CN104230635B - The method of hydrogenation of acetophenone ethylbenzene processed - Google Patents
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Abstract
The present invention relates to the method for a kind of hydrogenation of acetophenone ethylbenzene processed, mainly solve existing dicumyl peroxide method has acetophenone residual in production expoxy propane technology, the low problem of the existing hydrogenation of acetophenone choice of technology. The present invention adopts taking the mixing material containing acetophenone, isopropylbenzene and hydrogen as raw material, raw material and catalyst haptoreaction, make the hydrogenation of acetophenone in raw material be converted into ethylbenzene, catalyst used comprises following component in parts by weight: a) 10.0～35.0 parts of Cu or its oxide; B) 10.0～30.0 parts of Ni or its oxide; C) 30.0～75.0 parts of Al2O3; D) 3.0～10.0 parts of at least one technical schemes that are selected from Mg or its oxide, Ca or its oxide, Ba or its oxide have solved this problem preferably, can be used in the industrial production of hydrogenation of acetophenone ethylbenzene processed.
Description
Technical field
The present invention relates to the method for a kind of hydrogenation of acetophenone ethylbenzene processed, particularly about a kind of method that hydrogenation of acetophenone in the mixed liquor producing in production expoxy propane process is converted into ethylbenzene.
Background technology
Expoxy propane is a kind of important petrochemical industry Organic Ingredients, and the main production method of this material is chlorohydrination and ethylbenzene hydroperoxide method. Chlorohydrination is seriously polluted to environment, and ethylbenzene hydroperoxide method has a large amount of coproduction accessory substances-styrene to generate, thereby makes the production cost of expoxy propane be subject to the impact of the price fluctuation of co-product. In recent years, taking dicumyl peroxide as oxygen source, the method that propylene oxide is produced expoxy propane grows up gradually, this process environmental protection, safe, co-product α, alpha-alpha-dimethyl benzylalcohol can generate isopropylbenzene by catalytic hydrogenolytic cleavage, and isopropylbenzene can return to the realization of peroxidating unit and recycle. Produce the technique ratio of expoxy propane with ethylbenzene hydroperoxide method oxidation, it is short that this process has process route, and equipment investment is few, without co-product and the advantage such as production prices are more stable. CHP legal system comprises cumene oxidation for the technique of expoxy propane, and three operations of epoxidation of propylene and benzylalcohol hydrogenolysis, are not subject to the impact of accessory substance styrene price fluctuation, can bring more stable economic benefit for manufacturer. The benzylalcohol in benzylalcohol hydrogenolysis operation, reaction being produced is converted into isopropylbenzene, thereby realizes recycling of isopropylbenzene. Wherein in benzylalcohol hydrogenolysis process, adopt that Cu catalyst basedly exists that reaction velocity is low, contaminated environment, the low problem of anti-impurity ability. Adopt that Pd is noble metal catalyst based can be realized benzylalcohol hydrogenolysis and prepare isopropylbenzene under larger air speed, but a small amount of acetophenone producing in cumene oxidation process cannot be removed in the lump by Pd is catalyst based, a small amount of acetophenone is separated and is removed comparatively complexity by rectifying, by hydrogenation be translated into ethylbenzene remove comparatively easy. The present invention adopts benzylalcohol first to generate isopropylbenzene by first stage reactor hydrogenolysis, and the method that acetophenone is converted into ethylbenzene through second stage reactor catalytic hydrogenation has well solved this problem.
Radix Cynanchi Paniculatis etc. (chemical reagent, 2005,27 (3), 129 ~ 132) adopt the catalyst based Hydrogenation to acetophenone of different Ni in three to compare, and find Ni-B/SiO2The activity of amorphous alloy catalyst and stability are obviously better than RaneyNi catalyst and Uru shibara nickel catalyst. 120oC，H2Under pressure 3.0MPa, taking ethanol as solvent, acetophenone conversion 100%, generates ethylbenzene selectivity 89.2%.
Li Guangxing etc. (Journal of Molecular Catalysis, 2004,18 (4), 281 ~ 285) adopt Ni-B/SiO2Catalyst, taking acetophenone and hydrogen as raw material, in reaction temperature 120oC, Hydrogen Vapor Pressure 3.0MPa, under reaction time 5h condition, acetophenone conversion 100%, generating ethylbenzene selectivity is 90.2%.
