CN1810369A - Dehydrogenating catalyst for preparing alkyl alkenyl arene - Google Patents
Dehydrogenating catalyst for preparing alkyl alkenyl arene Download PDFInfo
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- CN1810369A CN1810369A CNA2005100236123A CN200510023612A CN1810369A CN 1810369 A CN1810369 A CN 1810369A CN A2005100236123 A CNA2005100236123 A CN A2005100236123A CN 200510023612 A CN200510023612 A CN 200510023612A CN 1810369 A CN1810369 A CN 1810369A
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Abstract
The present invention relates to one kind of alkyl arene preparing dehydrogenating catalyst and aims at avoiding potassium loss of catalyst during reaction, raising the carbon deposit resistance of catalyst and increasing catalyst life. The technological scheme of the present invention includes replacing partial soluble potassium compound in the Fe-K-Ce-Mo catalyst system with potash feldspar, and adding carbon separation resisting assistant to inhibit carbon separation reaction to the Fe-K-Ce-Mo catalyst system. The dehydrogenating catalyst system may be used in industrial alkyl arene preparing production.
Description
Technical field
The present invention relates to a kind of dehydrogenation that is used to prepare alkyl alkenyl arene, particularly about being used for the catalyst of ethyl benzene dehydrogenation preparation of styrene.
Background technology
Ethylbenzene dehydrogenation is strong heat absorption, increase the reversible reaction of molecule.Industrial common employing inert gas is made diluent to reduce the ethylbenzene dividing potential drop, impels reaction to move to the product direction.The acting body of water vapour in production of styrene is present:
(1) the heating reaction raw materials is avoided ethylbenzene directly is heated to higher temperature to temperature required, suppresses the generation of side reaction;
(2) additional heat is in order to avoid owing to endothermic heat of reaction is lowered the temperature;
(3) reduce the ethylbenzene dividing potential drop, impel balance to move to the styrene direction;
(4) constantly get rid of carbon deposit on the catalyst by water gas reaction, make the catalyst automatic regeneration.
But the water vapour addition is subjected to the reaction system authorized pressure falls restriction with these two factors of energy consumption.Production of styrene consumes a large amount of water vapours as the dehydrogenation medium, and energy consumption is big, the product condensation number is big, process device expense height, and production cost is high.Advanced ethylbenzene dehydrogenation technology is all pursued with lower water and is obtained higher styrene yield than (ratio of water vapour and the quality of ethylbenzene in the charging), and whether advanced the water vapour unit consumption has become weighs ethylbenzene dehydrogenation process route important evaluation index.Reduce water than except energy-conservation, can also alleviate after-treatment system pressure, reduce the load of commercial plant weak link-steam superheater, help the device long-term operation.
Phenylethylene catalyst is to be that main active component, potassium oxide are the Fe-series catalyst of main co-catalyst with the iron oxide.Potassium can become the activity of order of magnitude ground increase iron oxide, and can promote water gas reaction that carbon deposit is got rid of, made the catalyst automatic regeneration, but potassium migration and loss easily in course of reaction, this is a major reason that causes catalysqt deactivation.Carry out the alkyl aromatics dehydrogenation reaction under 2.0 (weight) if general catalyst is lower than than (water/ethylbenzene) at water, water gas reaction speed is slack-off, and the catalyst surface carbon deposit increases, and catalytic activity has decline significantly.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 magnesia that adds 1.8～5.4% (weight) in catalyst as disclosed European patent 0177832, catalyst can be lower than under 2.0 (weight) at the water ratio and shows stable premium properties, but the potassium content of this catalyst is higher.Reported that as laid-open U.S. Patents 4535067 a part of potassium adds with kaliophilite double salt form in the catalyst, but this catalyst conversion ratio is less than 65% in the time of 614 ± 2 ℃, selectivity is the highest by 93%, singly can not receive 60%, and is relatively low.And, do not relate to life of catalyst.Therefore, how the potassium in the fixed catalyst in course of reaction improves the catalyst anti-carbon deposition ability, is the target that the researcher makes great efforts at low water than implement device long-term operation under the condition always.
Summary of the invention
Technical problem to be solved by this invention is that migration and the loss easily in course of reaction of potassium in the catalyst that exists in the conventional art, catalyst anti-carbon deposition ability are not high, influence the catalyst problem in service life, a kind of new dehydrogenation that is used to prepare alkyl alkenyl arene is provided.This catalyst is used for the dehydrogenating alkyl arene in preparing alkyl alkenyl arene reaction and has good stability, the characteristics of catalyst long service life.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of dehydrogenation that is used to prepare alkyl alkenyl arene comprises following component by weight percentage:
(a) 60～87% Fe
2O
3
(b) 6～15% K
2O;
(c) 5～10% CeO
2
(d) 0.5～5% MoO
3
(e) 0.5～5% La
2O
3
(f) 0.001～8% at least a oxide that is selected from Cu, Sn, Pb, Ni;
Wherein 15～35% of the potassium oxide weight consumption derive from potassic feldspar.
