CN1245254C - A load of Pd hydrogenation catalyst and preparation method as well as method for preparing cyclohexanone from phenol by using the catalyst - Google Patents
A load of Pd hydrogenation catalyst and preparation method as well as method for preparing cyclohexanone from phenol by using the catalyst Download PDFInfo
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- CN1245254C CN1245254C CN 03115159 CN03115159A CN1245254C CN 1245254 C CN1245254 C CN 1245254C CN 03115159 CN03115159 CN 03115159 CN 03115159 A CN03115159 A CN 03115159A CN 1245254 C CN1245254 C CN 1245254C
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Abstract
The present invention relates to a catalyst for cyclohexanone through the catalytic hydrogenation of phenol, a catalyst preparation method, and a method for preparing the cyclohexanone by using the catalyst for the catalytic hydrogenation of the phenol. The catalyst preparation method of the present invention comprises the following steps: a dried gel method is used for synthesizing a carrier of SiO2; then, a conventional dipping method is adopted for preparing a catalyst of Pd/SiO2. The catalyst is used in a heterogeneous catalytic reaction for preparing the cyclohexanone through selectively catalyzing and hydrogenating the liquid phases of the phenol; the catalyst has very high reactivity to the phenol and has very high selectivity to the cyclohexanone.
Description
Technical field
The present invention relates to hydrogenation catalyst of a kind of load P d and preparation method thereof.Also relate to and use described catalyst to carry out the method that the phenol selective catalytic hydrogenation prepares cyclohexanone.
Background technology
Phenol is the accessory substance of petrochemical industry, also is the important fraction in the coai-tar product, and along with the development of petrochemical industry and coking industry, the output of phenol also rises year by year, but because the purposes of phenol is limited, therefore causes a large amount of overstocking, and is badly in need of seeking new outlet.
Cyclohexanone is the main intermediate of preparation nylon 6, caprolactam and adipic acid.Be used for industry such as medicine, paint, coating, rubber, dye well agricultural chemicals, it can be used as the solvent of aircraft with lube oil sludge.Also as the degreasing agent of polishing metal.After the stain for wood japanning, available cyclohexanone demoulding, decontamination, bate pits.
The cyclohexanone purposes is extremely wide, and the domestic market breach is bigger, wherein 1/3rd depends on external import.Prepare cyclohexanone with phenol for the raw material selective catalytic hydrogenation, not only help reducing overstocking of phenol in domestic petroleum chemical enterprise and the coal chemical enterprise, but also can reduce environmental pollution, because of much containing phenol in the waste water of chemical enterprise, also help satisfying the demand of domestic market, have significant potential economic and social benefit cyclohexanone.
The method of now producing cyclohexanone both at home and abroad has following several:
Disclosing cyclohexanone among US 0578063 and the US 5208392 can be made by the cyclohexane catalytic oxidation; US 4670605 has described to be set out by cyclohexanol and has made the method for cyclohexanone through catalytic oxidation.
Usually make by the phenol catalytic hydrogenation according to US 5015787 described cyclohexanol.Such method reactions steps is many, to the requirement height of chemical reagent and equipment, therefore generally considers that from ecological and economic angle this is quite disadvantageous.
Cyclohexanone can prepare through heterogeneous catalyzed hydration by phenol.At U.S.4,203,923,4,200,553,3,076,810,06,046,365; J.P.Nos.11 has disclosed with the method for Pd/C catalyst in 035,512 and 11,035,513 and has carried out phenol catalytic hydrogenation preparing cyclohexanone, and the activity of such catalysts component is a palladium, and active carbon is as carrier.These courses of reaction only can provide low selectivity when high reactivity is provided; Or when being provided, high selectivity only can provide low reactivity.Yet from angle economic and reaction, the course of reaction of phenol catalytic hydrogenation preparing cyclohexanone needs high reactivity and high selectivity, thereby obtains highly purified cyclohexanone, and this point is very important to industrial production.
