CN105562023A - Catalyst for preparation of p-methyl styrene, and preparation method and application thereof - Google Patents
Catalyst for preparation of p-methyl styrene, and preparation method and application thereof Download PDFInfo
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- CN105562023A CN105562023A CN201410537968.8A CN201410537968A CN105562023A CN 105562023 A CN105562023 A CN 105562023A CN 201410537968 A CN201410537968 A CN 201410537968A CN 105562023 A CN105562023 A CN 105562023A
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Abstract
The invention relates to a catalyst for preparation of p-methyl styrene and a preparation method thereof. The main objective of the invention is to overcome the problem of low catalyst activity in the prior art. The catalyst used for preparation of p-methyl styrene comprises, by weight, (a) 65 to 81% of Fe2O3, (b) 8 to 14% of K2O, (c) 6 to 13% of CeO2, (d) 0.3 to 5% of Mo2O3 or/and WO3 and (e) 0.3 to 7% of at least one selected from alkaline earth oxides. The catalyst provided by the invention perfectly overcomes the above-mentioned problem and can be used for industrial production of p-methyl styrene from p-methyl ethylbenzene through dehydrogenation.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and the application of preparing p-methylstyrene.
Background technology
P-methylstyrene monomer can at single aggressiveness, resistance toly rush polymer, acrylonitrile-butadiene terpolymers, special EVA, elastomer and thermosetting polyester substituted phenylethylene.The single polymers using p-methylstyrene to produce is compared with styrene with copolymer, and proportion is smaller, and mobility and heat endurance will be got well.In thermosetting polyester application, better heat stability, the utilization rate of grinding tool improves, and the electric property of product is better simultaneously.Simultaneously in fire-retardant application, p-methylstyrene polymer only needs less fire retardant just can play identical flame retardant effect, also changes the molecular structure of polymer by chemical crosslinking and radiation simultaneously.In addition, because toluene resource is abundanter, be the new way of toluene chemical utilization as waste p-methylstyrene.
For the basic composition of p-methylstyrene catalyst, major catalyst, co-catalyst, perforating agent and binding agent etc. are comprised to methyl-ethyl benzene Oxidative Dehydrogenation.As published United States Patent (USP) 4504594 and 4404123, although the activity and selectivity of catalyst is all better, containing the oxide of Cr in catalyst, certain pollution is caused to environment.Substitute Cr with Ce, activity and the stability of catalyst can be improved preferably, overcome again Cr toxicity large, the drawback of contaminated environment simultaneously.As published EP502510, WO9710898, CN1233604 and CN1470325, in the catalyst of ethyl benzene dehydrogenation preparation of styrene, Ce's adds activity and the stability that significantly can improve catalyst.In the catalyst of ethyl benzene dehydrogenation preparation of styrene, potassium is main co-catalyst, and adding of potassium can make catalyst activity improve a more than order of magnitude, and potassium plays vital effect in the catalyst.But potassium washes away lower meeting at high-temperature vapor and slowly runs off and move, be the one of the main reasons of the irreversible inactivation of catalyst, therefore generally adopt the catalyst for phenylethylene dehydrogenation of low potassium content at present.As published United States Patent (USP) 4804799,5190906 and 5376613 etc., this kind of catalyst activity and selectivity is higher, and stability is better.But the preparation method of catalyst generally adopts and all components solid phase mixing is obtained catalyst in these documents, and these documents all do not report that Fe-K-Ce-Mo catalyst system and catalyzing is to the activity data of methyl-ethyl benzene Oxidative Dehydrogenation for p-methylstyrene.Find in research, in catalyst preparation process, active component potassium adopts two-step method to be incorporated into the performance impact of the mode in catalyst to catalyst very big.For this reason, find Suitable preparation methods improve prepare p-methylstyrene catalyst activity, be the target that researcher makes great efforts.
Summary of the invention
The problem that the catalyst activity existed in one of technical problem to be solved by this invention conventional art is lower, provides a kind of catalyst for p-methylstyrene processed newly, has active high feature with the catalyst that the method obtains.
Two of the technical problem to be solved in the present invention is to provide preparation method that the is a kind of and catalyst-compatible of one of technical solution problem.
