CN102040466A - Method for preparing styrene through ethylbenzene dehydrogenation - Google Patents
Method for preparing styrene through ethylbenzene dehydrogenation Download PDFInfo
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Abstract
The invention relates to a method for preparing styrene through ethylbenzene dehydrogenation under the condition of a low water ratio, which mainly solves the problem that a low-potassium catalyst has poor stability under the condition of low water ratio in the prior art. In the invention, ethylbenzene is used as a raw material, the raw material and a catalyst are in contact to react to produce styrene under the conditions that the reaction air speed is 0.2-3.0/h and the weight ratio of steam/ethylbenzene is 0.5-2.5, wherein the adopted catalyst is formed by adding at least two elements of IIA-IVA families into the iron- potassium-cerium-molybdenum system, and the roasting temperature of the catalyst is 800-950 DEG C. for the technical scheme for preparing styrene through ethylbenzene dehydrogenation better solves the problem, and can be used for the industrial production of ethylbenzene dehydrogenation under the condition of low water ratio.
Description
Technical field
The present invention relates to the method for a kind of low water than ethyl benzene dehydrogenation preparation of styrene under the condition.
Background technology
Ethylbenzene dehydrogenation is strong heat absorption, increase the reversible reaction of molecule.Industrial common employing water vapor is made thinner to reduce the ethylbenzene dividing potential drop, impels reaction to move to the product direction.Water vapor has following effect in reaction: (1) reacting by heating is former to be expected temperature requiredly, avoids the ethylbenzene direct heating suppressing the generation of side reaction to higher temperature; (2) additional heat is in order to avoid owing to endothermic heat of reaction is lowered the temperature; (3) constantly get rid of carbon deposit on the catalyzer by water-gas reaction, make the catalyzer autoregeneration.(4) keep the middle mutually Fe of catalyst activity
3+Stable, prevent its over reduction, keep the stability of catalyzer.But the water vapor add-on is subjected to the reactive system authorized pressure falls restriction with these two factors of energy consumption.Advanced ethylbenzene dehydrogenation technology is all pursued with lower water and is obtained higher vinylbenzene yield than (ratio of water vapor and the quality of ethylbenzene in the charging), and adopting low water is one of energy-saving and cost-reducing important measures of styrene device than operation.
Catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene is to be that main active component, potassium oxide are the Fe-series catalyst of main promotor with the ferric oxide.Potassium can become the activity of order of magnitude ground increase ferric oxide, and can promote water-gas reaction that carbon deposit is got rid of, made the catalyzer autoregeneration, but potassium migration and loss easily in reaction process, this is a major reason that causes catalyst deactivation.Full scale plant is generally operated under the condition of adiabatic reactor, negative pressure, working pressure is 45kPa, the water ratio is 1.3, be equivalent to wait hotbed, normal pressure, reaction water than the operational condition that is 2.0, under condition of normal pressure, if being lower than under 2.0 (weight) than (water/ethylbenzene) at water, general catalyzer carries out ethylbenzene dehydrogenation reaction, water-gas reaction speed is slack-off, the catalyst surface carbon deposit increases, poor stability.To this, according to relevant reported in literature up to now, the scientific research personnel had done a lot of the trial.After having reported the magnesium oxide that adds 1.8～5.4% (weight) in catalyzer as disclosed European patent 0177832, catalyzer can be lower than under 2.0 (weight) at the water ratio and shows stable premium properties, but the potassium content of this catalyzer is higher.Reported that as laid-open U.S. Patents 4535067 a part of potassium adds with kaliophylite double salt form in the catalyzer, but this catalyzer transformation efficiency is less than 65% in the time of 614 ± 2 ℃, selectivity is the highest by 93%, singly can not receive 60%, relatively low, and, do not relate to life of catalyst.Patent CN101279269A has reported that a kind of low water compares catalyzer, but kaolin, diatomite or cement effect binding agent have been adopted in this catalyzer, though binding agent can improve the intensity of catalyzer, but the active site of the introducing meeting part covering catalyst of inert binder causes activity of such catalysts to reduce.Therefore, how suppress carbon deposit at low water in than reaction process, prevent the reduction of active phase, improve the stability of catalyzer and active simultaneously, cut down the consumption of energy is the target that the researchist makes great efforts always.
