CN1226462A - Alkyl aromatic hydrocarbon dehydrogenation catalyst and preparation thereof - Google Patents
Alkyl aromatic hydrocarbon dehydrogenation catalyst and preparation thereof Download PDFInfo
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- CN1226462A CN1226462A CN 98113777 CN98113777A CN1226462A CN 1226462 A CN1226462 A CN 1226462A CN 98113777 CN98113777 CN 98113777 CN 98113777 A CN98113777 A CN 98113777A CN 1226462 A CN1226462 A CN 1226462A
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Abstract
A catalyst for dehydrogenating alkylarene contains Fe2O3 (55-91%), K2O (5-20%) and Ce2O4 (4-25%) and is prepared through adding the aqueous solutions of potassium salt and cerium salt to the mixture of iron oxide and binder, fully stirring, press shaping, ageing at ordinary temp, drying and activating by raising temp to 300-800 deg.C. Its advantages are less components, better physical and chemical properties, and higher activity, selectivity and stabilizity. It is used in low water ratio condition.
Description
The present invention relates to a kind of alkyl aromatics dehydrogenation that is applicable to, particularly be applicable to the manufacture method of dehydrogenation and this kind catalyst of ethyl benzene dehydrogenation preparation of styrene.This catalyst can be used for the certain embodiments of normal pressure or negative pressure, the weight ratio of water vapour and ethylbenzene less than 1.4 situation under, still can obtain higher conversion of ethylbenzene and selectivity of styrene and good stable.
The catalyst for phenylethylene dehydrogenation that uses on the general industry is to be active component with the iron oxide, adds alkali metal or alkaline earth metal compound, also adds one or more oxides additives such as chromium, molybdenum, cerium, magnesium, copper, tungsten, calcium, tin, zinc.At United States Patent (USP) 3360579,3385073,3703593,4134858,4152300,4496662, having disclosed with iron-potassium-chromium in the Chinese patent 87100517 is main component, adds the dehydrogenation of one or more above-mentioned oxides additives again.At United States Patent (USP) 3904552,4144197, having disclosed with iron-potassium-cerium-molybdenum in the Chinese patent 91109968 is main component, adds one or more other oxides additives again.Disclose in Chinese patent 88103900 with iron-potassium-rare earth-calcium-Xi is the catalyst of main component.Disclose in Chinese patent 86102324 with iron-potassium-cerium-molybdenum-magnesium is the catalyst of main component.More than these catalytic components various, preparation process is cumbersome, the factor complexity of influence preparation repeatability, it is lower than the performance of the catalyst of small lot preparation to produce the catalyst that comes out often in enormous quantities.
Use big heavy water vapour in ethylbenzene dehydrogenation process, the dividing potential drop that both can reduce product is to obtain more styrene, and the carbon deposit that also can suppress catalyst increases the service life.Along with the ratio of water and ethylbenzene increases, reach under the situation of identical styrene yield, the reaction temperature that needs can reduce, and the cinnamic selectivity of generation will raise.But concerning energy-conservation, low water is that people pursue with the ratio of ethylbenzene always.
In the catalyst that general industry uses, alkali metal or alkaline earth metal compound content are nearly more than 30% (weight), cause catalyst in air, to have strong absorptive like this, and can move gradually or run off, make the corrosion of granule strength decline and equipment at dehydrogenation reaction process alkali metal.
As everyone knows, has loose structure and the low specific surface area catalyst demonstrates high activity, selectivity and stability in catalytic dehydrogenation.The manufacture method that in above-mentioned disclosed patent, seldom relates to catalyst for phenylethylene dehydrogenation, such as aging and the activation phenomenon and the activation method etc. of the proterties of raw material, reinforced program, article shaped to catalyst rerum natura and active influence.But after years of research and found that above-mentioned factor (be called for short " structure modulation ") has considerable influence to the performance of dehydrogenation, and not second to the influence of " component modulation ".
Therefore, people expect that the component of catalyst for phenylethylene dehydrogenation wants simple, and alkali metal content should not be too high, can be applicable to the condition of low water and ethylbenzene ratio, and are active and selectivity is good, and the repeatability for preparing will be got well.