Wang Youzhen etc. (chemical journal, 2004,62(14), 1349～1352) employing high selectivity hydrogenation of acetophenone Ni-Sn-B/SiO2Amorphous catalyst, has carried out hydrogenation research to acetophenone, works as Sn/SiO2When percentage by weight is 10%, the yield that hydrogenation of acetophenone generates benzyl carbinol reaches 97.5%, and benzene ring hydrogenation product content is 0.5%.
Chinese patent CN200410015896.7 has reported hydrogenation of acetophenone amorphous nickel-boron Catalysts and its preparation method, and nickel exists with Ni-B or Ni-M-B form, and metallic addition M is the one in Sn, Cr, Mo, W, Fe, Co, La. This catalyst has good hydrogenation of acetophenone performance, and primary product is benzyl carbinol.
From the above mentioned, prepare ethylbenzene with existing techniques in realizing hydrogenation of acetophenone and have selective low problem, and current research is all to adopt batch reactor, cannot realize serialization and produce.
Summary of the invention
Technical problem to be solved by this invention is the problem that existing hydrogenation of acetophenone is prepared ethylbenzene technology and exist poor selectivity, and a kind of method of new hydrogenation of acetophenone ethylbenzene processed is provided. It is selectively good that the method has advantages of for hydrogenation of acetophenone ethylbenzene processed.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: the method for a kind of hydrogenation of acetophenone ethylbenzene processed, taking the mixing material containing acetophenone, isopropylbenzene and hydrogen as raw material, be 5 ~ 15:1 in the mol ratio of hydrogen/mixing material, reaction temperature is 100～180oC, reaction pressure is 1.0～5.0MPa, liquid volume air speed is 2.0～10.0 hours-1Under condition, raw material and catalyst haptoreaction, make the hydrogenation of acetophenone in raw material be converted into ethylbenzene, and catalyst used comprises following component in parts by weight:
A) 10.0～35.0 parts of Cu or its oxide;
B) 10.0～30.0 parts of Ni or its oxide;
C) 30.0～75.0 parts of Al2O3；
D) 3.0～10.0 parts of at least one that are selected from Mg or its oxide, Ca or its oxide, Ba or its oxide.
In technique scheme, be preferably by weight percentage the acetophenone that contains 0.5～2.0% in mixed liquor, 97.0～99.0% isopropylbenzene, more preferably contains 0.5～1.5% acetophenone; The mol ratio of hydrogen/mixing material is preferably 6～10:1; Reaction temperature is preferably 140～170oC; Reaction pressure is preferably 1.0～3.0MPa; Liquid volume air speed is preferably 2.0～8.0 hours-1。
In technique scheme, catalyst is in parts by weight, and the consumption of Cu or its oxide is preferably 15.0～30.0 parts, and the consumption of Ni or its oxide is preferably 15.0～30.0 parts, Al2O3Consumption be preferably 40.0～70.0 parts, at least one the consumption being selected from Mg or its oxide, Ca or its oxide, Ba or its oxide is preferably 5.0～10.0 parts.
Catalyst preparation adopts following steps: take a certain amount of solid Al2O3Be uniformly mixed at a certain temperature and form slurries I with water, take a certain amount of Cu (NO3)2?3H2O，Ni(NO3)2?6H2O, and be selected from Mg (NO3)2?6H2O、Ca(NO3)2?4H2O、Ba(NO3)2In at least one, formation solution I soluble in water. Solution I and wet chemical drop to the mixture I that forms certain pH value in slurries I simultaneously, and mixture I is precipitated thing through aging, washing, filtration. Sediment obtains catalyst through super-dry, roasting.
