CN103752306A - Preparation method of catalyst for producing cyclohexane through benzene hydrogenation, and product and application of catalyst - Google Patents
Preparation method of catalyst for producing cyclohexane through benzene hydrogenation, and product and application of catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a catalyst for producing cyclohexane through benzene hydrogenation. The preparation method comprises the following steps: dissolving ruthenium salt in deionized water or an ethanol solution according to a certain ratio to prepare a solution A; uniformly dispersing at least one of graphene oxide and a carbon nano tube, adding the dispersed substance into the prepared solution A, and performing uniform stirring to obtain a solution B; weighing a chemical reducing agent, preparing a water solution, dropwise adding the water solution of the chemical reducing agent into the solution B, and performing stirring to obtain a turbid solution C; centrifugally separating the turbid solution C to remove a supernatant, adding water into a bottom precipitate, performing uniform mixing, performing centrifugal separation again to remove the supernatant, and repeatedly performing the operation until the supernatant is neutral, thereby obtaining the needed catalyst product. The method can be used for preparing the ruthenium catalyst product which is extremely small in ruthenium usage amount, high in dispersion, high in activity and high in selectivity. Moreover, the catalyst has the characteristics of mild process condition, convenience in operation and control, high catalysis efficiency and the like during the production of cyclohexane.
Description
Technical field
The invention belongs to industrial catalyst technical field, more specifically, relate to preparation method of catalyst and products thereof and application for a kind of prepared from benzene and hydrogen thiacyclohexane.
Background technology
Cyclohexane is a kind of important Organic Chemicals, and it is mainly for the production of cyclohexanol, cyclohexanone and manufacture the products such as monomer caprolactam, hexamethylene adipamide of nylon-66 and nylon-6; Cyclohexane can also dissolve gas chromatography, and toxicity is less than benzene, is a kind of important organic solvent.At present, the method for industrial production cyclohexane mainly contains petroleum distillate partition method and benzene catalytic hydrogenation method, and wherein, benzene catalytic hydrogenation method is the topmost method of preparing cyclohexane.In addition,, along with the purposes of caprolactam and cyclohexanone etc. is more and more wider, the production of cyclohexane is also increasingly important.
Up to the present, the catalyst that benzene hydrogenation is conventional mainly can be divided into according to the difference of its active component that nickel (Ni) is, ruthenium (Ru) is and platinum (Pt) such as is at several large classes.Most domestic benzene hydrogenation device is used Ni series hydrocatalyst, as the Ni-based homogeneous phase Ziegler of the HC-402-2 type type complex catalyst of Sinopec Group, the New NCG-6 Benzene Hydrogenation Catalyst of Nanjing Chemical Industrial Co., Ltd catalyst plant research etc.But the catalytic performance of most of Ni series hydrocatalysts is unsatisfactory, as low in traditional Raney Ni catalyst price, but resistance to sulphur, poor heat resistance, service life is short, to cyclohexane poor selectivity; Deng Jingfa etc. improve Ni series catalysts, have prepared a series of Ni base amorphous alloys, for preparing cyclohexane by hydrogenating benzene, result shows that this kind of catalyst performance is significantly better than traditional Raney Ni, and better heat stability, has industrial applications prospect, but yield is not high.
Compare with Ni series catalysts, Pt series catalysts sulfur tolerance is good, poisoning rear renewable, good heat resistance, and cyclohexane is selectively good, and product does not need separation, and service life is generally longer, therefore be used for large production equipment all the time.But because price is high, at home in industry not as Ni series catalysts is widely used, domestic industry production and application mostly is import catalyst at present.In recent years, it was benzene hydrogenating catalyst that Research Institute of Nanjing Chemical Industry Group has successfully been developed Pt, and built up domestic first to adopt domestic Pt be the process units of benzene hydrogenating catalyst.But Pt series catalysts is in catalytic benzene hydrogenation preparing cyclohexane process, reaction condition fails to reduce preferably, and yield neither be very high.
