CN104230635A - Preparation method of ethylbenzene from acetophenone hydrogenation - Google Patents
Preparation method of ethylbenzene from acetophenone hydrogenation Download PDFInfo
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- CN104230635A CN104230635A CN201310237168.XA CN201310237168A CN104230635A CN 104230635 A CN104230635 A CN 104230635A CN 201310237168 A CN201310237168 A CN 201310237168A CN 104230635 A CN104230635 A CN 104230635A
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Abstract
The invention relates to a preparation method of ethylbenzene from acetophenone hydrogenation, and mainly solves the problems of acetophenone residual and low selectivity of acetophenone in the prior art for production epoxypropane by dicumyl peroxide method. The invention adopts hydrogen and a mixed liquid containing acetophenone and isopropyl benzene as raw materials, and the raw materials contacts with the catalyst, so that acetophenone in the raw material is converted into ethylbenzene through hydrogenation. The catalyst comprises the following components 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; and d) 3.0-10.0 parts of at least one selected from Mg or its oxide, Ca or its oxide, Zn or its oxide, and Ba and its oxide. The technical scheme well solves the problems, and can be used in the industrial production of ethylbenzene by acetophenone hydrogenation.
Description
Technical field
The present invention relates to a kind of method of hydrogenation of acetophenone ethylbenzene, particularly about a kind of method hydrogenation of acetophenone in the mixed solution produced in production propylene oxide process being converted into ethylbenzene.
Background technology
Propylene oxide is a kind of important petrochemical complex organic raw material, and the main production method of this material is chlorohydrination and ethylbenzene hydroperoxide method.Seriously polluted to environment of chlorohydrination, ethylbenzene hydroperoxide method has a large amount of coproduction by product-vinylbenzene to generate, thus makes the production cost of propylene oxide be subject to the impact of the price volalility of co-product.In recent years, take dicumyl peroxide as oxygen source, the method that propylene oxide produces propylene oxide grows up gradually, this process environmental protection, security are high, co-product α, alpha-alpha-dimethyl benzylalcohol can generate isopropyl benzene by catalytic hydrogenolytic cleavage, and isopropyl benzene can return peroxidic units and realize recycle.Be oxidized with ethylbenzene hydroperoxide method the technique ratio producing propylene oxide, it is short that this process has operational path, and facility 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 propylene oxide, epoxidation of propylene and benzylalcohol hydrogenolysis three operations, not by the impact of by product vinylbenzene price volalility, can bring more stable economic benefit for manufacturer.In benzylalcohol hydrogenolysis operation, the benzylalcohol that reaction produces is converted into isopropyl benzene, thus realizes recycling of isopropyl benzene.Wherein adopt Cu catalyst basedly to have that reaction velocity is low in benzylalcohol hydrogenolysis process, contaminate environment, problem that anti-impurity ability is low.Adopt that Pd is noble metal catalyst based can be realized benzylalcohol hydrogenolysis and prepare isopropyl benzene under larger air speed, but a small amount of methyl phenyl ketone produced in cumene oxidation process cannot remove in the lump by Pd is catalyst based, a small amount of methyl phenyl ketone is removed comparatively complicated by rectifying separation, be translated into ethylbenzene removing comparatively easy by hydrogenation.The present invention adopts benzylalcohol first to generate isopropyl benzene by first stage reactor hydrogenolysis, and the method that methyl phenyl ketone is ethylbenzene through second stage reactor catalytic hydroconversion well solves this problem.
Radix Cynanchi Paniculatis etc. (chemical reagent, 2005,27 (3), 129 ~ 132) adopt the catalyst based Hydrogenation to methyl phenyl ketone of different Ni in three to compare, and find Ni-B/SiO
2the activity of amorphous alloy catalyst and stability are obviously better than Raney Ni catalyzer and Uru shibara nickel catalyst.120
oc, H
2under pressure 3.0 MPa, take 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/SiO
2catalyzer, with methyl phenyl ketone and hydrogen for raw material, in temperature of reaction 120
oc, hydrogen pressure 3.0 MPa, under reaction times 5 h, acetophenone conversion 100%, generating ethylbenzene selectivity is 90.2%.
