CN108097260A - A kind of catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene and preparation method - Google Patents

A kind of catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene and preparation method Download PDF

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CN108097260A
CN108097260A CN201611055115.6A CN201611055115A CN108097260A CN 108097260 A CN108097260 A CN 108097260A CN 201611055115 A CN201611055115 A CN 201611055115A CN 108097260 A CN108097260 A CN 108097260A
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catalyst
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oxides
potassium
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CN108097260B (en
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杨红强
全民强
姚文君
王学丽
程浩
王斌
何崇慧
刘俊涛
王继龙
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China Petroleum and Natural Gas Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/322—Catalytic processes with metal oxides or metal sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The present invention relates to a kind of catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene and preparation methods, are remembered with mass content, and catalyst includes following component：A) 65~75% ferrous acid kalium composite oxides, with K2Fe10O16Meter；B) 1~4% K oxides, with K2O is counted；C) 6~12% Ce oxides, with CeO2Meter；D) 0.6~4% W oxides, with WO3Meter；E) oxide of 2~6% Mg or/and Ca, in terms of MgO or/and CaO；F) 2~4% at least one alkali metal oxide selected from Rb, Cs.Good catalyst activity has high-phenylethylene yield and selectivity of styrene under low-water ratio conditions, while has the characteristics that stability is good.

Description

A kind of catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene and preparation method
Technical field
The present invention relates to a kind of catalyst and preparation method for ethyl benzene dehydrogenation preparation of styrene under low water ratio.
Background technology
Ethylbenzene catalytic dehydrogenation reaction increases for molecular number, highly endothermic reversible process, need to be under the conditions of high temperature, low pressure reaction It carries out.It is industrial to be usually passed through in the process greatly in order to improve the conversion of ethylbenzene of ethylbenzene dehydrogenation reaction and styrene yield The superheated vapour of amount.Water vapour mainly play a part of three aspect, (1) be used as heat source, provide heat for pyroreaction, avoid by Ethylbenzene is heated to higher temperature, inhibits the generation of side reaction；(2) as diluent, ethylbenzene partial pressure is reduced, promotes reaction to production Object space is to movement；(3) water gas reaction occurs, removes catalyst surface carbon distribution, makes catalyst automatic regeneration.But water vapour Addition be subject to reaction system two factors of pressure drop and energy consumption is allowed to be restricted, production of styrene consumes a large amount of water vapours, Energy consumption is big, product condensation number is big, process device is costly, is the major reason that its production cost remains high.Therefore, it is advanced Ethylbenzene dehydrogenation technique, which is pursued, obtains higher styrene with relatively low water ratio (mass ratio of water vapour and ethylbenzene in charging) Yield is one of energy-saving important measures of styrene device using low water ratio operation.
Conventional catalyst for phenylethylene dehydrogenation, since water gas reaction is slack-off, is urged when being reacted under conditions of water ratio is less than 2.0 Agent area carbon increases, and catalyst stability and activity is caused to decline, this is to develop the most disaster that low water ratio catalyst faces Topic, emphatically improve catalyst carbon accumulation resisting ability, disappear carbon ability and catalyst stability, be low water ratio catalyst exploitation master Want direction.Patent CN200510111471.0 (CN1981929) discloses a kind of ethylbenzene dehydrogenation catalyst with low water ratio, with weight percent Include following component than meter：(a) 60~80% Fe2O3；(b) 6~11% K2O；(c) 6~11% CeO2；(d) 0.5~ 5% WO3；(e) at least two light rare earth compounds of except cerium, content are calculated as 0.1~10% with oxide；(f) 0.001~7% at least one oxide selected from Ca, Mg, Ba, B, Sn, Pb, Cu, Zn, Ti, Zr, V or Mo；Wherein catalyst system Portland cement is not added during standby.Catalytic component is light at least two beyond the addition Ce in Fe-K-Ce-W systems Rare earth compound is co-catalyst, while adds at least one in Ca, Mg, Ba, B, Sn, Pb, Cu, Zn, Ti, Zr, V or Mo Kind metal oxide；Catalyst using dry pigmentation prepare, i.e., all components after mixing, addition deionized water mediated, Extrusion, pelletizing, then finished catalyst is made through drying, roasting；The catalyst is evaluated under conditions of water is than 1.8, it is impossible to Complete activity and stability of the catalysts under low water ratio.Patent CN200710039046.4 (CN101279266) is open A kind of energy saving catalyst for phenylethylene dehydrogenation, by weight percentage including consisting of：(a) 60~81% Fe2O3；(b) 7~ 12% K2O；(c) 6~11% CeO2；(d) 0.5~5% WO3；(e) 0.5~5% MgO；(f) 1~5% NiO； (g) at least one light rare earth component containing except cerium, content are calculated as 0.5~5% with oxide in catalyst；(h) it is remaining It measures as binding agent.It is solved using the method that NiO and another light rare earth oxide are added in Fe-K-Ce-W-Mg systems Under low-water ratio conditions the problem of easy carbon distribution, stable difference, which is prepared