Ni system and Pt series catalysts are when carrying out hydrogenation catalyst to benzene, and reaction condition is generally higher, and the yield of cyclohexane is lower.From energy-saving and cost-reducing angle, the Performance Ratio Ni of Ru series catalysts system and Pt series catalysts will be got well, so the new and effective Ru series catalysts of developmental research has great significance.A kind of ionic-liquid catalyst [BMIM] Cl/[RuCl is disclosed in CN101602015B
2], wherein, containing ruthenium 0.0258g, catalysis 10mL producing cyclohexane by benzene hydrogenation reacts 3 hours in autoclave, conversion ratio 80% left and right of benzene, selective 100%.This reaction condition is gentleer, but Ru consumption is still higher, and the conversion ratio of benzene is lower, and the amount of unit mass catalyst benzene is lower.
Summary of the invention
Above defect or Improvement requirement for prior art, the invention provides preparation method of catalyst and products thereof and application for a kind of prepared from benzene and hydrogen thiacyclohexane, wherein, by its key reaction condition and parameter thereof are improved, can in the situation that ruthenium consumption is few, make the benzene hydrogenating catalyst product of high dispersive, high activity and high selectivity; In addition, adopt this benzene hydrogenating catalyst prepare cyclohexane and its technical process is optimized, possess process conditions gentleness, be convenient to control and catalytic efficiency high, thereby be particularly useful for industrial use low-cost and that high usage is produced cyclohexane.
To achieve these goals, according to one aspect of the present invention, provide the preparation method of a kind of prepared from benzene and hydrogen thiacyclohexane with catalyst, it is characterized in that, the method comprises the following steps:
(1) ruthenium salt is dissolved in deionized water or ethanolic solution according to a certain percentage, makes thus solution A, wherein, in solution A, the mass percent of ruthenium is 0.01%～0.02%;
(2) after at least one material in graphene oxide and CNT is uniformly dispersed, the mass percent according to 0.09%～0.25% joins in the prepared solution A of step (1), then stirs 10min～60min, after stirring, obtains solution B;
(3) take chemical reducing agent and be made into the aqueous solution, the aqueous solution of chemical reducing agent is dropwise joined in the prepared solution B of step (2) and carries out and stir simultaneously, obtaining thus dirty solution C;
(4) resulting dirty solution C is carried out to centrifugation to remove supernatant, after bottom precipitation adds water and mixes, again centrifugal and remove supernatant, so repeatedly for several times, until upper strata liquid is neutrality, make thus required catalyst product.
As further preferably, in step (1), described ruthenium salt is preferably ruthenium trichloride or its aquo-compound; The soluble-salt that can also add transition elements metal or thulium together makes described solution A as auxiliary agent, and wherein, in solution A, the mass percent of promoter metal is 0.02%～0.5%.
As further preferably, in step (3), described chemical reducing agent is preferably NaBH
4or KBH
4, and the molar concentration of its aqueous solution is 0.25mol/L～0.5mol/L.
As further preferably, in step (4), preferably described turbid solution C is carried out to centrifugal treating with the centrifugal speed of 12000rpm～14000rpm, until that supernatant stops while being neutrality is centrifugal.
According to another aspect of the present invention, also provide corresponding catalyst prod.
As further preferably, in described catalyst prod, ruthenium presents amorphous state and its particle diameter is 15nm～30nm, and disperses on the surface of distribution redox graphene (RGO).
According to another aspect of the present invention, the method for utilizing above-mentioned catalyst to generate cyclohexane is also provided, it is characterized in that, the method comprises the following steps:
(i) described catalyst is prepared into the aqueous dispersion dirty solution that concentration is 0.12wt%～0.15wt%, is then placed in autoclave, pass into H
2remove air in still;
(ii) make autoclave be heated to 90 ℃～150 ℃;
(iii) in the aqueous dispersion turbid solution of described catalyst, add reaction raw materials benzo to pass into H
2, wherein the ratio of quality and the number of copies of benzene and catalyst aqueous dispersion turbid solution is that 1:1～1:2 is, H
2air pressure be controlled between 2.0MPa～6.0MPa, then open to stir and react;
(iv) after reaction starts, sample at regular intervals, standing separation also detects oil phase composition, until generate cyclohexane completely.
For further preferably, step (iii) in, the rotating speed stirring during reaction is set to 400rpm～500rpm, the reaction time is 20min～30min.
