CN103724152B - Selective hydrogenation method for methyl-alpha-methyl styrene - Google Patents
Selective hydrogenation method for methyl-alpha-methyl styrene Download PDFInfo
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- CN103724152B CN103724152B CN201210382508.3A CN201210382508A CN103724152B CN 103724152 B CN103724152 B CN 103724152B CN 201210382508 A CN201210382508 A CN 201210382508A CN 103724152 B CN103724152 B CN 103724152B
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Abstract
The invention provides a selective hydrogenation method for methyl-alpha-methyl styrene, which comprises: methyl-alpha-methyl styrene-containing raw material circulation passes through nickel-based catalyst and palladium-based catalyst with hydrogen in sequence, after one-step hydrogenation, the methyl-alpha-methyl styrene is converted into isopropyltoluene. Optimally, nickel-based catalyst and palladium-based catalyst are contacted directly. According to the hydrogenation method provided by the invention, the reaction material circulation continuously passes through different catalysts, thereby realizing one-step hydrogenation, and simplifying reaction equipment and reaction technology, and saving cost. In addition, according to the invention, the hydrogenation reaction condition is mild, and the catalyst activity is high, and the hydrogenation conversion rate and hydrogenation selectivity are high.
Description
Technical field
The present invention relates to the selec-tive hydrogenation method of petroleum hydrocarbon, relate in particular to a kind of methyl-alpha-methyl selec-tive hydrogenation method.
Background technology
Methyl-alpha-methyl is the main ingredient in the tar light oil by product produced in meta-cresol production process.Produce in the device of 12000 tons of meta-cresols and 8000 ton of 2,6-d-tert-butyl-p-cresol annual, tar light oil by product output is respectively 1.0 ~ 1.2 tons and 1.2 ~ 1.5 tons.Isopropyl toluene (50 ~ 60wt%) and methyl-alpha-methyl (20 ~ 30wt%) is rich in tar light oil by product.Tar light oil by product is separated, the tar light oil by product extracting 88 ~ 90wt% carries out hydrofining, methyl-alpha-methyl is wherein made to change into isopropyl toluene, then turn back to oxidation unit and continue oxidation regeneration product meta-cresol or p-cresol, the material consumption of device can be reduced so widely, obtain considerable economic benefit.
For the hydrogenation of alpha-methyl styrene class, in prior art, once use slurry process, wherein adopt Reney nickel catalyzator to be hydrogenation catalyst.This method needs such as two distillation towers and relevant device, and needs the energy providing cooling and pressure.In addition, Reney nickel catalyst has excessive hydrogenation to produce less desirable by product and needs frequent shortcoming of adding live catalyst.Meanwhile, owing to usually there is the loss of arene compound in this method, institute in this way major part be fixed bed process replace.Such as Chinese patent CN100335165C discloses a kind of method of hydrotreating of Styrene and its derivatives, and wherein hydrogenation carries out in fixed-bed reactor, and the catalyzer used is nickel-base catalyst.But, the leeway that the feed stock conversion of this method is still improved.
Methyl-alpha-methyl hydrogenation is had the advantage of high conversion and highly selective by use noble metal catalyst, such as palladium catalyst.But experiment proves, use palladium system noble metal catalyst in reaction process for nickel catalyst initial reaction temperature higher; In addition, noble metal catalyst high cost is used alone.
Summary of the invention
In order to overcome the above-mentioned problems in the prior art, the invention provides a kind of method of the selec-tive hydrogenation for methyl-alpha-methyl newly, it is simple that this method has technique, and hydroconversion condition is gentle, hydrogenation conversion and hydrogenation selectivity advantages of higher.
According to the present invention, provide a kind of method of methyl-alpha-methyl selec-tive hydrogenation, comprise: by the feed stream containing methyl-alpha-methyl in presence of hydrogen successively by nickel-base catalyst and palladium-based catalyst, through a step hydrogenation, then methyl-alpha-methyl changes into isopropyl toluene.Wherein, the tar light oil by product containing methyl-alpha-methyl of feed stream such as producing in meta-cresol production process.
The present inventor finds after deliberation, and the initial reaction temperature of nickel-base catalyst in methyl-alpha-methyl hydrogenation process is low 3 ~ 10 DEG C relative to palladium-based catalyst.Because olefin hydrogenation is thermopositive reaction, therefore for adiabatic reactor, reaction bed temperature along with the bed temperature that carries out of reaction be constantly raise.The present invention is according to Ni-based and response feature that is palladium-based catalyst, make full use of reaction heat, reactant flow is adopted first to pass through nickel-base catalyst, afterwards by the order of palladium-based catalyst, make two kinds of catalyzer in reaction interval, play preferably catalytic effect, ensure that the hydrogenation rate of methyl-alpha-methyl in raw material.