Acetophenone exists in situation and carries out hydrogenation reaction at catalyst, can generate benzyl carbinol, and benzyl carbinol dehydration generates styrene, can generate ethylbenzene by direct hydrogenation, and excessive hydrogenation will generate ethyl cyclohexane etc. In hydrogenation of acetophenone process, can easily cause acetophenone excessive hydrogenation to generate ethyl cyclohexane at the acid centre of catalyst, reduce catalyst selectivity. The quantity in the acid site of catalyst and acid strength can regulate by the content of aluminium oxide and handling procedure, also can regulate by introducing basic anhydride simultaneously. Adopt separately Ni as catalyst, because the hydrogenation activity of Ni is stronger, be difficult to product to rest on isopropylbenzene, adopt Cu and Ni to form alloy, can partly weaken on the one hand the hydrogenation activity of Ni, can improve the hydrogenation activity of Cu, thereby after this bimetallic alloy catalyst, hydrogenolysis is active good simultaneously. Because CuNi alloy is stable compared with simple substance Cu, thereby the introducing of Ni can improve the stability of Cu catalyst.
Adopt technical scheme of the present invention, adopt and consist of 24.60 parts of CuO-21.62 part NiO-5.49 part BaO-1.48 part MgO-46.81 part Al2O3Catalyst, answer 170 ° of C of temperature, reaction pressure 2.0MPa, H at entrance2The mol ratio 5.0 of/mixed liquor, liquid volume air speed is 5.0h-1Condition under react 500h, acetophenone conversion is 100%, ethylbenzene selectivity is 98.4%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but these embodiment are in no case construed as limiting scope of the present invention.
Detailed description of the invention
[embodiment 1]
50.0g alumina powder is mixed through 70 with wateroC oil bath stirring to pulp obtains slurries I, takes 100.0gCu (NO3)2?3H2O、50.0gNi(NO3)2?6H2O、15.0gMg(NO3)2?6H2O is dissolved in and in 0.5L water, forms solution I. Solution I and 1.0mol/L wet chemical drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 70oC, controlling the pH value of solution is 7.5, after precipitation 75oCAfter lower aging 10h, then by washing of precipitate, filter after 120oAfter C is dry, 400oC4 hours aftershapings of roasting obtain catalyst 1. Consisting of of catalyst 1: 33.24 parts of CuO-12.98 part NiO-3.20 part MgO-50.58 part Al2O3。
Pack 40.0ml catalyst 1 into fixed bed reactors, through 300oC hydrogen reducing 4.0 hours. Raw material mixed liquor contains 0.75% acetophenone by weight percentage, 98.5% isopropylbenzene, and surplus impurity. Reaction process condition is: 140 ° of C of entrance reaction temperature, reaction pressure 2.5MPa, H2The mol ratio 10.0 of/mixed liquor, liquid volume air speed is 6.0h-1. Reaction 24h and 500h the results are shown in Table 1.
[embodiment 2]
50.0g alumina powder is mixed through 70 with wateroC oil bath stirring to pulp obtains slurries I, takes 80.0gCu (NO3)2?3H2O、60.0gNi(NO3)2?6H2O、15.0gMg(NO3)2?6H2O is dissolved in and in 0.5L water, forms solution I. Solution I and 1.0mol/L wet chemical drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 70oC, controlling the pH value of solution is 7.5, after precipitation 75oCAfter lower aging 10h, then by washing of precipitate, filter after 120oAfter C is dry, 400oC4 hours aftershapings of roasting obtain catalyst 2. Consisting of of catalyst 2: 27.71 parts of CuO-16.23 part NiO-3.33 part MgO-52.73 part Al2O3。
Pack 40.0ml catalyst 2 into fixed bed reactors, through 300oC hydrogen reducing 4.0 hours. Raw material mixed liquor contains 0.75% acetophenone by weight percentage, 98.5% isopropylbenzene, and surplus impurity. Reaction process condition is: 180 ° of C of entrance reaction temperature, reaction pressure 2.5MPa, H2The mol ratio 10.0 of/mixed liquor, liquid volume air speed is 8.0h-1. Reaction 24h and 500h the results are shown in Table 1.