According to U.S.4,092,360; 3,932,514; British Patent Specification Nos.1,063,367; 890,095 and document S.Narayanan et.al., Appl.Catal.A 174 (1998) 221-229; 198 (2000) 13-21; Catal.Today.49 (1999) 57-63; N.Mahata et.al., Catal.Today.49 (1999) 65-69; Appl.Catal.A 182 (1999) 183-187; Y.Z.Chenet.al., Appl.Catal.A 177 (1999) 1-8 have described the process for preparing cyclohexanone from phenol, and used catalyst mainly is Pd/Al
2O
3Catalyst, these courses of reaction only can provide low selectivity equally when high reactivity is provided; Or when being provided, high selectivity only can provide low reactivity.In order to improve the yield of cyclohexanone, document S.Narayanan et.al., Appl.Catal.A 174 (1998) 221-229; 198 (2000) 13-21; Catal.Today.49 (1999) 57-63; N.Mahata et.al., Catal.Today.49 (1999) 65-69; Appl.Catal.A 182 (1999) 183-187; Y.Z.Chen et.al., Appl.Catal.A177 (1999) 1-8 is disclosed in Pd/Al
2O
3Add the alkaline earth oxide of 0.1-5% in the catalyst, as CaO and MgO etc.Document S.Narayanan et.al., Appl.Catal.A 174 (1998) 221-229; 198 (2000) 13-21; The conversion ratio of Catal.Today.49 (1999) 57-63 phenol is up to 66%, and the selectivity of cyclohexanone is up to 95%.Document N.Mahata et.al., Catal.Today.49 (1999) 65-69; The conversion ratio that discloses phenol among Appl.Catal.A 182 (1999) 183-187 reaches 60%, and the selectivity of cyclohexanone is 90%; The conversion ratio that reaches phenol is up to 85%, and the selectivity of cyclohexanone is up to 85%.Document Z.Chen et.al., the conversion ratio of phenol is 40% among Appl.Catal.A 177 (1999) 1-8, the selectivity of cyclohexanone is 95%.Though the yield of cyclohexanone increases, the selectivity of cyclohexanone is 85-95%, also has the cyclohexanol impurity of 5-15% in product, and this purification to cyclohexanone brings difficulty, because the boiling point of cyclohexanone and cyclohexanol differs very little.Patent U.S.No.3,932,514 and British Patent Specification No.1,063,367 has described the process for preparing cyclohexanone from the phenol vapor phase method, and the used carrier of catalyst is γ-Al of 40-98%
2O
3With the alkaline earth oxide of 2-60%, though obtained higher cyclohexanone yield, selectivity also reaches 93%, and the conversion of the phenol rate that hastens is very slow, and this reduces industrial production efficient.
In above-mentioned patent and document, use Pd/C, Pd/Al
2O
3Catalyst carries out in the catalytic hydrogenation, under employed reaction condition, has all produced the cyclohexanol accessory substance.Therefore, press for the catalyst that can prepare cyclohexanone with high activity and selectivity.
Summary of the invention
Purpose of the present invention provides a kind of phenol catalytic hydrogenation that is used for and prepares the high activity of cyclohexanone and the hydrogenation catalyst and preparation method thereof of load P d optionally.Another object of the present invention provides the method that phenol hydrogenation prepares cyclohexanone.
Described catalyst is Pd/Si
2The O catalyst, Pd is carried on the silica supports with 1-10% (weight) load capacity, and the specific area of described silica supports is 400-850m
2/ g, the aperture is 2.3-2.5nm, pore volume is 0.9-1.1cm
3/ g.
Described Preparation of catalysts method comprises the following steps:
A. with xerogel method synthetic vectors silica, the silica specific area is 400-850m
2/ g, the aperture is 2.3-2.5nm, pore volume is 0.9-1.1cm
3/ g;
B. the silica supports that makes is immersed in PdCl
2In the solution, make PdCl
2/ SiO
2
C. in 100 ℃ of oven dry;
D. under the logical nitrogen, be warming up to about 200 ℃, better be warming up to about 200 ℃, be incubated 2-4 hour, be cooled to room temperature, under logical hydrogen, better be warming up to about 400 ℃ then, reduced 4-6 hour, make Pd/SiO with 5 ℃/min speed with 5 ℃/min speed
2Catalyst.