low potassium catalyst using dry pigmentation；In temperature 620 DEG C, air speed 1.0h-1, water is than under 1.6, normal pressure, conversion of ethylbenzene~75%, selectivity of styrene~95% of catalyst are urged Conversion ratio declines 0.5 percentage point after when the continuous operation 450 of agent is small.Patent CN200910057803.x discloses a kind of low water ratio Catalyst for phenylethylene dehydrogenation is selected from middle rare earth using Rb compounds are added in Fe-K-Ce-W-Ca systems at least one Pm2O3、Eu2O3、Gd2O3Or Dy2O3Technical solution, solve the problems, such as that low potassium catalyst is poor in low-water ratio conditions stability inferior, urge Agent is prepared using dry pigmentation；Not adding additives, Ce used are added in the form of cerium oxalate or cerous carbonate rather than cerous nitrate, on the one hand The alkalescence of system is improved, catalytic inner soda acid more matches, and is conducive to keep higher activity, while has good anti- Crushing strength；On the other hand part potassium compound is replaced with rubidium compound, improves alkali metal compound in ethylbenzene catalytic dehydrogenation Stability in reaction process accelerates the rate that water gas reaction occurs with catalyst surface carbon deposit for water vapour, enhances Catalyst from power of regeneration.The catalyst is in normal pressure, air speed 1.0h-1, 620 DEG C, water than 1.5 under the conditions of operation 500 it is small when, second Benzene conversion ratio maintains 75%, selectivity of styrene~95%；Similar also has European patent 0177832, CN101829576A, CN102040466A, CN103028419A, CN101279263, CN10142273.Patent CN200910057807.8 discloses one kind Ethylbenzene dehydrogenation catalyst with low water ratio is added in La, Pr, Nd, Pm, Sm, Th, Pa or Yb at least using in Fe-K-Ce-Mo systems A kind of element forms catalyst, solves the problems, such as that low potassium catalyst is poor in low-water ratio conditions stability inferior；In 620 DEG C of temperature, sky Fast 1.0h-1, water than 1.6 under the conditions of, catalyst stability reach 1000 it is small when.Patent CN200910201627.2 discloses a kind of second The method of benzene dehydrogenation preparation of styrene is selected from Pm using Rb compounds are added in Fe-K-Ce-W-Ca systems at least one2O3、 Eu2O3、Gd2O3Or Dy2O3Middle rare earth prepare catalyst, solve low potassium catalyst strength it is not high enough, in low water ratio The problem of condition stability inferior is poor；Catalyst is prepared using dry pigmentation, and rubidium is added in iron-potassium-cerium-tungsten-calcium treating system Close object and selected from middle rare earth Pm2O3、Eu2O3、Gd2O3Or Dy2O3At least one, not adding additives, Ce used is with oxalic acid Cerium or cerous carbonate rather than cerous nitrate form add in, and on the one hand improve the alkalescence of system, and catalytic inner soda acid is more matched, had Beneficial to the higher activity of holding, while there is good crush strength；On the other hand part potassium chemical combination is replaced with rubidium compound Object improves stability of the alkali metal compound in ethylbenzene catalytic dehydrogenation reaction process, accelerates water vapour and catalyst The rate of water gas reaction occurs for surface carbon deposit, enhance catalyst from power of regeneration, use 1000 it is small when after, performance Substantially remain unchanged.Patent CN201010261733.2 discloses a kind of ethylbenzene dehydrogenation catalyst with low water ratio and preparation method thereof, leads to It crosses and Cs compounds and at least one is added in Fe-K-Ce-W-Mg systems selected from middle rare earth Sm2O3、Eu2O3、Gd2O3Or Dy2O3Technical solution, solve the problems, such as that low potassium catalyst is poor in low-water ratio conditions stability inferior；In 620 DEG C of temperature, air speed 1.0h-1, water than under 1.5, condition of normal pressure, when catalyst operation 500 is small after conversion ratio reach 74.6%, be selectively maintained at 95.2%；The invention is similar with CN200910201627.2, and patent CN201410778920.6 discloses a kind of low water ratio ethylbenzene The preparation method of dehydrogenation catalyst for preparing phenylethylene, by adding Rb, Cs compound in Fe-K-Ce-Mo-Mg-Ca systems and removing The method of La, Pr, Nb light rare earth oxide beyond Ce solves the problems, such as that catalyst activity under low-water ratio conditions is low.It is logical Light rare earth metal ion in catalyst surface modification alkali metal and in addition to Ce is crossed, catalyst surface acidity is reduced, and enhances The water imbibition of catalyst surface improves catalyst surface water gas reaction rate, improves catalyst in low water ratio reaction process Under stability；So that catalyst is suitable for low water ratio reaction process, effectively solve under low water ratio reaction process, due to vapor Catalyst activity, the problem of stability is low caused by content is reduced.What the invention solved is that catalyst surface carbon distribution inactivates Problem is not involved with inside catalyst activity phase potassium ferrite the problem of carbon distribution inactivation occurs.In 4L thermal insulation negative pressure evaluating apparatus On, in anti-610 DEG C of an entrance, two anti-615 DEG C of entrances, water than 1.2, liquid air speed 0.42h-1, two anti-outlet pressure 40KPa item Under part, conversion of ethylbenzene >=65.6%, but since potassium content is higher, urging caused by potassium lost easily occurs catalyst in the phase after the reaction The problems such as agent stability is bad, poor selectivity.