Three of technical problem to be solved by this invention is to provide the application process of the catalyst of one of a kind of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of for the catalyst of methyl-ethyl benzene Oxidative Dehydrogenation for p-methylstyrene, comprises following component by weight percentage:
The Fe of (a) 65 ~ 81%
2o
3;
The K of (b) 8 ~ 14%
2o;
The CeO of (c) 6 ~ 13%
2;
The Mo of (d) 0.3 ~ 5%
2o
3or/and WO
3;
At least one in the alkaline earth oxide of (e) 0.3 ~ 7%.
In technique scheme, described (d) component is preferably Mo
2o
3and WO
3; Described (e) component is preferably at least two kinds in alkaline earth oxide.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of for the preparation method of methyl-ethyl benzene Oxidative Dehydrogenation for the catalyst of p-methylstyrene, comprises the following steps:
1) by weight percentage, by the source of iron of Part I potassium source and aequum, cerium source, molybdenum source or/and tungsten source, alkaline earth oxide, perforating agent and water mix, after extrusion, shaping, drying, at 600 ~ 1000 DEG C, roasting 0.5 ~ 24 hour, obtains catalyst precarsor I;
2) adopt infusion process to be carried on catalyst precarsor I by Part II potassium source, then drying, at 500 ~ 900 DEG C, roasting obtains required catalyst for 0.5 ~ 24 hour;
Wherein, to contain K
2the gauge of O, the weight summation in Part I potassium source and Part II potassium source is the gross weight in the potassium source of aequum, and Part I potassium source is 50 ~ 95% of the potassium source gross weight of aequum.
In above technical scheme, catalyst all components preferably includes following composition by weight percentage: the Fe of 63 ~ 81%
2o
3, 7 ~ 14% K
2o, 5 ~ 15% CeO
2, 0.3 ~ 5% Mo
2o
3or/and WO
3, 0.3 ~ 7% alkaline earth oxide at least one; Described step 2) in Part II potassium source be preferably carried on catalyst precarsor I in the mode of at least one in potassium hydroxide aqueous solution, wet chemical; Described step 1) in the preferred autoxidation iron oxide red of source of iron, at least one in iron oxide yellow; Be more preferably iron oxide red and iron oxide yellow; Described Part I potassium source preferably adds with at least one form in sylvite, potassium hydroxide; Described cerium source is preferably with cerium salt; Described molybdenum source preferably adds with at least one form in the oxide of molybdenum salt, molybdenum; Described tungsten source preferably adds with at least one form in the oxide of tungsten salt, tungsten; Described alkaline earth oxide preferably adds with at least one form in alkali salt, alkaline earth oxide, alkaline earth metal hydroxide; Described perforating agent is preferably at least one in graphite, polystyrene microsphere, methylcellulose, hydroxyethylcellulose, carboxymethyl cellulose, and its addition is preferably 2 ~ 6% of total catalyst weight; Described step 1) in baking temperature be preferably 50 ~ 120 DEG C, be preferably 2 ~ 12 hours drying time; Described step 1) in sintering temperature be preferably 700 ~ 850 DEG C, roasting time is preferably 4 ~ 12 hours; Described step 2) in dipping time be preferably 2 ~ 24 hours; Step 2) in dry temperature be preferably 80 ~ 150 DEG C, be preferably 2 ~ 12 hours drying time; Described step 2) in sintering temperature be preferably 550 ~ 700 DEG C, roasting time is preferably 4 ~ 10 hours.
In technique scheme, to contain K
2the gauge of O, described step 1) in Part I potassium source be preferably 65 ~ 85% of the potassium source gross weight of aequum, now gained is the highest for the preparation of the activity of the catalyst of p-methylstyrene.
The catalyst granules that the present invention obtains can be the various shapes such as solid cylindrical, hollow cylinder, trilobal, rhombus, quincunx, honeycomb type, the restriction that its diameter and particle length are also unfixing, recommendation catalyst employing diameter is the solid cylindrical particle of 3 millimeters, long 5 ~ 10 millimeters.Impregnation method in preparation method can adopt incipient impregnation, excessive dipping, repeatedly impregnating mode, recommends to adopt incipient impregnation method.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of method to methyl-ethyl benzene Oxidative Dehydrogenation p-methylstyrene, and its Raw and above-mentioned catalyst exposure react prepares p-methylstyrene.