The method that phenol hydrogenation prepares cyclohexanone comprises the following steps:
A. use Pd/SiO of the present invention
2Catalyst feeds hydrogen, makes phenol be selected from ethanol, oxolane, 1, and the following or body of the solvent of 4-dioxane in the body, under 20-200 ℃ of reaction temperature and 0.1-10Mpa pressure, carried out catalytic hydrogenation 4-40 hour more fortunately;
B. separated product and catalyst.
The specific embodiment
When preparing cyclohexanone by the phenol selective catalytic hydrogenation, phenol at first generates cyclohexenol through catalytic hydrogenation, and the unstable tautomerism of cyclohexenol generates cyclohexanone, and cyclohexanone continues catalytic hydrogenation and generates cyclohexanol.On thermodynamic (al) principle, it is more favourable that the cyclohexanone catalytic hydrogenation generates cyclohexanol, and it is difficult making thalidomide stay this step of cyclohexanone, so must study this reaction from dynamics and catalyst angle.If catalyst activity very higher position generates cyclohexanol easily, if the conversion ratio of active low phenol is just low, this is a pair of contradiction.Solve this contradiction, just must study from catalyst and reaction condition, promptly prepared catalyst must have high reaction activity and high and very high selectivity.
The catalyst that discloses in the above-mentioned document, the problem of existence be, only can provide low selectivity when high reactivity is provided; When perhaps being provided, high selectivity only can provide low reactivity.If selection of catalysts is not high, in the phenol hydrogenation process, produce cyclohexanol, and the boiling point of cyclohexanol and cyclohexanone differs very little, the existence of cyclohexanol is purified to cyclohexanone and is brought difficulty, therefore, require selection of catalysts high as far as possible, preferably can reach more than 95%.
Catalytic reaction is normally carried out at the inner surface of catalyst, because inner surface is than big many of outer surface, and phenol is a bigger ring molecule, so having under the high optionally situation, the aperture of improving catalyst helps increasing the reactivity of catalyst.Improve selectivity and then need to select active component and carrier.For this reason, among the present invention, the catalytic active component of use is selected from period of element Table VIII B family, for example palladium, ruthenium, rhodium, platinum, nickel, and preferred palladium, load capacity is preferably 5% (weight) in 1-10% (weight) scope; Require carrier to have bigger aperture and specific surface, carrier can adopt active carbon, Al
2O
3, SiO
2Deng, preferred SiO
2Carrier.
SiO
2Carrier can adopt dry gel method synthetic, and this synthetic method can be according to the size of reaction molecular, and the carrier of synthetic corresponding big small-bore helps improving activity of such catalysts and selectivity.The SiO that uses in the catalyst of the present invention
2The specific area of carrier is at 400-850m
2/ g scope, 500-700m more fortunately
2/ g scope, aperture are 2.3-2.5nm, and pore volume is 0.9-1.1cm
3/ g.
Among the present invention, gel method has synthesized carrier S iO
2Afterwards, adopt conventional dipping method then, with this carrier impregnation at PdCl
2Make PdCl in the solution
2/ SiO
2Catalyst precarsor.After 100 ℃ of dryings, under feeding nitrogen, be warming up to about 200 ℃, better heat up with 5 ℃/min speed, and under this temperature, kept 2-4 hour, be cooled to room temperature, under feeding hydrogen, be warming up to 400 ℃, better be warming up to about 400 ℃ with 5 ℃/min speed, and under this temperature, keep reducing in 4-6 hour, make Pd/SiO
2Catalyst.
Phenol catalytic hydrogenation of the present invention prepares the reaction of cyclohexanone and can carry out in 4-dioxane solvent or the body at ethanol, oxolane, 1.Preferably without solvent, so both economical, convenient again.Reacting on 20-200 ℃ carries out under stirring under the hydrogen pressure of 0.1-10Mpa.Temperature should be at 100-160 ℃, and Hydrogen Vapor Pressure is preferably 2.5-7.5Mpa, is preferably 5Mpa.In hydrogenation, in order to obtain desirable conversion ratio and selectivity, need to observe hydrogen gas consumption and in course of reaction sample analysis at any time so that in time stop this hydrogenation.This can realize by stopping stirring, reduction temperature and termination adding hydrogen.
After hydrogenation is finished, adopt routine techniques for example catalyst separation to be gone out by filtering.
The high activity of the present invention's preparation and the Pd/SiO of high selectivity
2Catalyst is used for preparing cyclohexanone from the phenol selective catalytic hydrogenation, and this catalyst Pyrogentisinic Acid has high reaction activity and high, and cyclohexanone is had very high reaction selectivity.Prepare in the course of reaction of cyclohexanone at the phenol selective catalytic hydrogenation, the conversion ratio of phenol is reached more than 90%, the selectivity of cyclohexanone reaches 95-100%, has avoided the purification of product.Therefore this catalyst has very high reactivity and selectivity, and can recycle, and regeneration is convenient.