Summary of the invention
Technical problem to be solved by this invention is to use low potassium catalyzer to have poor stability, active low problem at low water than being used for ethylbenzene dehydrogenation reaction under the condition in the conventional art, provides a kind of new low water to make cinnamic method than ethylbenzene dehydrogenation under the condition.This method is used for ethyl benzene dehydrogenation preparation of styrene when reaction, has at low water than under the condition advantage that catalyst stability is good, activity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of low water is raw material than the method for ethyl benzene dehydrogenation preparation of styrene under the condition with ethylbenzene, and reaction pressure is a normal pressure, and ethylbenzene liquid air speed is for being 0.2～3.0 hour
-1, water/ethylbenzene weight ratio is that raw material contacts with catalyzer under 0.5～2.5 the condition, reaction of styrene, and used catalyzer comprises following component by weight percentage:
a)Fe
2O
3：70～85％；
b)K
2O：3～15％；
c)MoO
3：0.5～7％；
d)CeO
2：3～20％；
E) 0.01～5% oxide compound that is selected from least 2 kinds of elements among IIIA～IVA does not wherein contain binding agent in the catalyzer, and in the Preparation of catalysts process, the maturing temperature of catalyzer is 800～950 ℃.
In the technique scheme, IIIA～IVA element preferred version is for being selected from Al, Ga, Sn, Sb, Pb or Bi, and by weight percentage, its consumption preferable range is 0.1～3%, and more preferably scope is 0.1～1%.The maturing temperature preferable range is 800～900 ℃ in the catalyzer roasting process, and more preferably scope is 820～860 ℃.The weight ratio preferable range of water/ethylbenzene is 0.7～2.0, and more preferably scope is 0.8～1.8; Ethylbenzene liquid air speed preferable range is 0.4～2 hour
-1, more preferably scope is 0.6～1.5 hour
-1
The used raw material of the catalyst component that the present invention relates to is as follows:
Fe
2O
3Be made up of red iron oxide and iron oxide yellow, its proportioning is Fe
2O
3: Fe
2O
3H
2O=0.2～5: 1 is preferably 1～4.5: 1; Used K adds with sylvite or hydroxide form; Used Ce adds with oxide compound, oxyhydroxide or cerium salt form; Used Mo adds with its salt or oxide form.Remaining element adds with its salt.In preparation process of the present invention, except that the body of catalyst composition, also should add perforating agent, perforating agent can be selected from graphite, polystyrene microsphere, shuttle methylcellulose gum, and its add-on is 1～6% of a total catalyst weight.
Method for preparing catalyst of the present invention is as follows:
After will mixing by oxide compound among Fe, the K of proportioning weighing, Mo, Ce and at least two kinds of Al, Ga, Sn, Sb, Pb, the Bi and perforating agent, add an amount of deionized water, make the paste of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 8～10 millimeters particle, in 60～120 ℃ of dryings 4 hours, 400～1000 ℃ of following roastings 4 hours, just can obtain finished catalyst then.
The catalyzer that makes as stated above carries out activity rating in the isotherm formula fixed bed, for the ethyl benzene dehydrogenation preparation of styrene activity rating, the summary process is as follows:
Deionized water and ethylbenzene are imported preheating mixer through volume pump respectively, and preheating enters reactor after being mixed into gaseous state, and reactor adopts the nichrome wire heating, makes it to reach preset temperature.Reactor inside diameter is 1 cun a stainless steel tube, interiorly loads 100 milliliters, and particle diameter is 3 millimeters a catalyzer.Analyzing it with gas chromatograph by the reactant of reactor outflow behind water condensation forms.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
In ethylbenzene dehydrogenation reaction, after reaction water was than reduction, the reductibility in the reaction atmosphere strengthened.The present invention is by adding the oxide compound among at least a Al, Ga, Sn, Sb, Pb, the Bi in iron-potassium-cerium-molybdenum system, improve the bonding force between the Fe-O key, so can effectively improve the resistance to reduction of many potassium ferrites in the catalyzer, improve the resistance to reduction of catalyzer, improve active stability under the strong reducing property atmospheric condition, significantly improved low potassium catalyzer at low water than the stability under the condition, prolonged catalyzer work-ing life.The present invention is not owing to contain binding agent, in reaction process, there is more active sites to contact with reactant, have higher activity, the maturing temperature scope that the present invention adopts be 800～950 ℃ under the situation of not adding binding agent, catalyzer has kept than higher intensity.Data show the method for the present invention of using, at water than 1.6 air speed 1.0h
-1Condition under, the stability of catalyzer can reach 1000 hours, is more than doubled than in the past, than under the condition, activity can reach 79.2% at normal water, improves 2% than conventional art, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
With 272.0 gram red iron oxides, 142.0 gram iron oxide yellow, 70 gram salt of wormwood, 78 gram cerous nitrates, 9.2 gram ammonium molybdates, 0.9 gram stannic oxide (SnO
2), 1 gram ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb
2O
3), 17.6 carboxymethyl celluloses stirred in kneading machine 1 hour, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 8～10 millimeters of length, put into baking oven, 80 ℃ were dried by the fire 2 hours, 120 ℃ were dried by the fire 2 hours, placed muffle furnace then, made catalyzer in 4 hours in 900 ℃ of roastings.
