CN101121135A - Method for preparing catalysts for dehydrogenating ethylbenzene to styrene - Google Patents
Method for preparing catalysts for dehydrogenating ethylbenzene to styrene Download PDFInfo
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- CN101121135A CN101121135A CNA2006100299593A CN200610029959A CN101121135A CN 101121135 A CN101121135 A CN 101121135A CN A2006100299593 A CNA2006100299593 A CN A2006100299593A CN 200610029959 A CN200610029959 A CN 200610029959A CN 101121135 A CN101121135 A CN 101121135A
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- ethylbenzene
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a preparation method of a cinnamic catalyst manufactured by an ethylbenzene dehydrogenation and mainly solves the technical problem in the former technology that an intensity of the prepared catalyst is not high enough, and a service life is not long enough. The present invention solves the problem well by a technical proposal that at least one material of a natural or processed composite oxide or a mixed oxide which is soaked in a potassium salt solution and is selected from a porcelain or alpha-alumina is used as a support, the surface of which is uniformly coated by an active component slurry which includes Fe2O3, K2O, Ce2O3 and MoO3 or WO3. The catalyst can be used for a cinnamic industrial production.
Description
Technical field
The present invention relates to a kind of ethyl benzene dehydrogenation preparation of styrene Preparation of catalysts method that is used for.
Background technology
As the styrene of one of most important raw material of basic organic synthesis, industrial 85 percent realizes by the hot dehydrogenation of the direct catalysis of ethylbenzene under negative pressure.The basic composition of catalyst system therefor comprises major catalyst, co-catalyst and pore-foaming agent, reinforcing agent etc.At present by a lot of production of styrene in countries in the world producer adopt what be that early eighties succeeds in developing is the serial compound/mixed oxide catalyst of basic composition with Fe-K-Ce-Mo, the Preparation of catalysts method is general adopt with catalytic components such as Fe, K, Ce, Mo with the form solid phase mixing of oxide or salt, add water kneading, extrusion, drying, roasting and form, as laid-open U.S. Patents US4804799, US5023225 and US5190906 etc.The characteristics of this type of catalyst are: active, selectivity is higher, stability better, and environmental friendliness.But the compression strength of such catalyst was generally 2 years generally in 15～25 Newton/millimeter service life, and minority is more than 2 years, and catalyst is using the later stage, and catalytic performance descends obviously.Along with modern industry improves constantly reacting production-scale, and the continuous prolongation of commercial plant production cycle, to the compression strength of catalyst and requirements at the higher level have been arranged service life.In order to increase catalyst compression strength, usually way is to add reinforcing agent cement in catalytic component, but acidic materials such as the silica in the cement, aluminium oxide, sulfate radical have certain influence to the selectivity of reaction, cause the increase of by-product benzene, toluene, bring difficulty for principal product output and later separation step.In addition, the people who is familiar with the industry knows, the loss of the active ingredient potassium of catalyst can cause the permanent deactivation of catalyst, directly influences the service life of catalyst, how slowing down the loss of potassium component is an at present domestic and international researcher aspect maximum to such catalyst research, for this reason, seek a kind of effective method for preparing catalyst, make institute's controlling catalyst promptly have good catalytic performance, suitable compression strength and long life are arranged again, are the very interested problems of people.
Summary of the invention
Technical problem to be solved by this invention is to exist the not high enough and catalyst of prepared catalyst strength because of potassium lost causes the problem of catalyst permanent deactivation in the prior art, and a kind of new preparation method who is used for catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene is provided.The catalyst that makes with this method except that have high conversion of ethylbenzene, high-phenylethylene selectivity, catalyst stability well, have also that catalyst strength is good, the advantage of long service life.