Use Pd/SiO of the present invention
2Catalyst prepares cyclohexanone by the phenol selective catalytic hydrogenation and has simplified the equipment of industrial product and production technology, therefore considers that from ecological and economic angle this is quite favourable.Not only help reducing overstocking of phenol in domestic petroleum chemical enterprise and the coal chemical enterprise, but also can reduce environmental pollution, also help satisfying the demand of domestic market, have significant potential economic and social benefit cyclohexanone.
Embodiment
Preparation embodiment 1: preparation SiO
2Carrier
In the 500ml round-bottomed flask, (TEOS) is dissolved in the 40ml absolute ethyl alcohol with the 0.3mol ethyl orthosilicate, stirs down at 60 ℃, drips 4%HCL (being dissolved in the 30ml absolute ethyl alcohol) then, and hydrolysis adds the 100ml absolute ethyl alcohol again after 1 hour, make H
2O: TEOS: the HCl mol ratio is 4: 1: 0.1, and solution stirs into glue under 60 ℃.This colloidal sol 60 ℃ aging 2 days, then 105 ℃ of dryings 24 hours, 550 ℃ of calcinings 4 hours are crushed to the 60-80 order, become xerogel (Xerogel) SiO
2This SiO by analysis
2Specific surface be 634m
2/ g, the aperture is 2.4nm, pore volume is 0.9cm
3/ g.
Embodiment 2-5: preparation SiO
2Carrier
According to the method identical with preparing embodiment 1, preparation SiO
2, difference is to dissolve the consumption of the absolute ethyl alcohol of ethyl orthosilicate.The SiO that makes
2Specific area, aperture and pore volume are listed in the table below 1.
Table 1
| Embodiment | Absolute ethyl alcohol consumption (ml) | Specific area (m 2/g) | Aperture (nm) | Pore volume (cm 3/g) |
| 2 | 80 | 750 | 2.5 | 1.1 |
| 3 | 30 | 423 | 2.3 | 0.9 |
| 4 | 35 | 565 | 2.4 | 0.9 |
| 5 | 100 | 836 | 2.4 | 1.0 |
Preparation embodiment 6: preparation Pd/SiO
2Catalyst
Adopt conventional dipping method to prepare Pd/SiO
2Catalyst, the SiO that uses 10 gram examples 1 to prepare
2Carrier is immersed in the PdCl that 88ml concentration is 10mg/ml
2Solution stirs after 3 hours to filter and makes PdCl
2/ SiO
2, this pdcl
2/ SiO
2In 100 ℃ of oven dry, under logical nitrogen, be warming up to 200 ℃ then with 5 ℃/min speed program, be incubated 2 hours, be cooled to room temperature.Then, under logical hydrogen, be warming up to 400 ℃, reduced 4 hours, make the Pd/SiO that the Pd load capacity is 5% (weight) with 5 ℃/min speed program
2Catalyst.
Preparation embodiment 7: preparation Pd/SiO
2Catalyst
Adopt the conventional dipping method identical and the SiO of preparation embodiment 1 preparation with preparation embodiment 6
2Carrier, preparation PdCl
2/ SiO
2Catalyst, difference are, with 10 gram SiO
2Carrier impregnation is the PdCl of 10mg/ml in 18ml concentration
2In the solution, make the Pd/SiO that the Pd load capacity is 1% (weight)
2Catalyst.
Preparation embodiment 8: preparation Pd/SiO
2Catalyst
Adopt the conventional dipping method identical and the SiO of preparation embodiment 1 preparation with preparation embodiment 6
2Carrier, preparation PdCl
2/ SiO
2Catalyst, difference are, with 10 gram SiO
2Carrier impregnation is the PdCl of 10mg/ml in 175ml concentration
2In the solution, make the Pd/SiO that the Pd load capacity is 10% (weight)
2Catalyst.
Preparation embodiment 9-12: preparation Pd/SiO
2Catalyst
Adopt the conventional dipping method identical, use the SiO of preparation embodiment 2-5 preparation respectively with preparation embodiment 6
2Carrier makes the Pd/SiO that the Pd load capacity is 5% (weight) respectively
2Catalyst.