The purpose of this invention is to provide a kind of dehydrogenation that is used for alkylaromatic hydrocarbon, dehydrogenation composition than present industrial use is simple, physical and chemical performance is good, is applicable at low water to operate under than (water/ethylbenzene is less than 1.4) condition, has higher activity, selectivity and stability again.Another object of the present invention provides a kind of new technology for preparing dehydrogenation.
Dehydrogenation provided by the invention is to be active principle with iron-potassium-cerium, needn't contain other auxiliary agents such as molybdenum, tungsten, vanadium, magnesium, tin, adds the catalyst that an amount of expanding agent and binding agent are made.
Specifically, dehydrogenation of the present invention comprises component (by weight percentage) Fe
2O
355～91%, K
2O5～20%, Ce
2O
34～25%; With K
2O/Fe
2O
3=0.10～0.25; Ce
2O
3/ Fe
2O
3=0.10～0.25 is more suitable.The iron oxide that is used to prepare this catalyst can be the iron oxide red or the iron oxide yellow of powdery, and suitable is the iron oxide red of pigmentary purity 98% (weight), 2～50 meters of its specific areas
2/ gram is preferably 5～30 meters
2/ gram, average diameter 40～100 in duct are preferably 40～80 , and pore volume is 0.001～0.10 a milliliter/gram, is preferably 0.005～0.08 milliliter/gram, and granularity＞160 orders is preferably＞190 orders.Suitable alkali metal compound such as potassium, rubidium and caesium all are that effectively widely used is potassium, for example their carbonate, nitrate and acetate etc.Used rare earth element has cadmium, cerium, praseodymium, neodymium, hard iron etc., preferably uses the compound of cerium, for example its carbonate, nitrate, sulfate and acetate.Expanding agent can be used graphite, methylcellulose and sesbania powder.Binding agent can adopt aluminium oxide, silica, alumina silicate and calcium aluminate etc.
Preparation of catalysts method of the present invention is that the aqueous solution with the salt of potassium and cerium adds in iron oxide (but adding additives) mixture, fully mixes and pinches, and makes the thickness dough, extrusion modling, at room temperature aging, through 300～800 ℃ of activation that heat up, drying gets product catalyst more then.Comparatively Shi Yi technological parameter is that aging temperature is lower than 40 ℃, ageing time 2～24 hours; 100～150 ℃ of baking temperatures, 6～12 hours time; During activation heating schedule be 300 ℃ to 500 ℃ 1～1.5 hour, 500 ℃ to 800 ℃ 1～1.5 hour, 800 ℃ of following constant temperature 2～4 hours, activation phenomenon use relative humidity less than 80% air or other inert gas.
When Preparation of Catalyst above-mentioned material fully mix with high degree of dispersion evenly be very necessary, adopt the aqueous solution mode of alkali metal salt and rare-earth element salt to be added in the brown iron oxide, can obtain the optimum efficiency of above-mentioned purpose.Catalyst can be done into strips, spherical or different form, and the wet particle after the moulding is preferably in aging a few hours under the room temperature (as less than 40 ℃), can obtain better granule strength.Activation temperature and activation phenomenon have a direct impact catalyst performance, adopt the temperature programming activation method, impurity (as water and the organic matter etc.) content that strict control enters gas in the activation furnace can improve catalyst and activity, selectivity and stability, especially the moisture humidity of activation phenomenon generally will be controlled＜80% (relative humidity), preferably＜65%.Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Use raw material: red iron oxide purity 98% (weight), powdered granule＞220 orders; Potash purity 99% (weight); Cerous carbonate and cerous nitrate purity 99% (weight); Pure water.
According to percentage by weight Fe
2O
369.5%, K
2O19.0% and Ce
2O
311.5% batching is made with following method, with red iron oxide powder (10 meters of specific surfaces
2/ gram, average pore diameter 70 ) putting into kneading machine blends, potash and cerous nitrate dissolve with pure water, add 2% (weight) methylcellulose in addition, the aqueous solution that configures is added in the top kneading machine gradually, mix and pinched 30 minutes, make the walk of suitable stiffness, be extruded into 3 millimeters of diameters, long 5～8 millimeters strip particle wore out 10 hours under 25 ℃ room temperature, drying is 10 hours under 120 ℃, in the temperature programming activation furnace, feed the air of relative humidity＜65%, heated up one hour, heated up one hour from 500 ℃ to 800 ℃ from 300 ℃ to 500 ℃, then 800 ℃ of following constant temperature 2 hours, the catalyst that gets product after the cooling, bulk density 1.24 grams per milliliters, 2.02 meters of specific areas
2/ gram, average pore diameter 60 .
