CN102040462B - Method for producing styrene by ethylbenzene dehydrogenation-hydrogen selective oxidization - Google Patents
Method for producing styrene by ethylbenzene dehydrogenation-hydrogen selective oxidization Download PDFInfo
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Abstract
The invention relates to a method for producing styrene by ethylbenzene dehydrogenation-hydrogen selective oxidization, which mainly solves the problem of low conversion ratio of raw materials and low utilization ratio of energy in the process of producing styrene by ethylbenzene catalytic dehydrogenation in the prior art. In the invention, by using a product of the ethylbenzene catalytic dehydrogenation and oxygen or oxygen-containing gas as raw materials and with the reaction temperature of 400-800 DEG C, the reaction pressure of 1-1000KPa and the liquid hourly space velocity (LHSV) of 0.01-100 hours<-1>, the reaction raw materials come into contact with an oxidizing catalyst to burn hydrogen and promote balanced material moving so that the conversion ratio of ethylbenzene is improved. The technical scheme for preparing the styrene excellently is beneficial to the solving of the problems and can be applied to industrial production for producing the styrene by ethylbenzene dehydrogenation.
Description
Technical field
The present invention relates to a kind of cinnamic production method.
Background technology
Vinylbenzene is a kind of important basic organic chemical industry raw material, is widely used in to produce plastics, rubber and resin etc.Ethylbenzene catalytic dehydrogenation is to produce cinnamic main method.The dehydrogenation reaction of ethylbenzene adopts the ferriferous oxide of modifying in steam atmosphere be catalyzer, at 540～675 ℃ of temperature of reaction, reaction pressure 20～150KPa, air speed 0.5～2h
-1Under carry out.Ethylbenzene catalytic dehydrogenation generates vinylbenzene and hydrogen is a balanced reaction that heat absorption, molecule number increase, be subjected to the obvious reduction of reaction bed temperature in the restriction of thermodynamic(al)equilibrium and the reaction process, the transformation efficiency of ethylbenzene dehydrogenation reaction can only maintain a lower level.For improving the turnover ratio of ethylbenzene, common way is to pass into superheated vapour the product vapor of last process is reheated between two dehydrogenation reactors, but so undoubtedly can so that the expense of dehydrogenation reaction obviously increase, nonetheless, the turnover ratio of ethylbenzene also only maintains about 65%.Therefore, the mode of a kind of economy of needs reaches the method for superheated vapour.One of method is to introduce oxygen or contain the gas of oxygen in reaction system so that the hydrogen that produces in the reaction process and oxygen generation combustion reactions, and the forward that spurs the dehydrogenation reaction balance moves.As a result, higher conversion of ethylbenzene and selectivity of styrene have just been obtained.Can promote that not only balance moves and the by product hydrogen of dehydrogenation reaction is carried out selective combustion, improve the transformation efficiency of reaction; The heat of simultaneously combustion of hydrogen generation can for the thermo-negative reaction ethylbenzene dehydrogenation provides heat, be realized heat-matter alliance again.
Compare with technique before, CN86104653 discloses a kind of hydrocarbon dehydrogenation method that oxidation reheats of using.But the method is with the hydro carbons of dehydrogenation, and for example alkyl aromatics (such as ethylbenzene) is raw material, with the several reactor catalysis dehydrogenations that contain dehydrogenation catalyst that are together in series, and the hydrogen that simultaneously selective oxidation produces in certain embodiments.CN86106197 discloses a kind of method that adopts oxidation to reheat step raising hydrogen consumption in dehydrogenation of hydrocarbons technique.The method is carried out catalytic dehydrogenation in the reactor that has two dehydrogenation catalyst beds that separate at least, by using a kind of intermediate bed that the hydrogen selective oxide catalyst is housed, carrying out reactant reheats, and make hydrogen consumption, thereby make the discharging cooling of the first dehydrogenation bed increase the hydrogen consumption of combustion phases with direct or indirect heat-exchanging method.US5997826 discloses the reactor of ethylbenzene catalytic dehydrogenation and hydrogen selective oxidation.US6388154 discloses cinnamic production method.The method is divided into three steps: the again dehydrogenation of product after ethylbenzene dehydrogenation, hydrogen selective oxidation, the oxidation, thus the turnover ratio of ethylbenzene is significantly improved.Reduce selectivity of catalyst on the oxide catalyst in order to prevent that K is lost in the dehydrogenation catalyst, this patent uses sial Ceramic Balls sorbent material to avoid the damage of oxide catalyst.