With the 100ml catalyzer reactor of packing into, normal pressure, liquid air speed 1.0 hours
-1, 620 ℃, water are than carrying out activity rating under (weight) 1.5 conditions, test result is listed in table 1 and table 3.
[embodiment 2]
Method according to embodiment 1 prepares catalyzer, and different is with 290 gram red iron oxides, 100 gram iron oxide yellow, 60 gram salt of wormwood, 54 gram cerous nitrates, 4 gram magnesium oxide (MgO), 4.2 gram calcium oxide (CaO), 12 gram ammonium molybdates, 3 gram ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb
2O
3), 2 gram bismuthous oxide bismuth trioxide (Bi
2O
3) 15 gram carboxymethyl celluloses.
Evaluation method according to embodiment 1 is carried out activity rating, and test result is listed in table 1 and table 3.
[embodiment 3]
Method according to embodiment 1 prepares catalyzer, and different is with 210 gram red iron oxides, 190 gram iron oxide yellow, 52 gram salt of wormwood, 56 gram Sedemesiss, 3 gram ammonium molybdates, 4 gram bismuthous oxide bismuth trioxide (Bi
2O
3), 3 gram aluminum oxide (Al
2O
3), 18 the gram carboxymethyl celluloses.
Evaluation method according to embodiment 1 is carried out activity rating, and test result is listed in table 1 and table 3.
[embodiment 4]
Method according to embodiment 1 prepares catalyzer, and different is with 250 gram red iron oxides, 98 gram iron oxide yellow, 46 gram salt of wormwood, 132 gram Sedemesiss, 17 gram ammonium molybdates, 3 gram aluminum oxide (Al
2O
3), 3 gram plumbous oxide (PbO
2), 15 the gram carboxymethyl celluloses.
Evaluation method according to embodiment 1 is carried out activity rating, and test result is listed in table 1 and table 3.
[embodiment 5]
Method according to embodiment 1 prepares catalyzer, and different is with 260 gram red iron oxides, 140 gram iron oxide yellow, 70 gram salt of wormwood, 108 gram cerous nitrates, 9.2 gram ammonium molybdates, 1 gram stannic oxide, 1 gram aluminum oxide (Al
2O
3), 18 the gram carboxymethyl celluloses.
Evaluation method according to embodiment 1 is carried out activity rating, and test result is listed in table 1 and table 3.
[embodiment 6]
Method according to embodiment 1 prepares catalyzer, and different is with 220 gram red iron oxides, 120 gram iron oxide yellow, 80 gram salt of wormwood, 110 gram cerous nitrates, 10 gram ammonium molybdates, 2 gram stannic oxide, 3 gram ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb
2O
3), 2 gram bismuthous oxide bismuth trioxide (Bi
2O
3), 18 the gram carboxymethyl celluloses.
Evaluation method according to embodiment 1 is carried out activity rating, and test result is listed in table 1 and table 3.
[embodiment 7]
Method according to embodiment 1 prepares catalyzer, and different is with 210 gram red iron oxides, 110 gram iron oxide yellow, 80 gram salt of wormwood, 105 gram cerous nitrates, 6 gram ammonium molybdates, 1.5 gram ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb
2O
3), 2.5 gram bismuthous oxide bismuth trioxide (Bi
2O
3), 1 gram aluminum oxide (Al
2O
3), 18 the gram carboxymethyl celluloses.
Evaluation method according to embodiment 1 is carried out activity rating, and test result is listed in table 1 and table 3.