Wang Youzhen etc. (chemical journal, 2004,62(14), 1349 ~ 1352) adopt highly selective hydrogenation of acetophenone Ni-Sn-B/ SiO
2amorphous catalyst, has carried out hydrogenation research to methyl phenyl ketone, has worked as Sn/SiO
2when weight percent is 10%, the yield that hydrogenation of acetophenone generates phenylethyl alcohol reaches 97.5%, and benzene ring hydrogenation product assay is 0.5%.
Chinese patent CN 200410015896.7 reports hydrogenation of acetophenone amorphous nickel-boron Catalysts and its preparation method, and nickel exists with Ni-B or Ni-M-B form, and metal additive M is the one in Sn, Cr, Mo, W, Fe, Co, La.This catalyzer has good hydrogenation of acetophenone performance, and primary product is phenylethyl alcohol.
From the above mentioned, prepare ethylbenzene with existing techniques in realizing hydrogenation of acetophenone and there is the low problem of selectivity, and current research is all adopt batch reactor, cannot realize continuous prodution.
Summary of the invention
Technical problem to be solved by this invention is the problem that existing hydrogenation of acetophenone prepares that ethylbenzene technology exists poor selectivity, provides a kind of method of new hydrogenation of acetophenone ethylbenzene.The method is used for hydrogenation of acetophenone ethylbenzene and has the good advantage of selectivity.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: a kind of method of hydrogenation of acetophenone ethylbenzene, with containing methyl phenyl ketone, the mixing liquid of isopropyl benzene and hydrogen for raw material, be 5 ~ 15:1 in the mol ratio of hydrogen/mixing liquid, temperature of reaction is 100 ~ 180
oc, reaction pressure is 1.0 ~ 5.0 MPa, and liquid volume air speed is 2.0 ~ 10.0 hours
-1under condition, raw material and catalyst exposure react, and make the hydrogenation of acetophenone in raw material be converted into ethylbenzene, catalyzer used comprises following component with weight parts:
A) 10.0 ~ 35.0 parts of Cu or its oxide compound;
B) 10.0 ~ 30.0 parts of Ni or its oxide compound;
C) 30.0 ~ 75.0 parts of Al
2o
3;
D) 3.0 ~ 10.0 parts are selected from least one in Mg or its oxide compound, Ca or its oxide compound, Ba or its oxide compound.
In technique scheme, be preferably the methyl phenyl ketone containing 0.5 ~ 2.0% in mixed solution by weight percentage, the isopropyl benzene of 97.0 ~ 99.0%, is more preferably the methyl phenyl ketone containing 0.5 ~ 1.5%; The mol ratio of hydrogen/mixing liquid is preferably 6 ~ 10:1; Temperature of reaction is preferably 140 ~ 170
oc; Reaction pressure is preferably 1.0 ~ 3.0 MPa; Liquid volume air speed is preferably 2.0 ~ 8.0 hours
-1.
In technique scheme, catalyzer is with weight parts, and the consumption of Cu or its oxide compound is preferably 15.0 ~ 30.0 parts, and the consumption of Ni or its oxide compound is preferably 15.0 ~ 30.0 parts, Al
2o
3consumption be preferably 40.0 ~ 70.0 parts, the consumption being selected from least one in Mg or its oxide compound, Ca or its oxide compound, Ba or its oxide compound is preferably 5.0 ~ 10.0 parts.
Catalyst preparing adopts following steps: take a certain amount of solid Al
2o
3be uniformly mixed at a certain temperature with water and form slurries I, take a certain amount of Cu (NO
3)
23H
2o, Ni (NO
3)
26H
2o, and be selected from Mg (NO
3)
26H
2o, Ca (NO
3)
24H
2o, Ba (NO
3)
2in at least one, formation solution I soluble in water.Solution I and wet chemical drop to the mixture I forming certain pH value in slurries I simultaneously, and mixture I is precipitated thing through aging, washing, filtration.Throw out obtains catalyzer through super-dry, roasting.
