CN101279269A - Low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane - Google Patents
Low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane Download PDFInfo
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- CN101279269A CN101279269A CNA2007100390498A CN200710039049A CN101279269A CN 101279269 A CN101279269 A CN 101279269A CN A2007100390498 A CNA2007100390498 A CN A2007100390498A CN 200710039049 A CN200710039049 A CN 200710039049A CN 101279269 A CN101279269 A CN 101279269A
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Abstract
The invention relates to a catalyst for preparing styrene by phenylethane catalytic dehydrogenation with a low water ratio which mainly solves the problem that the low-kalium catalyst in the prior art is easy to accumulate carbon and has poor stability and low activity under a low water ratio condition. The present invention adopts a technical proposal of adding bismuth oxide and berillia into a Fe-K-Ce-W-Mg system, thus better solving the problem. The present invention can be used for the industrial production of styrene by phenylethane dehydrogenation.
Description
Technical field
The present invention relates to a kind of low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane.
Background technology
Ethylbenzene dehydrogenation is strong heat absorption, increase the reversible reaction of molecule.Industrial employing water vapour is made diluent to reduce the ethylbenzene dividing potential drop, impels balance to move to the product direction, and the important function of water vapour also has:
(1) provides heat to reaction;
(2) constantly get rid of the carbon deposit of catalyst surface by water gas reaction, make the catalyst automatic regeneration;
(3) reducing atmosphere that the water vapour of weak oxide can balanced reaction, the valence state of stabilizing catalyst activity component makes catalyst keep high activity, high selectivity, prolongs catalyst service life.
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, 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).
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 order of magnitude ground to increase the activity of iron oxide, and can promote water gas reaction that carbon deposit is got rid of, and makes the catalyst automatic regeneration, but potassium migration and loss easily in course of reaction, this is a major reason that causes catalysqt deactivation.If general catalyst carries out ethylbenzene dehydrogenation reaction at water under than (water/ethylbenzene) 1.7 (weight), the catalyst surface carbon deposit increases, stability and active decline.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 to improve the anti-carbon deposition ability and the activity of low potassium catalyst, reduce plant energy consumption is the target that the researcher makes great efforts always.
Summary of the invention
Technical problem to be solved by this invention is the low potassium catalyst that exists in the conventional art at low water than carbon deposit, poor stability and active low shortcoming easily under the condition, and a kind of new catalyst that is used for preparing phenylethylene from dehydrogenation of phenylethane is provided.This catalyst is used for ethylbenzene dehydrogenation reaction and not only than under has good performance at normal water, has especially at low water than good stability, active high characteristics under the condition.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane comprises following composition by weight percentage:
(a) 65～80% Fe
2O
3
(b) 7～12% K
2O;
(c) 6～10% CeO
2
(d) 0.5～5% WO
3
(e) 0.5～5% CaO;
(f) 1～5% Bi
2O
3
(g)0.5～3％BeO；
(h) surplus is a binding agent.
In the technique scheme, by weight percentage, Fe
2O
3Be made up of iron oxide red and iron oxide yellow, its proportioning is Fe
2O
3: Fe
2O
3H
2O=1～2.5: 1.One of preferred version be in the catalyst by weight percentage, also contain 0.05～1% magnesia.By weight percentage, two of preferred version for also contain in the catalyst 0.01～0.5% be selected from CuO, ZnO, TiO
2Or MnO
2In at least a.Used binding agent is selected from a kind of in kaolin, diatomite or the cement.