It improves catalyst surface water gas reaction rate by adding in cocatalyst component, reduce catalyst surface area Carbon is that have the important channel that ethylbenzene dehydrogenation catalyst with low water ratio stability is improved in document, but it checks and rates catalyst stability Process conditions can not match that (water of low water ratio Styrene Process is more left than generally 1.3 with current production technology The right side, and evaluating catalyst condition is commonly water than more than 1.5 in document), and low water ratio reaction process causes catalyst activity Loss do not improved.Therefore, while how inhibiting carbon distribution in low water ratio reaction process, prevent active mutually reduction, The activity and stability, reduction energy consumption for improving catalyst are still scientific research personnel's problem urgently to be resolved hurrily.
The content of the invention
The present invention provides a kind of catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene and preparation method, the technical issues of solving is existing There is low potassium catalyst present in technology under low water ratio reaction process, the bulk density of catalyst and radial direction resistance to crusing force difference, After the reaction the phase easily there is potassium lost caused by the problems such as the bad, poor selectivity of catalyst stability.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of low-water ratio ethylbenzene dehydrogenation benzene Catalyst for ethylene remembers that catalyst includes following component with mass content：
A) 65~75% ferrous acid kalium composite oxides, with K2Fe10O16Meter；
B) 1~4% K oxides, with K2O is counted；
C) 6~12% Ce oxides, with CeO2Meter；
D) 0.6~4% W oxides, with WO3Meter；
E) oxide of 2~6% Mg or/and Ca, in terms of MgO or/and CaO；
F) 2~4% at least one alkali metal oxide selected from Rb, Cs, respectively with Rb2O、Cs2O is counted, wherein, alkali gold Belong to oxide to modify in potassium ferrite oxide surface in the form of salting liquid；
G) the light rare earth metal oxide of 1.5~4% at least one La, Pr, Nd selected from addition to Ce, respectively with La2O3、Pr2O3、Nd2O3Meter, wherein, light rare earth metal oxide is modified in the form of salting liquid in catalyst surface；
H) 0.3~2.5% Mn oxides, with MnO2Meter；
I) 0.3~2.5% Zn oxides, in terms of ZnO；
J) 0.3~2.5% Sn oxides, with SnO2Meter.
Catalyst preparation process is as follows：
1) source of iron purifies, and by iron oxide red when 500~1000 DEG C of roastings 1~10 are small, removes impurity and moisture therein；
2) preparation of the potassium ferrite oxide precursor I of Mg, Ca ion doping, by iron, potassium raw material amount than 5:1 claims Whole iron material iron oxide reds is measured, sequentially adds 10~50% potassium raw material and 10~60% Mg, Ca raw material, dry-mixed 1~5 After hour, when 500~1000 DEG C of roastings 1~10 are small, by alkali metal oxide Rb2O、Cs2O in the form of its nitrate solution, Using spray-on process modification in potassium ferrite oxide surface, presoma I is formed；
3) presoma I is ground or is crushed to 50~100 mesh by the preparation of presoma II, by content match add in Ce, W, Mn, Zn, Sn co-catalyst raw material and remaining K, Mg, Ca raw material, it is dry-mixed 1~5 it is small when after add in deionized water, be formed with gluing Property, be suitble to the paste of extrusion, through extrusion, pelletizing into about 3 millimeters of diameter, particle 6~8 millimeters long, in 80~150 DEG C of dryings 1~10 it is small when, form presoma II.
4) preparation of finished catalyst, using infusion process or spray-on process by La, Pr, Nd light rare earth metal oxygen in addition to Ce The salting liquid modification of compound on catalyst precursor II, then through 80~120 DEG C it is dry 2~8 it is small when, 500~1000 DEG C of roastings Finished catalyst is made when small in burning 2~8.