In the technique scheme, by weight percentage, the catalyst preferred version is also to contain 0.5～10% magnesia in the catalyst, and more preferably scheme is also to contain 0.5～3.0% magnesia in the catalyst.By weight percentage, the oxide consumption preferable range of at least a Cu of being selected from, Sn, Pb, Ni is 0.005～5%.
The used raw material of the catalyst component that the present invention relates to is as follows:
Fe
2O
3Formed by iron oxide red and iron oxide yellow; Used K adds with sylvite or hydroxide form, and wherein a part of potassium is with potassic feldspar (KAlSi
3O
8) the form adding; Used Ce adds with oxide, hydroxide or cerium salt form; Used Mo adds with its salt or oxide form; Used La adds with oxide form; Remaining element adds with its salt or oxide form.In preparation process of the present invention, except that the catalyst body composition, also should add perforating agent and binding agent, perforating agent can be selected from graphite, polystyrene microsphere, carboxymethyl cellulose, and its addition is 2～6% of a total catalyst weight; Binding agent can be selected from kaolin, diatomite or cement, and its addition is 1～6% of a total catalyst weight.
Method for preparing catalyst of the present invention is as follows:
After other catalyst component, binding agent and the perforating agent of will be by the pressed powder of Fe, the Ce of proportioning weighing, Mo, potassic feldspar and needing to add mixes, add proper amount of deionized water, make the face dough of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 8～10 millimeters particle, in 80～120 ℃ of dryings 4 hours, 500～1000 ℃ of following roastings 4 hours, just can obtain finished catalyst then.
The catalyst that makes as stated above carries out activity rating in the isotherm formula fixed bed, for the catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene activity rating, process is summarized as follows:
Deionized water and ethylbenzene are imported preheating mixer through measuring pump respectively, and preheating enters reactor after being mixed into gaseous state, and reactor adopts the heating wire heating, makes it to reach predetermined temperature.Reactor inside diameter is 1 " stainless steel tube, it is interior that to load 100 milliliters, particle diameter be 3 millimeters catalyst.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:
The present invention replaces the potassium compound of a part of solubility by adopt potassic feldspar in iron-potassium-cerium-molybdenum system, and part potassium source is provided, and introduces carbon resistance auxiliary agent lanthana simultaneously.Under the water vapour condition, complex compound slowly decomposes the caustic potash that discharges low concentration, and the rate of release of control potassium promotes the removing of carbon deposit.Because this catalyst has improved the stability of potassium, than not only having good activity and selectivity under the condition, and anti-carbon deposition ability is strong, can satisfy the needs of long-term operation, has obtained better technical effect at low water for the gained catalyst.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 260.0 gram iron oxide reds, 118.0 gram iron oxide yellow, 50.0 gram potash, 60.0 gram potassic feldspar, 100.0 gram cerous nitrate, 11.5 gram ammonium molybdate, 7.8 gram lanthana, 6.0 gram magnesia, 3.6 gram cupric oxide, 2.6 gram tin oxide and 24.0 gram cement, 12.0 the gram carboxymethyl cellulose stirred in kneader 1 hour, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into 3 millimeters of diameters, the particle that length is 8～10 millimeters, put into baking oven, 80 ℃ were dried by the fire 2 hours, 120 ℃ were dried by the fire 2 hours, place muffle furnace then, obtained finished catalyst in 4 hours in 900 ℃ of roastings.
With 100 milliliters of catalyst reactor of packing into, than carrying out activity rating under the condition, the evaluating catalyst condition is as follows at low water: normal pressure, liquid air speed 1.0 hours
-1, 620 ℃, water are than carrying out activity rating under (weight) 1.7 conditions, activity rating the results are shown in table 1.
[embodiment 2]
Method by embodiment 1 prepares catalyst, and different is with 340.0 gram iron oxide reds, 150.0 gram iron oxide yellows, 40.0 gram potash, 90.0 gram potassic feldspars, 64.3 gram cerium oxalates, 5.0 gram ammonium molybdates, 7.8 gram lanthanas, 8.0 gram magnesia, 1.6 gram cupric oxide, 2.6 gram lead oxide and 24.0 gram cement, 12.0 gram carboxymethyl celluloses.
Condition by embodiment 1 is carried out activity rating, and evaluation result is listed in table 1.
[embodiment 3]
Method by embodiment 1 prepares catalyst, and different is with 240.0 gram iron oxide reds, 150.0 gram iron oxide yellows, 55.0 gram potash, 160.0 gram potassic feldspars, 125.0 gram cerous nitrates, 10.0 gram ammonium molybdates, 16.1 gram lanthanas, 6.4 gram magnesia, 3.2 gram tin oxide, 2.6 gram nickel oxide and 26.0 gram cement, 18.0 gram carboxymethyl celluloses.