For the hydrogenation using multiple catalysts, the method of a few step hydrogenation is often adopted in the prior art of this technical field of alpha-methyl styrene class material hydrogenation, different catalyzer is in different beds respectively, reactant flow circulates respectively in the different catalytic hydrogenation stages, or need to be separated cooling etc., the condition of each hydrogenation stage also needs to control respectively, and therefore conversion unit is comparatively complicated, technique is comparatively loaded down with trivial details.But according to the present invention, methyl-alpha-methyl by a step hydrogenation, can obtain good hydrogenation effect under composite catalyst effect.In the present invention, nickel-base catalyst and palladium-based catalyst are filled in the same beds of fixed-bed reactor, and feed stream continues through different catalyzer, do not need to control reaction conditions respectively for different catalyzer, thus at least eliminate loaded down with trivial details operation, save cost.
Preferably, nickel-base catalyst and palladium-based catalyst are placed in same beds.It is further preferred that nickel-base catalyst directly contacts with palladium-based catalyst.Such as two kinds of catalyzer can load and simple superposition successively, also can mix in junction part.These two kinds of catalyzer can also separate with apertured partition.
In a preferred embodiment of the invention, nickel-base catalyst and palladium-based catalyst fill in the bed of composite bed reactor successively, and feed stream downflow system ground is successively by nickel-base catalyst and palladium-based catalyst.
The granularity of nickel-base catalyst is such as Ф (2 ~ 6) × (2 ~ 5) mm, and the granularity of palladium-based catalyst is such as Ф (1.0 ~ 3.5) × (2 ~ 15) mm.
Preferably, the filling ratio of nickel-base catalyst and palladium-based catalyst, by volume of 0.3 ~ 4:1, is more preferably 0.5 ~ 3:1.The filling cumulative volume of catalyzer can be selected according to factors such as feedstock property, temperature of reaction and Feed space velocities.
According to method of the present invention, the condition optimization of a step hydrogenation is: reaction pressure is 0.2 ~ 0.3MPa; Temperature of reaction is 35 ~ 80 DEG C, is more preferably 40 ~ 50 DEG C; The mol ratio of the methyl-alpha-methyl in hydrogen and raw material is 4 ~ 15:1, is more preferably 6:1; Feed space velocity is 1 ~ 2h
-1, be more preferably 1.5h
-1; Reactant flow recycle ratio is 2 ~ 6:1, is more preferably 3:1.Wherein, feed space velocity refers to the air speed of the original raw material not comprising recycle stream part.Visible, according to method of the present invention, hydroconversion condition relaxes, and do not need multiple external energy, the loss caused equipment is little.
Preferably, nickel-base catalyst for carrier, take metallic nickel as active ingredient with aluminum oxide and silicon oxide; Wherein metallic nickel in atom based on nickel-base catalyst for 20 ~ 50wt%, be preferably 30 ~ 45wt%.
Preferably, palladium-based catalyst for carrier, take palladium metal as active ingredient with aluminum oxide or aluminum oxide and titanium oxide; Wherein palladium metal in atom based on the carrier of palladium-based catalyst for 0.1 ~ 1wt%, be preferably 0.3 ~ 0.8wt%.
According to method of the present invention, can be 0.1 ~ 30wt% containing methyl-alpha-methyl in feed stream, be preferably 15 ~ 30wt%.
The method of methyl-alpha-methyl selec-tive hydrogenation synthetic isopropyl toluene provided by the invention, hydrogenation conversion can up to 99.8%, hydrogenation selectivity can reach 100.0%, and substantially can not detect the by product of over-hydrogenation generation in the product, such as isopropyl methyl hexanaphthene.
In a word, according to method of the present invention, there is outstanding advantage: use different catalyzer to realize a step hydrogenation, technique is simple, and hydrogenation conditions is gentle, and catalyst activity is high, methyl-alpha-methyl hydrogenation conversion and hydrogenation selectivity high, the by product without excessive hydrogenation produces.
Embodiment
Below in conjunction with specific embodiment, the invention will be further elaborated, but protection scope of the present invention is not limited to this.
