CN104230643B - Prepare the method for isopropyl benzene - Google Patents
Prepare the method for isopropyl benzene Download PDFInfo
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Abstract
The present invention relates to a kind of method preparing isopropyl benzene, mainly solve the problem of poor catalyst stability in benzylalcohol hydrogenolysis, hydrogenation of acetophenone process. The present invention adopt taking containing alpha, alpha-dimethyl benzyl alcohol, the hydrocarbon material of methyl phenyl ketone and hydrogen as raw material, the mol ratio of the alpha, alpha-dimethyl benzyl alcohol in hydrogen/hydrocarbon material is 5��15:1, and temperature of reaction is 160��240oC, reaction pressure is 0.5��5.0MPa, and the volume space velocity of hydrocarbon material is 1.0��10.0 hours-1When, raw material contacts with catalyst B with catalyst A successively, react, wherein the volume ratio of catalyst A and catalyst B is 0.5��3:1, catalyst A is Pd catalyzer, the technical scheme that catalyst B is copper catalyst solves this problem preferably, can be used for the industrial production that dicumyl peroxide method prepares propylene oxide.
Description
Technical field
The present invention relates to a kind of method preparing isopropyl benzene, particularly about one by alpha, alpha-dimethyl benzyl alcohol catalytic material hydrogenolysis preparing isopropylbenzene, and hydrogenation of acetophenone is converted into the method for ethylbenzene.
Background technology
Propylene oxide (is called for short PO), and Commercial processes mainly contains chlorohydrination, conjugated oxidation and dicumyl peroxide circulation method (CHP). In addition, it is also possible to adopt hydrogen peroxide direct oxidation method, oxygen to directly oxidize method to be used for produce PO. At present, in Synthesis of Propylene Oxide, American-European countries is based on conjugated oxidation, according to raw material and coproduction product, can be divided into again ethylbenzene conjugated oxidation and Trimethylmethane conjugated oxidation (PO/TBA method), and other areas are then based on chlorine alcoholization process.
Japan's beginning of this century Sumitomo chemistry (Sumitomo) develops produces PO novel process, comprises cumene oxidation, epoxidation of propylene and ��, �� dimethyl benzyl alcohol (C9H12O) hydrogenolysis three operations. This technique realized industrialization (250,000 tons/year) in 2003 at Chiba, Japan. This technique has the following advantages: the transformation efficiency of whole technique and selectivity are very high; Product is PO only, not by the impact of by product vinylbenzene price volalility, it is possible to for manufacturer brings more stable economic benefit; This technical process is relatively simple, and fixed investment is lower than PO/SM method by 1/3, and equipment anticorrosion is required also lower by CHP technique. Using the method at propylene oxidation unit, dicumyl peroxide is converted into benzylalcohol, has a small amount of methyl phenyl ketone to generate simultaneously.
US Patent No. 6646139B2 discloses the technological process that catalytic hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol produces isopropyl benzene, and this technology take hydrogen as hydrogen source, taking Cu-Cr oxide compound as catalyzer, and temperature of reaction 180oC, catalyst activity is lower, and simultaneously due to the existence of Cr species, environmental pollution is serious.
Chinese patent CN1257138C proposes and uses H2With the method for CO gas mixture reduction Cu catalyzer, it is still Cu-Cr catalyzer that this catalyzer can be applied to benzylalcohol hydrogenolysis due to its used catalyst, there is problem of environmental pollution equally.
Chinese patent CN1308273C discloses a kind of ��, the method of alpha-alpha-dimethyl phenylcarbinol liquid phase hydrogenolysis preparing isopropylbenzene, benzylalcohol hydrogenolysis, taking 2.0wt%Pd/ cocoanut active charcoal as catalyzer, can be converted into isopropyl benzene by the method, the transformation efficiency 96��98% of benzylalcohol, generates isopropyl benzene selectivity and reaches 99%. Being used one yuan of low-carbon alcohol solvent and formic acid, acetic acid etc. to be additive in this technique, its usage quantity can reach the 20��150% of benzylalcohol consumption by weight percentage. Adopting the method to be removed by methyl phenyl ketone a small amount of in mixing liquid, and this technique adopts batch operation, production efficiency is low.
Described in upper, existing propylene oxide technology the catalyzer that hydrogenolysis unit adopts mainly contain precious metals pd and Cu catalyst based. Pd catalyst based hydrogenation of acetophenone activity is low, catalyst based with Cu prepared by prior art, is applied to catalytic hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol and prepares in isopropyl benzene process, there is the problem that poor catalyst stability, environmental pollution are serious.