In technique scheme, described reaction condition is preferably: reaction pressure is normal pressure, liquid air speed 0.5 ~ 2.5 hour
- 1, temperature 580 ~ 640 DEG C, steam/to the weight ratio of methyl-ethyl benzene is 1.0 ~ 4.0.
Obtained catalyst carries out activity rating in isotherm formula fixed bed, and for the evaluation of methyl-ethyl benzene Oxidative Dehydrogenation p-methylstyrene catalyst activity, process is summarized as follows:
By reaction raw materials respectively through measuring pump input preheating mixer, preheating enters reactor after being mixed into gaseous state, and reactor adopts electric-heating-wire-heating, makes it to reach predetermined temperature.Reactor inside diameter is 1 " stainless steel tube, interiorly load 100 milliliters of catalyst.After water condensation, with chromatographic, it forms the reactant flowed out by reactor.
To methyl-ethyl benzene conversion ratio, the selective calculating as follows of p-methylstyrene:
The present invention is by adopting two-step method to be incorporated in catalyst in active component potassium, and the potassium that the first step is added and iron oxide form predecessor's slow releasing potassium in course of reaction of active phase through roasting; Second step then can make potassium ion reach individual layer balanced distribution fast at catalyst surface by the potassium that infusion process adds, thus significantly improves the activity of catalyst.By the catalyst that said method is obtained, normal pressure, liquid air speed 1.0 hours
-1, temperature 620 DEG C, steam/under methyl-ethyl benzene (weight ratio) 2.5 condition, the activity of catalyst can reach 61.5%, selectively reaches 93.7%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated:
Detailed description of the invention
[embodiment 1]
303.0 grams of iron oxide reds, 165.0 grams of iron oxide yellows, 57.0 grams of potash, 85.0 grams of cerous nitrates, 4.2 grams of ammonium tungstates, 12.8 grams of magnesia, 10.3 grams of calcium carbonate, 5.0 grams of cupric oxide, 4.0 grams of graphite, 10.6 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 5 millimeters, put into baking oven, 50 DEG C are dried 2 hours, 100 DEG C are dried 10 hours, then be placed in muffle furnace, within 4 hours, obtain semi-finished product catalyst in 800 DEG C of roastings.Taking 3.0 grams of potash is dissolved in 55.0 ml waters, and semi-finished product catalyst is flooded 2 hours in this solution, dries 12 hours afterwards in 80 DEG C, then within 24 hours, obtains finished catalyst in 500 DEG C of roastings.
100 milliliters of finished catalysts are loaded reactors, normal pressure, liquid air speed 1.0 hours
-1, 620 DEG C, steam/carry out activity rating under methyl-ethyl benzene (weight ratio) 2.5 condition, test result lists in table 2.
[embodiment 2]
255.0 grams of iron oxide reds, 100.5 grams of iron oxide yellows, 59.5 grams of potash, 88.0 grams of cerium oxalates, 11.0 grams of ammonium molybdates, 19.2 grams of magnesia, 8.6 grams of barium hydroxides, 1.0 grams of manganese dioxide, 2.0 grams of polystyrene microspheres, 16.5 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 10 millimeters, put into baking oven, 50 DEG C are dried 6 hours, then be placed in muffle furnace, within 1.0 hours, obtain semi-finished product catalyst in 950 DEG C of roastings.Taking 8.5 grams of potassium hydroxide is dissolved in 40.0 ml waters, and semi-finished product catalyst is flooded 10 hours in this solution, dries 6 hours afterwards in 120 DEG C, then within 6 hours, obtains finished catalyst in 600 DEG C of roastings.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 2.
[embodiment 3]
213.0 grams of iron oxide reds, 90.0 grams of iron oxide yellows, 54.0 grams of potash, 82.0 grams of cerium oxalates, 14.8 grams of ammonium molybdates, 1.4 grams of ammonium tungstates, 5.0 grams of calcium carbonate, 8.2 grams of magnesia, 2.3 grams of strontium carbonates, 5.0 grams of hydroxyethylcelluloses, 20.3 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 7 millimeters, put into baking oven, 50 DEG C are dried 2 hours, 100 DEG C are dried 10 hours, then be placed in muffle furnace, within 10 hours, obtain semi-finished product catalyst in 780 DEG C of roastings.Taking 18.0 grams of potash is dissolved in 40.0 ml waters, and semi-finished product catalyst is flooded 16 hours in this solution, dries 3 hours afterwards in 130 DEG C, then within 5 hours, obtains finished catalyst in 750 DEG C of roastings.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 2.