In general, according to above technical scheme of the present invention compared with prior art, mainly possess following technological merit:
1, by key reaction condition and parameter thereof to ruthenium catalyst preparation technology, improve, can in the situation that ruthenium consumption is few, can generate the benzene hydrogenating catalyst product of high activity and high selectivity, wherein ruthenium particle diameter is between 15nm～30nm after tested, and high degree of dispersion is on the surface of redox graphene; In addition, this method for preparing catalyst technique is simple, be convenient to quality control, low for equipment requirements;
2, in employing, according to catalyst of the present invention, prepare in the process of cyclohexane, the ruthenium catalyst of minute quantity just can be converted into cyclohexane by complete catalytic benzene hydrogenation, test chart express contract 0.01g noble ruthenium can be converted into cyclohexane by catalysis 50mL benzene completely, the advantage and the reaction time that show high-activity high-selectivity are short, have highly economical and practical value; In addition, this catalyst range of application is wider, is not only applicable to producing cyclohexane by benzene hydrogenation, is equally applicable to the hydrogenation reaction of other aromatic hydrocarbons.
Accompanying drawing explanation
Fig. 1 is the preparation technology's flow chart with catalyst according to producing cyclohexane by benzene hydrogenation of the present invention;
Fig. 2 be take the embodiment of the present invention 1 as example, for showing the XRD figure of prepared ruthenium catalyst;
Fig. 3 be take the embodiment of the present invention 1 as example, for showing the SEM figure of prepared ruthenium catalyst;
Fig. 4 is to be example according to the embodiment of the present invention 1, for the SEM figure that shows that prepared ruthenium catalyst ruthenium grain diameter is measured.
The specific embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.In addition,, in each embodiment of described the present invention, involved technical characterictic just can not combine mutually as long as do not form each other conflict.
Embodiment 1
Get the RuCl of 0.0310g
33H
2o is dissolved in 50mL deionized water or ethanolic solution, is solution A; Get mass percent and be 0.09% graphene oxide aqueous dispersions 30ml and join in solution A and stir 10min, obtain solution B; Then,, under stirring action, in solution B, dropwise add fast 20mL0.5mol/L NaBH
4the aqueous solution, continue to stir 10min, obtain dirty solution C; Dirty solution C is placed in to centrifuge, under 14000rpm rotating speed, centrifugation, abandoning supernatant; Bottom product adds water and mixes, then centrifugation, abandoning supernatant; So for several times, until supernatant is neutrality, obtain product ruthenium catalyst, wherein show after tested containing ruthenium 10%(wt%), this ruthenium catalyst is designated as 1#.
Embodiment 2
Get the RuCl of 0.0155g
3being dissolved in 50mL deionized water or ethanolic solution, is solution A; Take again mass percent and be 0.25% graphene oxide aqueous dispersions and join in solution A and stir 30min, obtain solution B; Then,, under stirring action, in solution B, dropwise add fast 20mL0.25mol/L NaBH
4the aqueous solution, continue to stir 10min, obtain dirty solution C; Dirty solution C is placed in to centrifuge, under 12000rpm rotating speed, centrifugation, abandoning supernatant; Bottom product adds water and mixes, then centrifugation, abandoning supernatant; So for several times, until supernatant is neutrality, obtain product ruthenium catalyst, wherein show after tested containing ruthenium 5%(wt%), this ruthenium catalyst is designated as 2#.
Embodiment 3
Get 0.0265gRuCl
33H
2the CuSO of O and 0.0005g
45H
2o is dissolved in the deionized water or ethanolic solution of 100ml, is solution A; Take again mass percent and be 0.04% graphene oxide aqueous dispersions 25ml and ultrasonic being uniformly dispersed of CNT of 0.02g, then this mixture is joined in solution A and stirs 30min, obtain solution B; Then,, under stirring action, in solution B, dropwise add fast 20mL0.25mol/L KBH
4the aqueous solution, continue to stir 10min, obtain dirty solution C; Dirty solution C is placed in to centrifuge, under 13000rpm rotating speed, centrifugation, abandoning supernatant; Bottom product adds water and mixes, then centrifugation, abandoning supernatant; So for several times, until supernatant is neutrality, obtain product ruthenium catalyst, wherein show after tested that this ruthenium catalyst is designated as 3# containing ruthenium 7.8wt%, containing Cu0.1wt%.
