 32%.Not only cyclohexene yield is lower, and the ruthenium utilization rate of catalyst efficiency and unit mass is low and the life-span is short, causes catalyst price very expensive, per kilogram catalyst 200,000 yen, amounts to RMB 1.4 ten thousand yuan.And the element of trace just can cause catalysqt deactivation, particularly sulfide, have a strong impact on the selective of reaction.Reduce catalyst cost, improving the stability of catalyst and the utilization rate of active component, is one of key of producing cyclohexene with benzene selective hydrogenation.
Chinese patent is as CN01122208, CN200410060451.0, CN03115666.5, CN200410101806.6, CN200510126062.8 etc., and method for preparing catalyst adopts the method for sodium borohydride reduction ruthenium salt and another transition metal to prepare amorphous alloy catalyst.Although improve the utilization rate of noble metal Ru, the thermally-stabilised difference of catalyst, be easy to crystallization, catalyst performance stabilised is poor.
Chinese patent, as CN1424293A and CN101219391A etc., has prepared the Ru of inert metal oxides load by active component presoma, auxiliary agent presoma and support precursor coprecipitation and solvent pairs infusion process catalyst based respectively.Although improve utilization rate and the stability of noble metal Ru, catalyst activity, cyclohexene are selective and yield is all lower.
Summary of the invention
For solving the problem, the object of this invention is to provide a kind of Ru-YNi of producing cyclohexene with benzene selective hydrogenation catalyst based and preparation method thereof.
In one aspect of the invention, relate to a kind of nano metal Ni load Ru-Y catalyst with hydrogenation activity, it is characterized in that described catalyst agent has shell stratum nucleare structure, central core layer is W metal, and shell is by metal Ru and Y
2o
3composition.
In a preferred embodiment of the present invention, wherein Ru:Y:Ni mol ratio=1:0.005 ~ 0.30:0.10 ~ 50, preferably, Ru:Y:Ni mol ratio 1:0.02 ~ 0.20:4 ~ 25.
In a preferred embodiment of the present invention, it is characterized in that described catalyst prepares by the following method, described method comprises the steps: configuration 0.2 ~ 2mol/LNi (NO
3)
2solution, regulates pH to 6 ~ 7 with ammoniacal liquor, adds PEG-6000 0 (quality and the W metal of polyethylene glycol control in 1:0.02 ~ 5), slowly add 2 ~ 20mol/LNaBH4 solution under agitation in above-mentioned solution; After dropwising, continue to stir, react fully; Filter out black precipitate, be washed with distilled water to filtrate for neutral, obtaining carrier nanogold belongs to Ni; Configuration 0.0031 ~ 0.05mol/LRuCl
3with 0.0002 ~ 0.01mol/LY (NO
3)
3mixed solution; In above-mentioned solution, add 0.028 ~ 0.45mol/LNaOH solution, stir 30min at 80 DEG C after precipitation, make to react completely.Gained black precipitate is joined in return stirring device and heats.Then in this mixed liquor, add PEG-6000 0, if with the material amount of Ru for 1, polyethylene glycol with the ratio of the material amount of Ru is: 0.0001 ~ 1:1.In this mixed solution, add 0.01mol/LHCl again and make peptizing agent, until mixed solution is the colloidal sol of transparent and homogeneous.Then W metal carrier is joined in this sol solution.Then this mixed liquor is joined in Rotary Evaporators, revolve and steam all moisture.Then with distilled water, the washing of this black solid is extremely neutral.Add in reactor by gained solid and distilled water mixing, be 0.5 ~ 10MPa at hydrogen pressure, temperature controls at 50 ~ 200 DEG C, and reduction 0.5 ~ 36h under the reducing condition of stir speed (S.S.) 800r/min, gained solid is Ru-YNi catalyst.
In a preferred embodiment, raw material RuCl
3, Y (NO
3)
3with Ni (NO
3)
2proportioning should control in mol ratio Ru:Y:Ni=1:0.02 ~ 0.20:4 ~ 25.
The present invention also relate on the other hand described catalyst is used for the interval stirred or continuously in Hastelloy autoclave catalysis benzene selective hydrogenation generate cyclohexene.