Methyl phenyl ketone carries out hydrogenation reaction under catalyzer exists situation, can generate phenylethyl alcohol, and phenylethyl alcohol dehydration generates vinylbenzene, and can generate ethylbenzene by direct hydrogenation, excessive hydrogenation will generate ethylcyclohexane etc.Methyl phenyl ketone excessive hydrogenation easily can be caused to generate ethylcyclohexane at the acid sites of catalyzer in hydrogenation of acetophenone process, reduce catalyst selectivity.The quantity in the acid site of catalyzer and strength of acid can be regulated by the content of aluminum oxide and handling procedure, also can regulate by introducing basic oxide simultaneously.Independent employing Ni is as catalyzer, because the hydrogenation activity of Ni is stronger, reaction product is difficult to rest on isopropyl benzene, Cu and Ni is adopted to form alloy, on the one hand can the hydrogenation activity of partial impairment Ni, can improve the hydrogenation activity of Cu, thus after this bimetallic alloy catalyzer, hydrogenolysis activity is good simultaneously.Due to CuNi alloy comparatively simple substance Cu stablize, thus the introducing of Ni can improve the stability of Cu catalyzer.
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 Al
2o
3catalyzer, answer temperature 170 ° of C at entrance, reaction pressure 2.0 MPa, H
2the mol ratio 5.0 of/mixed solution, liquid volume air speed is 5.0 h
-1condition under react 500 h, acetophenone conversion is 100%, and ethylbenzene selectivity is 98.4%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated, but these embodiments are in no case construed as limiting scope of the present invention.
Embodiment
[embodiment 1]
50.0 g alumina powders are mixed through 70 with water
oc oil bath stirring to pulp obtains slurries I, takes 100.0 g Cu (NO
3)
23H
2o, 50.0 gNi (NO
3)
26H
2o, 15.0 g Mg (NO
3)
26H
2o is dissolved in 0.5 L water and forms solution I.Solution I and 1.0 mol/L wet chemicals drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 70
oC, the pH value controlling solution is 7.5,75 after precipitation
oCafter lower aging 10 h, then by washing of precipitate, filter after 120
oafter C drying, 400
oCroasting 4 hours aftershapings obtain catalyzer 1.Consisting of of catalyzer 1: 33.24 parts of CuO-12.98 part NiO-3.20 part MgO-50.58 part Al
2o
3.
40.0 ml catalyzer 1 are loaded fixed-bed reactor, through 300
oc hydrogen reducing 4.0 hours.Raw material mixed solution contains 0.75% methyl phenyl ketone by weight percentage, 98.5% isopropyl benzene, and surplus impurity.Reaction process condition is: entrance temperature of reaction 140 ° of C, reaction pressure 2.5 MPa, H
2the mol ratio 10.0 of/mixed solution, liquid volume air speed is 6.0 h
-1.That reacts 24 h and 500 h the results are shown in Table 1.
[embodiment 2]
50.0 g alumina powders are mixed through 70 with water
oc oil bath stirring to pulp obtains slurries I, takes 80.0 g Cu (NO
3)
23H
2o, 60.0 gNi (NO
3)
26H
2o, 15.0 g Mg (NO
3)
26H
2o is dissolved in 0.5 L water and forms solution I.Solution I and 1.0 mol/L wet chemicals drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 70
oC, the pH value controlling solution is 7.5,75 after precipitation
oCafter lower aging 10 h, then by washing of precipitate, filter after 120
oafter C drying, 400
oCroasting 4 hours aftershapings obtain catalyzer 2.Consisting of of catalyzer 2: 27.71 parts of CuO-16.23 part NiO-3.33 part MgO-52.73 part Al
2o
3.
40.0 ml catalyzer 2 are loaded fixed-bed reactor, through 300
oc hydrogen reducing 4.0 hours.Raw material mixed solution contains 0.75% methyl phenyl ketone by weight percentage, 98.5% isopropyl benzene, and surplus impurity.Reaction process condition is: entrance temperature of reaction 180 ° of C, reaction pressure 2.5 MPa, H
2the mol ratio 10.0 of/mixed solution, liquid volume air speed is 8.0 h
-1.Reaction 24h and 500 h the results are shown in Table 1.