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 preparation method who is used for catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene may further comprise the steps:
1) the activity of such catalysts component is evenly made slurry after the mixing by institute's expense, wherein activity of such catalysts component part comprises following component by weight percentage: a) 55～85% Fe
2O
3B) 5～30% K
2O; C) 3～10% Ce
2O
3D) 0.5～5% MoO
3Or WO
3E) 0.05～8% MgO, CaO or their mixture;
2) will be selected from biscuiting porcelain, Alpha-alumina, natural or through at least a material in the compound or mixed oxide of processing, behind the potassium salt soln dipping, drying is handled the supporter that the back obtains catalyst;
3) with 1) slurry that obtains of step is coated on 2 equably) supporting body surface after the step process, drying, roasting get required catalyst.
In the technique scheme, the weight ratio of supporter and catalyst activity part is a preferable range 1～500: 1, and more preferably scope is 50～100: 1; The active component thickness preferable range that evenly is coated on supporting body surface is 0.01～2 millimeter, and more preferably scope is 0.1～1 millimeter; The compression strength preferred version of supporter is 〉=30 Newton/millimeter; The pore volume preferable range of supporter is 0.01～0.1 a cubic centimetre/gram; Dipping is 0.01 mol～saturated solution with the concentration preferable range of potassium salt soln, and more preferably scope is 0.1 mol～saturated solution; Be used to flood the sylvite preferred version of supporter for being selected from potash or potassium hydroxide; The weight ratio preferable range of the pickup of sylvite and supporter is 0.01～0.5: 1.The shape preferred version of supporter is selected from least a in circle, cylinder, three leaves, five-pointed star or the gear-like; Length is 2～10 millimeters; External diameter is 2～5 millimeters.Supporter after 2～24 hours, 2～8 hour is obtained supporter through 80～150 ℃ of dryings at dipping under 0～80 ℃ by potassium salt soln.3) the baking temperature preferable range is 40～150 ℃ in the step, and drying time, preferable range was 1～10 hour, and the sintering temperature preferable range is 400～1000 ℃, and the roasting time preferable range is 1～8 hour.
The used raw material of catalyst component of the present invention is as follows:
Fe
2O
3Be made up of iron oxide red and/or iron oxide yellow, potassium adds with the form of sylvite, and cerium adds with oxide, hydroxide or metallic salt form.Also can add the oxide that is selected from alkaline-earth metal in the catalyst activity component in addition, its consumption is generally 0.05～8% of catalyst weight.
Also can comprise perforating agent in the catalyst of the present invention, its consumption is 1～4% of a catalyst weight, can choose from graphite, polystyrene microsphere, carboxymethyl cellulose etc.
Comprise in the catalyst of the present invention in advance catalyst support is flooded in the concentration preferable range is the potassium salt soln of 0.1 mol～saturated, more preferably scope is 1 mol～saturated potassium salt soln, to guarantee in the use of catalyst, the potassium component reaches the prolongation catalyst purpose in service life because concentration difference slowly discharges the potassium lost with the make-up catalyst surface.
The method of operating of the concrete recommendation of Preparation of Catalyst of the present invention is as follows:
After will evenly mixing by Fe, K, Ce, Mo (or W) and the co-catalyst component that need add, the perforating agent of proportioning weighing, add proper amount of deionized water, make slurry and constitute the activity of such catalysts part A, in slurry, add an amount of stirred by the impregnated supporter B of potassium salt soln after, formation is evenly applied certain thickness catalyst granules by A, in 40～150 ℃ of dryings 1～10 hour, 400～1000 ℃ of following roastings 1～8 hour, just can obtain finished catalyst then.
Dehydrogenation of the present invention under certain process conditions, can be applicable to fully by ethylbenzene, diethylbenzene, monomethyl ethylbenzene and make styrene, divinylbenzene and monomethyl styrene.
The catalyst 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:
With ethylbenzene and deionized water preheating in the measuring pump input mixer respectively, enter reactor with gaseous form, reactor adopts the heating wire heating, makes it to reach predetermined temperature.Reactor inside diameter is 1 " stainless steel tube, interiorly load 100 milliliters of catalyst.Analyzing it with gas chromatograph by the dehydrogenation product of reactor outflow behind water condensation forms.