Embodiment 2
According to percentage by weight Fe
2O
374.0%, K
2O 8.5% and Ce
2O
317.5% batching, the preparation method is as follows, and the red iron oxide powder is added in the kneading machine, adds 2.8% in addition
(weight)Gibbsite binding agent (granularity＞200 orders) mixed 20 minutes, with potash and 2%
(weight)The aqueous solution of methylcellulose adds in the kneading machine gradually, mixes and pinches 10 minutes, adds the aqueous solution of cerous nitrate again, and other preparation method is identical with embodiment 1, bulk density 1.28 grams per milliliters of gained catalyst, 2.05 meters of specific areas
2/ gram, average pore diameter 56 .
Embodiment 3
According to percentage by weight Fe
2O
377.5%, K
2O 13.5% and Ce
2O
39.0% batching, binding agent uses 3% instead
(weight)Calcium aluminate (granularity＞200 orders), the preparation method is identical with embodiment 2, prepared finished catalyst bulk density 1.34 grams per milliliters, 1.94 meters of specific areas
2/ gram, average pore diameter 52 .
Comparative Examples 1
Proportioning is identical with embodiment 1, uses 28 meters of surface areas instead
2/ gram, the red iron oxide powder of average pore diameter 65 , granularity＞150 orders, the preparation method is as follows, and iron oxide, potash and cerous nitrate are added in the kneading machine simultaneously, mixes broken 30 minutes, adds pure water gradually and (includes 2%
(weight)Methylcellulose) make the suitable walk of hardness, later preparation method is identical with embodiment 1, bulk density 1.20 grams per milliliters of the catalyst that obtains, 3.70 meters of specific areas
2/ gram, average pore diameter 69 .
Comparative Examples 2
Proportioning is according to embodiment 3, the preparation method is substantially the same manner as Example 2, only changes convection drying behind the extruded moulding, and the air that feeds relative humidity＞90% then in the temperature programming stove is finished the temperature programming activation, bulk density 1.23 grams per milliliters of gained catalyst, 3.05 meters of specific surfaces
2/ gram, average pore diameter 72 .
Embodiment 4
The dehydrogenation that makes by said method, estimate in internal diameter is 26 millimeters fixed bed reactors, 100 milliliters of loading catalysts adopt normal pressure (0.13MPa absolute pressure) or negative pressure (0.05MPa absolute pressure), 600 ℃ or 620 ℃ of reaction temperatures are during ethylbenzene liquid volume air speed 0.5
-1, the weight ratio of water and ethylbenzene is under 1.30～1.35 the reaction condition, reactor effluent is analyzed with gas-chromatography after cooling.Conversion ratio and selectivity are calculated by following formula:
The mensuration of the abrasive wear rate of catalyst, the catalyst of getting constant weight is in online running under the condition of dehydrogenation reaction after 100 hours, and take out catalyst and make charcoal through 540 ℃, the weight of the reacted catalyst of weighing then, the abrasive wear rate is calculated as follows the face formula:
Reaction result is listed in the table 1.
Reaction result explanation in the table 1, in iron-potassium of the present invention-cerium system, add expanding agent and binding agent, adopt the dehydrogenation that the preparation method produced of invention, be applicable under normal pressure or negative pressure and the low condition of water and operate than (as less than 1.4), and can obtain high conversion of ethylbenzene and selectivity of styrene, catalytic component of the present invention is simple, and physical property is good, the intensity height, the preparation good reproducibility can have been produced the dehydrogenation that to be fit to industrial use in enormous quantities.