Embodiment 1
Taking by weighing 3, restrain to be equipped with embodiment 6 prepared Pd load capacity be the Pd/SiO of 5% (weight)
2Catalyst, put into the boiling flask that fills 100 milliliters of phenol, and place on the magnetic stirring apparatus, load onto condenser pipe, normal pressure is heating and feeding hydrogen (hydrogen flowing quantity is 120ml/min) (hydrogen that is equivalent to pressure 0.1MPa) down, and reaction temperature is 160 ℃, reacts after 40 hours, cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 98.9%, and the selectivity of cyclohexanone is 98.6%.
Embodiment 2
Taking by weighing 3, restrain to be equipped with embodiment 7 prepared Pd load capacity be the Pd/SiO of 1% (weight)
2Catalyst, put into the boiling flask that fills 100 milliliters of phenol, and place on the magnetic stirring apparatus, load onto condenser pipe, normal pressure is heating and feeding hydrogen (hydrogen flowing quantity is 120ml/min) (hydrogen that is equivalent to pressure 0.1MPa) down, and reaction temperature is 160 ℃, reacts after 40 hours, cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 85.6%, and the selectivity of cyclohexanone is 98.1%.
Embodiment 3
Taking by weighing 3, restrain to be equipped with embodiment 8 prepared Pd load capacity be the Pd/SiO of 10% (weight)
2Catalyst, put into the boiling flask that fills 100 milliliters of phenol, and place on the magnetic stirring apparatus, load onto condenser pipe, normal pressure is heating and feeding hydrogen (hydrogen flowing quantity is 120ml/min) (hydrogen that is equivalent to pressure 0.1MPa) down, and reaction temperature is 160 ℃, reacts after 40 hours, cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 99.5%, and the selectivity of cyclohexanone is 98.5%.
Comparative example 1
Taking by weighing 3 gram Pd load capacity is the Pd/C catalyst of 5% (weight), put into the boiling flask that fills 100 milliliters of phenol, and place on the magnetic stirring apparatus, load onto condenser pipe, normal pressure is the logical hydrogen (hydrogen flowing quantity 120ml/min) of heating down, and reaction temperature is 160 ℃, reacts after 40 hours, cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 61.7%, and the selectivity of cyclohexanone is 95.2%, and the selectivity of impurity cyclohexanol is 4.8%.
Embodiment 4
Taking by weighing the 3 Pd load capacity that restrain to be equipped with preparation among the embodiment 6 is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 100 ℃ to 5Mpa, and reaction is after 4 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 99.3%, and the selectivity of cyclohexanone is 99.8%.
Embodiment 5
Taking by weighing the 3 Pd load capacity that restrain to be equipped with preparation among the embodiment 7 is the Pd/SiO of 1% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 100 ℃ to 5Mpa, and reaction is after 4 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 90.4%, and the selectivity of cyclohexanone is 98.9%.
Embodiment 6
Taking by weighing the 3 Pd load capacity that restrain to be equipped with preparation among the embodiment 8 is the Pd/SiO of 10% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 100 ℃ to 5Mpa, and reaction is after 4 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 99.5%, and the selectivity of cyclohexanone is 97.4%.
Comparative example 2
The Pd/C catalyst that takes by weighing 3 gram Pd load capacity and be 5% (weight) is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, logical then hydrogen exchange three times, logical pressurized with hydrogen is to 5Mpa, be heated to 100 ℃, reaction is after 4 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 72.4%, and the selectivity of cyclohexanone is 94.7%.
Embodiment 7
Taking by weighing the 3 Pd load capacity that restrain to be equipped with preparation among the embodiment 6 is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 100 ℃ to 0.1Mpa, and reaction is after 32 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 90.4%, and the selectivity of cyclohexanone is 99.0%.
Embodiment 8
Taking by weighing the 3 Pd load capacity that restrain to be equipped with preparation among the embodiment 6 is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 100 ℃ to 2.5Mpa, and reaction is after 24 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 99.0%, and the selectivity of cyclohexanone is 98.8%.
Embodiment 9
Taking by weighing the 3 Pd load capacity that restrain to be equipped with preparation among the embodiment 6 is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 100 ℃ to 7.5Mpa, and reaction is after 4 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 99.6%, and the selectivity of cyclohexanone is 95.4%, and the selectivity of impurity cyclohexanol is 4.6%.