[embodiment 4]
190.0 grams of iron oxide reds, 156.0 grams of iron oxide yellows, 58.5 grams of potash, 100.1 grams of cerium oxalates, 7.4 grams of ammonium tungstates, 7.4 grams of ammonium molybdates, 8.0 grams of calcium hydroxides, 11.4 grams of strontium carbonates, 17.9 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 8 millimeters, put into baking oven, 60 DEG C are dried 3 hours, 100 DEG C are dried 8 hours, then be placed in muffle furnace, within 8 hours, obtain semi-finished product catalyst in 780 DEG C of roastings.Taking 31.5 grams of potash is dissolved in 45.0 ml waters, and semi-finished product catalyst is flooded 24 hours in this solution, dries 2 hours afterwards in 140 DEG C, then within 4 hours, obtains finished catalyst in 630 DEG C of roastings.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 2.
[embodiment 5]
240.0 grams of iron oxide reds, 150.0 grams of iron oxide yellows, 48.0 grams of potash, 100.0 grams of cerium oxalates, 35.2 grams of cerous nitrates, 6.6 grams of ammonium molybdates, 10.0 grams of ammonium tungstates, 4.0 grams of magnesia, 5.0 grams of zinc oxide, 3.5 grams of methylcellulose, 16.2 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 9 millimeters, put into baking oven, 80 DEG C are dried 2 hours, 120 DEG C are dried 2 hours, then be placed in muffle furnace, within 24 hours, obtain semi-finished product catalyst in 600 DEG C of roastings.Taking 25.9 grams of potassium hydroxide is dissolved in 45.0 ml waters, and semi-finished product catalyst is flooded 20 hours in this solution, dries 2 hours afterwards in 150 DEG C, then within 4 hours, obtains finished catalyst in 650 DEG C of roastings.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 2.
[embodiment 6]
195.0 grams of iron oxide reds, 156.0 grams of iron oxide yellows, 42.5 grams of potash, 128.0 grams of cerium oxalates, 12.3 grams of ammonium molybdates, 14.8 grams of ammonium tungstates, 10.1 grams of calcium carbonate, 6.2 grams of magnesia, 13.9 grams of strontium carbonates, 5.0 grams of zinc oxide, 19.8 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 6 millimeters, put into baking oven, 80 DEG C are dried 2 hours, 120 DEG C are dried 2 hours, then be placed in muffle furnace, within 4 hours, obtain semi-finished product catalyst in 810 DEG C of roastings.Taking 42.5 grams of potash is dissolved in 45.0 ml waters, and semi-finished product catalyst is flooded 24 hours in this solution, dries 3 hours afterwards in 130 DEG C, then within 0.5 hour, obtains finished catalyst in 850 DEG C of roastings.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 2.
The percentage by weight table 1 composed as follows of gained catalyst:
Table 1
[comparative example 1]
303.0 grams of iron oxide reds, 165.0 grams of iron oxide yellows, 60.0 grams of potash, 85.0 grams of cerous nitrates, 4.2 grams of ammonium tungstates, 12.8 grams of magnesia, 10.3 grams of calcium carbonate, 5.0 grams of cupric oxide, 4.0 grams of graphite, 10.6 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 5 millimeters, put into baking oven, 50 DEG C are dried 2 hours, 100 DEG C are dried 10 hours, then be placed in muffle furnace, within 4 hours, obtain finished catalyst in 800 DEG C of roastings.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 2.
[comparative example 2]
255.0 grams of iron oxide reds, 100.5 grams of iron oxide yellows, 88.0 grams of cerium oxalates, 11.0 grams of ammonium molybdates, 19.2 grams of magnesia, 8.6 grams of barium hydroxides, 1.0 grams of manganese dioxide, 2.0 grams of polystyrene microspheres, 16.5 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 10 millimeters, put into baking oven, 50 DEG C are dried 6 hours, then be placed in muffle furnace, within 1.0 hours, obtain semi-finished product catalyst in 950 DEG C of roastings.Taking 56.8 grams of potassium hydroxide is dissolved in 40.0 ml waters, and semi-finished product catalyst is flooded 10 hours in this solution, dries 6 hours afterwards in 120 DEG C, then within 6 hours, obtains finished catalyst in 600 DEG C of roastings.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 2.