[embodiment 3]
50.0g alumina powder is mixed through 75 with wateroC oil bath stirring to pulp obtains slurries I, takes 120.0gCu (NO3)2?3H2O、100.0gNi(NO3)2?6H2O、25.0gCa(NO3)2?4H2O is dissolved in and in 0.5L water, forms solution I. Solution I and 1.0mol/L wet chemical drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 75oC, controlling the pH value of solution is 8.0, after precipitation 75oCAfter lower aging 10h, then by washing of precipitate, filter after 120oAfter C is dry, 500oC4 hours aftershapings of roasting obtain catalyst 3. Consisting of of catalyst 3: 32.58 parts of CuO-21.20 part NiO-4.90 part CaO-41.32 part Al2O3。
Pack 40.0ml catalyst 3 into fixed bed reactors, through 300oC hydrogen reducing 4.0 hours. Raw material mixed liquor contains 0.75% acetophenone by weight percentage, 98.5% isopropylbenzene, and surplus impurity. Reaction process condition is: entrance is answered 160 ° of C of temperature, reaction pressure 2.0MPa, H2The mol ratio 5.0 of/mixed liquor, liquid volume air speed is 8.0h-1. Reaction 24h and 500h the results are shown in Table 1.
[embodiment 4]
50.0g alumina powder is mixed through 80 with wateroC oil bath stirring to pulp obtains slurries I, takes 60.0gCu (NO3)2?3H2O、80.0gNi(NO3)2?6H2O、25.0gCa(NO3)2?4H2O is dissolved in and in 0.5L water, forms solution I. Solution I and 1.0mol/L wet chemical drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 80oC, controlling the pH value of solution is 8.0, after precipitation 80oCAfter lower aging 24h, then by washing of precipitate, filter after 120oAfter C is dry, 500oC2 hours aftershapings of roasting obtain catalyst 4. Consisting of of catalyst 4: 20.50 parts of CuO-21.34 part NiO-6.17 part CaO-51.99 part Al2O3。
Pack 40.0ml catalyst 4 into fixed bed reactors, through 300oC hydrogen reducing 4.0 hours. Raw material mixed liquor contains 0.75% acetophenone by weight percentage, 98.5% isopropylbenzene, and surplus impurity. Reaction process condition is: entrance is answered 160 ° of C of temperature, reaction pressure 2.0MPa, H2The mol ratio 5.0 of/mixed liquor, liquid volume air speed is 5.0h-1. Reaction 24h and 500h the results are shown in Table 1.
[embodiment 5]
50.0g alumina powder is mixed through 80 with wateroC oil bath stirring to pulp obtains slurries I, takes 50.0gCu (NO3)2?3H2O、90.0gNi(NO3)2?6H2O、15.0gBa(NO3)2Be dissolved in and in 0.5L water, form solution I. Solution I and 1.0mol/L wet chemical drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 80oC, controlling the pH value of solution is 8.0, after precipitation 80oCAfter lower aging 24h, then by washing of precipitate, filter after 120oAfter C is dry, 500oC2 hours aftershapings of roasting obtain catalyst 5. Consisting of of catalyst 5: 16.71 parts of CuO-23.49 part NiO-8.94 part BaO-50.86 part Al2O3。
Pack 40.0ml catalyst 5 into fixed bed reactors, through 400oC hydrogen reducing 4.0 hours. Raw material mixed liquor contains 0.75% acetophenone by weight percentage, 98.5% isopropylbenzene, and surplus impurity. Reaction process condition is: entrance is answered 170 ° of C of temperature, reaction pressure 2.0MPa, H2The mol ratio 5.0 of/mixed liquor, liquid volume air speed is 5.0h-1. Reaction 24h and 500h the results are shown in Table 1.
[embodiment 6]
50.0g alumina powder is mixed through 80 with wateroC oil bath stirring to pulp obtains slurries I, takes 80.0gCu (NO3)2?3H2O、90.0gNi(NO3)2?6H2O、10.0gBa(NO3)2、10.0gMg(NO3)2?6H2O is dissolved in and in 0.6L water, forms solution I. Solution I and 1.5mol/L wet chemical drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 80oC, controlling the pH value of solution is 8.0, after precipitation 80oCAfter lower aging 24h, then by washing of precipitate, filter after 120oAfter C is dry, 500oC2 hours aftershapings of roasting obtain catalyst 6. Consisting of of catalyst 6: 24.60 parts of CuO-21.62 part NiO-5.49 part BaO-1.48 part MgO-46.81 part Al2O3。
Pack 40.0ml catalyst 6 into fixed bed reactors, through 350oC hydrogen reducing 4.0 hours. Raw material mixed liquor contains 1.20% acetophenone by weight percentage, 98.0% isopropylbenzene, and surplus impurity. Reaction process condition is: entrance is answered 170 ° of C of temperature, reaction pressure 2.0MPa, H2The mol ratio 5.0 of/mixed liquor, liquid volume air speed is 5.0h-1. Reaction 24h and 500h the results are shown in Table 1.