The evaluating catalyst condition is as follows in the isotherm formula fixed bed reactors: 100 milliliters of catalyst are put into internal diameter 1 " isothermal reactor, reaction pressure is normal pressure, liquid air speed 1.0 hours
-1, 620 ℃ of reaction temperatures, water be than (water/ethylbenzene) (weight) 2.0.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
The styrene list is received (%)=conversion of ethylbenzene (%) * selectivity of styrene (%)
Among the present invention because catalyst to be selected from biscuiting porcelain, Alpha-alumina, natural or be supporter through at least a material in the compound or mixed oxide of processing, makes catalyst have good compression strength.According to the material of supporter, generally be easy to reach compression strength more than 〉=30 (Newton/millimeter); In addition, the supporter of sylvite dipping is rich in active component potassium, because concentration difference slowly discharges in course of reaction, with the loss of make-up catalyst outer surface potassium, is 2.0 in water/ethylbenzene weight ratio in the catalyst use, and the ethylbenzene air speed is 1.0 hours
-1, to estimate on 620 ℃ of hotbeds such as grade, the yield of ethyl benzene dehydrogenation preparation of styrene can reach 72.9%, and catalyst used 1000 hours, and catalytic perfomance is constant substantially, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
190.5 iron oxide reds, 90.1 gram iron oxide yellows, 50.6 gram potash, 90.8 gram nitric acid persimmons, 10.3 gram ammonium molybdates, 10.4 gram magnesia and carboxymethyl cellulose were stirred in kneading machine 1 hour, add appropriate amount of deionized water, mix and stir half an hour again, making slurry takes out, under the room temperature, after in slurry, adding 4000 grams and being stirred evenly by the impregnated supporter B of the solution of potassium carbonate of 4 mol, the catalyst granules that formation is evenly applied by A, put into baking oven, 40 ℃ were dried by the fire 3 hours, place muffle furnace then, made catalyst in 2 hours in 800 ℃ of roastings.
[embodiment 2]
Each condition and operating procedure by embodiment 1 prepare catalyst, just change shape, material of different active component throwing amounts, supporter etc., see Table 1.
[comparative example 1]
In the catalyst of comparative example 1 except cement as bonding agent, the composition of other each component is all same with embodiment 1, its Preparation of catalysts method: with 190.5 iron oxide reds, 90.5 gram iron oxide yellow, 50.6 gram potash, 90.5 gram nitric acid persimmon, 10.3 gram ammonium molybdate, 10.4 gram magnesia and 15 gram cement, 7 gram carboxymethyl celluloses stirred in kneading machine 1 hour, add deionized water, mix and stir again and be the dough shape half an hour, take out extrusion, be extruded into 3 millimeters of diameters, the particle that length is 5～10 millimeters, put into baking oven, 40 ℃ were dried by the fire 3 hours, place muffle furnace then, made catalyst in 2 hours in 800 ℃ of roastings, its intensity is 20 Newton/millimeter.