In the catalyst preparation process of the present invention, in addition to bulk composition, pore-foaming agent is preferably added to, dosage is catalyst The 1~10% of weight, pore-foaming agent can be selected from graphite, styroflex ball (PS), carboxymethyl cellulose (CMC), preferably For carboxymethyl cellulose.
In above-mentioned technical proposal, K2Fe10O16Content preferred embodiment is 70~75%；K2O content preferred embodiment is 1~3%； CeO2Content preferred embodiment is 6~10%；WO3Content preferred embodiment is 1~4%；Alkaline earth oxide MgO or/and CaO contain Amount is preferably 2~4%；Alkali metal oxide Rb2O or/and Cs2O content is preferably 2~3%；Light rare earth metal in addition to Ce Oxide preferred embodiment is La2O3, content is preferably 2~3%；MnO2Content preferred embodiment is 0.5~2%；ZnO content is preferred Scheme is 0.5~2%；SnO2Content preferred embodiment is 0.5~2%.
In catalyst of the present invention, alkali metal oxide Rb2O、Cs2O is in the form of its nitrate solution, using spray Mist method is modified in potassium ferrite oxide surface, light rare earth metal oxide La in addition to Ce2O3、Pr2O3、Nd2O3Respectively with it The form of nitrate solution, using infusion process or spray-on process modification in catalyst surface, by alkali metal and light rare earth metal from The modification that son carries out ferrous acid potassium oxide and catalyst surface effectively increases the specific surface area and activearm of catalyst The dispersion degree divided, it is suppressed that the problem of excessive carbon distribution causes catalyst surface carbon distribution to inactivate under low water ratio operating mode, so that secondary Reaction reduces, and improves the selectivity of purpose product styrene.
Mn, Zn, Sn oxide must add component for catalyst of the present invention, by the synergistic effect of the combination of oxides, carry High ethylbenzene conversion ratio under low water ratio operating mode.
The made dehydrogenation of the present invention, under certain process conditions, can be completely suitable for by ethylbenzene, diethylbenzene, 1- methyl-ethyl benzenes manufacture styrene, divinylbenzene and 1- methyl styrenes.
The catalyst for phenylethylene dehydrogenation prepared through the method for the invention carries out activity in 4L thermal insulation suction side line apparatus and comments Valency, process are summarized as follows：
4L thermal insulation suction sides line apparatus totally 2 sections of reactors, each reactor load 2L catalyst, outside insulating layer points three sections with Electric-heating-wire-heating makes the temperature of insulating layer close to the temperature of reactor bed, to ensure insulation effect, and above and below reactor Position is equipped with heating iron, and iron block plays the role of adjusting reaction raw materials temperature and prevents axial heat leakage.It is reacted in first segment There is a mixer before device import, to ensure that the two bursts of chargings of water and ethylbenzene can be sufficiently mixed before the reaction, reach reaction requirement.
The inlet amount of reaction raw materials water and ethylbenzene is controlled by metering pump, and the water for accounting for total inflow 60% enters vapour after pump Change device, superheater, being heated to 600 DEG C or more becomes superheated vapour, and the water and material ethylbenzene in addition accounting for total Water 40% pass through Into vaporizer, superheater after pump mixing, 560 DEG C or so are heated to, then the superheated vapour with 600 DEG C or more enters jointly Mixer, two strands of materials after mixing, then through first segment reactor top heating iron, make reaction mixture gas reach reaction institute Temperature is needed, into catalyst bed, carries out dehydrogenation reaction, after first segment dehydrogenation reaction, reaction mass temperature is decreased obviously.So It is heated afterwards by the upper iron block of second segment reactor, gaseous mixture is risen to the temperature of requirement, into second segment dehydrogenation reactor.Second The condensed rear incoagulable gas such as gas-liquid separator, hydrogen that enter of outlets products of section reactor are discharged into big by vacuum pumped Gas, liquid are directed respectively into oil tank and water pot, wherein each 2 of oil tank and water pot after oil water separator, can automatic back-and-forth switching. Sampler is respectively provided in first reactor outlet and second reactor outlet, the liquid of two samplers is taken when 8 is small, It send to gas chromatograph and is analyzed.Reaction product composition is using Japan's Shimadzu GC-14C chromatographics (using correction Area normalization method).