[embodiment 7]
70.0g alumina powder is mixed through 85 with wateroC oil bath stirring to pulp obtains slurries I, takes 70.0gCu (NO3)2?3H2O、70.0gNi(NO3)2?6H2O、10.0gBa(NO3)2、20.0gMg(NO3)2?6H2O is dissolved in and in 0.6L water, forms solution I. Solution I and 1.5mol/L wet chemical drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 85oC, controlling the pH value of solution is 8.5, after precipitation 85oCAfter lower aging 24h, then by washing of precipitate, filter after 120oAfter C is dry, 500oC4 hours aftershapings of roasting obtain catalyst 7. Consisting of of catalyst 7: 19.17 parts of CuO-14.97 part NiO-4.89 part BaO-2.63 part MgO-58.34 part Al2O3。
Pack 40.0ml catalyst 7 into fixed bed reactors, through 350oC hydrogen reducing 12.0 hours. Raw material mixed liquor contains 1.20% acetophenone by weight percentage, 98.0% isopropylbenzene, and surplus impurity. Reaction process condition is: entrance is answered 170 ° of C of temperature, reaction pressure 2.0MPa, H2The mol ratio 5.0 of/mixed liquor, liquid volume air speed is 5.0h-1. Reaction 24h and 500h the results are shown in Table 1.
[embodiment 8]
70.0g alumina powder is mixed through 75 with wateroC oil bath stirring to pulp obtains slurries I, takes 40.0gCu (NO3)2?3H2O、60.0gNi(NO3)2?6H2O、20.0gMg(NO3)2?6H2O is dissolved in and in 0.6L water, forms solution I. Solution I and 1.5mol/L wet chemical drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 75oC, controlling the pH value of solution is 8.5, after precipitation 85oCAfter lower aging 24h, then by washing of precipitate, filter after 120oAfter C is dry, 500oC4 hours aftershapings of roasting obtain catalyst 8. Consisting of of catalyst 8: 12.92 parts of CuO-15.14 part NiO-3.11 part MgO-68.84 part Al2O3。
Pack 40.0ml catalyst 8 into fixed bed reactors, through 350oC hydrogen reducing 12.0 hours. Raw material mixed liquor contains 1.20% acetophenone by weight percentage, 98.0% isopropylbenzene, and surplus impurity. Reaction process condition is: entrance is answered 170 ° of C of temperature, reaction pressure 2.0MPa, H2The mol ratio 8.0 of/mixed liquor, liquid volume air speed is 3.0h-1. Reaction 24h and 500h the results are shown in Table 1.
[embodiment 9]
50.0g alumina powder is mixed through 75 with wateroC oil bath stirring to pulp obtains slurries I, takes 40.0gCu (NO3)2?3H2O、100.0gNi(NO3)2?6H2O、50.0gMg(NO3)2?6H2O is dissolved in and in 0.8L water, forms solution I. Solution I and 1.5mol/L wet chemical drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 75oC, controlling the pH value of solution is 8.5, after precipitation 75oCAfter lower aging 24h, then by washing of precipitate, filter after 120oAfter C is dry, 550oC4 hours aftershapings of roasting obtain catalyst 9. Consisting of of catalyst 9: 13.59 parts of CuO-26.53 part NiO-8.17 part MgO-51.71 part Al2O3。
Pack 40.0ml catalyst 9 into fixed bed reactors, through 400oC hydrogen reducing 12.0 hours. Raw material mixed liquor contains 1.50% acetophenone by weight percentage, 98.0% isopropylbenzene, and surplus impurity. Reaction process condition is: entrance is answered 175 ° of C of temperature, reaction pressure 4.0MPa, H2The mol ratio 8.0 of/mixed liquor, liquid volume air speed is 3.0h-1. Reaction 24h and 500h the results are shown in Table 1.