The different supporters of table 1 apply the inventory and the relevant physical parameter of Fe-K-Mo-Ce institute catalyst for preparing phenylethylene
| Raw material | Inventory (gram) inventory (gram) and relevant physical parameter | ||||||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | |
| Iron oxide red iron oxide yellow potash cerous nitrate ammonium molybdate magnesia cement carboxymethyl cellulose supporter material and shape *Supporter pore volume (cubic centimetre/gram) supporter inventory (gram) sylvite impregnation concentration (mol) active component thickness (millimeter) compression strength ** | 190.5 90.1 50.6 90.8 10.3 10.4-10.0 biscuiting porcelain circles 0.026 4,000 4 0.32 45.7 | 130.3 152.6 60.3 70.3 15.1 8.4-8.0 biscuiting porcelain knobs 0.027 4,000 5 0.45＞50 | 100.1 183.1 55.9 75.4 17.4 11.2-9.0 tri-lobeds 0.053 4,000 3 0.25 43.5 | 123.7 167.5 65.6 60.7 8.3 20.1-5.0 five-pointed star shapes 0.054 4,000 4.5 0.59 41.5 | 170.3 112.5 68.2 69.8 11.2 13.6-8.0 rounds 0.058 4,000 6 0.89 40.2 | 190.1 95.5 70.8 65.8 9.8 16.5-4.0 columns 0.054 4,000 10 0.68 46.5 | 190.5 90.1 50.6 90.8 10.3 10.4 15.0 7.0 - - - - - 20.1 |
*: supporter is to be satisfied or dense potassium salt soln dipping adding later, and except that indicating material, other material is through the kneading extruded moulding and through α-Al of 5 hours of 900 ℃ of roastings
2O
3
*: the anti-crushing power of catalyst is measured by the specification requirement of standard HG/T2782-1996 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 arithmetic mean of instantaneous value of getting its measurement result is final anti-crushing power value, is the resistance to crusing unit of force with the Newton/millimeter.
[embodiment 7～13]
At different temperatures, different sylvite concentration dipping different time, dry back evenly applies the active component slurry of embodiment 1, puts into oven drying, places the muffle furnace roasting then with biscuiting porcelain circle.The preliminary treatment treatment conditions of supporter and catalyst precursor and active component thickness, the compression strength of finished catalyst see Table 2:
The relevant physical parameter of institute's controlling catalyst behind the pretreatment condition of table 2 supporter and the coating active component
| Preliminary treatment | Physical parameter | ||||||
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | |
| Sylvite sylvite impregnation concentration, (mol/L) sylvite maceration extract temperature, (℃) the sylvite maceration extract time, (hour) the supporter baking temperature, (℃) supporter drying time, (hour) pickup and supporter weight ratio supporter and active component weight ratio precursor baking temperature, (℃) precursor drying time, (hour) the catalyst sintering temperature, (℃) the catalyst roasting time, (hour) active component thickness, (millimeter) compression strength | Potash 0.05 25 24 80 8 0.01: 1 10: 1 40 10 400 82 40.2 | Potash 1 40 12 100 5 0.2: 1 200: 1 80 5 800 4 1.4 42.8 | Potash 6 60 6 150 2 0.35: 1 500: 1 150 2 1,000 2 0.87 48.9 | Potash 12 80 2 120 1 0.5: 1 350: 1 140 3 750 3.5 1.12 49.1 | Potassium hydroxide 0.1 25 24 110 3 0.09: 1 400: 1 135 3.5 650 6.5 0.47 48.9 | Potassium hydroxide 8 50 8 125 2.5 0.43: 1 450: 1 145 2.5 720 5.5 0.95 48.5 | Potassium hydroxide 12 70 8 90 7 0.48: 1 420: 1 100 8 850 2 0.79 48.5 |
With the catalyst that obtains in embodiment 1～13, the comparative example 1, put into internal diameter 1 respectively " isothermal reactor, be normal pressure, liquid air speed 1.0 hours in reaction pressure
-1, 620 ℃ of reaction temperatures, water/ethylbenzene weight ratio be the catalytic performance test that carries out ethyl benzene dehydrogenation preparation of styrene under 2.0 the condition, the results are shown in Table 3:
Table 3 catalyst ethyl benzene dehydrogenation preparation of styrene performance
*
| Catalyst | Catalytic performance | ||
| Conversion of ethylbenzene (%) | Selectivity of styrene (%) | The styrene list is received (%) | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 comparative examples 1 | 77.0 76.5 77.2 77.1 77.0 76.4 77.0 77.1 77.2 76.8 76.7 76.9 76.6 76.5 | 94.2 94.2 94.4 94.3 94.3 94.3 94.2 94.1 94.0 94.3 94.3 94.2 94.3 94.2 | 72.5 72.1 72.9 72.7 72.6 72.0 72.5 72.6 72.6 72.4 72.3 72.4 72.2 72.1 |
*: catalyst performance is 200 hours a mean value after the stable reaction.