The reaction result of table 1 ethyl benzene dehydrogenation preparation of styrene
| The catalyst numbering | Reaction pressure (MPa) | Reaction temperature (℃) | Conversion of ethylbenzene (%) | Selectivity of styrene (%) | Abrasive wear rate (%) |
| Embodiment 1 | ???0.13 ???0.13 ???0.05 ???0.05 | ???600 ???620 ???600 ???620 | ????64.8 ????74.7 ????71.3 ????80.2 | ???94.8 ???92.4 ???97.3 ???95.6 | ????2.1 |
| Embodiment 2 | ???0.13 ???0.13 ???0.05 ???0.05 | ???600 ???620 ???600 ???620 | ????63.5 ????73.7 ????70.4 ????80.1 | ???95.0 ???92.8 ???97.4 ???95.8 | ????0.4 |
| Embodiment 3 | ???0.13 ???0.13 ???0.05 ???0.05 | ???600 ???620 ???600 ???620 | ????64.4 ????72.7 ????69.8 ????80.8 | ???95.1 ???93.2 ???97.5 ???96.1 | ????0.2 |
| Comparative Examples 1 | ???0.13 ???0.13 ???0.05 ???0.05 | ???600 ???620 ???600 ???620 | ????63.1 ????71.3 ????70.5 ????78.5 | ???91.5 ???89.7 ???93.6 ???91.8 | ????2.5 |
| Comparative Examples 2 | ???0.13 ???0.13 ???0.05 ???0.05 | ???600 ???620 ???600 ???620 | ????65.0 ????74.2 ????69.7 ????80.2 | ???92.1 ???90.5 ???95.3 ???93.2 | ????1.0 |
Claims (7)
1. a catalyst that is used for alkyl aromatics dehydrogenation is characterized in that this catalyst is to be made of iron oxide-potassium oxide-cerium oxide, and its percentage by weight is formed: Fe
2O
355～91%, K
2O5～20%, Ce
2O
34～25%.
2. according to the described Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst that is used for of claim 1, it is characterized in that K in the percentage by weight composition
2O/Fe
2O
3Be 0.10～0.25, Ce
2O
3/ Fe
2O
3Be 0.10～0.25.
3. according to claim 1, the 2 described catalyst that are used for alkyl aromatics dehydrogenation, the iron oxide that it is characterized in that being used to preparing this catalyst can be the iron oxide red or the iron oxide yellow of powdery, 2～50 meters of its specific areas
2/ gram, duct average diameter 40～100 , pore volume are 0.001～0.10 milliliter/gram, granularity＞160 orders.
4. according to the described catalyst that is used for alkyl aromatics dehydrogenation of claim 3, it is characterized in that 5～30 meters of specific areas
2/ gram, duct average diameter 40～80 , 0.005～0.08 milliliter/gram of pore volume, granularity＞190 orders.
5. the preparation method of the described Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst of claim 1, it is characterized in that the aqueous solution of the salt of potassium and cerium is added in iron oxide and the binder mixtures, fully mix and pinch, make the thickness dough, extrusion modling, at room temperature aging, dry then, through 300～800 ℃ of activation that heat up, catalyst gets product.
6. according to the described dehydrogenation preparation method of claim 5, it is characterized in that aging temperature is lower than 40 ℃, ageing time 2～24 hours; 100～150 ℃ of baking temperatures, 6～12 hours time; During activation heating schedule be 300 ℃ to 500 ℃ 1～1.5 hour, 500 ℃ to 800 ℃ 1～1.5 hour, 800 ℃ of following constant temperature 2～4 hours, activation phenomenon use relative humidity less than 80% air or other inert gas.
7. the catalyst of claim 1 can be used for the technical process that styrene, divinylbenzene, methyl styrene and AMS are produced in ethylo benzene, diethylbenzene, ethyl methyl benzene and isopropylbenzene dehydrogenation.
