CN100368364C - Multiple-step adiabatic negative dehydrogenation method for making styrene - Google Patents
Multiple-step adiabatic negative dehydrogenation method for making styrene Download PDFInfo
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- CN100368364C CN100368364C CNB2004100676237A CN200410067623A CN100368364C CN 100368364 C CN100368364 C CN 100368364C CN B2004100676237 A CNB2004100676237 A CN B2004100676237A CN 200410067623 A CN200410067623 A CN 200410067623A CN 100368364 C CN100368364 C CN 100368364C
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Abstract
The present invention relates to a multiple-step heat insulating negative dehydrogenation method which mainly solves the problems that the effects of the former technology which adopts a two-step reactor are not well, and catalytic activity and productive properties are low. The present invention fine solves the problems by the technical scheme that the present invention adopts a reaction system comprising at least two dehydrogenation reactors which are in series connected, wherein at least one reactor is filled with high activated catalyst, and at least one reactor is filled with high selectivity dehydrogenation catalysts; raw material ethylbenzene firstly passes through at least one reactor of the high activity dehydrogenation catalyst bed layer and then passes through at least one reactor which is filled with the high selectivity dehydrogenation catalyst bed layer. The present invention can be used for industrial production of the ethylbenzene dehydrogenation.
Description
Technical field
The present invention relates to a kind of cinnamic multiple-step adiabatic negative dehydrogenation method that is used to produce.
Background technology
The main reaction of ethylbenzene dehydrogenation is: C
6H
5-C
2H
5→ C
6H
5CH=CH
2+ H
2+ 124 kj/mol.It is the strong endothermic reaction that molecule number increases.From thermodynamics, improve temperature, reduce system pressure reacting favourable.Great majority adopt negative pressure device at present, but the per pass conversion of catalytic dehydrogenation is subjected to thermodynamics equilibrium limit, and reaction need at high temperature be carried out, and too high temperature of reaction not only causes the ethylbenzene cracking easily, and produce benzene, toluene, CO, CO
2Deng by product, and energy consumption is very big, and is unreasonable economically.Therefore, must select good catalyzer to solve.Therefore, since coming out the thirties 20th century of catalyst for phenylethylene dehydrogenation, people spend a large amount of energy its every performance are carried out Continual Improvement, and obtained significant progress, studied the precious metal that in the Fe-K-Ce-Mo-Mg system, adds minute quantity as laid-open U.S. Patents 6177602, thereby catalyst performance is increased substantially.
In the catalyzer R﹠D process, the researchist finds that activity of such catalysts and selectivity often are difficult to take into account, promptly active high catalyzer, and its selectivity is often lower; And the catalyzer of highly selective, its activity is often lower.How to give full play to the advantage separately of catalyzer, make catalyzer obtain the application of fullest, assistance device is obtained maximizing the benefits, also is the problem that enterprise is concerned about very much.
People also carry out overtesting to catalyst reactor type of feed radially.Report among the CN1153159A that the effect that low catalysts selective is seated in the high-selectivity catalyst upstream is undesirable, and the result is active and throughput descends.In upstream reactor, use the highly selective dehydrogenation catalyst and recommend to adopt, in the reactor in downstream, use the scheme of low catalysts selective subsequently.
Summary of the invention
Technical problem to be solved by this invention is only to adopt two section reactor in the conventional art, and be in upstream reactor, to use the highly selective dehydrogenation catalyst, in the reactor in downstream, use the scheme of low catalysts selective, effect is undesirable, the problem that catalytic activity and throughput descend provides a kind of new cinnamic multiple-step adiabatic negative dehydrogenation method that is used to produce.This method has the high characteristics of yield of excellent catalytic effect, throughput increase, alkenyl arene.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind ofly be used to produce cinnamic multiple-step adiabatic negative dehydrogenation method, the dehydrogenation reactor that comprises at least two arranged in series, wherein load high activity dehydrogenation catalysts at least one reactor, filling highly selective dehydrogenation catalyst at least one reactor, material ethylbenzene enters the reactor of at least one filling highly selective dehydrogenation catalyst bed then earlier by the reactor of at least one filling high activity dehydrogenation catalysts bed.
