CN103030521A - Method for preparing styrene through ethylbenzene dehydrogenation - Google Patents
Method for preparing styrene through ethylbenzene dehydrogenation Download PDFInfo
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- CN103030521A CN103030521A CN2011103006082A CN201110300608A CN103030521A CN 103030521 A CN103030521 A CN 103030521A CN 2011103006082 A CN2011103006082 A CN 2011103006082A CN 201110300608 A CN201110300608 A CN 201110300608A CN 103030521 A CN103030521 A CN 103030521A
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Abstract
The invention relates to a method for preparing styrene through ethylbenzene dehydrogenation and mainly solves the problem of low reaction activity caused by high catalyst bed layer resistance drop because of low compressive strength and poor pulverization resistance performance of catalysts in the prior art. According to the method, ethylbenzene is adopted as raw materials, a catalytic system containing Fe-K-Ce-Mo(W) is adopted, threaded or annular fluted catalysts with different widths, depths and shapes at the axial periphery are produced, and the ethylbenzene is converted into styrene through catalytic reaction under the conditions that the weight space velocity of liquid is 0.1 to 2.5 h<-1>, the reaction temperature is 580 to 645 DEG C, the reaction pressure is 0.04 to 0.1 MPa, and the water/hydrocarbon weight ratio is 1.0 to 3.0. Through the technical scheme, the problems are perfectly solved, and the method can be used in the industrial production of styrene production through ethylbenzene.
Description
Technical field
The present invention relates to a kind of method that adopts special-shaped catalyst to be used for ethyl benzene dehydrogenation preparation of styrene.
Background technology
Vinylbenzene as one of most important raw material of basic organic synthesis, industrial 85 percent by benzene and pure ethylene or dry gas alkylated reaction occurs in the presence of the catalyzer generate ethylbenzene after under negative pressure catalytic dehydrogenation realize that the essentially consist of used phenylethylene catalyst comprises Primary Catalysts, promotor and pore-creating agent, toughener etc.At present by a lot of production of styrene in countries in the world producer adopt be early eighties succeed in developing take Fe-K-Ce-Mo as essentially consist serial compound/mixed oxide catalyst, the preparation method of catalyzer is general adopt with the catalyst components such as Fe, K, Ce, Mo with the form solid phase mixing of oxide compound or salt, add water kneading, extrusion, drying, roasting and form, such as published US Patent No. 4804799, US5023225 and US5190906 etc.The characteristics of this type of catalyzer are: active, selectivity is higher, stability better, and environmental friendliness is generally 2 years work-ing life.But its Main Problems is that the specific surface utilization ratio is not high enough, cause the active on the low side of catalyzer, US Patent No. 04328130, US5097091 and some bibliographical informations substitute traditional cylinder shape catalyst with special-shaped catalyst, although make moderate progress aspect catalyst activity, the ultimate compression strength of catalyzer, anti-efflorescence and wear resistance are not high enough.
Increase reaction because ethyl benzene dehydrogenation preparation of styrene is molecule number, device vacuum tightness is higher more favourable to generating vinylbenzene, because the ultimate compression strength of catalyzer is bad, easily efflorescence certainly will cause bed pressure drop to rise, and directly affects transformation efficiency; And at present styrene device has tended to maximize, and capacity expansion revamping also often adopts on original old device increases a reactor, becomes two sections and is three sections mode, so can all propose requirements at the higher level to ultimate compression strength and the resistance to chalking of catalyzer.On the other hand, because what ethylbenzene dehydrogenation related to is more macromolecular reaction, the internal diffusion of reactant and product directly affects the catalyst reaction process, when catalyst component was updated, determining the catalyst performance quality and affect the catalyst pores distribution in catalyzer work-ing life also should be important research and development factor.The most of pore distribution of existing catalyzer is unreasonable, often aperture is more, this class aperture is easily coking and stop up in reaction process, catalytic activity reduces, affecting catalyzer work-ing life, is that the utmost point has Important Economic to be worth and the pressing issues of application prospect so how further to improve ethyl benzene dehydrogenation preparation of styrene efficient.