In the present invention, catalyst catalysis benzene selective hydrogenation reactions steps in batch reactor is as follows: join in reactor by the catalyst of certain mass, add zinc sulfate solution, with air in nitrogen displacement still, then hydrogen pressure 4.0-6.0MPa is maintained, heating rate controls at 1 DEG C/min, stir speed (S.S.) 600 ~ 800r/min between temperature raising period, adds benzene after being warming up to 140-160 DEG C, speed of agitator is increased to 1200-1600r/min to eliminate the impact of external diffusion simultaneously.
In the present invention, catalyst can use in 0.05 ~ 1.0mol/L zinc sulfate.
In the present invention, catalyst is after having carried out hydrogenation process, and after organic phase being separated, catalyst, zirconium dioxide and slurries can be directly used in hydrogenation reaction again.
The invention provides a kind of technology of preparing of new producing cyclohexene with benzene selective hydrogenation catalyst, utilize this technology can prepare a kind of producing cyclohexene with benzene selective hydrogenation Ru-YNi catalyst, this catalyst, to have the Ni of hydrogenation activity for carrier, take Ru as active component, Y
2o
3for auxiliary agent.This catalyst combines the feature of the selective and Ni high activity of catalyst of Ru-Y catalyst height cyclohexene, shows high activity and high cyclohexene is selective.The noble metal Ru content of catalyst of the present invention is lower than traditional industry catalyst, and catalyst activity and its height of cyclohexene selectivity ratios, noble metal utilisation is high.And this catalyst can be reused, there is good stability.
Accompanying drawing explanation
Fig. 1 embodiment 1 obtains the TEM figure of catalyst.
Fig. 2 embodiment 2 obtains the TEM figure of catalyst.
Fig. 3 embodiment 3 obtains the TEM figure of catalyst.
Detailed description of the invention
Below in conjunction with specific embodiment and accompanying drawing, invention is described further.
Embodiment 1
Configuration 0.85mol/LNi (NO
3)
2solution 400ml, regulates pH to 6 ~ 7 with ammoniacal liquor, adds 2g PEG-6000 0, slowly add 200ml8.5mol/LNaBH under agitation in above-mentioned solution
4solution.After dropwising, continue to stir 30min, react fully.Filter out black precipitate, be washed with distilled water to filtrate for neutral, obtain carrier nanogold and belong to Ni.Configuration 400ml0.05mol/LRuCl
3with 0.003mol/LY (NO
3)
3mixed solution.In above-mentioned solution, add 200ml0.2mol/LNaOH solution, stir 30min at 80 DEG C after precipitation, make to react completely.Gained black precipitate is joined in return stirring device and heats.Then in this mixed liquor, 0.8g PEG-6000 0 is added.In this mixed solution, add 0.01mol/LHCl again and make peptizing agent, until mixed solution is the colloidal sol of transparent and homogeneous.Then 20g W metal carrier is joined in this sol solution.Then this mixed liquor is joined in Rotary Evaporators, revolve and steam all moisture.Then with distilled water, the washing of this black solid is extremely neutral.Add in reactor by gained solid and the mixing of 400ml distilled water, be 5MPa at hydrogen pressure, temperature controls at 140 DEG C, reduces 3h under the reducing condition of stir speed (S.S.) 800r/min.Gained solid is Ru-Y (0.06) Ni catalyst (bracket inner digital is the theoretical atomic ratio of Y and Ru).As can be seen from Figure 1, catalyst agent crystallite dimension is at about 5nm.
Catalyst benzene selective hydrogenation step is as follows: the zinc sulfate of 5.5g catalyst and 280ml0.6mol/L joins in reactor, with air in nitrogen displacement still, then hydrogen pressure 5.0MPa is maintained, heating rate controls at about 1 DEG C/min, stir speed (S.S.) 600 ~ 800r/min between temperature raising period, benzene is added after being warming up to 150 DEG C, speed of agitator is increased to 1400r/min to eliminate the impact of external diffusion simultaneously, timing is started after adding benzene, sample every 5min, adopt chromatographic product composition, fid detector, area corrects normalization method and calculates production concentration, and then calculate benzene conversion ratio and cyclohexene selective, the results are shown in Table 1.