In the technique scheme, the dehydrogenation reactor preferred version of arranged in series is two, and material ethylbenzene enters the reactor of filling highly selective dehydrogenation catalyst bed then earlier by the reactor of a filling high activity dehydrogenation catalysts bed; Another preferred version of the dehydrogenation reactor of arranged in series is three, and material ethylbenzene enters the reactor of at least one filling highly selective dehydrogenation catalyst bed then earlier by the reactor of at least one filling high activity dehydrogenation catalysts bed; The 3rd preferred version of the dehydrogenation reactor of arranged in series is four, and material ethylbenzene enters the reactor of at least one filling highly selective dehydrogenation catalyst bed then earlier by the reactor of at least one filling high activity dehydrogenation catalysts bed.
Among the present invention, owing to adopt multiple-step adiabatic negative dehydrogenation method, promptly at least one reactor, load high activity dehydrogenation catalysts, filling highly selective dehydrogenation catalyst at least one reactor, material ethylbenzene loads the reactor of high activity dehydrogenation catalysts bed earlier by at least one, enter the reactor of at least one filling highly selective dehydrogenation catalyst bed then, the catalysis dehydrogenation activity can improve about 10%, selectivity can improve 1.2%, the vinylbenzene list is received and can be improved more than 10%, has obtained better technical effect.
Method for preparing catalyst of the present invention:
Will be by behind Fe, the K of proportioning weighing, Ce, Mo, alkaline-earth metal, B family element, A family element, tackiness agent, the perforating agent uniform mixing, add an 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 catalyzer that makes as stated above carries out activity rating in multistage insulation formula negative dehydrogenation reactor, for the ethyl benzene dehydrogenation preparation of styrene activity rating, the summary process is as follows:
This installs mainly by the raw material supply system, material vaporization superheating system, and dehydrogenation reactor system and after-treatment system several sections are formed.Its core is to guarantee that dehydrogenation reaction carries out under adiabatic, condition of negative pressure, and the entire operation process is all by computer control.Catalyzer is contained in the bottom of reactor apart from about 45 centimeters of outlet.Two anti-, three anti-, four anti-tops be provided with electrically heated in order to heat one conversely reactant gases and regulate two anti-, three anti-, four anti-temperature ins.Two anti-, three loadings and loading positions anti-, four anti-inner catalysts are same anti-, the dehydrogenation reaction gas of its outlet is squeezed into water-and-oil separator by infusion pump and is carried out automatic oily water separation after cooling off.The negative pressure of system is to be provided by vacuum pump.The loadings of every section reactor catalyst is 750 milliliters, and reaction conditions is: each section temperature in is 620 ℃, ethylbenzene air speed 0.50 hour
-1, water vapor/ethylbenzene (w/w)=1.30, reactor pressure are 50KPaA.
Phlegma is analyzed its composition with gas chromatograph.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1～5 and comparative example 1～4]
Highly active weight is consisted of Fe
2O
3(70%)-K
2O (12%)-Ce
2O
3(10%)-MoO
3(3%)-CuO (5%) catalyst A is seated in first reactor, with the Fe that consists of of highly selective
2O
3(72%)-K
2O (10%)-Ce
2O
3(9%)-WO
3(4%)-and CaO (5%) dehydrogenation catalyst B is seated in second reactor, and reaction pressure is normal pressure, liquid air speed 0.5 hour
-1, 620 ℃ of temperature of reaction, water vapor/ethylbenzene (weight)=1.30, reactor pressure is to carry out performance evaluation under the 50KPaA condition.Loadings, the appreciation condition of embodiment 2,3,4 and Comparative Examples 1,2,3,4 all kinds of catalyzer are identical with embodiment 1, and just array mode changes to some extent.Array mode sees Table 1, and evaluation result sees Table 2.
The filling scheme of two kinds of catalyzer of table 1
| First reactor | Second reactor | The 3rd reactor | The 4th reactor | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 comparative examples 1 comparative example 2 comparative examples 3 comparative examples 4 | A A A A A B B B B | B B B A B A A B A | - A B A A - B B A | - - - - B - - - - |
The effect comparison of the various schemes of table 2
| Conversion of ethylbenzene % | Selectivity of styrene % | The vinylbenzene list is received % | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 comparative examples 1 comparative example 2 comparative examples 3 comparative examples 4 | 67.14 76.24 76.02 77.19 83.73 65.32 74.76 74.67 75.16 | 97.54 96.58 96.43 95.92 93.78 97.03 96.09 96.75 96.21 | 65.49 73.63 73.30 74.04 78.52 63.38 71.83 72.24 72.31 |
The invention provides dehydrogenation catalyst assembled scheme best in a kind of multistage negative pressure adiabatic reactor, the dehydrogenation reactor that comprises three arranged in series, wherein load high activated catalyst in first reactor, load high-selectivity catalyst in second reactor, load high activated catalyst in the 3rd reactor, both helped improving the transformation efficiency of catalyzer, make reaction keep higher selectivity again, promptly improve catalytic efficiency, improve device capbility.