[comparative example 3]
213.0 grams of iron oxide reds, 90.0 grams of iron oxide yellows, 54.0 grams of potash, 82.0 grams of cerium oxalates, 16.3 grams of ammonium molybdates, 16.8 grams of strontium carbonates, 5.0 grams of hydroxyethylcelluloses, 20.3 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 7 millimeters, put into baking oven, 50 DEG C are dried 2 hours, 100 DEG C are dried 10 hours, then be placed in muffle furnace, within 10 hours, obtain semi-finished product catalyst in 780 DEG C of roastings.Taking 18.0 grams of potash is dissolved in 40.0 ml waters, and semi-finished product catalyst is flooded 16 hours in this solution, dries 3 hours afterwards in 130 DEG C, then within 5 hours, obtains finished catalyst in 750 DEG C of roastings.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 2.
[comparative example 4]
190.0 grams of iron oxide reds, 156.0 grams of iron oxide yellows, 100.1 grams of cerium oxalates, 7.4 grams of ammonium tungstates, 7.4 grams of ammonium molybdates, 10.6 grams of calcium hydroxides, 17.9 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 8 millimeters, put into baking oven, 60 DEG C are dried 3 hours, 100 DEG C are dried 8 hours, are then placed in muffle furnace, within 8 hours, obtain semi-finished product catalyst in 780 DEG C of roastings.Taking 90.0 grams of potash is dissolved in 128.6 ml waters, and semi-finished product catalyst is flooded 24 hours in this solution, dries 2 hours afterwards in 140 DEG C, then within 4 hours, obtains finished catalyst in 630 DEG C of roastings.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 2.
[comparative example 5]
240.0 grams of iron oxide reds, 150.0 grams of iron oxide yellows, 48.0 grams of potash, 100.0 grams of cerium oxalates, 35.2 grams of cerous nitrates, 17.3 grams of ammonium molybdates, 4.0 grams of magnesia, 5.0 grams of zinc oxide, 3.5 grams of methylcellulose, 16.2 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 9 millimeters, put into baking oven, 80 DEG C are dried 2 hours, 120 DEG C are dried 2 hours, then be placed in muffle furnace, within 24 hours, obtain semi-finished product catalyst in 600 DEG C of roastings.Taking 25.9 grams of potassium hydroxide is dissolved in 45.0 ml waters, and semi-finished product catalyst is flooded 20 hours in this solution, dries 2 hours afterwards in 150 DEG C, then within 4 hours, obtains finished catalyst in 650 DEG C of roastings.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 2.
[comparative example 6]
195.0 grams of iron oxide reds, 156.0 grams of iron oxide yellows, 42.5 grams of potash, 128.0 grams of cerium oxalates, 26.3 grams of ammonium tungstates, 10.1 grams of calcium carbonate, 6.2 grams of magnesia, 13.9 grams of strontium carbonates, 5.0 grams of zinc oxide, 19.8 grams of carboxymethyl celluloses are stirred 1 hour in kneader, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of diameter 3 millimeters, length 6 millimeters, put into baking oven, 80 DEG C are dried 2 hours, 120 DEG C are dried 2 hours, then be placed in muffle furnace, within 4 hours, obtain semi-finished product catalyst in 810 DEG C of roastings.Taking 42.5 grams of potash is dissolved in 45.0 ml waters, and semi-finished product catalyst is flooded 24 hours in this solution, dries 3 hours afterwards in 130 DEG C, then within 0.5 hour, obtains finished catalyst in 850 DEG C of roastings.
Carry out activity rating by the appreciation condition of embodiment 1, test result lists in table 2.
Table 2
Above embodiment illustrates, active component potassium adopts two-step method to be incorporated in catalyst, effectively can improve and prepare the activity and selectivity of p-methylstyrene catalyst and the yield of p-methylstyrene.