Summary of the invention
Technical problem to be solved by this invention is that existing isopropyl benzene technology of preparing exists the serious problem of poor catalyst stability, environmental pollution, it is provided that an a kind of step newly realizes benzylalcohol hydrogenolysis, the method for hydrogenation of acetophenone. The cost that the method has catalyst agent is low, good stability, selectivity height, eco-friendly advantage.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method preparing isopropyl benzene, with containing ��, the hydrocarbon material of alpha-alpha-dimethyl benzylalcohol, methyl phenyl ketone and hydrogen are raw material, �� in hydrogen/hydrocarbon material, the mol ratio of alpha-alpha-dimethyl benzylalcohol is 5��15:1, and temperature of reaction is 160��240oC, reaction pressure is 0.5��5.0MPa, and the volume space velocity of hydrocarbon material is 1.0��10.0 hours-1When, raw material contacts with catalyst B with catalyst A successively, reacts, and the hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol in raw material generates isopropyl benzene, and the hydrogenation of acetophenone in raw material is converted into ethylbenzene, and wherein the volume ratio of catalyst A and catalyst B is 0.5��3:1;
Catalyst A comprises following component with weight parts: 0.1��2.0 part of Pd metal or oxide compound; 90.0��99.0 parts of SiO2; 0.5 ~ 10.0 part of at least one being selected from Mg or its oxide compound, Ca or its oxide compound, Zn or its oxide compound, Ba or its oxide compound;
Catalyst B comprises following component with weight parts: 20.0��65.0 parts of Cu or its oxide compound; 5.0��25.0 parts of Zn or its oxide compound; 1.0��10.0 parts of Mn or its oxide compound; 10.0��40.0 parts of Al2O3; 5.0��25.0 parts of SiO2; 1.0��10.0 at least one being selected from Mg or its oxide compound, Zr or its oxide compound, Ca or its oxide compound, Ba or its oxide compound.
In technique scheme, the volume ratio of catalyst A and catalyst B is preferably 1��3:1, it is more preferable to be 1��2.5:1;
The mol ratio of the alpha, alpha-dimethyl benzyl alcohol in hydrogen/hydrocarbon material is preferably 5 ~ 10:1; Temperature of reaction is preferably 170��230oC; Reaction pressure is preferably 1.0��3.0MPa; The volume space velocity of hydrocarbon material is preferably 3��8 hours-1��
In technique scheme, catalyst A is preferably 0.1��1.0 part with weight parts, the consumption of Pd metal or oxide compound; SiO2Consumption be preferably 91.0��98.0 parts; The consumption of at least one being selected from Mg or its oxide compound, Ca or its oxide compound, Zn or its oxide compound, Ba or its oxide compound is preferably 2.0��8.0 parts;Catalyst B is preferably 25.0��60.0 parts with the consumption of weight parts, Cu or its oxide compound; The consumption of Zn or its oxide compound is preferably 8.0��25.0 parts; The consumption of Mn or its oxide compound is preferably 3.0��8.0 parts; Al2O3Consumption be preferably 15.0��40.0 parts; SiO2Consumption be preferably 5.0��20.0 parts; The consumption of at least one being selected from Mg or its oxide compound, Zr or its oxide compound, Ca or its oxide compound, Ba or its oxide compound is preferably 5.0��10.0 parts.
In technique scheme, hydrocarbon material preferably contains the alpha, alpha-dimethyl benzyl alcohol of 10��50% by weight percentage, the methyl phenyl ketone of 0.1��1.5%.
In technique scheme, the preparation of catalyst A comprises the following steps: adopt pickling process will be selected from Mg2+��Ca2+��Zn2 +��Ba2+In at least one solubility solution impregnation at SiO2Surface, through 400 ~ 1000 after dryoC roasting obtains carrier; According to the method for incipient impregnation, by institute's requirement containing Pd2+Solution impregnation is on carrier, and dry, roasting obtains Pd catalyzer. The preparation of catalyst B comprises the following steps: be added to the water by silicon sol, and heated and stirred forms solution I; The soluble species of Cu, Zn, Al, Mn will be contained, and at least one soluble species being selected from Mg, Zr, Ca, Ba is added to the water dissolving, form solution II; Solution II and basic solution are dripped in solution I simultaneously, wait drip complete after, obtain slurries ��, slurries �� after filtration, washing, dry after 300 ~ 600oAfter C roasting, after shaping, obtain catalyzer.