Embodiment 4
Get the RuCl of 0.052g
33H
2o and 0.001g La (NO
3) 6H
2o is dissolved in the deionized water or ethanolic solution of 100ml, is solution A; Take again mass percent and be 0.15% graphene oxide 20ml and ultrasonic being uniformly dispersed of CNT of 0.04g, then this mixture is joined in solution A and stirs 60min, obtain solution B; Then,, under stirring action, in solution B, dropwise add fast 20mL0.2mol/L KBH
4the aqueous solution, continue to stir 10min, obtain dirty solution C; Dirty solution C is placed in to centrifuge, under 13000rpm rotating speed, centrifugation, abandoning supernatant; Bottom product adds water and mixes, then centrifugation, abandoning supernatant; So for several times, until supernatant is neutrality, obtain product ruthenium catalyst, wherein show after tested that this ruthenium catalyst is designated as 4# containing ruthenium 15wt%, containing La0.3wt%.
Embodiment 5
Get 0.007gRuCl
33H
2o and 0.0025g CuSO
45H
2o is dissolved in the deionized water or ethanolic solution of 100ml, is solution A; The aqueous dispersions 30ml that takes again 0.25% graphene oxide, joins in solution A and stirs 30min, obtains solution B; Then,, under stirring action, in solution B, dropwise add fast 20mL0.30mol/L KBH
4the aqueous solution, continue to stir 60min, obtain dirty solution C; Dirty solution C is placed in to centrifuge, under 12000rpm rotating speed, centrifugation, abandoning supernatant; Bottom product adds water and mixes, then centrifugation, abandoning supernatant; So for several times, until supernatant is neutrality, obtain product ruthenium catalyst, wherein show after tested ruthenium 2.5wt%, contain Cu0.5wt%, this ruthenium catalyst is designated as 5#.
The prepared ruthenium catalyst of embodiment 1 of take is below example, and the SEM figure that obtains respectively its XRD collection of illustrative plates, SEM figure and ruthenium grain diameter is measured, and the measurement result of other embodiment is similar therewith.From Fig. 2-Fig. 4, can find out respectively, catalyst main component is redox graphene RGO and amorphous ruthenium; In prepared catalyst, metal Ru is disperseed at RGO apparent height, and likeness in form is interspersed the stars in the night sky, and metal Ru grain diameter is between 15nm～30nm.
Below for adopting above-mentioned prepared ruthenium catalyst 1#～4# to generate respectively the embodiment of cyclohexane.
Embodiment A
The aqueous dispersion turbid solution 50ml of the ruthenium catalyst that outfit concentration is 0.12wt%, adds in autoclave, passes into a small amount of H
2purge for several times to remove air in still; Open controller, be heated to 90 ℃; In the aqueous dispersion dirty solution of ruthenium catalyst, add the reaction raw materials benzo of 50mL to pass into H
2, H
2pressure is controlled between 2.0MPa; Then open and stir, rotating speed 450rpm, starts reaction.The whole reaction time is controlled as more than 30Min, and every 5min sampling once, standing separation, analyzes organic phase with gas chromatograph and form.
Embodiment B
The ruthenium catalyst aqueous dispersion turbid solution that outfit concentration is 0.15wt% adds in autoclave, passes into a small amount of H
2purge for several times to remove air in still; Open controller, be heated to 120 ℃; In the aqueous dispersion dirty solution of ruthenium catalyst, add the reaction raw materials benzo of 50mL to pass into H
2, H
2pressure is controlled between 4.0MPa; Then open and stir, rotating speed 400rpm, starts reaction.The whole reaction time is controlled as more than 30Min, and every 5min sampling once, standing separation, analyzes organic phase with gas chromatograph and form.
Embodiment C
The aqueous dispersion turbid solution 90ml of the ruthenium catalyst that outfit concentration is 0.135wt% adds in autoclave, passes into a small amount of H
2purge for several times to remove air in still; Open controller, be heated to 150 ℃; In the aqueous dispersion dirty solution of ruthenium catalyst, add the reaction raw materials benzo of 35ml to pass into H
2, H
2pressure is controlled between 6.0MPa; Then open and stir, rotating speed 500rpm, starts reaction.The whole reaction time is controlled as more than 30Min, and every 5min sampling once, standing separation, analyzes organic phase with gas chromatograph and form.