Conversion of ethylbenzene and selectivity of styrene calculate as follows：
In the case where low water ratio reacts operating mode, catalyst surface disappears carbon caused by vapor largely reduces in reaction system Reaction less than carbon distribution reaction, so that catalyst activity reduction is rapid, make catalyst for phenylethylene dehydrogenation under the reaction process condition Easily inactivate, since catalyst for phenylethylene dehydrogenation is full active component, during the reaction, catalyst surface and active phase potassium ferrite The problem of carbon distribution inactivation, can occur for inside, the method that the present invention prepares presoma I, II by adding in Ca, Mg ion in two steps, Enhance the bonding power between K atoms and Fe atoms, the very big main active phase K of limit generation2Fe10O16(Mg, Ca ion doping Ferrous acid potassium oxide), it is suppressed that the problem of carbon distribution inactivation occurs under low water ratio operating mode inside active phase potassium ferrite, so as to improve Catalyst activity.The bulk density and anti-crushing power of catalyst also significantly improve；The present invention is with the potassium ferrite of Mg, Ca ion doping The form of oxide precursor prepares catalyst, can effectively reduce potassium content；And using the side for adding in potassium promoter substep Method makes the effect of co-catalyst K be not fully exerted, efficiently solve high potassium catalyst after the reaction the phase caused by potassium lost The problems such as catalyst stability is bad, poor selectivity, improve stability that catalyst runs under low water ratio operating mode and Selectivity；By the present invention by purifying of the high-temperature roasting to source of iron-iron oxide red, eliminate present in raw material about 3% it is miscellaneous Matter by as-reduced metal oxidation of impurities contained in raw material, prevents it in high-temperature calcination process into the main active phase of catalyst Potassium ferrite lattice reduces catalyst activity；The catalyst for phenylethylene dehydrogenation prepared in the present invention, in 4L thermal insulation negative pressure evaluating apparatus On, in anti-623 DEG C of an entrance, two anti-627 DEG C of entrances, water than 1.05, liquid air speed 0.36h-1, two anti-outlet pressure 40KPa Under the conditions of, catalyst activity significantly improves, conversion of ethylbenzene >=66%, selectivity of styrene >=97%, and catalyst stability Be improved significantly, deactivation rate is substantially reduced, and achieves good technique effect.The present invention is made below by embodiment It is further elucidated above.
Specific embodiment
【Embodiment 1】
315g iron oxide reds, 58.7g potassium carbonate, 71.5g cerium oxalates, 11g ammonium tungstates, 8g magnesia, 15.8g are weighed respectively Calcium carbonate, 8.9g rubidium nitrates, 5.9g cesium nitrates, 9g lanthanum nitrates, 2.5g zinc oxide, 2.5g manganese dioxide, 1.8g stannic oxides and 30g carboxymethyl celluloses, catalyst preparation step are：By 315g iron oxide reds after 700 DEG C roast 4h, 42.5g carbonic acid is added in Potassium, 4g magnesia and the dry-mixed 2h of 7.1g calcium carbonate, 4h is roasted in 750 DEG C, rubidium nitrate and cesium nitrate is configured to 100mL solution, Using spray-on process by solution even application to potassium ferrite oxide surface, presoma I is obtained；Add after presoma I is ground to 80 mesh Enter remaining magnesia, calcium carbonate, potassium carbonate, cerium oxalate, ammonium tungstate, zinc oxide, manganese dioxide, stannic oxide and carboxymethyl Cellulose adds in 130mL deionized waters after dry-mixed 2h and is kneaded into viscosity, the paste for being suitble to extrusion, through extrusion, pelletizing into diameter About 3 millimeters, particle 6~8 millimeters long, in 120 DEG C it is dry 4 it is small when, 900 DEG C of roastings 4 it is small when after presoma II；By lanthanum nitrate Be configured to 100mL solution, using spray-on process by solution even application to presoma II surfaces, then 100 DEG C it is dry 4 it is small when, 750 DEG C of roastings 4 obtain finished catalyst when small.
【Embodiment 2】
Weigh respectively 340g iron oxide reds, 51.4g potassium carbonate, 40g cerium oxalates, 8.2g ammonium tungstates, 10.5g magnesia, 20.3g calcium carbonate, 2.9g rubidium nitrates, 2.4g cesium nitrates, 18.9g lanthanum nitrates, 1.25g zinc oxide, 1.25g manganese dioxide, 0.9g Stannic oxide and 30g carboxymethyl celluloses, catalyst preparation step are：By iron oxide red after 900 DEG C roast 4h, add in 38.2g potassium carbonate, 2.5g magnesia and the dry-mixed 2h of 4.5g calcium carbonate, after 550 DEG C roast 4h, rubidium nitrate and cesium nitrate are configured Into 100mL solution, using spray-on process by solution even application to potassium ferrite oxide surface, presoma I is obtained；Presoma I is ground Remaining magnesia, calcium carbonate, potassium carbonate, cerium oxalate, ammonium tungstate, zinc oxide, manganese dioxide, titanium dioxide are added in after being milled to 80 mesh Tin and carboxymethyl cellulose add in 130mL deionized waters after dry-mixed 2h and are kneaded into viscosity, the paste for being suitble to extrusion, through squeezing Item, pelletizing into about 3 millimeters of diameter, particle 6~8 millimeters long, in 120 DEG C it is dry 4 it is small when, 800 DEG C of roastings 4 it is small when after forerunner Body II；Praseodymium nitrate and neodymium nitrate are configured to 100mL solution, using infusion process by solution uniform load to presoma II surfaces, Then 100 DEG C it is dry 4 it is small when, 600 DEG C of roastings 4 it is small when obtain finished catalyst.