Benzylalcohol dehydration reaction activity depends on acid site type and acidity. Owing to liquid acid exists the problem such as equipment corrosion and environmental pollution, current dehydration of alcohols catalyzer is substituted by solid acid gradually. Aluminum oxide, amorphous silicon aluminium oxide compound, acid clay and zeolite molecular sieve all can as dehydration catalysts. The side reactions such as etherificate, olefinic polymerization and cyclisation, except promoting dehydration reaction, also can be accelerated in strongly-acid center, therefore selects the carrier with moderate acidity extremely important. The AMS that DMBA dehydration generates in a metal in the heart further hydrogenation directly generate isopropyl benzene, the normal active metal adopted comprises precious metal and Ni, Co, the Cu etc. such as Pt, Pd at present. Owing to different metal species has different hydrogenation activities, become hydrogenation performance it is thus desirable to adjusted by charge capacity, modification, realize DMBA hydrogenolysis on the one hand, suppress the side reactions such as deep hydrogenation on the other hand. Owing to hydrogenolysis process there being water generate, thus the hydrothermal stability of catalyzer there is higher requirement.
Carry out load hydrogenation catalyzer of good performance by selecting suitable carrier and can realize dehydration and the coupling of hydrogenation two reaction. Dehydration reaction is thermo-negative reaction, and hydrogenation reaction is thermopositive reaction, and therefore the coupling of dehydration and hydrogenation two reaction also can effectively utilize the heat that reaction generates.
Adopt the technical scheme of the present invention, consisting of of catalyst A: 0.58 part of Pd-3.11 part MgO-2.78 part CaO-93.56 part SiO2, consisting of of catalyst B: 37.44 parts of CuO-18.66 part ZnO-18.23 part Al2O3-13.68 parts of SiO2-5.34 parts of BaO-6.64 part MnO2, the volume ratio of catalyst A and catalyst B is 1:1, at temperature of reaction 190 �� of C, and reaction pressure 3.0MPa, H2The mol ratio 10.0 of/benzylalcohol, liquid volume air speed 3.0h-1Reaction conditions under be applied in mixing liquid benzylalcohol hydrogenolysis and hydrogenation of acetophenone, reaction 240h benzylalcohol transformation efficiency is 100%, the selectivity generating isopropyl benzene reaches 99.8%, acetophenone conversion is 100%, generate ethylbenzene selectivity and reach 99.1%, catalyst activity selectivity is good, and this catalyzer environmental friendliness, achieves good technique effect simultaneously.
Below by embodiment, the invention will be further elaborated, but in any case the scope of the present invention is not construed as limiting by these embodiments.
Embodiment
[embodiment 1]
By 100.0g silicon-dioxide and 100.0gMg2+Content is the aqueous solution incipient impregnation of 3%, drying, 500oObtaining the carrier I that MgO modifies after C roasting, it consists of: 4.76%MgO-95.24%SiO2; By 1.0gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 89g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 500 after dryoUnder C, roasting 4.0h obtains catalyzer. The concrete composition of catalyst A 1 is in table 1.
Take 50.0gAl2O3, 10.0gSiO2Carrier, is placed in 200ml water 75oStir under C and form slurries I; Take 150.0gCu (NO3)2?3H2O, 50.0gZn (NO3)2?6H2O, 32.0gCa (NO3)2?4H2O, 30.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 0.8L water in the lump in solution I. Drip in solution I and add K2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 75oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 450oC roasting 4 hours, shaping obtains catalyst B 1. The concrete composition of catalyst B 1 is in table 1.
Getting 20 milliliters of catalyst A 1 and 20 milliliters of catalyst B 1, point upper and lower bed filling, raw material by being equipped with catalyst A 1 and the composite bed reactor of catalyst B 1, contacts with catalyzer successively. Catalyzer reduces 3��5 hours when temperature 220 DEG C before use. By weight percentage containing 78.5% isopropyl benzene in hydrocarbon material, 20% dimethyl benzyl alcohol, 0.7% methyl phenyl ketone, surplus impurity. Reaction process condition is: temperature of reaction 180 �� of C, reaction pressure 2.5MPa, H2The mol ratio 8.0 of/benzylalcohol, liquid volume air speed 4.0h-1. Reaction 240h the results are shown in Table 2.
[embodiment 2]
By 100.0g silicon-dioxide and 100.0gCa2+Content is the aqueous solution incipient impregnation of 6%, drying, 500oObtaining the carrier I that CaO modifies after C roasting, it consists of: 7.7%CaO-92.3%SiO2; By 0.8gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 89.2g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 500 after dryoUnder C, roasting 4.0h obtains catalyst A 2. The concrete composition of catalyst A 2 is in table 1.
Take 40.0gAl2O3, 20.0gSiO2Carrier, is placed in 200ml water 75oStir under C and form slurries I; Take 200.0gCu (NO3)2?3H2O, 50.0gZn (NO3)2?6H2O, 30.0gMg (NO3)2?6H2O, 40.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 0.8L water in the lump in solution I. Drip in solution I and add K2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 75oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 500oC roasting 2 hours, shaping obtains catalyst B 2. The concrete composition of catalyst B 2 is in table 1.