The used raw material of the catalyst component that the present invention relates to is as follows:
Fe
2O
3Add with iron oxide red and iron oxide yellow form; Used K adds with sylvite or potassium hydroxide form; Used Ce adds with cerium oxide, cerium hydroxide or cerium salt form; Used W adds with its salt or oxide form; Used Bi adds with oxide form; Used Be adds with beryllium oxide, beryllium hydroxide or beryllium nitrate 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, sodium carboxymethylcellulose, and its addition is 1～5% of a total catalyst weight; The binding agent addition is 0.5～5% 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 that will add by Fe, K, Ce, W, Bi, Be and the need of proportioning weighing mixes, add an amount of deionized water, make the face dough of toughness, suitable extrusion, through extrusion, drying, pelletizing becomes 3 millimeters of diameters, long 5～8 millimeters particle, in 80 ℃～120 ℃ dryings 2 hours, 150 ℃～300 ℃ following roastings 2 hours, 500 ℃～1000 ℃ 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, selectivity of styrene calculate as follows:
The present invention adopts the technical scheme of adding bismuth component and beryllium oxide in iron-potassium-cerium-tungsten-calcium catalyst system and catalyzing, and the electronics that has improved on the one hand between active sites transmits channel, makes Fe
2+And Fe
3+Between mutual conversion stabilisation, promoted catalyst oxygen to shift dehydrogenation and direct dehydrogenation reactive activity, promoted the formation of ferripotassium spinelle on the other hand, stablized potassium, reversed general catalyst at low water than the predicament of performing poor under the condition, this catalyst is used for dehydrogenation of ethylbenzene to styrene and not only than under has good performance at normal water, conversion of ethylbenzene is higher than 77.0%, selectivity of styrene reaches 95.3%, have especially at low water than good stability under the condition, active high characteristics, catalyst remains unchanged than 400 hours conversion of ethylbenzene of the following operation continuously of 1.7 (weight) at water, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 310.0 gram iron oxide reds, 160.0 gram iron oxide yellow, 62.0 gram potash, 74.2 gram cerium oxalate, 9.2 gram ammonium tungstate, 14.3 gram calcium carbonate, 8.0 gram bismuth oxide, 5.2 gram beryllium hydroxide, 1.0 gram magnesia, 0.2 gram titanium oxide, 4.0 gram cement and 12.0 gram sodium carboxymethylcelluloses stirred in kneader 1 hour, add deionized water, mix and stir half an hour again, take out extrusion, dry, pelletizing becomes 3 millimeters of diameters, long 5～8 millimeters particle, put into baking oven, in 100 ℃ of dryings 2 hours, place muffle furnace 200 ℃ of following roastings 2 hours then, 900 ℃ of following roastings 4 hours, obtain finished catalyst.
With 100 milliliters of catalyst reactor of packing into, normal pressure, liquid air speed 1.0 hours
-1, 620 ℃, water are than carrying out activity rating under (weight) 2.0 and 1.7 conditions, test result is listed in table 1.
[embodiment 2]
Method by embodiment 1 prepares catalyst, and different is with 300.0 gram iron oxide reds, 150.0 gram iron oxide yellows, 65.0 gram potash, 102.6 gram cerous nitrates, 8.0 gram tungstic acids, 8.0 gram calcium oxide, 12.0 gram bismuth oxides, 8.0 gram beryllium oxide, 1.0 gram magnesia, 0.6 gram zinc oxide, 0.6 gram cupric oxide, 6.0 gram kaolin and 11.0 gram graphite.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
[embodiment 3]
Method by embodiment 1 prepares catalyst, and different is with 230.0 gram iron oxide reds, 150.0 gram iron oxide yellows, 75.0 gram potash, 123.0 gram cerous nitrates, 18.4 gram ammonium tungstates, 21.4 gram calcium carbonate, 22.0 gram bismuth oxides, 12.0 gram beryllium oxide, 5.0 gram magnesia, 1.2 gram cupric oxide, 1.2 manganese oxide, 8.0 gram cement and 13.0 gram sodium carboxymethylcelluloses.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
[embodiment 4]
Method by embodiment 1 prepares catalyst, and different is with 220.0 gram iron oxide reds, 150.0 gram iron oxide yellows, 85.0 gram potash, 45.0 gram cerium oxide, 12.0 gram tungstic acids, 17.0 gram calcium oxide, 18.0 gram bismuth oxides, 15.0 gram beryllium oxide, 3.0 gram magnesia, 0.6 gram manganese oxide, 12.0 gram diatomite and 15.0 gram polystyrene microspheres.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
[embodiment 5]
Method by embodiment 1 prepares catalyst, and different is with 332.0 gram iron oxide reds, 135.0 gram iron oxide yellows, 68.0 gram potash, 92.8 gram cerium oxalates, 17.3 gram ammonium tungstates, 46.4 gram calcium carbonate, 13.0 gram bismuth oxides, 20.0 gram beryllium oxide, 21.0 gram cement and 19.1 gram sodium carboxymethylcelluloses.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
[embodiment 6]
Method by embodiment 1 prepares catalyst, and different is with 350.0 gram iron oxide reds, 180.0 gram iron oxide yellows, 82.0 gram potash, 55.0 gram cerium oxide, 7.0 gram tungstic acids, 9.0 gram calcium oxide, 12.0 gram magnesia, 7.0 gram bismuth oxides, 12.0 gram beryllium oxide, 28.0 gram kaolin and 22.2 gram graphite.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
The weight percent of gained catalyst is composed as follows:
[comparative example 1]
Method by embodiment 4 prepares catalyst, and different is not add bismuth oxide, beryllium oxide, magnesia and manganese oxide.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
[comparative example 2]
Method by embodiment 5 prepares catalyst, and different is not add bismuth oxide and beryllium oxide.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
[comparative example 3]
Method by embodiment 6 prepares catalyst, and different is not add bismuth oxide, beryllium oxide and magnesia.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
The weight percent of gained catalyst is composed as follows:
The contrast of table 1 catalyst performance
Above embodiment explanation, in iron-potassium-cerium-tungsten-calcium catalyst system and catalyzing, add bismuth component and beryllium oxide, improved low potassium catalyst and hanged down water, can be used for the normal water ratio and hang down water preparing in the cinnamic industrial production than ethylbenzene catalytic dehydrogenation under the condition than the stability under the condition and active.This catalyst uses than under the condition at low water, has obvious energy-saving effect, is a kind of recommendable energy-saving catalyst.