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|---|---|---|---|
| CN98113777A CN1095399C (en) | 1998-02-20 | 1998-02-20 | Alkyl aromatic hydrocarbon dehydrogenation catalyst and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113777A CN1095399C (en) | 1998-02-20 | 1998-02-20 | Alkyl aromatic hydrocarbon dehydrogenation catalyst and preparation thereof |
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|---|---|
| CN1226462A true CN1226462A (en) | 1999-08-25 |
| CN1095399C CN1095399C (en) | 2002-12-04 |
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| US7387982B2 (en) | 2001-12-28 | 2008-06-17 | Mitsubishi Rayon Co., Ltd. | Method of producing catalyst for synthesis of unsaturated aldehyde and unsaturated carboxylic acid and catalyst prepared by this method |
| CN100460069C (en) * | 2005-12-14 | 2009-02-11 | 中国石油化工股份有限公司 | Production of phenylethylene catalyst by low-water ratio ethylbenzene dehydrogenation |
| CN101992095B (en) * | 2009-08-31 | 2012-10-10 | 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 |
| CN102728371A (en) * | 2011-04-15 | 2012-10-17 | 廖仕杰 | High cerium content alkylaromatic dehydrogenation catalyst and preparation method thereof |
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| CN102909011A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Activation and sulfurization method for dehydrogenation catalyst |
| CN103028419A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Catalyst for low-water ratio ethylbenzene dehydrogenation |
| CN111420673A (en) * | 2020-03-19 | 2020-07-17 | 湖南城市学院 | Preparation method of catalyst for alkyl aromatic dehydrogenation |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58177148A (en) * | 1982-04-13 | 1983-10-17 | Mitsubishi Petrochem Co Ltd | Catalyst for preparing styrene |
| EP0112754B1 (en) * | 1982-12-14 | 1986-11-05 | Institut Français du Pétrole | Catalyst containing oxides of iron, chrominium, potassium and lanthanum, its preparation and its use in dehydrogenation reactions |
| JPS6190741A (en) * | 1984-10-11 | 1986-05-08 | Nissan Gaadoraa Shokubai Kk | Catalyst for dehydrogenation |
| DE3442636A1 (en) * | 1984-11-22 | 1986-05-22 | Süd-Chemie AG, 8000 München | DEHYDRATION CATALYST |
-
1998
- 1998-02-20 CN CN98113777A patent/CN1095399C/en not_active Expired - Fee Related
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| US7387982B2 (en) | 2001-12-28 | 2008-06-17 | Mitsubishi Rayon Co., Ltd. | Method of producing catalyst for synthesis of unsaturated aldehyde and unsaturated carboxylic acid and catalyst prepared by this method |
| CN100404133C (en) * | 2001-12-28 | 2008-07-23 | 三菱丽阳株式会社 | Method of producing catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid, catalyst produced by this method, and method of synthesizing unsaturated aldehyde and unsaturated ca |
| CN100384532C (en) * | 2005-01-26 | 2008-04-30 | 中国石油化工股份有限公司 | Catalyst for dehydrogenating alkyl arene in preparing alkyl alkenyl arene |
| CN100460069C (en) * | 2005-12-14 | 2009-02-11 | 中国石油化工股份有限公司 | Production of phenylethylene catalyst by low-water ratio ethylbenzene dehydrogenation |
| CN101992095B (en) * | 2009-08-31 | 2012-10-10 | 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 |
| CN102728371A (en) * | 2011-04-15 | 2012-10-17 | 廖仕杰 | High cerium content alkylaromatic dehydrogenation catalyst and preparation method thereof |
| CN102909099A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for the reductive activation of dehydrogenation catalyst by using gas mixture of hydrocarbon/hydrogen |
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| CN102909013A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Preparation method for dehydrogenation catalyst with steam dechlorination and reduction performed simultaneously |
| CN102909017A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for stepwise activating dehydrogenation catalyst by using synthesis gas and CO-containing gas |
| CN102909100A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for sectionally activating dehydrogenation catalyst by using hydrocarbon/hydrogen mixed gas and synthetic gas |
| CN102909011A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Activation and sulfurization method for dehydrogenation catalyst |
| CN102909100B (en) * | 2011-08-01 | 2015-01-14 | 中国石油化工股份有限公司 | Method for sectionally activating dehydrogenation catalyst by using hydrocarbon/hydrogen mixed gas and synthetic gas |
| CN103028419A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Catalyst for low-water ratio ethylbenzene dehydrogenation |
| CN103028419B (en) * | 2011-09-30 | 2014-11-26 | 中国石油化工股份有限公司 | Catalyst for low-water ratio ethylbenzene dehydrogenation |
| CN111420673A (en) * | 2020-03-19 | 2020-07-17 | 湖南城市学院 | Preparation method of catalyst for alkyl aromatic dehydrogenation |
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