[embodiment 3]
50.0 g alumina powders are mixed through 75 with water
oc oil bath stirring to pulp obtains slurries I, takes 120.0 g Cu (NO
3)
23H
2o, 100.0 gNi (NO
3)
26H
2o, 25.0 g Ca (NO
3)
24H
2o is dissolved in 0.5 L water and forms solution I.Solution I and 1.0 mol/L wet chemicals drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 75
oC, the pH value controlling solution is 8.0,75 after precipitation
oCafter lower aging 10 h, then by washing of precipitate, filter after 120
oafter C drying, 500
oCroasting 4 hours aftershapings obtain catalyzer 3.Consisting of of catalyzer 3: 32.58 parts of CuO-21.20 part NiO-4.90 part CaO-41.32 part Al
2o
3.
40.0 ml catalyzer 3 are loaded fixed-bed reactor, through 300
oc hydrogen reducing 4.0 hours.Raw material mixed solution contains 0.75% methyl phenyl ketone by weight percentage, 98.5% isopropyl benzene, and surplus impurity.Reaction process condition is: entrance answers temperature 160 ° of C, reaction pressure 2.0 MPa, H
2the mol ratio 5.0 of/mixed solution, liquid volume air speed is 8.0 h
-1.Reaction 24h and 500 h the results are shown in Table 1.
[embodiment 4]
50.0 g alumina powders are mixed through 80 with water
oc oil bath stirring to pulp obtains slurries I, takes 60.0 g Cu (NO
3)
23H
2o, 80.0 gNi (NO
3)
26H
2o, 25.0 g Ca (NO
3)
24H
2o is dissolved in 0.5 L water and forms solution I.Solution I and 1.0 mol/L wet chemicals drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 80
oC, the pH value controlling solution is 8.0,80 after precipitation
oCafter lower aging 24 h, then by washing of precipitate, filter after 120
oafter C drying, 500
oCroasting 2 hours aftershapings obtain catalyzer 4.Consisting of of catalyzer 4: 20.50 parts of CuO-21.34 part NiO-6.17 part CaO-51.99 part Al
2o
3.
40.0 ml catalyzer 4 are loaded fixed-bed reactor, through 300
oc hydrogen reducing 4.0 hours.Raw material mixed solution contains 0.75% methyl phenyl ketone by weight percentage, 98.5% isopropyl benzene, and surplus impurity.Reaction process condition is: entrance answers temperature 160 ° of C, reaction pressure 2.0 MPa, H
2the mol ratio 5.0 of/mixed solution, liquid volume air speed is 5.0 h
-1.That reacts 24 h and 500 h the results are shown in Table 1.
[embodiment 5]
50.0 g alumina powders are mixed through 80 with water
oc oil bath stirring to pulp obtains slurries I, takes 50.0 g Cu (NO
3)
23H
2o, 90.0 gNi (NO
3)
26H
2o, 15.0 g Ba (NO
3)
2be dissolved in 0.5 L water and form solution I.Solution I and 1.0 mol/L wet chemicals drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 80
oC, the pH value controlling solution is 8.0,80 after precipitation
oCafter lower aging 24 h, then by washing of precipitate, filter after 120
oafter C drying, 500
oCroasting 2 hours aftershapings obtain catalyzer 5.Consisting of of catalyzer 5: 16.71 parts of CuO-23.49 part NiO-8.94 part BaO-50.86 part Al
2o
3.
40.0 ml catalyzer 5 are loaded fixed-bed reactor, through 400
oc hydrogen reducing 4.0 hours.Raw material mixed solution contains 0.75% methyl phenyl ketone by weight percentage, 98.5% isopropyl benzene, and surplus impurity.Reaction process condition is: entrance answers temperature 170 ° of C, reaction pressure 2.0 MPa, H
2the mol ratio 5.0 of/mixed solution, liquid volume air speed is 5.0 h
-1.That reacts 24 h and 500 h the results are shown in Table 1.
[embodiment 6]
50.0 g alumina powders are mixed through 80 with water
oc oil bath stirring to pulp obtains slurries I, takes 80.0 g Cu (NO
3)
23H
2o, 90.0 gNi (NO
3)
26H
2o, 10.0 g Ba (NO
3)
2, 10.0 g Mg (NO
3)
26H
2o is dissolved in 0.6 L water and forms solution I.Solution I and 1.5 mol/L wet chemicals drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 80
oC, the pH value controlling solution is 8.0,80 after precipitation
oCafter lower aging 24 h, then by washing of precipitate, filter after 120
oafter C drying, 500
oCroasting 2 hours aftershapings obtain catalyzer 6.Consisting of of catalyzer 6: 24.60 parts of CuO-21.62 part NiO-5.49 part BaO-1.48 part MgO-46.81 part Al
2o
3.