Getting 26.7 milliliters of catalyst A 2 and 13.3 milliliters of catalyst B 2, point upper and lower bed filling, raw material by being equipped with catalyst A 2 and the composite bed reactor of catalyst B 2, contacts with catalyzer successively. Catalyzer reduces 3��5 hours when temperature 210 DEG C before use. By weight percentage containing 78.5% isopropyl benzene in hydrocarbon material, 20% dimethyl benzyl alcohol, 0.7% methyl phenyl ketone, surplus impurity.Reaction process condition is: temperature of reaction 180 �� of C, reaction pressure 2.5MPa, H2The mol ratio 8.0 of/benzylalcohol, liquid volume air speed 4.0h-1. Reaction 240h the results are shown in Table 2.
[embodiment 3]
By 100.0g silicon-dioxide and 100.0gZn2+Content is the aqueous solution incipient impregnation of 5%, drying, 600oObtaining the carrier I that ZnO modifies after C roasting, it consists of: 5.9%ZnO-94.1%SiO2; By 1.5gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 88.5g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 450 after dryoUnder C, roasting 4.0h obtains catalyst A 3. The concrete composition of catalyst A 3 is in table 1.
Take 40.0gAl2O3, 30.0gSiO2Carrier, is placed in 200ml water 80oStir under C and form slurries I; Take 150.0gCu (NO3)2?3H2O, 100.0gZn (NO3)2?6H2O, 20.0gZr (NO3)4?5H2O, 40.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 0.8L water in the lump in solution I. Drip in solution I and add Na2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 80oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 550oC roasting 2 hours, shaping obtains catalyst B 3. The concrete composition of catalyst B 3 is in table 1.
Getting 20 milliliters of catalyst A 3 and 20 milliliters of catalyst B 3, point upper and lower bed filling, raw material by being equipped with catalyst A 3 and the composite bed reactor of catalyst B 3, contacts with catalyzer successively. Catalyzer is reductase 12��4 hour when temperature 210 DEG C before use. By weight percentage containing 72% isopropyl benzene in hydrocarbon material, 26% dimethyl benzyl alcohol, 1.0% methyl phenyl ketone, surplus impurity. Reaction process condition is: temperature of reaction 165 �� of C, reaction pressure 2.5MPa, H2The mol ratio 8.0 of/benzylalcohol, liquid volume air speed 5.0h-1. Reaction 240h the results are shown in Table 2.
[embodiment 4]
By 100.0g silicon-dioxide and 100.0gBa2+Content is the aqueous solution incipient impregnation of 2%, drying, 600oObtaining the carrier I that BaO modifies after C roasting, it consists of: 2.2%BaO-97.8%SiO2; By 0.5gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 89.5g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 550 after dryoUnder C, roasting 4.0h obtains catalyst A 4. The concrete composition of catalyst A 4 is in table 1.
Take 60.0gAl2O3, 30.0gSiO2Carrier, is placed in 200ml water 85oStir under C and form slurries I; Take 140.0gCu (NO3)2?3H2O, 150.0gZn (NO3)2?6H2O, 20.0gBa (NO3)2, 20.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 0.7L water in the lump in solution I. Drip in solution I and add K2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 85oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 550oC roasting 4 hours, shaping obtains catalyst B 4. The concrete composition of catalyst B 4 is in table 1.
Getting 30 milliliters of catalyst A 4 and 10 milliliters of catalyst B 4, point upper and lower bed filling, raw material by being equipped with catalyst A 4 and the composite bed reactor of catalyst B 4, contacts with catalyzer successively. Catalyzer is reductase 12��4 hour when temperature 230 DEG C before use. By weight percentage containing 72% isopropyl benzene in hydrocarbon material, 26% dimethyl benzyl alcohol, 1.0% methyl phenyl ketone, surplus impurity.Reaction process condition is: temperature of reaction 190 �� of C, reaction pressure 2.0MPa, H2The mol ratio 10.0 of/benzylalcohol, liquid volume air speed 5.0h-1. Reaction 240h the results are shown in Table 2.
[embodiment 5]
By 100.0g silicon-dioxide and 100.0gMg2+Content is 2%, Ca2+Content is the aqueous solution incipient impregnation of 2%, drying, 600oObtaining the carrier I that MgO/CaO modifies after C roasting, it consists of: 3.13%MgO-2.64%CaO-94.22%SiO2; By 1.0gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 89g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 550 after dryoUnder C, roasting 4.0h obtains catalyst A 5. The concrete composition of catalyst A 5 is in table 1.