Embodiment 10
Taking by weighing the 3 Pd load capacity that restrain to be equipped with preparation among the embodiment 6 is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 100 ℃ to 10Mpa, and reaction is after 4 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 100%, and the selectivity of cyclohexanone is 93.6%, and the selectivity of impurity cyclohexanol is 6.4%.
Embodiment 11
Taking by weighing the 3 Pd load capacity that restrain to be equipped with preparation among the embodiment 9 is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 100 ℃ to 5Mpa, and reaction is after 4 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 99.1%, and the selectivity of cyclohexanone is 98.5%.
Embodiment 12
Taking by weighing the 3 Pd load capacity that restrain to be equipped with preparation among the embodiment 10 is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 100 ℃ to 5Mpa, and reaction is after 4 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 93.5%, and the selectivity of cyclohexanone is 95.3%.
Embodiment 13
Taking by weighing the 3 Pd load capacity that restrain to be equipped with preparation among the embodiment 11 is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 100 ℃ to 5Mpa, and reaction is after 4 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 99.2%, and the selectivity of cyclohexanone is 96.8%.
Embodiment 14
Taking by weighing the 3 Pd load capacity that restrain to be equipped with preparation among the embodiment 12 is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 100 ℃ to 5Mpa, and reaction is after 4 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 98.3%, and the selectivity of cyclohexanone is 97.7%.
Table 2
The Pd/SiO of different Pd load capacity (weight %)
2Catalyst
Optionally influence to the conversion ratio and the cyclohexanone of phenol under the normal pressure
| Embodiment | Pd load capacity (weight %) | Phenol conversion (%) | Cyclohexanone selectivity (%) |
| 2 | 1 | 85.6 | 98.1 |
| 1 | 5 | 98.9 | 98.6 |
| 3 | 10 | 99.5 | 98.5 |
Table 3
The Pd/SiO of different Pd load capacity (weight %)
2Catalyst
Optionally influence to the conversion ratio and the cyclohexanone of phenol under the 5MPa pressure
| Embodiment | Pd load capacity (weight %) | Phenol conversion (%) | Cyclohexanone selectivity (%) |
| 5 | 1 | 90.4 | 98.9 |
| 4 | 5 | 99.3 | 99.8 |
| 6 | 10 | 99.5 | 97.4 |
Table 4
The optionally influence of Pyrogentisinic Acid's conversion ratio and cyclohexanone under the different pressures
| Embodiment | Pressure (MPa) | Phenol conversion (%) | Cyclohexanone selectivity (%) |
| 7 | 0.1 | 90.4 | 99.0 |
| 8 | 2.5 | 99.0 | 98.8 |
| 4 | 5 | 99.3 | 99.8 |
| 9 | 7.5 | 99.6 | 95.4 |
| 10 | 10 | 100 | 93.6 |
Table 4
Character Pyrogentisinic Acid's conversion ratio of carrier and optionally influence
| Specific surface (m 2/g) | Aperture (nm) | Pore volume (cm 3/g) | Phenol conversion (%) | Cyclohexanone selectivity (%) | |
| Embodiment 4 | 634 | 2.4 | 0.9 | 99.3 | 99.8 |
| Embodiment 11 | 750 | 2.5 | 1.1 | 99.1 | 98.5 |
| Embodiment 12 | 423 | 2.3 | 0.9 | 93.5 | 95.3 |
| Embodiment 13 | 565 | 2.4 | 0.9 | 99.2 | 96.8 |
| Embodiment 14 | 836 | 2.4 | 1.0 | 98.3 | 97.7 |
Embodiment 15
Taking by weighing the 3 Pd load capacity of restraining embodiment 6 preparations fully is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is to 10Mpa, and 20 ℃ of reaction temperatures were reacted under mechanical agitation after 40 hours, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 85.8%, and the selectivity of cyclohexanone is 98.5%.
Embodiment 16
Taking by weighing the 3 Pd load capacity of restraining embodiment 6 preparations fully is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 60 ℃ to 5Mpa, and reaction is after 20 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 91.6%, and the selectivity of cyclohexanone is 99.2%.