In the present invention:
Hydrogenation conversion=(raw material bromine valency-product bromine valency)/raw material bromine valency × 100%;
In hydrogenation selectivity=product isopropyl toluene mass content/(in raw material methyl-alpha-methyl mass content+raw material in the mass content of isopropyl toluene) × 100%;
The components such as methyl-alpha-methyl adopt gc analysis, and analytical instrument model is Shimadzu 14A;
Raw material and product bromine valency adopt the analysis of conventional potassiumiodide chemical titration.
Embodiment 1
To take aluminum oxide content as the Tai-Ace S 150 of 28.49 grams and be mixed to form glue 2000 milliliters in the water glass (alumina/silica weight ratio is for 1/2) that silicon oxide content is 56.98 grams, under temperature 70 C, pH value 6.0, normal pressure and violent stirring condition, the nickel nitrate aqueous solution 1000 milliliters in nickel oxide content being 114.53 grams is joined in above-mentioned alumina-silica silicone fluid, precipitate 40 minutes, filter, with the deionized water wash 40 minutes of 20 times of filter cake volumes, filter, wash, refilter, this process repeats four times.
Filter cake at the temperature of 100 DEG C dry 10 hours, in the roasting temperature 5 hours of 500 DEG C, is cooled to normal temperature, pulverize, break into cylindrical shape, obtained nickel content is 44.1wt%, and granularity is the nickel-base catalyst of Ф (2 ~ 6) × (2 ~ 5) mm.
Getting specific surface area is 110 meters
2/ gram, pore volume is 0.59 ml/g, most probable pore size is 130 dusts, granularity is 88 grams, the aluminum oxide of Ф (1.0 ~ 3.5) × (2 ~ 15) mm, with the dilution heat of sulfuric acid 65 milliliters dipping that titanium sulfate content is 0.557 grams per milliliter, stir 15 minutes, in 120 DEG C of dryings after 8 hours, in 900 DEG C of roastings 4 hours, obtained Titanium oxide-aluminum oxide compound.In this mixture, titanium oxide content is 11.87 % by weight, and specific surface area is 87 meters
2/ gram, pore volume is 0.53 ml/g, and most probable pore size is 123 dusts.
The palladium content Titanium oxide-aluminum oxide compound that 90 grams are prepared being immersed 85 milliliters is above in the palladium chloride aqueous solution of 0.318 gram/100 milliliters, take out after 1.5 hours, leach the complexes carrier of dipping, at room temperature reduce 1 hour with the hydrazine hydrate aqueous solution that 120 ml concns are 10 % by weight, repeatedly rinse with deionized water, to cleaning chlorion, after draining away the water at 120 DEG C dry 6 hours, then roasting 4 hours at 480 DEG C, obtained palladium content is 0.30 % by weight, and granularity is the Pd/TiO of Ф (1.0 ~ 3.5) × (2 ~ 15) mm
2-Al
2o
3catalyzer.
Palladium catalyst is filled in beds middle and lower part, then load nickel-base catalyst thereon, wherein the volume ratio of nickel-base catalyst and palladium-based catalyst is 1:1, and the two cumulative volume is 100 milliliters.
Before hydrogenation, be 0.2MPa by catalyzer at hydrogen pressure, temperature is 150 DEG C and hydrogen flowing quantity is activate 6 hours under the condition of 500 ml/min, is then cooled to the temperature needed for hydrogenation.
Be 0.2MPa at hydrogen pressure, temperature is pass into feed stream under the condition of 35 DEG C downflow system, and its air speed is 1.5h
-1.Wherein, methyl-alpha-methyl mol ratio in hydrogen and raw material is 6:1, the recycle ratio of reactant flow is 3:1, in the raw material passed into, methyl-alpha-methyl content is 20.02wt%, isopropyl toluene content is 77.09wt%, bromine valency is 22.35 grams of bromine/100 gram oil, and density is 0.872g/cm
3.
Hydrogenation the results are shown in Table shown in 1.
Embodiment 2
Repeat the process of embodiment 1, unlike, temperature of reaction becomes 40 DEG C, the results are shown in Table shown in 1.
Embodiment 3
Repeat the process of embodiment 1, unlike, temperature of reaction becomes 60 DEG C, the results are shown in Table shown in 1.
Table 1
Embodiment 4
Repeat the process of embodiment 2, unlike, the volume ratio of nickel-base catalyst and palladium-based catalyst is 0.5:1, the results are shown in Table shown in 2.
Embodiment 5
Repeat the process of embodiment 2, unlike, the volume ratio of nickel-base catalyst and palladium-based catalyst is 3:1, the results are shown in Table shown in 2.