Summary of the invention
Technical problem to be solved by this invention be exist the ultimate compression strength of catalyzer low in the prior art, resistance to chalking can be bad and the beds resistance drop that causes is high, active low problem induces reaction.A kind of new method that is used for ethyl benzene dehydrogenation preparation of styrene is provided.The catalyzer that uses in the method has the selectivity of high conversion of ethylbenzene, high-phenylethylene and the characteristics of 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 method for ethyl benzene dehydrogenation preparation of styrene, take ethylbenzene as raw material, it is 580～640 ℃ in temperature of reaction, reaction pressure is 0.04～0.1MPa, water/hydrocarbon weight ratio is 1.0～3.0, and the raw material liq air speed is 0.1～2.5 hour
-1Condition under, raw material contacts with catalyzer by beds, reaction of styrene;
Wherein the active ingredient of catalyst system therefor part comprises following component by weight percentage: 55～85% Fe
2O
3, 5～30% K
2O, 1～3% MoO
3Or WO
3In at least a, 3～15% Ce
2O
3Catalyzer is the axial outer bar that is with width, the depth, variform screw thread or endless groove line.
In the technique scheme, the outside diameter preferable range of catalyzer is 2～8mm.The catalyzer axially groove line cross-sectional geometry preferred version of periphery is trilateral, rectangle, trapezoidal or all kinds of combinations garden shape.The dark preferable range of groove line of catalyzer is 0.1～4mm.The wide preferable range of groove line of catalyzer is 0.1～3mm.The groove line spacing preferable range of catalyzer is 1～5mm.
Wherein catalyst system therefor is except comprising above active ingredient, in the Kaolinite Preparation of Catalyst process, can also add with catalyst weight count 1～5% be selected from the pore-creating agents such as graphite, polystyrene microsphere, carboxymethyl cellulose, methylcellulose gum or sesbania powder have at least a kind of, the outside diameter of catalyzer is 2～8mm, is preferably 3～5mm.
In the technique scheme, water/hydrocarbon weight ratio preferable range is 1.5～2.0; The temperature of reaction preferable range is 590～640 ℃; The preferred pressure preferable range is 0.05～0.1MPa; Raw material liq air speed preferable range is 0.35～2.0 hour-1.
The raw material of catalyst system therefor component of the present invention can be as follows:
Fe
20
3All derive from and do not add binding agent cement in iron oxide red and the catalyst preparation process.Potassium adds with the form of sylvite, and cerium adds with the composite form of oxide compound, oxyhydroxide, metal-salt or above-mentioned several compounds, and other component adds with the form of its oxide compound, oxyhydroxide or its salt.
The concrete operation method of catalyst system therefor preparation is as follows in the inventive method:
After will evenly mixing by Fe, K, Ce, Mo (or W) and the perforating agent of proportioning weighing, add an amount of deionized water, wet mixing becomes piece, the banded extruder that is equipped with special card extrude catalyzer axially outside be with the bar of width, the depth, variform screw thread or endless groove line, in 40～150 ℃ of dryings 1～10 hour, the catalyzer raw material are made in pelletizing again, and raw material are made finished catalyst through 700～950 ℃ of roastings after 1～8 hour.
Dehydrogenation catalyst of the present invention under certain processing condition, can be applicable to make vinylbenzene, divinylbenzene and vinyl toluene by ethylbenzene, diethylbenzene, methyl-ethyl benzene fully.