Claims (5)
1. low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane comprises following composition by weight percentage:
(a) 65～80% Fe
2O
3
(b) 7～12% K
2O;
(c) 6～10% CeO
2
(d) 0.5～5% WO
3
(e) 0.5～5% CaO;
(f) 1～5% Bi
2O
3
(g)0.5～3％BeO；
(h) surplus is a binding agent.
2. according to the described low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane of claim 1, it is characterized in that Fe
2O
3By Fe
2O
3And Fe
2O
3H
2O forms, and proportioning is Fe with the weight ratio
2O
3: Fe
2O
3H
2O=1～2.5: 1.
3. according to the described low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane of claim 1, it is characterized in that by weight percentage, also contain 0.05～1% magnesia in the catalyst.
4. according to the described low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane of claim 1, it is characterized in that by weight percentage, also contain in the catalyst 0.01～0.5% be selected from CuO, ZnO, TiO
2Or MnO
2In at least a.
5. according to the described low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane of claim 1, it is characterized in that binding agent is selected from a kind of in kaolin, diatomite or the cement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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|---|---|---|---|
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| CN101279269B CN101279269B (en) | 2010-10-27 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040466B (en) * | 2009-10-13 | 2012-10-10 | 中国石油化工股份有限公司 | Method for preparing styrene through ethylbenzene dehydrogenation |
| CN101993336B (en) * | 2009-08-31 | 2013-01-09 | 中国石油化工股份有限公司 | Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition |
| CN109569639A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | It is used to prepare the dehydrogenation and preparation method thereof of styrene |
| CN110681392A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
| CN112237920A (en) * | 2019-07-16 | 2021-01-19 | 中国石油化工股份有限公司 | Ultralow-potassium-content low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5023225A (en) * | 1989-07-21 | 1991-06-11 | United Catalysts Inc. | Dehydrogenation catalyst and process for its preparation |
| JPH04277030A (en) * | 1991-03-05 | 1992-10-02 | Nissan Gaadoraa Shokubai Kk | Ethylbenzene dehydrogenation catalyst |
| CN1204098C (en) * | 2002-03-13 | 2005-06-01 | 中国石油化工股份有限公司 | Oxide catalyst for ethylbenzene dehydrogenation to prepare styrene |
| CN1302847C (en) * | 2003-09-03 | 2007-03-07 | 中国石油化工股份有限公司 | Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene |
| CN100490971C (en) * | 2005-01-26 | 2009-05-27 | 中国石油化工股份有限公司 | Oxide catalyst for dehydrogenating ethyl benzene to prepare styrene |
-
2007
- 2007-04-04 CN CN2007100390498A patent/CN101279269B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993336B (en) * | 2009-08-31 | 2013-01-09 | 中国石油化工股份有限公司 | Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition |
| CN102040466B (en) * | 2009-10-13 | 2012-10-10 | 中国石油化工股份有限公司 | Method for preparing styrene through ethylbenzene dehydrogenation |
| CN109569639A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | It is used to prepare the dehydrogenation and preparation method thereof of styrene |
| CN109569639B (en) * | 2017-09-29 | 2020-06-09 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for preparing styrene and preparation method thereof |
| CN110681392A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
| CN112237920A (en) * | 2019-07-16 | 2021-01-19 | 中国石油化工股份有限公司 | Ultralow-potassium-content low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
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