Claims (10)
1., for the catalyst of methyl-ethyl benzene Oxidative Dehydrogenation for p-methylstyrene, comprise following component by weight percentage:
The Fe of (a) 65 ~ 81%
2o
3;
The K of (b) 8 ~ 14%
2o;
The CeO of (c) 6 ~ 13%
2;
The Mo of (d) 0.3 ~ 5%
2o
3or/and WO
3;
At least one in the alkaline earth oxide of (e) 0.3 ~ 7%.
2., for the preparation method of methyl-ethyl benzene Oxidative Dehydrogenation for p-methylstyrene catalyst, comprise the following steps:
1) by the source of iron of Part I potassium source and aequum, cerium source, molybdenum source or/and tungsten source, alkaline earth oxide, perforating agent and water mix, after extrusion, shaping, drying, at 600 ~ 1000 DEG C, roasting 0.5 ~ 24 hour, obtains catalyst precarsor I;
2) adopt infusion process to be carried on catalyst precarsor I by Part II potassium source, then drying, at 500 ~ 900 DEG C, roasting obtains required catalyst for 0.5 ~ 24 hour;
Wherein, to contain K
2the gauge of O, the weight summation in Part I potassium source and Part II potassium source is the gross weight in the potassium source of aequum, and the weight in Part I potassium source is 50 ~ 95% of the potassium source gross weight of aequum.
3., according to claim 2 for the preparation method of methyl-ethyl benzene Oxidative Dehydrogenation for p-methylstyrene catalyst, it is characterized in that described step 1) in source of iron be selected from least one in iron oxide red, iron oxide yellow; Part I potassium source adds with at least one form in sylvite, potassium hydroxide; Cerium source is with cerium salt; Molybdenum source adds with at least one form in the oxide of molybdenum salt, molybdenum; Tungsten source adds with at least one form in the oxide of tungsten salt, tungsten; Alkaline earth oxide adds with at least one form in alkali salt, alkaline earth oxide, alkaline earth metal hydroxide.
4., according to claim 2 for the preparation method of methyl-ethyl benzene Oxidative Dehydrogenation for p-methylstyrene catalyst, it is characterized in that described step 2) in Part II potassium source be selected from and be carried on catalyst precarsor I in the mode of at least one in potassium hydroxide aqueous solution, wet chemical.
5. according to claim 2 for the preparation method of methyl-ethyl benzene Oxidative Dehydrogenation for p-methylstyrene catalyst, it is characterized in that described perforating agent is selected from least one in graphite, polystyrene microsphere, methylcellulose, hydroxyethylcellulose, carboxymethyl cellulose, its addition is 2 ~ 6% of total catalyst weight.
6., according to claim 2 for the preparation method of methyl-ethyl benzene Oxidative Dehydrogenation for p-methylstyrene catalyst, it is characterized in that described step 1) in baking temperature be 50 ~ 120 DEG C, drying time is 2 ~ 12 hours; Sintering temperature is preferably 700 ~ 850 DEG C, and roasting time is preferably 4 ~ 12 hours.
7., according to claim 2 for the preparation method of methyl-ethyl benzene Oxidative Dehydrogenation for p-methylstyrene catalyst, it is characterized in that described step 2) in dipping time be 2 ~ 24 hours; Dry temperature is 80 ~ 150 DEG C, and drying time is 2 ~ 12 hours.
8., to a method for methyl-ethyl benzene Oxidative Dehydrogenation p-methylstyrene, it is characterized in that p-methylstyrene is prepared in the catalyst exposure reaction described in raw material and claim 1.
9. the method to methyl-ethyl benzene Oxidative Dehydrogenation p-methylstyrene according to claim 8, is characterized in that described raw material comprises steam and to methyl-ethyl benzene.
10. the method to methyl-ethyl benzene Oxidative Dehydrogenation p-methylstyrene according to claim 9, is characterized in that the condition of described reaction is: reaction pressure is normal pressure, liquid air speed 0.5 ~ 2.5 hour
-1, temperature 580 ~ 640 DEG C, steam/to the weight ratio of methyl-ethyl benzene is 1.0 ~ 4.0.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111054369A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of alkyl aromatic hydrocarbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111054369A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of alkyl aromatic hydrocarbon |
| CN111054369B (en) * | 2018-10-16 | 2021-05-11 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of alkyl aromatic hydrocarbon |
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