【Embodiment 3】
315g iron oxide reds, 58.7g potassium carbonate, 45g cerium oxalates, 16.4g ammonium tungstates, 7g magnesia, 10.5g are weighed respectively Calcium carbonate, 10.8g rubidium nitrates, 9.4g cesium nitrates, 17.9g lanthanum nitrates, 5g zinc oxide, 5g manganese dioxide, 3.6g stannic oxides and 30g carboxymethyl celluloses, catalyst preparation step are：By iron oxide red after 500 DEG C roast 4h, addition 42.5g potassium carbonate, 4.5g magnesia and the dry-mixed 3h of 8g calcium carbonate, after 850 DEG C roast 4h, rubidium nitrate and cesium nitrate are configured to 100mL solution, adopted With spray-on process by solution even application to potassium ferrite oxide surface, presoma I is obtained；It is added in after presoma I is ground to 80 mesh Remaining magnesia, calcium carbonate, potassium carbonate, cerium oxalate, ammonium tungstate, zinc oxide, manganese dioxide, stannic oxide and carboxymethyl cellulose Element adds in 130mL deionized waters after dry-mixed 2h and is kneaded into viscosity, the paste for being suitble to extrusion, through extrusion, pelletizing into diameter about 3 Millimeter, particle 6~8 millimeters long, in 120 DEG C it is dry 4 it is small when, 900 DEG C of roastings 4 it is small when after presoma II；Lanthanum nitrate is matched somebody with somebody Be set to 100mL solution, using spray-on process by solution even application to presoma II surfaces, then 120 DEG C it is dry 4 it is small when, 800 DEG C roasting 3 it is small when obtain finished catalyst.
【Embodiment 4】
Weigh respectively 300g iron oxide reds, 88g potassium carbonate, 47.2g cerium oxalates, 16.4g ammonium tungstates, 6.5g magnesia, 11.4g calcium carbonate, 2.9g rubidium nitrates, 2.4g cesium nitrates, 10g praseodymium nitrates, 9.8g neodymium nitrates, 2.5g zinc oxide, 2.5g titanium dioxides Manganese, 1.8g stannic oxides and 30g polyethylene fibre balls, catalyst preparation step is with embodiment 1, wherein adding when forming presoma I It is respectively 0.75g and 1.34g to enter magnesia and calcium carbonate.
【Embodiment 5】
365g iron oxide reds, 51.4g potassium carbonate, 47.2g cerium oxalates, 3.8g ammonium tungstates, 4g magnesia, 7.9g are weighed respectively Calcium carbonate, 2.9g rubidium nitrates, 3.4g cesium nitrates, 10g lanthanum nitrates, 10g praseodymium nitrates, 9.8g neodymium nitrates, 0.5g zinc oxide, 0.5g bis- Manganese oxide, 0.35g stannic oxides and 30g graphite, catalyst preparation step is with embodiment 1, wherein adding in oxygen when forming presoma I It is respectively 1.5g and 2.7g to change magnesium and calcium carbonate.
【Embodiment 6】
Weigh respectively 320g iron oxide reds, 58.7g potassium carbonate, 107.3g cerium oxalates, 21.8g ammonium tungstates, 2g magnesia, 3.5g calcium carbonate, 11.8g rubidium nitrates, 10.4g cesium nitrates, 20g lanthanum nitrates, 10g praseodymium nitrates, 9.8g neodymium nitrates, 2g zinc oxide, 2g Manganese dioxide, 1.4g stannic oxides and 30g carboxymethyl celluloses, catalyst preparation step is with embodiment 1, wherein forming presoma It is respectively 1.2g and 2.1g that magnesia and calcium carbonate are added in during I.
【Embodiment 7】
Weigh respectively 330g iron oxide reds, 58.7g potassium carbonate, 64.4g cerium oxalates, 5.5g ammonium tungstates, 2.5g magnesia, 4.5g calcium carbonate, 19.7g rubidium nitrates, 17.3g cesium nitrates, 5g lanthanum nitrates, 5g praseodymium nitrates, 7.5g zinc oxide, 7.5g manganese dioxide, 5.4g stannic oxides and 30g polyethylene fibre balls, catalyst preparation step is with embodiment 1, wherein adding in oxygen when forming presoma I It is respectively 1g and 1.8g to change magnesium and calcium carbonate.