Take 40.0gAl2O3, 30.0gSiO2Carrier, is placed in 200ml water 85oStir under C and form slurries I; Take 250.0gCu (NO3)2?3H2O, 150.0gZn (NO3)2?6H2O, 20.0gBa (NO3)2, 60.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 1.0L water in the lump in solution I. Drip in solution I and add K2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 85oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 450oC roasting 4 hours, shaping obtains catalyst B 5. The concrete composition of catalyst B 5 is in table 1.
Getting 20 milliliters of catalyst A 5 and 20 milliliters of catalyst B 5, point upper and lower bed filling, raw material by being equipped with catalyst A 4 and the composite bed reactor of catalyst B 4, contacts with catalyzer successively. Catalyzer is reductase 12��4 hour when temperature 230 DEG C before use. By weight percentage containing 65% isopropyl benzene in hydrocarbon material, 34% dimethyl benzyl alcohol, 1.0% methyl phenyl ketone, surplus impurity. Reaction process condition is: temperature of reaction 190 �� of C, reaction pressure 3.0MPa, H2The mol ratio 10.0 of/benzylalcohol, liquid volume air speed 3.0h-1. Reaction 240h the results are shown in Table 2.
[embodiment 6]
By 100.0g silicon-dioxide and 100.0gZn2+Content is the aqueous solution incipient impregnation of 5%, drying, 600oObtaining the carrier I that ZnO modifies after C roasting, it consists of: 5.9%ZnO-94.1%SiO2; By 1.5gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 88.5g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 450 after dryoUnder C, roasting 4.0h obtains catalyst A 3. The concrete composition of catalyst A 3 is in table 1.
Take 60.0gAl2O3, 30.0gSiO2Carrier, is placed in 200ml water 85oStir under C and form slurries I; Take 140.0gCu (NO3)2?3H2O, 150.0gZn (NO3)2?6H2O, 20.0gBa (NO3)2, 20.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 0.7L water in the lump in solution I. Drip in solution I and add K2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 85oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 550oC roasting 4 hours, shaping obtains catalyst B 4. The concrete composition of catalyst B 4 is in table 1.
Getting 24 milliliters of catalyst A 3 and 16 milliliters of catalyst B 4, point upper and lower bed filling, raw material by being equipped with catalyst A 3 and the composite bed reactor of catalyst B 4, contacts with catalyzer successively. Catalyzer is reductase 12��4 hour when temperature 230 DEG C before use. By weight percentage containing 75% isopropyl benzene in hydrocarbon material, 24% dimethyl benzyl alcohol, 0.5% methyl phenyl ketone, surplus impurity.Reaction process condition is: entrance temperature of reaction 180 �� of C, reaction pressure 2.5MPa, H2The mol ratio 10.0 of/benzylalcohol, liquid volume air speed 4.0h-1. Reaction 240h the results are shown in Table 2.
[embodiment 7]
By 100.0g silicon-dioxide and 100.0gZn2+Content is the aqueous solution incipient impregnation of 5%, drying, 600oObtaining the carrier I that ZnO modifies after C roasting, it consists of: 5.9%ZnO-94.1%SiO2; By 1.5gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 88.5g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 450 after dryoUnder C, roasting 4.0h obtains catalyst A 3. The concrete composition of catalyst A 3 is in table 1.
Take 40.0gAl2O3, 30.0gSiO2Carrier, is placed in 200ml water 85oStir under C and form slurries I; Take 250.0gCu (NO3)2?3H2O, 150.0gZn (NO3)2?6H2O, 20.0gBa (NO3)2, 60.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 1.0L water in the lump in solution I. Drip in solution I and add K2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 85oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 450oC roasting 4 hours, shaping obtains catalyst B 5. The concrete composition of catalyst B 5 is in table 1.
Getting 26.7 milliliters of catalyst A 3 and 13.3 milliliters of catalyst B 5, point upper and lower bed filling, raw material by being equipped with catalyst A 3 and the composite bed reactor of catalyst B 5, contacts with catalyzer successively. Catalyzer is reductase 12��4 hour when temperature 230 DEG C before use. By weight percentage containing 75% isopropyl benzene in hydrocarbon material, 24% dimethyl benzyl alcohol, 0.5% methyl phenyl ketone, surplus impurity. Reaction process condition is: entrance temperature of reaction 180 �� of C, reaction pressure 2.5MPa, H2The mol ratio 10.0 of/benzylalcohol, liquid volume air speed 4.0h-1. Reaction 240h the results are shown in Table 2.
[embodiment 8]
By 100.0g silicon-dioxide and 100.0gBa2+Content is the aqueous solution incipient impregnation of 2%, drying, 600oObtaining the carrier I that BaO modifies after C roasting, it consists of: 2.2%BaO-97.8%SiO2; By 0.5gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 89.5g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 550 after dryoUnder C, roasting 4.0h obtains catalyst A 4. The concrete composition of catalyst A 4 is in table 1.