The present invention is used for the method for preparing styrene from ethylbenzene and carries out at the isotherm formula fixed bed, and for the ethyl benzene dehydrogenation preparation of styrene activity rating, the summary process is as follows:
With ethylbenzene and respectively preheating in the volume pump input mixer of deionized water, enter reactor with gaseous form, reactor adopts electric-heating-wire-heating, makes it to reach preset temperature.Reactor inside diameter is 1 " stainless steel tube; load 100 milliliters of catalyzer; react under than (water/ethylbenzene) (weight) at certain reaction pressure, liquid air speed, temperature of reaction, water, the dehydrogenation product that is flowed out by reactor is analyzed it with gas chromatograph and is formed behind water condensation.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
The vinylbenzene list is received (%)=conversion of ethylbenzene (%) * selectivity of styrene (%)
The main side reaction of ethylbenzene dehydrogenation is to generate toluene and benzene, and related is more macromolecular reaction, and the internal diffusion of reactant and product directly affects the catalyst reaction process.Prove after deliberation: it is necessary that suitable catalyst pores structure has good catalytic performance to catalyzer, but too much aperture (specific surface is excessive), long duct (excessive particle diameter) all can be conducive to the generation of side reaction.Therefore catalyzer is made abnormity, can increase catalyzer the useful area utilization ratio, reduce orifice throat length, can guarantee high reactivity and the highly selective of catalyzer; In addition, ethyl benzene dehydrogenation preparation of styrene is again that molecule number increases reaction, and device vacuum tightness is higher more favourable to generating vinylbenzene, because the ultimate compression strength of catalyzer is bad, easily efflorescence certainly will cause bed pressure drop to rise, and directly affects transformation efficiency; And at present styrene device has tended to maximize, and capacity expansion revamping also often adopts on original old device increases a reactor, becomes two sections and is three sections mode.This patent is by carving width in the catalyzer axial external surface, the depth, variform screw thread or endless groove line, can effectively utilize catalyst surface on the one hand, reduce orifice throat length, both being conducive to reactant contacts with catalyst surface, product is sloughed rapidly, the charcoal agent (water) that is conducive to again disappear enters the charcoal that disappears in the reaction duct, thereby guarantee that catalyzer has good reactivity worth and work-ing life, its groove line of aspect is screw thread or ring-type in addition, but the ultimate compression strength of Effective Raise catalyzer and resistance to chalking energy, the conversion of ethylbenzene of its ethyl benzene dehydrogenation preparation of styrene, selectivity of styrene is respectively by 75.5%, 94.3% brings up to 77.3%, 95.0%, thus preferably technique effect obtained.
Description of drawings
Fig. 1 thread groove catalyst appearance synoptic diagram.
Fig. 2 endless groove catalyst appearance synoptic diagram.
A among Fig. 1: groove depth; B: groove width; L: separation; Φ: diameter.A among Fig. 2: groove depth; B: groove width; L: separation; Φ: diameter.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
290.8 gram red iron oxides, 76.3 gram salt of wormwood, 6.5 gram cerium oxide, 67.5 gram nitric acid persimmons, 6.5 gram ammonium molybdates, 15.0 gram carboxymethyl celluloses (seeing Table 1) were stirred 1 hour in kneading machine, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the cylindrical strip thing of 3 millimeters of diameters, 5～10 millimeters of length, put into baking oven, 80 ℃ were dried by the fire 4 hours, then place muffle furnace, made catalyzer in 4 hours in 850 ℃ of roastings.The preparation method of embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6, embodiment 7, embodiment 8 just adds different ratios with embodiment 1.
The Fe-K-Ce-Mo catalyzer of table 1 different ratios pore-creating agent and composition prepares charging capacity and physical property thereof
*: sample through 200 ℃ of dryings accurately weigh after 2 hours with sample experience wear experiment after cross 20 mesh sieves and get the per-cent that difference that particle accurately weighs accounts for raw sample weight, this is worth, and more the resistance to chalking of I indirect measurement catalyzer can be better.
Be not difficult to draw embodiment 5 from table 1 and show preferably ultimate compression strength and larger porosity.
[embodiment 9～17]
To make the bar that axial external surface is carved width, the depth, variform screw thread or endless groove line with the wet cream block extrusion on the banded extruder of equipment different shapes card, different propelling techniques of pinching of component by embodiment 5, the physicals of then pelletizing, oven dry, roasting institute controlling catalyst sees Table 2:
The physical property of table 2 different slots line catalyzer
See Table 3 with the embodiment in the table 1,2, the comparative example catalyzer ethyl benzene dehydrogenation preparation of styrene performance take pure ethylbenzene as raw material respectively:
Table 3 catalyzer ethylbenzene dehydrogenation Performance Ratio
*
*: catalyst performance is 200 hours mean value after the stable reaction.
[embodiment 18～27]
The catalyzer of embodiment 14 is made Performance under the differential responses processing condition, the results are shown in Table 4:
The catalyzed reaction result of the ethyl benzene dehydrogenation preparation of styrene of embodiment 14 under the table 4 differential responses condition
Get several embodiment catalyzer with the meaning of representing and see Table 5 in the life-span performance that ethyl benzene dehydrogenation preparation of styrene reacts:
The Performance Ratio that the different embodiment catalyzer of table 5 represent with the vinylbenzene once through yield in ethylbenzene dehydrogenation reaction
*
*: be 2.0 in water/ethylbenzene weight ratio, the ethylbenzene air speed is 1.0 hours
-1, obtain under the evaluating catalyst condition in 620 ℃ of isotherm formula fixed-bed reactor.