Table 2
Embodiment 6
Repeat the process of embodiment 2, unlike, in nickel-base catalyst the charge capacity of nickel be 20wt%(in nickle atom based on nickel-base catalyst), the results are shown in Table shown in 3.
Embodiment 7
Repeat the process of embodiment 2, unlike, in palladium-based catalyst, the charge capacity of palladium is that 0.8wt%(is in the carrier of palladium atom based on palladium-based catalyst), the results are shown in Table shown in 3.
Table 3
Embodiment 8
Repeat the process of embodiment 2, unlike, the carrier of palladium-based catalyst changes aluminum oxide into, and result is as shown in table 4.
Embodiment 9
Repeat the process of embodiment 2, unlike, the carrier of palladium-based catalyst changes aluminum oxide into, and the charge capacity of palladium becomes 1wt%, and result is as shown in table 4.
Table 4
Embodiment 10
Repeat the process of embodiment 2, be just in 100 ~ 1000 hours, reaction product is detected in the reaction times, investigate the stabilizing effect of this law.Result is as shown in table 5.
Table 5
Claims (12)
1. the method for a methyl-alpha-methyl selec-tive hydrogenation, comprise: by the feed stream containing methyl-alpha-methyl in presence of hydrogen successively by nickel-base catalyst and palladium-based catalyst, through a step hydrogenation, then methyl-alpha-methyl changes into isopropyl toluene; Wherein, the reaction pressure of a step hydrogenation reaction is 0.2 ~ 0.3MPa, and temperature of reaction is 35 ~ 80 DEG C.
2. method according to claim 1, is characterized in that, nickel-base catalyst and palladium-based catalyst are placed in same beds.
3. method according to claim 2, is characterized in that, described nickel-base catalyst directly contacts with described palladium-based catalyst.
4. the method according to any one of claim 1-3, is characterized in that, the filling ratio of nickel-base catalyst and palladium-based catalyst is by volume of 0.3 ~ 4:1.
5. method according to claim 4, is characterized in that, the filling ratio of nickel-base catalyst and palladium-based catalyst is by volume of 0.5 ~ 3:1.
6. the method according to any one of claim 1-3, is characterized in that, the condition of a described step hydrogenation is: temperature of reaction is 40 ~ 50 DEG C; The mol ratio of the methyl-alpha-methyl in hydrogen and raw material is 4 ~ 15:1; Feed space velocity is 1 ~ 2h
-1; Reactant flow recycle ratio is 2 ~ 6:1.
7. the method according to any one of claim 1-3, is characterized in that, nickel-base catalyst for carrier, take metallic nickel as active ingredient with aluminum oxide and silicon oxide; Wherein metallic nickel in atom based on nickel-base catalyst for 20 ~ 50wt%.
8. method according to claim 7, is characterized in that, in described nickel-base catalyst metallic nickel in atom based on nickel-base catalyst for 30 ~ 45wt%.
9. the method according to any one of claim 1-3, is characterized in that, palladium-based catalyst for carrier, take palladium metal as active ingredient with aluminum oxide or aluminum oxide and titanium oxide; Wherein palladium metal in atom based on the carrier of palladium-based catalyst for 0.1 ~ 1wt%.
10. method according to claim 9, is characterized in that, in described palladium-based catalyst palladium metal in atom based on the carrier of palladium-based catalyst for 0.3 ~ 0.8wt%.
11. methods according to any one of claim 1-3, is characterized in that, are 0.1 ~ 30wt% containing methyl-alpha-methyl in feed stream.
12. methods according to claim 11, is characterized in that, containing methyl-alpha-methyl in feed stream is 15 ~ 30wt%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200418782A (en) * | 2003-01-07 | 2004-10-01 | Sumitomo Chemical Co | Hydrogenation method of aromatic compound |
| CN1793089A (en) * | 2004-12-20 | 2006-06-28 | 凯洛格.布朗及鲁特有限公司 | Selective hydrogenation of alpha-methyl-styrene to cumene |
| CN101475439A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Phenylacetylene selective hydrogenation method using compound bed in the presence of phenylethylene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200418782A (en) * | 2003-01-07 | 2004-10-01 | Sumitomo Chemical Co | Hydrogenation method of aromatic compound |
| CN1793089A (en) * | 2004-12-20 | 2006-06-28 | 凯洛格.布朗及鲁特有限公司 | Selective hydrogenation of alpha-methyl-styrene to cumene |
| CN101475439A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Phenylacetylene selective hydrogenation method using compound bed in the presence of phenylethylene |
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