Claims (4)
1. one kind is used to produce cinnamic multiple-step adiabatic negative dehydrogenation method, the dehydrogenation reactor that comprises at least two arranged in series, wherein load high activity dehydrogenation catalysts at least one reactor, filling highly selective dehydrogenation catalyst at least one reactor, material ethylbenzene enters the reactor of at least one filling highly selective dehydrogenation catalyst bed then earlier by the reactor of at least one filling high activity dehydrogenation catalysts bed.
2. be used to produce cinnamic multiple-step adiabatic negative dehydrogenation method according to claim 1 is described, the dehydrogenation reactor that it is characterized in that arranged in series is two, material ethylbenzene enters the reactor of filling highly selective dehydrogenation catalyst bed then earlier by the reactor of a filling high activity dehydrogenation catalysts bed.
3. be used to produce cinnamic multiple-step adiabatic negative dehydrogenation method according to claim 1 is described, the dehydrogenation reactor that it is characterized in that arranged in series is three, material ethylbenzene enters the reactor of at least one filling highly selective dehydrogenation catalyst bed then earlier by the reactor of at least one filling high activity dehydrogenation catalysts bed.
4. be used to produce cinnamic multiple-step adiabatic negative dehydrogenation method according to claim 1 is described, the dehydrogenation reactor that it is characterized in that arranged in series is four, material ethylbenzene enters the reactor of at least one filling highly selective dehydrogenation catalyst bed then earlier by the reactor of at least one filling high activity dehydrogenation catalysts bed.
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|---|---|---|---|
| CNB2004100676237A CN100368364C (en) | 2004-10-29 | 2004-10-29 | Multiple-step adiabatic negative dehydrogenation method for making styrene |
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|---|---|---|---|
| CNB2004100676237A CN100368364C (en) | 2004-10-29 | 2004-10-29 | Multiple-step adiabatic negative dehydrogenation method for making styrene |
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|---|---|
| CN1765859A CN1765859A (en) | 2006-05-03 |
| CN100368364C true CN100368364C (en) | 2008-02-13 |
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| CN110605073B (en) * | 2018-06-15 | 2022-03-15 | 中国石油化工股份有限公司 | Catalyst loading method for olefin epoxidation process and olefin epoxidation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6177602B1 (en) * | 1998-04-01 | 2001-01-23 | United Catalysts, Inc. | Process for dehydrogenation of alkylaromatic hydrocarbons using a dehydrogenation catalyst |
| CN1064340C (en) * | 1995-06-07 | 2001-04-11 | 弗纳技术股份有限公司 | Process for dehydrogenation of ethylbenzene to styrene |
| CN1388799A (en) * | 2000-08-18 | 2003-01-01 | 三菱化学株式会社 | Process for producing styrene |
| CN1141279C (en) * | 2001-04-04 | 2004-03-10 | 中国石油化工股份有限公司 | Process for producing phenyl ethylene by ethyl benzene catalytic dehydrogenation |
-
2004
- 2004-10-29 CN CNB2004100676237A patent/CN100368364C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064340C (en) * | 1995-06-07 | 2001-04-11 | 弗纳技术股份有限公司 | Process for dehydrogenation of ethylbenzene to styrene |
| US6177602B1 (en) * | 1998-04-01 | 2001-01-23 | United Catalysts, Inc. | Process for dehydrogenation of alkylaromatic hydrocarbons using a dehydrogenation catalyst |
| CN1388799A (en) * | 2000-08-18 | 2003-01-01 | 三菱化学株式会社 | Process for producing styrene |
| CN1141279C (en) * | 2001-04-04 | 2004-03-10 | 中国石油化工股份有限公司 | Process for producing phenyl ethylene by ethyl benzene catalytic dehydrogenation |
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