【Comparative example 1~5】
The method for preparing catalyst of comparative example 1~5 is the same as embodiment 1.It purifies and walks without iron oxide wherein in comparative example 1 Suddenly, Mg, Ca component disposably add in during presoma II is formed in comparative example 2, and K components are before formation in comparative example 3 It is disposably added in during driving body I, the light rare earth metal element in comparative example 4 in addition to Ce is preparing the process of presoma II In be added in catalyst body rather than be supported on catalyst surface, in comparative example 5 prepared by alkali metal element rubidium, cesium component Potassium ferrite oxide surface is added in catalyst body rather than is supported on during presoma I, and catalyst composition situation is shown in Table 1.
The catalyst composition of 1 comparative example 1~5 of table
【Comparative example 6】
Catalyst composition uses dry pigmentation with embodiment 1, preparation method.By 350g iron oxide reds after 700 DEG C roast 4h, Be separately added into 58.7g potassium carbonate, 61.5g cerium oxalates, 11g ammonium tungstates, 8g magnesia, 15.8g calcium carbonate, 8.9g rubidium nitrates, 5.9g cesium nitrates, 9g lanthanum nitrates, 2.5g zinc oxide, 2.5g manganese dioxide, 1.8g stannic oxides and 30g carboxymethyl celluloses are done After powder mixing 2h, into suitable extrusion after addition 130mL deionized water kneadings about 1h after addition 130mL deionized water kneadings about 1h Dough object, extrusion, pelletizing are into about 3 millimeters of diameter, the particle of 6~8 millimeters of length；It is small in aged at room temperature 12h, 120 DEG C of dryings 4 When, be placed in 900 DEG C of Muffle furnace high temperature roasting 6 it is small when obtain finished catalyst.
【Comparative example 7】
Catalyst prepared by 1 the method for patent CN201410778920.6 embodiments：Weigh respectively 300g iron oxide reds, When the dry-mixed mixing 1 of 73.5g potassium carbonate, 5g zinc oxide, 5g manganese dioxide, 5g brown lead oxide is small when 600 DEG C of roastings 2 are small, 83g cerium oxalates, 28.9g ammonium tetramolybdates, 25g magnesia, 35.6g calcium carbonate and 30g carboxymethyl celluloses are added in product of roasting Element after dry powder blend 2h, adds in 130mL deionized waters and mediates after about 1h into the dough object of suitable extrusion, extrusion, pelletizing Cheng Zhi About 3 millimeters of footpath, the particle of 6~8 millimeters of length；When aged at room temperature 12h, 120 DEG C of dryings 4 are small, Muffle furnace high temperature 900 is placed in DEG C roasting 6 it is small when, obtain catalyst precursor, measure presoma volume with 500mL graduated cylinders；It prepares by 7.9g rubidium nitrates, 6.9g Mixed solution that cesium nitrate and 10g lanthanum nitrates form, identical with catalyst precursor volume, then using equi-volume impregnating Mixing salt solution is carried on catalyst precursor, through 120 DEG C it is dry 6 it is small when, 750 DEG C of roastings 4 it is small when be made catalyst into Product.
Catalyst physical property detection project includes bulk density and radial direction anti-crushing power；Comparative example and embodiment catalyst performance Evaluation carries out on 4L thermal insulation negative pressure evaluating apparatus, and reaction process is：One anti-inlet temperature is 623 DEG C, two anti-inlet temperatures It is that 1.05, ethylbenzene liquid air speed is 0.36h for 627 DEG C, water ratio (mass ratio of vapor and ethylbenzene)-1, two anti-outlet pressures be 40KPa (absolute pressure).Catalyst physical data is shown in Table 2, and catalyst activity evaluation result is shown in Table 3, catalyst stability evaluation result It is shown in Table 4.
The bulk density that table 2 lists comparative example and the made catalyst of embodiment detects data with radial direction anti-crushing power.From Table 2 is as can be seen that the method for preparing presoma I, II using Ca, Mg ion is added in two steps, the bulk density of catalyst and footpath It is improved significantly to anti-crushing power.