Take 50.0gAl2O3, 10.0gSiO2Carrier, is placed in 200ml water 75oStir under C and form slurries I; Take 150.0gCu (NO3)2?3H2O, 50.0gZn (NO3)2?6H2O, 32.0gCa (NO3)2?4H2O, 30.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 0.8L water in the lump in solution I. Drip in solution I and add K2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 75oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 450oC roasting 4 hours, shaping obtains catalyst B 1. The concrete composition of catalyst B 1 is in table 1.
Getting 13.3 milliliters of catalyst A 4 and 26.7 milliliters of catalyst B 1, point upper and lower bed filling, raw material by being equipped with catalyst A 4 and the composite bed reactor of catalyst B 1, contacts with catalyzer successively. Catalyzer is reductase 12��4 hour when temperature 230 DEG C before use. By weight percentage containing 75% isopropyl benzene in hydrocarbon material, 24% dimethyl benzyl alcohol, 0.5% methyl phenyl ketone, surplus impurity.Reaction process condition is: entrance temperature of reaction 180 �� of C, reaction pressure 2.5MPa, H2The mol ratio 10.0 of/benzylalcohol, liquid volume air speed 4.0h-1. Reaction 240h the results are shown in Table 2.
[embodiment 9]
By 100.0g silicon-dioxide and 100.0gCa2+Content is the aqueous solution incipient impregnation of 6%, drying, 500oObtaining the carrier I that CaO modifies after C roasting, it consists of: 7.7%CaO-92.3%SiO2; By 0.8gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 89.2g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 500 after dryoUnder C, roasting 4.0h obtains catalyst A 2. The concrete composition of catalyst A 2 is in table 1.
Take 40.0gAl2O3, 30.0gSiO2Carrier, is placed in 200ml water 80oStir under C and form slurries I; Take 150.0gCu (NO3)2?3H2O, 100.0gZn (NO3)2?6H2O, 20.0gZr (NO3)4?5H2O, 40.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 0.8L water in the lump in solution I. Drip in solution I and add Na2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 80oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 550oC roasting 2 hours, shaping obtains catalyst B 3. The concrete composition of catalyst B 3 is in table 1.
Getting 13.3 milliliters of catalyst A 2 and 26.7 milliliters of catalyst B 3, point upper and lower bed filling, raw material by being equipped with catalyst A 2 and the composite bed reactor of catalyst B 3, contacts with catalyzer successively. Catalyzer is reductase 12��4 hour when temperature 230 DEG C before use. By weight percentage containing 75% isopropyl benzene in hydrocarbon material, 24% dimethyl benzyl alcohol, 0.5% methyl phenyl ketone, surplus impurity. Reaction process condition is: entrance temperature of reaction 180 �� of C, reaction pressure 2.5MPa, H2The mol ratio 10.0 of/benzylalcohol, liquid volume air speed 4.0h-1. Reaction 240h the results are shown in Table 2.
[embodiment 10]
By 100.0g silicon-dioxide and 100.0gMg2+Content is 2%, Ca2+Content is the aqueous solution incipient impregnation of 2%, drying, 600oObtaining the carrier I that MgO/CaO modifies after C roasting, it consists of: 3.13%MgO-2.64%CaO-94.22%SiO2; By 1.0gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 89g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 550 after dryoUnder C, roasting 4.0h obtains catalyst A 5. The concrete composition of catalyst A 5 is in table 1.
Take 50.0gAl2O3, 10.0gSiO2Carrier, is placed in 200ml water 75oStir under C and form slurries I; Take 150.0gCu (NO3)2?3H2O, 50.0gZn (NO3)2?6H2O, 32.0gCa (NO3)2?4H2O, 30.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 0.8L water in the lump in solution I. Drip in solution I and add K2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 75oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 450oC roasting 4 hours, shaping obtains catalyst B 1. The concrete composition of catalyst B 1 is in table 1.
Getting 28.6 milliliters of catalyst A 5 and 11.4 milliliters of catalyst B 1, point upper and lower bed filling, raw material by being equipped with catalyst A 5 and the composite bed reactor of catalyst B 1, contacts with catalyzer successively. Catalyzer is reductase 12��4 hour when temperature 230 DEG C before use.By weight percentage containing 75% isopropyl benzene in hydrocarbon material, 24% dimethyl benzyl alcohol, 0.5% methyl phenyl ketone, surplus impurity. Reaction process condition is: entrance temperature of reaction 180 �� of C, reaction pressure 2.5MPa, H2The mol ratio 10.0 of/benzylalcohol, liquid volume air speed 4.0h-1. Reaction 240h the results are shown in Table 2.