Get the life-span of 1 controlling catalyst of embodiment 1,2,5,8,12 and comparative example its ethyl benzene dehydrogenation preparation of styrene reaction of examination under the identical reaction condition of embodiment 7, the results are shown in Table 4:
The performance that the different embodiment catalyst of table 4 are represented with the styrene once through yield in ethylbenzene dehydrogenation reaction relatively
*
*: obtain under the evaluating catalyst condition in the isotherm formula fixed bed reactors.
From the embodiment explanation, Preparation of Catalyst of the present invention, on the basis of Fe-K-Ce-Mo basic composition, introduce different pretreatment conditions and handle supporter, made dehydrogenation had both had high activity, selectivity, stability has suitable compression strength and long service life simultaneously, is a kind of good method for preparing catalyst.
Claims (8)
1. preparation method who is used for catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene may further comprise the steps:
1) the activity of such catalysts component is evenly made slurry after the mixing by institute's expense, wherein activity of such catalysts component part comprises following component by weight percentage:
A) 55～85% Fe
2O
3
B) 5～30% K
2O;
C) 3～10% Ce
2O
3
D) 0.5～5% MoO
3Or WO
3
E) 0.05～8% MgO, CaO or their mixture;
2) will be selected from biscuiting porcelain, Alpha-alumina, natural or through at least a material in the compound or mixed oxide of processing, behind the potassium salt soln dipping, drying is handled the supporter that the back obtains catalyst;
3) with 1) slurry that obtains of step is coated on 2 equably) supporting body surface after the step process, drying, roasting get required catalyst.
2. according to the described preparation method who is used for catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene of claim 1, it is characterized in that the weight ratio of supporter and catalyst activity part is 1～500: 1; The active component thickness that evenly is coated on supporting body surface is 0.01～2 millimeter.
3. according to the described preparation method who is used for catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene of claim 1, the shape that it is characterized in that supporter is selected from least a in circle, cylinder, three leaves, five-pointed star or the gear-like; Length is 2～10 millimeters; External diameter is 2～5 millimeters.
4. according to the described preparation method who is used for catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene of claim 1, it is characterized in that supporter by potassium salt soln at 0～80 ℃ of dipping after 2～24 hours down, through 80～150 ℃ of dryings 2～8 hours.
5. according to the described preparation method who is used for catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene of claim 1, it is characterized in that the pickup of sylvite and the weight ratio of supporter are 0.01～0.5: 1.
6. according to the described preparation method who is used for catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene of claim 1, the potassium salt soln concentration that it is characterized in that being used to flooding supporter is 0.01 mol～saturated solution.
7. according to the described preparation method who is used for catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene of claim 1, the sylvite that it is characterized in that being used to flooding supporter is selected from potash or potassium hydroxide.
8. according to the described preparation method who is used for catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene of claim 1, it is characterized in that 3) baking temperature is 40～150 ℃ in the step, and be 1～10 hour drying time, and sintering temperature is 400～1000 ℃, and roasting time is 1～8 hour.
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Cited By (4)
| 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 |
| CN102039204B (en) * | 2009-10-13 | 2012-11-14 | 中国石油化工股份有限公司 | Method for preparing styrene catalyst by ethyl benzene dehydrogenation |
| CN103030523A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing styrene by ethylbenzene dehydrogenation |
| CN103418399A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof |
-
2006
- 2006-08-11 CN CNB2006100299593A patent/CN100553766C/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 |
| CN102039204B (en) * | 2009-10-13 | 2012-11-14 | 中国石油化工股份有限公司 | Method for preparing styrene catalyst by ethyl benzene dehydrogenation |
| CN103030523A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing styrene by ethylbenzene dehydrogenation |
| CN103418399A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof |
| CN103418399B (en) * | 2012-05-16 | 2015-04-08 | 中国石油化工股份有限公司 | Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof |
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