2 bulk density of table and radial direction anti-crushing power data comparison
Catalyst Bulk density (g/mL) Radial direction anti-crushing power (N/mm)
Embodiment 1 1.42 30
Embodiment 2 1.41 29
Embodiment 3 1.40 29
Embodiment 4 1.39 29
Embodiment 5 1.40 28
Embodiment 6 1.38 28
Embodiment 7 1.39 29
Comparative example 1 1.30 24
Comparative example 2 1.32 25
Comparative example 3 1.35 26
Comparative example 4 1.36 27
Comparative example 5 1.25 20
Comparative example 6 1.26 21
Comparative example 7 1.41 28
3 catalyst low water ratio catalytic dehydrogenation performance comparison of table
The stability appraisal result comparison of 4 catalyst of table
Table 3 and table 4 list respectively comparative example and the made catalyst of embodiment activity and study on the stability as a result, from table In as can be seen that by source of iron is purified, is reduced potassium content, by K, Mg, Ca auxiliary agent substep be added to the medium system of catalyst Standby process modification, catalyst is under low water ratio operating mode, and for activity more than 65.0%, catalyst activity is high；It is reacted by 1000h Afterwards, conversion of ethylbenzene is substantially unchanged, remains at 65% or so, and catalyst deactivation rate is low, and stability is good.Comparative example 1-6 Made catalyst activity is poor, and after 1000h reacts, activity declines substantially, and stability is poor.According to patent CN201410778920.6 the methods prepare catalyst (comparative example 7), the physical property of the catalyst is preferable, initial activity compared with Height, but the stability of catalyst long-term operation is poor, due to the loss of potassium element, under low water ratio operating mode in active phase potassium ferrite Carbon distribution occurs for portion, and catalyst deactivation rate is too fast, and activity declines substantially, and stability is poor.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art The protection domain of the claims in the present invention should all be belonged to.

Claims (9)

1. a kind of catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene, which is characterized in that remembered with mass content, catalyst includes following component：
A) 65~75% ferrous acid kalium composite oxides, with K2Fe10O16Meter；
B) 1~4% K oxides, with K2O is counted；
C) 6~12% Ce oxides, with CeO2Meter；
D) 0.6~4% W oxides, with WO3Meter；
E) oxide of 2~6% Mg or/and Ca, in terms of MgO or/and CaO；
F) 2~4% at least one alkali metal oxide selected from Rb, Cs, respectively with Rb2O、Cs2O is counted, wherein, alkali metal oxygen Compound is modified in the form of salting liquid in potassium ferrite oxide surface；
G) 1.5~4% at least one light rare earth metal oxide selected from La, Pr, Nd in addition to Ce, respectively with La2O3、 Pr2O3、Nd2O3Meter, wherein, light rare earth metal oxide is modified in the form of salting liquid in catalyst surface；
H) 0.3~2.5% Mn oxides, with MnO2Meter；
I) 0.3~2.5% Zn oxides, in terms of ZnO；
J) 0.3~2.5% Sn oxides, with SnO2Meter.
2. catalyst according to claim 1, it is characterised in that the content of ferrous acid kalium composite oxides is 70~75%.
3. catalyst according to claim 1, it is characterised in that the content of potassium oxide is 1~3%, and cerium oxide contains It measures as 6~10%.
4. catalyst according to claim 1, it is characterised in that the content of tungsten oxide is 1~4%.
5. catalyst according to claim 1, it is characterised in that alkaline earth oxide Rb2O and/or Cs2The content of O is 2 ~3%.
6. catalyst according to claim 1, it is characterised in that the content of light rare earth metal oxide in addition to Ce is 1.5~4%.
7. catalyst according to claim 1, it is characterised in that the light rare earth metal oxide of addition is La2O3, content is 2~3%.
8. according to the preparation method of any one of claim 1~7 catalyst, it is characterised in that catalyst preparation process is such as Under：1) source of iron purifies, and by iron oxide red when 500~1000 DEG C of roastings 1~10 are small, removes impurity and moisture therein；
2) preparation of the potassium ferrite oxide precursor I of Mg, Ca ion doping, by iron, potassium raw material amount than 5:1 weighs entirely The iron material iron oxide red in portion, sequentially adds 10~50% potassium raw material and 10~60% Mg, Ca raw material, it is dry-mixed 1~5 it is small when Afterwards, when 500~1000 DEG C of roastings 1~10 are small, by alkali metal oxide Rb2O、Cs2O is used in the form of its nitrate solution Spray-on process modification forms presoma I in potassium ferrite oxide surface；
3) presoma I is ground or is crushed to 50~100 mesh by the preparation of presoma II, by content match add in Ce, W, Mn, Zn, Sn co-catalysts raw material and remaining K, Mg, Ca raw material, it is dry-mixed 1~5 it is small when after add in deionized water, be made toughness, be suitble to The paste of extrusion is small in 80~150 DEG C of dryings 1~10 through extrusion, pelletizing into about 3 millimeters of diameter, particle 6~8 millimeters long When, form presoma II；
4) preparation of finished catalyst, using infusion process or spray-on process by La, Pr, Nd light rare earth metal oxide in addition to Ce Salting liquid modification on catalyst precursor II, then through 80~120 DEG C it is dry 2~8 it is small when, 500~1000 DEG C of roastings 2~ 8 are made finished catalyst when small.
9. according to the preparation method of catalyst described in right 8, it is characterised in that be additionally added at least one in catalyst preparation process Pore-foaming agent in graphite, polystyrene microsphere, carboxymethyl cellulose, the dosage of pore-foaming agent for catalyst weight 1~ 10%.
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