[embodiment 8]
Method according to embodiment 1 prepares catalyzer, and different is with 255 gram red iron oxides, 110 gram iron oxide yellow, 77 gram salt of wormwood, 82 gram cerous nitrates, 10 gram ammonium molybdates, 1.6 gram bismuthous oxide bismuth trioxide (Bi
2O
3), 1.2 gram aluminum oxide (Al
2O
3), 1.5 gram plumbous oxide (PbO
2), 12 the gram carboxymethyl celluloses.
Evaluation method according to embodiment 1 is carried out activity rating, and test result is listed in table 1 and table 3.
[embodiment 9]
Method according to embodiment 1 prepares catalyzer, and different is with 262 gram red iron oxides, 108 gram iron oxide yellow, 90 gram salt of wormwood, 106 gram cerous nitrates, 9.5 gram ammonium molybdates, 1.1 gram ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb
2O
3), 1.2 gram bismuthous oxide bismuth trioxide (Bi
2O
3), 1.3 gram aluminum oxide (Al
2O
3), 1.4 gram plumbous oxide (PbO
2), 16 the gram carboxymethyl celluloses.
Evaluation method according to embodiment 1 is carried out activity rating, and test result is listed in table 1 and table 3.
[embodiment 10]
Method according to embodiment 1 prepares catalyzer, and different is with 280 gram red iron oxides, 135 gram iron oxide yellow, 65 gram salt of wormwood, 77 gram cerous nitrates, 9.5 gram ammonium molybdates, 2 gram stannic oxide (SnO
2), 1.3 gram ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb
2O
3), 1.4 gram bismuthous oxide bismuth trioxide (Bi
2O
3), 1.5 gram aluminum oxide (Al
2O
3), 20 the gram carboxymethyl celluloses.
Evaluation method according to embodiment 1 is carried out activity rating, and test result is listed in table 1 and table 3.
Table 1
*The anti-crushing power of catalyzer is measured according to the technical requirements of HG/T 2782-1996 regulation among the present invention, uses DL-II type intelligence granule strength instrument.Sample selects the sample of 5 millimeters of length, is one group with 40 and tests that the arithmetical av of getting its measurement result is final anti-crushing power value, is the resistance to crusing unit of force with the Newton/millimeter.
[comparative example 1]
Method according to embodiment 1 prepares catalyzer, does not add SnO
2And Sb
2O
3
Appreciation condition according to embodiment 1 carries out activity rating, and test result is listed in table 2 and table 3.
[comparative example 2]
Method according to embodiment 2 prepares catalyzer, has added 10 gram binding agents (cement) simultaneously, does not add Sb
2O
3And Bi
2O
3
Appreciation condition according to embodiment 1 carries out activity rating, and test result is listed in table 2 and table 3.
[comparative example 3]
Method according to embodiment 3 prepares catalyzer, does not add Bi
2O
3And Al
2O
3
Appreciation condition according to embodiment 1 carries out activity rating, and test result is listed in table 2 and table 3.
[comparative example 4]
Method according to embodiment 4 prepares catalyzer, does not add Al
2O
3And PbO
2
Appreciation condition according to embodiment 1 carries out activity rating, and test result is listed in table 2 and table 3.
The weight percent of table 2 gained catalyzer is formed
| Form | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Fe 2O 3 | 81.78 | 80.0 | 84.75 | 74.54 |
| K 2O | 10.24 | 9.04 | 8.27 | 7.25 |
| CeO 2 | 6.37 | 6.56 | 6.4 | 14.98 |
| MoO 3 | 1.61 | 2.16 | 0.57 | 3.21 |
| Cement | - | 2.21 | - | - |
| Maturing temperature, ℃ | 900 | 800 | 850 | 820 |
The contrast of table 3 catalyzer dehydrogenation
| Catalyzer | Transformation efficiency % | Selectivity % | Single % that receives |
| Embodiment 1 | 76.6 | 95.6 | 73.2 |
| Embodiment 2 | 79.2 | 95.5 | 75.6 |
| Embodiment 3 | 78.5 | 95.5 | 74.9 |
| Embodiment 4 | 78.6 | 95.6 | 75.1 |
| Embodiment 5 | 77.3 | 95.0 | 73.4 |
| Embodiment 6 | 76.5 | 95.1 | 72.8 |
| Embodiment 7 | 76.8 | 94.9 | 72.9 |
| Embodiment 8 | 77.2 | 95.3 | 73.6 |
| Embodiment 9 | 78.2 | 95.5 | 74.7 |
| Embodiment 10 | 78.1 | 95.2 | 74.2 |
| Comparative Examples 1 | 72.3 | 94.3 | 68.2 |
| Comparative Examples 2 | 70.5 | 92.3 | 65.1 |
| Comparative Examples 3 | 74.2 | 94.3 | 70.0 |
| Comparative Examples 4 | 72.3 | 94.0 | 67.8 |
The catalyzer of embodiment 1 is done the performance examination under the differential responses processing condition, the results are shown in Table 4.