Embodiment D
The aqueous dispersion turbid solution 100ml of the ruthenium catalyst that outfit concentration is 0.12wt% adds in autoclave, passes into a small amount of H
2purge for several times to remove air in still; Open controller, be heated to 150 ℃; In the aqueous dispersion dirty solution of ruthenium catalyst, add the reaction raw materials benzo of 50mL to pass into H
2, H
2pressure is controlled between 2.0MPa; Then open and stir, rotating speed 400rpm, starts reaction.The whole reaction time is controlled as more than 30Min, and every 5min sampling once, standing separation, analyzes organic phase with gas chromatograph and form.
Be below according to concrete technology flow process of the present invention and parameter, carry out benzene catalytic hydrogenation reaction respectively according to embodiment A to D, by every 5min sampling, once analyze, the data obtained is as shown in the table:
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. a preparation method for catalyst for prepared from benzene and hydrogen thiacyclohexane, is characterized in that, the method comprises the following steps:
(1) ruthenium salt is dissolved in deionized water or ethanolic solution according to a certain percentage, makes thus solution A, wherein, in solution A, the mass percent of ruthenium is 0.01%～0.02%;
(2) after at least one material in graphene oxide and CNT is uniformly dispersed, the mass percent according to 0.09%～0.25% joins in the prepared solution A of step (1), then stirs 10min～60min, after stirring, obtains solution B;
(3) take chemical reducing agent and be made into the aqueous solution, the aqueous solution of chemical reducing agent is dropwise joined in the prepared solution B of step (2) and carries out and stir simultaneously, obtaining thus dirty solution C;
(4) resulting dirty solution C is carried out to centrifugation to remove supernatant, after bottom precipitation adds water and mixes, again centrifugal and remove supernatant, so repeatedly for several times, until upper strata liquid is neutrality, make thus required catalyst product.
2. preparation method as claimed in claim 1, is characterized in that, in step (1), described ruthenium salt is preferably ruthenium trichloride or its aquo-compound; The soluble-salt that can also add transition elements metal or thulium together makes described solution A as auxiliary agent, and wherein, in solution A, the mass percent of promoter metal is set to 0.0025%～0.005%.
3. preparation method as claimed in claim 1 or 2, is characterized in that, in step (3), described chemical reducing agent is preferably NaBH
4or KBH
4, and the molar concentration of its aqueous solution is 0.25mol/L～0.5mol/L.
4. the preparation method as described in claim 1-3 any one, is characterized in that, in step (4), preferably described turbid solution C is carried out to centrifugal treating with the centrifugal speed of 12000rpm～14000rpm, until that supernatant stops while being neutrality is centrifugal.
5. the prepared catalyst prod of method as described in claim 1-4 any one.
6. catalyst prod as claimed in claim 5, is characterized in that, wherein ruthenium presents amorphous state and its particle diameter is 15nm～30nm, and is dispersed on the surface of redox graphene (RGO).
7. the catalyst of utilization as described in claim 5 or 6 generates a method for cyclohexane, it is characterized in that, the method comprises the following steps:
(i) described catalyst is prepared into concentration and is 0.05%～0.25% aqueous dispersion dirty solution, be then placed in autoclave, pass into H
2remove air in still;
(ii) make autoclave be heated to 90 ℃～150 ℃;
(iii) in the aqueous dispersion turbid solution of described catalyst, add reaction raw materials benzo to pass into H
2, wherein the ratio of quality and the number of copies of benzene and catalyst aqueous dispersion turbid solution is that 1:1～1:2 is, H
2air pressure be controlled between 2.0MPa～6.0MPa, then open to stir and react;
(iv) after reaction starts, sample at regular intervals, standing separation also detects oil phase composition, until generate cyclohexane completely.
8. method as claimed in claim 7, is characterized in that, step (iii) in, the rotating speed stirring during reaction is set to 400rpm～500rpm, the reaction time is 20min～30min.
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