40.0 ml catalyzer 6 are loaded fixed-bed reactor, through 350
oc hydrogen reducing 4.0 hours.Raw material mixed solution contains 1.20% methyl phenyl ketone by weight percentage, 98.0% isopropyl benzene, and surplus impurity.Reaction process condition is: entrance answers temperature 170 ° of C, reaction pressure 2.0 MPa, H
2the mol ratio 5.0 of/mixed solution, liquid volume air speed is 5.0 h
-1.That reacts 24 h and 500 h the results are shown in Table 1.
[embodiment 7]
70.0 g alumina powders are mixed through 85 with water
oc oil bath stirring to pulp obtains slurries I, takes 70.0 g Cu (NO
3)
23H
2o, 70.0 gNi (NO
3)
26H
2o, 10.0 g Ba (NO
3)
2, 20.0 g Mg (NO
3)
26H
2o is dissolved in 0.6 L water and forms solution I.Solution I and 1.5 mol/L wet chemicals drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 85
oC, the pH value controlling solution is 8.5,85 after precipitation
oCafter lower aging 24 h, then by washing of precipitate, filter after 120
oafter C drying, 500
oCroasting 4 hours aftershapings obtain catalyzer 7.Consisting of of catalyzer 7: 19.17 parts of CuO-14.97 part NiO-4.89 part BaO-2.63 part MgO-58.34 part Al
2o
3.
40.0 ml catalyzer 7 are loaded fixed-bed reactor, through 350
oc hydrogen reducing 12.0 hours.Raw material mixed solution contains 1.20% methyl phenyl ketone by weight percentage, 98.0% isopropyl benzene, and surplus impurity.Reaction process condition is: entrance answers temperature 170 ° of C, reaction pressure 2.0 MPa, H
2the mol ratio 5.0 of/mixed solution, liquid volume air speed is 5.0 h
-1.That reacts 24 h and 500 h the results are shown in Table 1.
[embodiment 8]
70.0 g alumina powders are mixed through 75 with water
oc oil bath stirring to pulp obtains slurries I, takes 40.0 g Cu (NO
3)
23H
2o, 60.0 gNi (NO
3)
26H
2o, 20.0 g Mg (NO
3)
26H
2o is dissolved in 0.6 L water and forms solution I.Solution I and 1.5 mol/L wet chemicals drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 75
oC, the pH value controlling solution is 8.5,85 after precipitation
oCafter lower aging 24 h, then by washing of precipitate, filter after 120
oafter C drying, 500
oCroasting 4 hours aftershapings obtain catalyzer 8.Consisting of of catalyzer 8: 12.92 parts of CuO-15.14 part NiO-3.11 part MgO-68.84 part Al
2o
3.
40.0 ml catalyzer 8 are loaded fixed-bed reactor, through 350
oc hydrogen reducing 12.0 hours.Raw material mixed solution contains 1.20% methyl phenyl ketone by weight percentage, 98.0% isopropyl benzene, and surplus impurity.Reaction process condition is: entrance answers temperature 170 ° of C, reaction pressure 2.0 MPa, H
2the mol ratio 8.0 of/mixed solution, liquid volume air speed is 3.0 h
-1.That reacts 24 h and 500 h the results are shown in Table 1.
[embodiment 9]
50.0 g alumina powders are mixed through 75 with water
oc oil bath stirring to pulp obtains slurries I, takes 40.0 g Cu (NO
3)
23H
2o, 100.0 gNi (NO
3)
26H
2o, 50.0 g Mg (NO
3)
26H
2o is dissolved in 0.8 L water and forms solution I.Solution I and 1.5 mol/L wet chemicals drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 75
oC, the pH value controlling solution is 8.5,75 after precipitation
oCafter lower aging 24 h, then by washing of precipitate, filter after 120
oafter C drying, 550
oCroasting 4 hours aftershapings obtain catalyzer 9.Consisting of of catalyzer 9: 13.59 parts of CuO-26.53 part NiO-8.17 part MgO-51.71 part Al
2o
3.