Embodiment 2
By 0.003mol/LY (NO in embodiment 1
3)
3be changed to 0.006mol/LY (NO
3)
3, other condition is with embodiment 1.Gained solid is Ru-Y (0.12) Ni catalyst.Evaluation result is in table 1.As can be seen from Figure 2, catalyst agent crystallite dimension is at about 5nm.
Embodiment 3
20g W metal carrier in embodiment 1 is changed to 20gZrO
2, other condition is with embodiment 1.Gained solid is Ru-Y (0.06) ZrO
2catalyst.Evaluation result is in table 1.As can be seen from Figure 2, catalyst agent crystallite dimension at about 4nm, and is unevenly dispersed in ZrO
2on.
Embodiment 4
5.5g catalyst in embodiment 1, by method hydrogenation in embodiment 1.After hydrogenation completes, after isolating organic phase, catalyst, zirconium dioxide and slurries can be directly used in next hydrogenation.So, catalyst circulation uses 5 times, and evaluation result is in table 2.
Embodiment 1 ~ embodiment 3 the results are shown in Table 1
As can be seen from Table 1, the catalyst prepared with the present invention, when 10min benzene transforms 70.15%, cyclohexene is selective is respectively 80.29% and 56.32% with yield, has exceeded current Catalyst operation level.This shows the catalyst utilizing the present invention to prepare, and the key technical indexes can meet industrial needs, thus has important industrial application value.Can find out that Y auxiliary agent is conducive to reducing the activity of catalyst from embodiment 2, improve cyclohexene selective.Can find out from embodiment 3 and carrier Ni is changed to inert carrier ZrO
2after, the selective and yield of catalyst activity, cyclohexene all reduces.As can be seen here, making carrier with the Ni with hydrogenation activity, is maximum innovative point of the present invention, and combine the feature of the selective and Ni high activity of catalyst of Ru-Y catalyst height cyclohexene, therefore catalyst has high activity and high cyclohexene optionally feature.Find out from the TEM photo of embodiment 3, active component Ru is at carrier ZrO simultaneously
2and it is easily dispersed, therefore active and cyclohexene is selective all lower.
The result of 5 times reused by table 2 embodiment 4 catalyst
As can be seen from Table 2, reuse in process at 5 times, benzene conversion ratio, cyclohexene are selective and yield change is very little, illustrate that catalyst has good repeat performance and good heat endurance.
The above is the preferred embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from principle of the present invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. a producing cyclohexene with benzene selective hydrogenation Ru-YNi catalyst, is characterized in that: it is by active component Ru, auxiliary agent Y
2o
3form with carrier Ni, active component Ru and auxiliary agent Y
2o
3be dispersed on the surface of carrier Ni; Wherein active component Ru, auxiliary agent Y
2o
3all calculate with the atomicity of metallic element with carrier metal Ni, and with the atomicity of Ru for 1, then in catalyst, the atomicity proportioning of each component is Ru be 1, Y be 0.02 ~ 0.30, Ni is 0.1 ~ 50.
2. catalyst according to claim 1, is characterized in that described catalyst prepares as follows: configuration 0.2 ~ 2mol/LNi (NO
3)
2solution, regulates pH to 6 ~ 7 with ammoniacal liquor, adds PEG-6000 0, and PEG-6000 0 controls 0.02 ~ 5 with the mass ratio of W metal, slowly adds 2 ~ 20mol/LNaBH under agitation in above-mentioned solution
4solution; After dropwising, continue to stir, react fully; Filter out black precipitate, be washed with distilled water to filtrate for neutral, obtaining carrier nanogold belongs to Ni; Configuration 0.0031 ~ 0.05mol/LRuCl
3with 0.0002 ~ 0.01mol/LY (NO
3)
3mixed solution, adds 0.028 ~ 0.45mol/LNaOH solution in above-mentioned solution, stirs 30min, make to react completely after precipitation at 80 DEG C; Joined in return stirring device by gained mixed solution and heat, then in this mixed liquor, add PEG-6000 0, with the material amount of Ru for 1, PEG-6000 0 with the ratio of Ru material amount is: 0.0001 ~ 1:1; In gained mixed solution, add 0.01mol/LHCl again and make peptizing agent, until mixed solution is the colloidal sol of transparent and homogeneous; Then W metal carrier is joined in this sol solution, then gained mixed liquor is joined in Rotary Evaporators, revolve and steam all moisture; Then with distilled water, the washing of gained black solid is extremely neutral; Add in reactor by gained solid and distilled water mixing, be 0.5 ~ 10MPa at hydrogen pressure, temperature controls at 50 ~ 200 DEG C, and reduction 0.5 ~ 36h under the reducing condition of stir speed (S.S.) 800r/min, gained solid is Ru-YNi catalyst.