[embodiment 11]
By 100.0g silicon-dioxide and 100.0gMg2+Content is 2%, Ca2+Content is the aqueous solution incipient impregnation of 2%, drying, 600oObtaining the carrier I that MgO/CaO modifies after C roasting, it consists of: 3.13%MgO-2.64%CaO-94.22%SiO2; By 1.0gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 89g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 550 after dryoUnder C, roasting 4.0h obtains catalyst A 5. The concrete composition of catalyst A 5 is in table 1.
Take 40.0gAl2O3, 30.0gSiO2Carrier, is placed in 200ml water 80oStir under C and form slurries I; Take 150.0gCu (NO3)2?3H2O, 100.0gZn (NO3)2?6H2O, 20.0gZr (NO3)4?5H2O, 40.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 0.8L water in the lump in solution I. Drip in solution I and add Na2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 80oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 550oC roasting 2 hours, shaping obtains catalyst B 3. The concrete composition of catalyst B 3 is in table 1.
Get 26.7 milliliters of catalyst A 5 and 13.3 milliliters of catalyst B 3, point upper and lower bed filling, raw material by being equipped with catalyst A 5 and the composite bed reactor of catalyst B 3, contacts with catalyzer successively. Catalyzer is reductase 12��4 hour when temperature 230 DEG C before use. By weight percentage containing 75% isopropyl benzene in hydrocarbon material, 24% dimethyl benzyl alcohol, 0.5% methyl phenyl ketone, surplus impurity. Reaction process condition is: entrance temperature of reaction 180 �� of C, reaction pressure 2.5MPa, H2The mol ratio 10.0 of/benzylalcohol, liquid volume air speed 4.0h-1. Reaction 240h the results are shown in Table 2.
[embodiment 12]
By 100.0g silicon-dioxide and 100.0gCa2+Content is the aqueous solution incipient impregnation of 6%, drying, 500oObtaining the carrier I that CaO modifies after C roasting, it consists of: 7.7%CaO-92.3%SiO2; By 0.8gPdCl2Solid is dissolved in the solution being made up of 10g concentrated hydrochloric acid and 89.2g pure water and obtains solution I. According to the method for incipient impregnation, 50.0g solution I is immersed on 50.0g carrier I, 500 after dryoUnder C, roasting 4.0h obtains catalyst A 2. The concrete composition of catalyst A 2 is in table 1.
Take 40.0gAl2O3, 30.0gSiO2Carrier, is placed in 200ml water 85oStir under C and form slurries I; Take 250.0gCu (NO3)2?3H2O, 150.0gZn (NO3)2?6H2O, 20.0gBa (NO3)2, 60.0g weight percent is 50%Mn (NO3)2Solution is dissolved in 1.0L water in the lump in solution I. Drip in solution I and add K2CO3The aqueous solution is 7.0 formation solution II to the pH value of mixing solutions, and solution II is 85oUnder C, washing after aging 4 hours, filtration are precipitated thing. Throw out is through 120oDry 24 hours of C, 450oC roasting 4 hours, shaping obtains catalyst B 5. The concrete composition of catalyst B 5 is in table 1.
Getting 30 milliliters of catalyst A 2 and 10 milliliters of catalyst B 5, point upper and lower bed filling, raw material by being equipped with catalyst A 2 and the composite bed reactor of catalyst B 5, contacts with catalyzer successively.Catalyzer is reductase 12��4 hour when temperature 230 DEG C before use. By weight percentage containing 75% isopropyl benzene in hydrocarbon material, 24% dimethyl benzyl alcohol, 0.5% methyl phenyl ketone, surplus impurity. Reaction process condition is: entrance temperature of reaction 180 �� of C, reaction pressure 2.5MPa, H2The mol ratio 10.0 of/benzylalcohol, liquid volume air speed 4.0h-1. Reaction 240h the results are shown in Table 2.
[comparative example 1]
Adopt the catalyst A l of preparation in embodiment 1. Catalyzer reduces 4.0 hours before use at 220 DEG C. By weight percentage containing 75% isopropyl benzene in hydrocarbon material, 24% dimethyl benzyl alcohol, 0.5% methyl phenyl ketone, surplus impurity. Reaction process condition is: entrance temperature of reaction 180 �� of C, reaction pressure 2.5MPa, H2The mol ratio 10.0 of/benzylalcohol, liquid volume air speed 4.0h-1. Reaction 240h the results are shown in Table 2.