Condition by embodiment 1 is carried out activity rating, and evaluation result is listed in table 1.
[embodiment 4]
Method by embodiment 1 prepares catalyst, and different is with 320.0 gram iron oxide reds, 150.0 gram iron oxide yellows, 60.0 gram potash, 320.0 gram potassic feldspars, 120.0 gram cerous nitrates, 12.5 gram ammonium molybdates, 5.8 gram lanthanas, 8.2 gram magnesia, 3.0 gram cupric oxide, 3.0 gram nickel oxide and 16.0 gram cement, 21.0 gram carboxymethyl celluloses.
Condition by embodiment 1 is carried out activity rating, and evaluation result is listed in table 1.
[embodiment 5]
Method by embodiment 1 prepares catalyst, and different is with 280.0 gram iron oxide reds, 148.0 gram iron oxide yellows, 110.0 gram potash, 50.0 gram potassic feldspars, 95.0 gram cerous nitrates, 9.2 gram ammonium molybdates, 25.1 gram lanthanas, 8.1 gram magnesia, 4.2 gram lead oxide, 2.1 gram nickel oxide and 16.0 gram cement, 18.0 gram carboxymethyl celluloses.
Condition by embodiment 1 is carried out activity rating, and evaluation result is listed in table 1.
The weight percent of gained catalyst is composed as follows:
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Fe 2O 3 K 2O (deriving from potash) K 2O (deriving from potassic feldspar) CeO 2 MoO 3 La 2O 3 MgO CuO SnO 2 PbO 2 Ni 2O 3 | 72.46 7.08 1.25 8.11 1.95 1.62 1.25 0.75 0.54 - - | 80.78 4.87 1.61 5.58 0.73 1.39 1.43 0.29 - 0.46 - | 68.45 7.18 3.07 9.35 1.56 3.07 1.23 - 0.61 - 0.50 | 72.31 6.82 5.34 7.82 1.70 0.97 1.37 0.50 - - 0.50 | 68.61 13.07 0.87 6.46 1.31 4.36 1.43 - - 0.73 0.37 |
[comparative example 1]
Method by embodiment 1 prepares catalyst, and different is with 340.0 gram iron oxide reds, 150.0 gram iron oxide yellows, 60.0 gram potash, 90.0 gram potassic feldspars, 64.3 gram cerium oxalates, 5.0 gram ammonium molybdates, 7.8 gram lanthanas, 8.0 gram magnesia, 1.6 gram cupric oxide, 2.6 gram lead oxide and 24.0 gram cement, 12.0 gram carboxymethyl celluloses.
Condition by embodiment 1 is carried out activity rating, and evaluation result is listed in table 1.
[comparative example 2]
Method by embodiment 1 prepares catalyst, and different is with 240.0 gram iron oxide reds, 150.0 gram iron oxide yellows, 75.0 gram potash, 125.0 gram cerous nitrates, 10.0 gram ammonium molybdates, 16.1 gram lanthanas, 6.4 gram magnesia, 3.2 gram tin oxide, 2.6 gram nickel oxide and 26.0 gram cement, 12.0 gram carboxymethyl celluloses.
Condition by embodiment 1 is carried out activity rating, and evaluation result is listed in table 1.
[comparative example 3]
Method by embodiment 1 prepares catalyst, and different is with 280.0 gram iron oxide reds, 160.0 gram iron oxide yellows, 100.0 gram potash, 80.0 gram cerium oxalates, 6.0 gram ammonium molybdates, 22.9 gram lanthanas, 12.0 gram magnesia, 3.0 gram tin oxide, 3.0 gram nickel oxide and 10.0 gram cement, 16.0 gram carboxymethyl celluloses.
Condition by embodiment 1 is carried out activity rating, and evaluation result is listed in table 1.
[comparative example 4]
Method by embodiment 1 prepares catalyst, and different is with 270.0 gram iron oxide reds, 150.0 gram iron oxide yellows, 75.0 gram potash, 120.0 gram cerous nitrates, 12.5 gram ammonium molybdates, 10.2 gram cupric oxide and 32.0 gram cement, 16.0 gram carboxymethyl celluloses.
Condition by embodiment 1 is carried out activity rating, and evaluation result is listed in table 1.