Above-mentioned patent is described in detail for reactor, catalyzer and the process of ethylbenzene dehydrogenation and hydrogen selective oxidation, but it has just introduced the condition of hydrogen selective oxidation according to the operating mode of ethylbenzene dehydrogenation, do not provide the optimum reaction conditions.In fact, affected by processing condition very large for the selective oxidation process of hydrogen in the ethylbenzene dehydrogenation, and and then affect cinnamic whole production process, comprise the aspects such as energy consumption, material consumption.
The selective oxidation reaction that hydrogen in the styrene is produced in ethylbenzene dehydrogenation carries out at oxide catalyst.This process has the requirement of many harshnesses to oxide catalyst.Most important requirement is the requirement to catalyst stability, because oxide catalyst must equally with the dehydrogenation ferrum-based catalyst have long hydrothermal stability.The second, oxidation catalyst activity must be very high, so that oxygen can transform fully, thereby avoids the existence of oxygen to poison iron based dehydrogenation catalyst.The 3rd, the necessary selective oxidation hydrogen of catalyzer, otherwise can cause ethylbenzene and cinnamic consumption, cause undesirable aromatic hydrocarbons loss.
Ethylbenzene dehydrogenation produces in the styrene there to be much at oxide catalyst the selective oxidation reaction of hydrogen.For example, introduced PtSnLi/Al among patent US4812597 and the US4914249
2O
3Catalyzer adopts Pt as Primary Catalysts, and Sn is as promotor, and Li or other basic metal or alkaline-earth metal adopt α-Al as modifier
2O
3As carrier, its shortcoming is that the precious metals pt consumption is higher in the catalyzer.Patent US6177381 and CN1479649A have reported the layered catalyst composition.This catalyzer has for example coating gama-alumina for example of Alpha-alumina and an inorganic oxide of a kernel.On the skin equably load platinum metals such as platinum and promotor such as tin, catalyzer also contains a kind of modifier such as lithium.And for example patent US6858769 and CN1705510A have reported a kind of H 2 selective oxidation catalyzer take lithium aluminate as carrier.This catalyzer is take trichroite as kernel, take lithium aluminate as coating, and load platinum metals and modified metal on coating, for example, platinum and tin.Oxidation has good effect to this catalyzer to hydrogen selective in dehydrogenation reaction, and the consumption of Pt obviously reduces in the catalyzer.When the standby catalyzer of above-mentioned patent system is used for the hydrogen selective burning, fall short of the work-ing life of catalyzer, under hydrothermal condition during long-term operation, its physics-chem characteristic generation considerable change, particularly its specific surface area reduction, texture destruction even recurring structure variation etc., increase such as the coating rate of wear, coating cracking, peel off etc., thereby affect selectivity of catalyst and long period use.
Summary of the invention
One of technical problem to be solved by this invention provides a kind of ethylbenzene dehydrogenation-hydrogen selective oxidizing process process, mainly solves prior art producing phenyl ethylene by ethyl benzene catalytic dehydrogenation process Raw transformation efficiency and the low problem of capacity usage ratio.Second purpose provides a kind of catalyzer that can as far as possible avoid again arene oxidizing for the oxidation of ethylbenzene dehydrogenation process hydrogen selective.When this catalyzer is used for the ethylbenzene dehydrogenation process H 2 selective oxidation, have catalyzer long service life, the oxidizes hydrogen gas selectivity is high, raw material aromatic hydrocarbons rate of loss is low advantage.
For one of addressing the above problem, the technical solution adopted in the present invention is as follows: cinnamic method is produced in a kind of ethylbenzene dehydrogenation-hydrogen selective oxidation, take product and the oxygen of ethylbenzene catalytic dehydrogenation or the gas that contains oxygen as raw material, be 0.01～100h in 400～800 ℃ of temperature of reaction, reaction pressure 1～1000KPa, liquid reactions air speed (LHSV)
-1Under the condition, reaction raw materials and oxide catalyst catalytic combustion hydrogen, promotion balance move material, thereby improve the transformation efficiency of ethylbenzene, generate vinylbenzene.
In the technique scheme, the product of ethylbenzene catalytic dehydrogenation includes unconverted ethylbenzene, vinylbenzene, hydrogen and water vapour.Then dehydrogenation product oxide catalyst and oxygen or contain oxygen gas in the presence of be water and the oxidation of aromatic hydrocarbons does not occur with oxidation of hydrogen.The gas that contains oxygen comprises air and oxygen, and wherein the mol ratio of oxygen and hydrogen is 0.5: 1～2: 1.Oxygen content is excessively low, and is then not enough for heat supply, has little significance to breaking chemical equilibrium; The mol ratio of oxygen and hydrogen surpasses 2: 1, and then excessive oxygen can cause inactivation and affect cinnamic selectivity on follow-up iron based dehydrogenation catalyst.Preferred 520～650 ℃ of temperature of reaction, the preferred 20～200KPa of reaction pressure, the preferred 0.1～10h of liquid reactions air speed
-1Product after the oxidation then enters second dehydrogenation reactor and carries out further dehydrogenation reaction.Dehydrogenation and oxidising process can hocket down in principle, thereby improve constantly the transformation efficiency of material ethylbenzene.