From the embodiment explanation, the present invention is owing to used the essentially consist at Fe-K-Ce-Mo, optimization of catalysts forms, can effectively increase the specific surface area of catalyzer by carving width, the depth, variform screw thread or endless groove line in the catalyzer axial external surface, reduce orifice throat length, made dehydrogenation catalyst had both had high activity, selectivity, have simultaneously suitable stability, its resistance to compression, resistance to chalking can be also very good.Such catalyzer has high activity, selectivity under suitable processing condition, have simultaneously suitable stability, the ethylbenzene raw material can be transformed production vinylbenzene efficiently.
Claims (6)
1. a method that is used for ethyl benzene dehydrogenation preparation of styrene take ethylbenzene as raw material, is 580～640 ℃ in temperature of reaction, and reaction pressure is 0.04～0.1MPa, and water/hydrocarbon weight ratio is 1.0～3.0, and the raw material liq air speed is 0.1～2.5 hour
-1Condition under, raw material contacts with catalyzer by beds, reaction of styrene;
Wherein the active ingredient of catalyst system therefor part comprises following component by weight percentage: 55～85% Fe
2O
3, 5～30% K
2O, 1～3% MoO
3Or WO
3In at least a, 3～15% Ce
2O
3Catalyzer is the axial outer bar that is with width, the depth, variform screw thread or endless groove line.
2. the method for described ethyl benzene dehydrogenation preparation of styrene according to claim 1, the outside diameter that it is characterized in that catalyzer is 2～8mm.
3. the method for described ethyl benzene dehydrogenation preparation of styrene according to claim 1, it is characterized in that catalyzer axially peripheral groove line cross-sectional geometry be trilateral, rectangle, trapezoidal or all kinds of combinations garden shape.
4. the method for described ethyl benzene dehydrogenation preparation of styrene according to claim 1 is characterized in that the dark 0.1～4mm of groove line of catalyzer.
5. the method for described ethyl benzene dehydrogenation preparation of styrene according to claim 1 is characterized in that the wide 0.1～3mm of groove line of catalyzer.
6. the method for described ethyl benzene dehydrogenation preparation of styrene according to claim 1 is characterized in that the groove line spacing of catalyzer is 1～5mm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1027928A1 (en) * | 1999-02-10 | 2000-08-16 | Basf Aktiengesellschaft | Catalyst for dehydrogenation of ethylbenzene to styrene |
| CN2477269Y (en) * | 2001-01-05 | 2002-02-20 | 中国石油化工股份有限公司 | Screw-type catalyst |
| CN1400052A (en) * | 2001-07-27 | 2003-03-05 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for preparing styrene |
| CN101148389A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Method for preparing styrene by ethylbenzene dehydrogenation |
| CN101623641A (en) * | 2008-07-08 | 2010-01-13 | 中国石油化工股份有限公司 | Method for preparing styrene catalyst through ethylbenzene dehydrogenation |
| CN101992095A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Catalyst for preparing styrene through dehydrogenation by using rough ethylbenzene and preparation method thereof |
-
2011
- 2011-09-29 CN CN2011103006082A patent/CN103030521A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1027928A1 (en) * | 1999-02-10 | 2000-08-16 | Basf Aktiengesellschaft | Catalyst for dehydrogenation of ethylbenzene to styrene |
| CN2477269Y (en) * | 2001-01-05 | 2002-02-20 | 中国石油化工股份有限公司 | Screw-type catalyst |
| CN1400052A (en) * | 2001-07-27 | 2003-03-05 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for preparing styrene |
| CN101148389A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Method for preparing styrene by ethylbenzene dehydrogenation |
| CN101623641A (en) * | 2008-07-08 | 2010-01-13 | 中国石油化工股份有限公司 | Method for preparing styrene catalyst through ethylbenzene dehydrogenation |
| CN101992095A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Catalyst for preparing styrene through dehydrogenation by using rough ethylbenzene and preparation method thereof |
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Application publication date: 20130410 |