Embodiment 17
Taking by weighing the 3 Pd load capacity of restraining embodiment 6 preparations fully is the Pd/SiO of 5% (weight)
2Catalyst is put into the autoclave that fills 100 milliliters of phenol, logical nitrogen replacement air three times, and logical then hydrogen exchange three times, logical pressurized with hydrogen is heated to 200 ℃ to 0.5Mpa, and reaction is after 12 hours under mechanical agitation, and cooling removes by filter catalyst.Gas chromatographic analysis shows that the conversion ratio of phenol is 96.2%, and the selectivity of cyclohexanone is 97.3%.
Claims (6)
1. the hydrogenation catalyst of a load P d is a benchmark with the total catalyst weight, and the Pd load capacity is at the 1-10% weight range, and described carrier is that specific area is 400-850m
2/ g, the aperture is 2.3-2.5nm, pore volume is 0.9-1.1cm
3The SiO of/g
2, described catalyst is made up of palladium and carrier.
2. the hydrogenation catalyst of load P d as claimed in claim 1 is characterized in that the Pd load capacity is 5% weight.
3. the hydrogenation catalyst of load P d as claimed in claim 1 is characterized in that described carrier S iO
2Specific area be 500-700m
2/ g.
4. method for preparing the hydrogenation catalyst of load P d, this method comprises the following steps:
A. with xerogel method synthetic vectors silica, the silica specific area is 400-850m
2/ g, the aperture is 2.3-2.5nm, pore volume is 0.9-1.1cm
3/ g;
B. the silica supports that makes is immersed in PdCl
2In the solution, make PdCl
2/ SiO
2
C. in 100 ℃ of oven dry;
D. under the logical nitrogen, be warming up to 200 ℃, be incubated 2-4 hour, be cooled to room temperature, under logical hydrogen, be warming up to 400 ℃ then, reduced 4-6 hour, make Pd/SiO
2Hydrogenation catalyst, wherein the load capacity of Pd is 1-10 weight %, is benchmark with the total catalyst weight.
5. the phenol catalytic hydrogenation prepares the method for cyclohexanone, and this method comprises the following steps:
A. use the hydrogenation catalyst of the described load P d of arbitrary claim among the claim 1-3, feed hydrogen, make phenol be selected from ethanol, oxolane or 1, under the solvent of 4-dioxane or in the body, under 20-200 ℃ of reaction temperature and 0.1-10Mpa pressure, carried out the catalyst hydrogenation 4-40 hour
B. separated product and catalyst.
6. method as claimed in claim 5 is characterized in that described hydrogenation 100-160 ℃ of reaction temperature, carries out under the 2.5-7.5Mpa pressure.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102791668A (en) * | 2009-12-18 | 2012-11-21 | 帝斯曼知识产权资产管理有限公司 | Catalysed phenol hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100347148C (en) * | 2004-07-28 | 2007-11-07 | 上海世景国际贸易有限公司 | Preparation of 2,5-dihalogenated p-phenylene diamine, catalyst utilized and preparation method |
| CN100467432C (en) * | 2006-07-03 | 2009-03-11 | 浙江工业大学 | Synthesis method of substituted cyclohexanone and/or substituted cyclohexanol |
| RU2528980C2 (en) * | 2013-01-10 | 2014-09-20 | Общество с ограниченной ответственностью "ДЕСКРИПТОР" | Method for selective hydrogenation of phenol to cyclohexanone |
| CN106861755B (en) * | 2017-02-24 | 2019-11-29 | 南开大学 | A kind of Pd catalyst of stimulating responsive material load and its preparation method and application research |
| CN113019435B (en) * | 2021-03-26 | 2023-02-03 | 福州大学 | Monoatomic palladium/molecular sieve catalyst, preparation thereof and application thereof in preparation of ketone by selective hydrogenation of biomass molecules |
| CN114308028B (en) * | 2022-01-05 | 2023-12-19 | 万华化学集团股份有限公司 | Rh-C/SiO 2 Heterogeneous catalyst and method for preparing 4, 4-dihydroxybiphenyl by using same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102791668A (en) * | 2009-12-18 | 2012-11-21 | 帝斯曼知识产权资产管理有限公司 | Catalysed phenol hydrogenation |
| CN102791668B (en) * | 2009-12-18 | 2015-06-17 | 帝斯曼知识产权资产管理有限公司 | Catalysed phenol hydrogenation |
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