Table 4
The stability of table 5 catalyzer relatively
From the embodiment explanation, catalyzer of the present invention, its essentially consist is with Fe
2O
3, K
2O, CeO
2, MoO
3Be main component, by adding the oxide compound among at least a Al, Ga, Sn, Sb, Pb, the Bi, made dehydrogenation catalyst than both having had high activity, selectivity under the condition, has good stability at end water again.
Claims (4)
1. a low water is raw material than the method for ethyl benzene dehydrogenation preparation of styrene under the condition with ethylbenzene, and reaction pressure is a normal pressure, and ethylbenzene liquid air speed is 0.2～3.0 hour
-1, water/ethylbenzene weight ratio is that raw material contacts with catalyzer under 0.5～2.5 the condition, reaction of styrene, and used catalyzer comprises following component by weight percentage:
a)Fe
2O
3：70～85％；
b)K
2O：3～15％；
c)MoO
3：0.5～7％；
d)CeO
2：3～20％；
E) 0.01～5% oxide compound that is selected from least 2 kinds of elements among IIIA～IVA does not wherein contain binding agent in the catalyzer, and in the Preparation of catalysts process, the maturing temperature of catalyzer is 800～950 ℃.
2. according to the method for the described low water of claim 1 than ethyl benzene dehydrogenation preparation of styrene under the condition, it is characterized in that IIIA～IVA element is selected from Al, Ga, Sn, Sb, Pb or Bi, maturing temperature is 800～900 ℃ in the catalyst preparation process.
3. according to the method for the described low water of claim 1 than ethyl benzene dehydrogenation preparation of styrene under the condition, it is characterized in that ethylbenzene dehydrogenation reaction water/ethylbenzene weight ratio is 0.7～2.0, ethylbenzene liquid air speed is 0.4～2 hour
-1, the consumption that is selected from the oxide compound of at least 2 kinds of elements among IIIA～IVA by weight percentage is 0.1～3%, maturing temperature is preferably 820～860 ℃ in the catalyst preparation process.
4. according to the method for the described low water of claim 3 than ethyl benzene dehydrogenation preparation of styrene under the condition, it is characterized in that ethylbenzene dehydrogenation reaction water/ethylbenzene weight ratio is 0.8～1.8, ethylbenzene liquid air speed is 0.6～1.5 hour
-1, the oxide compound consumption that is selected from least 2 kinds of elements among IIIA～IVA by weight percentage is 0.1～1%.
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| CN107790145A (en) * | 2016-09-06 | 2018-03-13 | 中国石油化工股份有限公司 | Prepare catalyst of alkyl alkenyl arene and its preparation method and application |
| CN107790145B (en) * | 2016-09-06 | 2023-06-06 | 中国石油化工股份有限公司 | Catalyst for preparing alkenyl arene and preparation method and application thereof |
| CN106994353A (en) * | 2017-04-24 | 2017-08-01 | 苏州拓瑞特新材料有限公司 | One kind is free of binding agent high intensity ethylbenzene dehydrogenation catalyst with low water ratio |
| CN106955682A (en) * | 2017-04-24 | 2017-07-18 | 苏州拓瑞特新材料有限公司 | Ethylbenzene dehydrogenation catalyst with low water ratio |
| CN111054375A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Diethylbenzene dehydrogenation catalyst, preparation method and application |
| CN115487833A (en) * | 2021-06-18 | 2022-12-20 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation under low water ratio environment, preparation method and application thereof, and ethylbenzene dehydrogenation method |
| CN115487833B (en) * | 2021-06-18 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation in low water ratio environment, preparation method and application thereof and ethylbenzene dehydrogenation method |
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