3. catalyst according to claim 2, raw material RuCl
3, Y (NO
3)
3with Ni (NO
3)
2proportioning should control in mol ratio Ru:Y:Ni=1:0.02 ~ 0.30:0.10 ~ 50.
4. the catalyst according to claim 1-3 any one be used for the interval stirred or continuously in Hastelloy autoclave catalysis benzene selective hydrogenation generate the application in cyclohexene.
5. application according to claim 4, catalyst catalysis benzene selective hydrogenation reactions steps in batch reactor is as follows: join in reactor by the catalyst of certain mass, add zinc sulfate solution, with air in nitrogen displacement still, then maintain hydrogen pressure 4.0 ~ 6.0MPa, heating rate controls at 1 DEG C/min, stir speed (S.S.) 600 ~ 800r/min between temperature raising period, add benzene after being warming up to 140 ~ 160 DEG C, speed of agitator is increased to 1200 ~ 1600r/min to eliminate the impact of external diffusion simultaneously.
6. application according to claim 5, described catalyst uses in 0.05 ~ 1.0mol/L zinc sulfate.
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| US9433932B2 (en) * | 2014-08-29 | 2016-09-06 | National Cheng Kung University | Hydrogenation catalyst and method of manufacturing the same |
| CN105772005B (en) * | 2014-12-16 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of method of hydrogenation catalyst and preparation method thereof and heavy oil hydrodesulfurization |
| CN105056971A (en) * | 2015-08-07 | 2015-11-18 | 郑州大学 | In-situ regeneration method of Ru-Zn catalyst for preparation of cyclohexene by benzene selective hydrogenation |
| CN105664931B (en) * | 2016-01-27 | 2018-12-07 | 华东理工大学 | To the ruthenium-based catalyst and its method of modifying of partial hydrogenation of benzene cyclohexene |
| CN109382101A (en) * | 2018-11-09 | 2019-02-26 | 南京师范大学 | A kind of Ru/Y (OH)3Heterozygosis nanostructure and its preparation method and application |
| CN109433201B (en) * | 2018-12-10 | 2021-09-14 | 郑州师范学院 | Preparation of cyclohexene Ru @ Y by selective hydrogenation of benzene2O3Catalyst, preparation method and application thereof |
| CN109569595B (en) * | 2018-12-10 | 2021-09-14 | 郑州师范学院 | Catalytic system for preparing cyclohexene Ru through benzene selective hydrogenation, and preparation method and application thereof |
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| TW340806B (en) * | 1995-03-28 | 1998-09-21 | Mitsui Toatsu Chemicals | Modified Raney catalyst and process for preparation thereof |
| CN102600888B (en) * | 2012-01-31 | 2015-02-18 | 湘潭大学 | Benzene hydrogenation catalyst as well as preparation method and application thereof |
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Inventor after: Sun Haijie Inventor after: Liu Zhongyi Inventor after: Liu Shouchang Inventor after: Chen Lingxia Inventor before: Sun Haijie Inventor before: Chen Lingxia Inventor before: Yuan Peng Inventor before: Li Yongyu Inventor before: Wang Dongbin Inventor before: Zhou Xiaoli Inventor before: Zhao Wenbo Inventor before: Wang Xin |
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Effective date of registration: 20171013 Address after: 450044 Henan city of Zhengzhou province Huiji District North University City Yingcai Street No. 6 Co-patentee after: Zhengzhou University Patentee after: Zhengzhou Normal University Address before: 450044 Zhengzhou North University City, Henan street, No. 6 Patentee before: Zhengzhou Normal University |