Table 1
Table 2
[embodiment 13]
The present embodiment illustrates that the composite bed that catalyst A 4 and catalyst B 1 form is preparing during isopropyl benzene reacts the test-results changing processing condition. Wherein the volume filling ratio of catalyst A 4 and catalyst B 1 is 1:1.
Getting 20 milliliters of catalyst A 4 and 20 milliliters of catalyst B 1, point upper and lower bed filling, raw material by being equipped with catalyst A 4 and the composite bed reactor of catalyst B 1, contacts with catalyzer successively. Catalyzer reduces 4.0��6.0 hours when temperature 220 DEG C before use. By weight percentage containing 74.5% isopropyl benzene in hydrocarbon material, 24% dimethyl benzyl alcohol, 0.65% methyl phenyl ketone, surplus impurity. Changing processing condition to test, the test-results after reaction 240h is in table 3.
Table 3
Claims (10)
1. prepare the method for isopropyl benzene for one kind, with containing ��, the hydrocarbon material of alpha-alpha-dimethyl benzylalcohol, methyl phenyl ketone and hydrogen are raw material, �� in hydrogen/hydrocarbon material, the mol ratio of alpha-alpha-dimethyl benzylalcohol is 5��15:1, temperature of reaction is 160��240 DEG C, and reaction pressure is 0.5��5.0MPa, and the volume space velocity of hydrocarbon material is 1.0��10.0 hours-1When, raw material contacts with catalyst B with catalyst A successively, reacts, and the hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol in raw material generates isopropyl benzene, and the hydrogenation of acetophenone in raw material is converted into ethylbenzene, and wherein the volume ratio of catalyst A and catalyst B is 0.5��3:1;
Catalyst A is composed of the following components with weight parts: 0.1��2.0 part of Pd metal or oxide compound; 90.0��99.0 parts of SiO2; 0.5��10.0 part of at least one being selected from Mg or its oxide compound, Ca or its oxide compound, Ba or its oxide compound;
Catalyst B is composed of the following components with weight parts: 20.0��65.0 parts of Cu or its oxide compound; 5.0��25.0 parts of Zn or its oxide compound; 1.0��10.0 parts of Mn or its oxide compound; 10.0��40.0 parts of Al2O3; 5.0��25.0 parts of SiO2; 1.0��10.0 at least one being selected from Mg or its oxide compound, Zr or its oxide compound, Ca or its oxide compound, Ba or its oxide compound.
2. the method preparing isopropyl benzene according to claim 1, it is characterised in that the volume ratio of catalyst A and catalyst B is 1��3:1.
3. the method preparing isopropyl benzene according to claim 2, it is characterised in that the volume ratio of catalyst A and catalyst B is 1��2.5:1.
4. the method preparing isopropyl benzene according to claim 1, it is characterised in that the mol ratio of the alpha, alpha-dimethyl benzyl alcohol in described hydrogen/hydrocarbon material is 5��10:1.
5. the method preparing isopropyl benzene according to claim 1, it is characterised in that described temperature of reaction is 170��230 DEG C.
6. the method preparing isopropyl benzene according to claim 1, it is characterised in that described reaction pressure is 1.0��3.0MPa.
7. the method preparing isopropyl benzene according to claim 1, it is characterised in that the volume space velocity of described hydrocarbon material is 3��8 hours-1��
8. the method preparing isopropyl benzene according to claim 1, it is characterised in that described catalyst A is with weight parts, and the consumption of Pd metal or oxide compound is 0.1��1.0 part; SiO2Consumption be 91.0��98.0 parts; The consumption of at least one being selected from Mg or its oxide compound, Ca or its oxide compound, Ba or its oxide compound is 2.0��8.0 parts.
9. the method preparing isopropyl benzene according to claim 1, it is characterised in that described catalyst B is 25.0��60.0 parts with the consumption of weight parts, Cu or its oxide compound; The consumption of Zn or its oxide compound is 8.0��25.0 parts; The consumption of Mn or its oxide compound is 3.0��8.0 parts; Al2O3Consumption be 15.0��40.0 parts; SiO2Consumption be 5.0��20.0 parts; The consumption of at least one being selected from Mg or its oxide compound, Zr or its oxide compound, Ca or its oxide compound, Ba or its oxide compound is 5.0��10.0 parts.
10. the method preparing isopropyl benzene according to claim 1, it is characterised in that contain the alpha, alpha-dimethyl benzyl alcohol of 10��50% in described hydrocarbon material by weight percentage, the methyl phenyl ketone of 0.1��1.5%.
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| CN113070060B (en) * | 2020-01-03 | 2022-08-05 | 万华化学集团股份有限公司 | Catalyst for preparing isopropylbenzene by hydrogenolysis of alpha-dimethyl benzyl alcohol and preparation method and application thereof |
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