[embodiment 10]
100.0g alumina powder is mixed through 80 with wateroC oil bath stirring to pulp obtains slurries I, takes 60.0gCu (NO3)2?3H2O、100.0gNi(NO3)2?6H2O、50.0gMg(NO3)2?6H2O is dissolved in and in 0.8L water, forms solution I. Solution I and 1.5mol/L wet chemical drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 80oC, controlling the pH value of solution is 8.5, after precipitation 80oCAfter lower aging 24h, then by washing of precipitate, filter after 120oAfter C is dry, 550oC4 hours aftershapings of roasting obtain catalyst 10. Consisting of of catalyst 10: 12.86 parts of CuO-16.74 part NiO-5.15 part MgO-65.25 part Al2O3。
Pack 40.0ml catalyst 10 into fixed bed reactors, through 400oC hydrogen reducing 12.0 hours. Raw material mixed liquor contains 1.50% acetophenone by weight percentage, 98.0% isopropylbenzene, and surplus impurity. Reaction process condition is: entrance is answered 170 ° of C of temperature, reaction pressure 4.0MPa, H2The mol ratio 8.0 of/mixed liquor, liquid volume air speed is 2.0h-1. Reaction 24h and 500h the results are shown in Table 1.
[comparative example 1]
Adopt the method for preparing catalyst in Chinese patent CN200410015896.7: take 100gNiCl2?6H2O is dissolved in 100ml distilled water, and wiring solution-forming I gets 50g through 110oThe SiO that C is dry2After carrier and 50ml solution I incipient impregnation, 110oDry 12h under C, then 200oRoasting 2h under C, is cooled to after room temperature, the lower 2.0mol/LKBH of employing under ice-water bath stirs4Solution drips after reduction, and being washed to pH is 7.0, and absolute ethanol washing three times, makes comparative example catalyst, and its composition is by weight percentage: 12.78 parts of NiB-87.22 part SiO2。
Pack 40.0ml comparative example catalyst into fixed bed reactors, raw material mixed liquor contains 0.75% acetophenone by weight percentage, 99% isopropylbenzene, and surplus impurity. Reaction process condition is: 150 ° of C of entrance reaction temperature, reaction pressure 2.0MPa, H2/ mixing material mol ratio is 15.0, and liquid volume air speed is 4.0h-1. Reaction 24h and 500h the results are shown in Table 1.
Table 1
As can be seen from Table 1, technical scheme of the present invention is converted into ethylbenzene for the hydrogenation of acetophenone in the mixing material that propylene oxide production process is produced, has obtained good result of the test. Be 2.0 ~ 10.0h at 100 ~ 180 ° of C of reaction temperature, reaction pressure 1.0 ~ 5.0Mpa, raw material volume space velocity-1Time, catalyst selectivity is good, obtains good technique effect.
Claims (9)
1. a method for hydrogenation of acetophenone ethylbenzene processed, taking the mixing material containing acetophenone, isopropylbenzene and hydrogen asRaw material, is 5～15:1 in the mol ratio of hydrogen/mixing material, and reaction temperature is 100～180 DEG C, reaction pressureBe 1.0～5.0MPa, liquid volume air speed is 2.0～10.0 hours-1Under condition, raw material contacts instead with catalystShould, make the hydrogenation of acetophenone in raw material be converted into ethylbenzene, catalyst used comprises following group in parts by weightPoint:
A) 10.0～35.0 parts of Cu or its oxide;
B) 10.0～30.0 parts of Ni or its oxide;
C) 30.0～75.0 parts of Al2O3；
D) 3.0～10.0 parts are selected from Mg or its oxide, Ca or its oxide, Ba or its oxide at leastA kind of;
In described mixed liquor, contain by weight percentage 0.5～2.0% acetophenone, 97.0～99.0% isopropylbenzene.
2. the method for hydrogenation of acetophenone ethylbenzene processed according to claim 1, is characterized in that described hydrogen/mixingThe mol ratio of liquid is 6～10:1.
3. the method for hydrogenation of acetophenone ethylbenzene processed according to claim 1, is characterized in that described reaction temperatureIt is 140～170 DEG C.
4. the method for hydrogenation of acetophenone ethylbenzene processed according to claim 1, is characterized in that described reaction pressureBe 1.0～3.0MPa.