40.0 ml catalyzer 9 are loaded fixed-bed reactor, through 400
oc hydrogen reducing 12.0 hours.Raw material mixed solution contains 1.50% methyl phenyl ketone by weight percentage, 98.0% isopropyl benzene, and surplus impurity.Reaction process condition is: entrance answers temperature 175 ° of C, reaction pressure 4.0 MPa, H
2the mol ratio 8.0 of/mixed solution, liquid volume air speed is 3.0 h
-1.That reacts 24 h and 500 h the results are shown in Table 1.
[embodiment 10]
100.0 g alumina powders are mixed through 80 with water
oc oil bath stirring to pulp obtains slurries I, takes 60.0 g Cu (NO
3)
23H
2o, 100.0 gNi (NO
3)
26H
2o, 50.0 g Mg (NO
3)
26H
2o is dissolved in 0.8 L water and forms solution I.Solution I and 1.5 mol/L wet chemicals drop in slurries I simultaneously and carry out co-precipitation, and precipitation temperature is 80
oC, the pH value controlling solution is 8.5,80 after precipitation
oCafter lower aging 24 h, then by washing of precipitate, filter after 120
oafter C drying, 550
oCroasting 4 hours aftershapings obtain catalyzer 10.Consisting of of catalyzer 10: 12.86 parts of CuO-16.74 part NiO-5.15 part MgO-65.25 part Al
2o
3.
40.0 ml catalyzer 10 are loaded fixed-bed reactor, through 400
oc hydrogen reducing 12.0 hours.Raw material mixed solution contains 1.50% methyl phenyl ketone by weight percentage, 98.0% isopropyl benzene, and surplus impurity.Reaction process condition is: entrance answers temperature 170 ° of C, reaction pressure 4.0 MPa, H
2the mol ratio 8.0 of/mixed solution, liquid volume air speed is 2.0 h
-1.That reacts 24 h and 500 h the results are shown in Table 1.
[comparative example 1]
Adopt the method for preparing catalyst in Chinese patent CN 200410015896.7: take 100gNiCl
26H
2o is dissolved in 100 ml distilled water, and wiring solution-forming I gets 50 g through 110
othe SiO of C drying
2after carrier and 50 ml solution I incipient impregnations, 110
odry 12 h under C, then 200
oroasting 2 h under C, after being cooled to room temperature, lower employing 2.0 mol/L KBH under ice-water bath stirs
4after solution drips reduction, being washed to pH is 7.0, absolute ethanol washing three times, and obtained comparative example catalyzer, its composition is by weight percentage: 12.78 parts of Ni B-87.22 part SiO
2.
40.0 ml comparative example catalyzer are loaded fixed-bed reactor, and raw material mixed solution contains 0.75% methyl phenyl ketone by weight percentage, 99% isopropyl benzene, and surplus impurity.Reaction process condition is: entrance temperature of reaction 150 ° of C, reaction pressure 2.0 MPa, H
2/ mixing liquid mol ratio is 15.0, and liquid volume air speed is 4.0 h
-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 used for the hydrogenation of acetophenone in the mixing liquid produced in propylene oxide production process is converted into ethylbenzene, achieves good test-results.Be 2.0 ~ 10.0 h in temperature of reaction 100 ~ 180 ° of C, reaction pressure 1.0 ~ 5.0 Mpa, raw material volume air speed
-1time, catalyst selectivity is good, obtains good technique effect.
Claims (10)
1. a method for hydrogenation of acetophenone ethylbenzene, with containing methyl phenyl ketone, the mixing liquid of isopropyl benzene and hydrogen for raw material, be 5 ~ 15:1 in the mol ratio of hydrogen/mixing liquid, temperature of reaction is 100 ~ 180
oc, reaction pressure is 1.0 ~ 5.0 MPa, and liquid volume air speed is 2.0 ~ 10.0 hours
-1under condition, raw material and catalyst exposure react, and make the hydrogenation of acetophenone in raw material be converted into ethylbenzene, catalyzer used comprises following component with weight parts:
A) 10.0 ~ 35.0 parts of Cu or its oxide compound;
B) 10.0 ~ 30.0 parts of Ni or its oxide compound;
C) 30.0 ~ 75.0 parts of Al
2o
3;
D) 3.0 ~ 10.0 parts are selected from least one in Mg or its oxide compound, Ca or its oxide compound, Ba or its oxide compound.