The weight percent of gained catalyst is composed as follows:
| Form | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Fe 2O 3 K 2O CeO 2 MoO 3 La 2O 3 MgO CuO SnO 2 PbO 2 Ni 2O 3 | 80.12 7.24 5.53 0.72 1.38 1.42 0.28 - 0.46 - | 68.76 9.84 9.39 1.57 3.08 1.23 - 0.62 - 0.50 | 71.26 12.02 6.85 0.86 4.06 2.12 - 0.53 - 0.53 | 71.95 9.53 8.74 1.90 - - 1.90 - - - |
The low water of table 1 is than the stability of catalyst under the condition
| Catalyst | Water is than (weight) | Reaction time | |||
| 100 hours | 500 hours | ||||
| Conversion ratio % | Selectivity % | Conversion ratio % | Selectivity % | ||
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 comparative examples 1 comparative example 2 comparative examples 3 comparative examples 4 | 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 | 76.2 76.0 76.3 75.7 76.2 76.0 76.1 76.0 75.9 | 94.9 94.6 95.0 94.9 94.8 94.6 94.9 95.0 94.7 | 75.1 75.1 75.5 74.8 74.7 74.0 73.9 73.7 72.4 | 94.8 94.7 95.1 94.8 94.7 94.5 95.0 94.8 94.5 |
Above embodiment explanation, in the Fe-K-Ce-Mo system, potassium compound with potassic feldspar instead of part solubility, in reaction, slowly discharge potassium, reduce the migration and the bleed rate of potassium, introduce the anti-charcoal auxiliary agent of analysing simultaneously, suppress to analyse the charcoal reaction, than not only having good activity and selectivity under the condition, and anti-carbon deposition ability is strong, has satisfied the needs of commercial plant long-term operation at low water for the gained catalyst.This catalyst component is simple, and preparation easily.
Claims (4)
1, a kind of dehydrogenation that is used to prepare alkyl alkenyl arene comprises following component by weight percentage:
(a) 60～87% Fe
2O
3
(b) 6～15% K
2O;
(c) 5～10% CeO
2
(d) 0.5～5% MoO
3
(e) 0.5～5% La
2O
3
(f) 0.001～8% at least a oxide that is selected from Cu, Sn, Pb, Ni;
Wherein 15～35% of the potassium oxide weight consumption derive from potassic feldspar.
2, according to the described dehydrogenation that is used to prepare alkyl alkenyl arene of claim 1, the consumption that it is characterized in that the oxide of at least a by weight percentage Cu of being selected from, Sn, Pb, Ni is 0.005～5%.
3,, it is characterized in that also containing 0.5～10% magnesia in the catalyst by weight percentage according to the described dehydrogenation that is used to prepare alkyl alkenyl arene of claim 1.
4,, it is characterized in that by weight percentage magnesian consumption is 0.5～3.0% in the catalyst according to the described dehydrogenation that is used to prepare alkyl alkenyl arene of claim 3.
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|---|---|---|---|
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|---|---|---|---|
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|---|---|
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| CN100391605C CN100391605C (en) | 2008-06-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602004B (en) * | 2008-06-12 | 2011-04-27 | 中国石油化工股份有限公司 | Method for preparing styrene catalyst by ethylbenzene dehydrogenation |
| CN105056966A (en) * | 2015-08-25 | 2015-11-18 | 营口市风光化工有限公司 | Catalyst for preparing styrene through ethylbenzene dehydrogenation |
| CN109569637A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst with low water ratio and preparation method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2617060A1 (en) * | 1987-06-29 | 1988-12-30 | Shell Int Research | DEHYDROGENATION CATALYST, APPLICATION TO PREPARATION OF STYRENE AND STYRENE THUS OBTAINED |
| CN1136047C (en) * | 1999-03-30 | 2004-01-28 | 中国石油化工集团公司 | Alkyl aromatics catalytic dehydrogenation catalyst |
| TWI267401B (en) * | 2002-01-30 | 2006-12-01 | Shell Int Research | A catalyst, its preparation and its use in a dehydrogenation process |
| US7244868B2 (en) * | 2002-06-25 | 2007-07-17 | Shell Oil Company | Process for the dehydrogenation of an unsaturated hydrocarbon |
-
2005
- 2005-01-26 CN CNB2005100236123A patent/CN100391605C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602004B (en) * | 2008-06-12 | 2011-04-27 | 中国石油化工股份有限公司 | Method for preparing styrene catalyst by ethylbenzene dehydrogenation |
| CN105056966A (en) * | 2015-08-25 | 2015-11-18 | 营口市风光化工有限公司 | Catalyst for preparing styrene through ethylbenzene dehydrogenation |
| CN105056966B (en) * | 2015-08-25 | 2018-09-25 | 营口风光新材料股份有限公司 | Catalyst for ethyl benzene dehydrogenation preparation of styrene |
| CN109569637A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst with low water ratio and preparation method |
| CN109569637B (en) * | 2017-09-29 | 2020-06-09 | 中国石油化工股份有限公司 | Low-water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
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| Publication number | Publication date |
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| CN100391605C (en) | 2008-06-04 |
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