5. the method for hydrogenation of acetophenone ethylbenzene processed according to claim 1, is characterized in that described liquid volumeAir speed is 2.0～8.0 hours-1。
6. the method for hydrogenation of acetophenone ethylbenzene processed according to claim 1, it is characterized in that described catalyst withParts by weight meter, the consumption of Cu or its oxide is 15.0～30.0 parts.
7. the method for hydrogenation of acetophenone ethylbenzene processed according to claim 1, it is characterized in that described catalyst withParts by weight meter, the consumption of Ni or its oxide is 15.0～30.0 parts.
8. the method for hydrogenation of acetophenone ethylbenzene processed according to claim 1, it is characterized in that described catalyst withParts by weight meter, Al2O3Consumption be 40.0～70.0 parts.
9. the method for hydrogenation of acetophenone ethylbenzene processed according to claim 1, it is characterized in that described catalyst withParts by weight meter, is selected from least one in Mg or its oxide, Ca or its oxide, Ba or its oxideConsumption be 5.0～10.0 parts.
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| CN115445629B (en) * | 2022-08-23 | 2024-02-27 | 万华化学集团股份有限公司 | Catalyst for preparing alpha-phenethyl alcohol by acetophenone hydrogenation and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1122702A (en) * | 1965-01-27 | 1968-08-07 | Halcon International Inc | Hydrogenolysis process |
| US3944627A (en) * | 1973-05-23 | 1976-03-16 | Shell Oil Company | Hydrogenolysis of phenyl alkyl ketones and 1-phenylalkanols |
| DD218090A1 (en) * | 1983-08-01 | 1985-01-30 | Leuna Werke Veb | METHOD FOR THE PRODUCTION OF CUMEN AND ETHYLENE BENZENE |
| JPH0632747A (en) * | 1992-07-15 | 1994-02-08 | Sumitomo Chem Co Ltd | Hydrogenation |
| WO1996027575A1 (en) * | 1995-03-06 | 1996-09-12 | Bar-Ilan University | A process for the reduction of carbonyl compounds |
| CN1305981A (en) * | 2000-01-12 | 2001-08-01 | 住友化学工业株式会社 | Method of preparing alpha-phenyl ethyl alcohol |
| CN1315226A (en) * | 2000-01-19 | 2001-10-03 | 住友化学工业株式会社 | Reduction treated copper-base catalyst and process for preparing alpha-phenylethyl alcohol therefrom |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009082464A1 (en) * | 2007-12-21 | 2009-07-02 | Exxonmobil Research And Engineering Company | Process for producing phenol and methyl ethyl ketone |
-
2013
- 2013-06-17 CN CN201310237168.XA patent/CN104230635B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1122702A (en) * | 1965-01-27 | 1968-08-07 | Halcon International Inc | Hydrogenolysis process |
| US3944627A (en) * | 1973-05-23 | 1976-03-16 | Shell Oil Company | Hydrogenolysis of phenyl alkyl ketones and 1-phenylalkanols |
| DD218090A1 (en) * | 1983-08-01 | 1985-01-30 | Leuna Werke Veb | METHOD FOR THE PRODUCTION OF CUMEN AND ETHYLENE BENZENE |
| JPH0632747A (en) * | 1992-07-15 | 1994-02-08 | Sumitomo Chem Co Ltd | Hydrogenation |
| WO1996027575A1 (en) * | 1995-03-06 | 1996-09-12 | Bar-Ilan University | A process for the reduction of carbonyl compounds |
| CN1305981A (en) * | 2000-01-12 | 2001-08-01 | 住友化学工业株式会社 | Method of preparing alpha-phenyl ethyl alcohol |
| CN1315226A (en) * | 2000-01-19 | 2001-10-03 | 住友化学工业株式会社 | Reduction treated copper-base catalyst and process for preparing alpha-phenylethyl alcohol therefrom |
Non-Patent Citations (1)
| Title |
|---|
| 醛酮的催化还原和RhO激酶抑制剂的设计合成及活性测试;刘帅;《中国博士学位论文全文数据库工程科技I辑》;20120815(第8期);参见第19页图1-2-2，第48页表1-3-7，第48页第1段 * |
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