2. the method for hydrogenation of acetophenone ethylbenzene according to claim 1, is characterized in that the methyl phenyl ketone by weight percentage containing 0.5 ~ 2.0% in described mixed solution, the isopropyl benzene of 97.0 ~ 99.0%.
3. the method for hydrogenation of acetophenone ethylbenzene according to claim 1, is characterized in that the mol ratio of described hydrogen/mixing liquid is 6 ~ 10:1.
4. the method for hydrogenation of acetophenone ethylbenzene according to claim 1, is characterized in that described temperature of reaction is 140 ~ 170
oc.
5. the method for hydrogenation of acetophenone ethylbenzene according to claim 1, is characterized in that described reaction pressure is 1.0 ~ 3.0 MPa.
6. the method for hydrogenation of acetophenone ethylbenzene according to claim 1, is characterized in that described liquid volume air speed is 2.0 ~ 8.0 hours
-1.
7. the method for hydrogenation of acetophenone ethylbenzene according to claim 1, it is characterized in that described catalyzer is with weight parts, the consumption of Cu or its oxide compound is 15.0 ~ 30.0 parts.
8. the method for hydrogenation of acetophenone ethylbenzene according to claim 1, it is characterized in that described catalyzer is with weight parts, the consumption of Ni or its oxide compound is 15.0 ~ 30.0 parts.
9. the method for hydrogenation of acetophenone ethylbenzene according to claim 1, is characterized in that described catalyzer is with weight parts, Al
2o
3consumption be 40.0 ~ 70.0 parts.
10. the method for hydrogenation of acetophenone ethylbenzene according to claim 1, it is characterized in that described catalyzer is with weight parts, the consumption being selected from least one in Mg or its oxide compound, Ca or its oxide compound, Ba or its oxide compound is 5.0 ~ 10.0 parts.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688915A (en) * | 2016-04-13 | 2016-06-22 | 凯凌化工(张家港)有限公司 | Dual-function catalyst for hydrogenating benzene rings and reducing carbonyl, preparation of dual-function catalyst and application thereof |
| RU2705589C1 (en) * | 2019-06-19 | 2019-11-11 | федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский национальный исследовательский технологический университет" (ФГБОУ ВО "КНИТУ") | Method of producing catalyst for liquid-phase hydrogenation of mixtures containing carbonyl and hydroxyl derivatives of aromatic hydrocarbons |
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| CN115445629A (en) * | 2022-08-23 | 2022-12-09 | 万华化学集团股份有限公司 | Catalyst for preparing alpha-phenylethyl alcohol by acetophenone hydrogenation and preparation method and application thereof |
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| CN105688915A (en) * | 2016-04-13 | 2016-06-22 | 凯凌化工(张家港)有限公司 | Dual-function catalyst for hydrogenating benzene rings and reducing carbonyl, preparation of dual-function catalyst and application thereof |
| CN105688915B (en) * | 2016-04-13 | 2017-03-08 | 凯凌化工(张家港)有限公司 | A kind of method for preparing 1,4 cyclohexanedimethanols |
| RU2705589C1 (en) * | 2019-06-19 | 2019-11-11 | федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский национальный исследовательский технологический университет" (ФГБОУ ВО "КНИТУ") | Method of producing catalyst for liquid-phase hydrogenation of mixtures containing carbonyl and hydroxyl derivatives of aromatic hydrocarbons |
| CN110813319A (en) * | 2019-12-03 | 2020-02-21 | 红宝丽集团股份有限公司 | Catalyst for hydrogenolysis and preparation method thereof |
| WO2021109611A1 (en) * | 2019-12-03 | 2021-06-10 | 红宝丽集团股份有限公司 | Catalyst for hydrogenolysis and preparation method therefor |
| CN110813319B (en) * | 2019-12-03 | 2022-03-08 | 红宝丽集团股份有限公司 | Catalyst for hydrogenolysis and preparation method thereof |
| CN115445629A (en) * | 2022-08-23 | 2022-12-09 | 万华化学集团股份有限公司 | Catalyst for preparing alpha-phenylethyl alcohol by acetophenone hydrogenation and preparation method and application thereof |
| 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 |
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