The present invention adopts a kind of catalyzer for ethylbenzene dehydrogenation reaction Hydrogen gas selective oxidation, by weight percentage, comprise 91.5～99% lamellar composite carrier, load on 0.001～1.0% platinum metals on the lamellar composite carrier, 0.01 IVA and the group of the lanthanides promotor component of～5.0% basic metal, alkaline-earth metal modifier and 0.001～2.5%, wherein lamellar composite carrier by weight percentage, comprises that 69～94% are selected from α-Al
2O
3, at least a inert support in trichroite, zirconium white, titanium oxide, spinel, mullite or the mullite kernel and be combined in 5%～30% on the kernel and be selected from γ-Al
2O
3, δ-Al
2O
3, η-Al
2O
3, θ-Al
2O
3, molecular sieve, silicon oxide, titanium oxide or zirconic at least a oxide compound and 0.001%～1% be selected from the porous coating material outer layer of nonmetal P auxiliary agent.
In the technique scheme, check in the lamellar composite carrier catalyst precursor adsorptive power a little less than, preferred α-Al
2O
3, at least a in spinel, mullite or the trichroite, consumption is 75～90% of lamellar composite carrier weight.The coating of lamellar composite carrier is heat-resisting porous oxide material, and preferably the sorptive material of porous is stronger to the catalyst precursor adsorptive power, and has high specific surface area, preferred θ-Al
2O
3, δ-Al
2O
3, γ-Al
2O
3Or at least a in the molecular sieve, consumption is 8～25% of lamellar composite carrier weight, and thickness is 50～250 microns, and specific surface area is 10～200 meters
2/ gram; Nonmetal P is selected from high temperature decomposable ammonia salt of inorganic phosphorus acids, organophosphorus acids or its in the coating, and such as phosphoric acid ammonia, phosphoric acid hydrogen ammonia etc., consumption is 0.001～1% of lamellar composite carrier weight, and preferred 0.005～0.1%.Bond by organic binder bond and mineral binder bond between the kernel of inert support and porous coating material outer layer, can long-period stable operation to guarantee lamellar composite carrier.Organic binder bond is selected from least a of polyvinyl alcohol, Walocel MT 20.000PV, hydroxypropylcellulose, methyl or ethyl or carboxyethyl cellulose, ring Hu Jingzhong, and consumption is 0.01～5% of coating wt.Mineral binder bond is selected from least a in inorganic clay, aluminium colloidal sol, silicon sol, water glass, Calucium Silicate powder, the potassium felspar sand, and consumption is 0.01～10% of coating wt.Also contain nonionogenic tenside in the coating slurries, such as tween, sapn, polyoxy second (third) alkene ether, alkylolamide etc., to reduce the surface tension of slurries, addition is controlled at 0.01～5.0% of slurries total mass.The preferred platinum of platinum group precious metal, consumption are 0.01～0.5% of catalyst weight.At least a among the preferred Li of modifier, K, Mg, the Ba, consumption is 0.05～2.0% of catalyst weight.Promotor one IVA is selected from least a among Ge, Sn, the Pb, and consumption is 0.01～1.0% of catalyst weight; Promotor two group of the lanthanides are selected from least a among La, Ce, Pr, the Nd, and consumption is 0.005～0.5% of catalyst weight.
The method for preparing catalyst of ethylbenzene dehydrogenation reaction Hydrogen gas selective oxidation comprises the steps:
(1) preparation of inert support kernel.After the former powder of required carrier and binding agent fully mixed, make certain shape, such as cylindric, spherical, sheet, tubular, cellular or Raschig ring etc., but spherical inner core is reasonable selection, and its diameter is preferably 1～5 millimeter, so that industrial application; In 50～300 ℃ of dryings 1～24 hour, can adopt vacuum-drying or blowing air dry when dry carrier kernel after the moulding; Then carry out roasting, 900～1500 ℃ of maturing temperatures, preferred 1100～1400 ℃, roasting time 1～10 hour, preferred 1～5 hour, calcination atmosphere can carry out in air, oxygen atmosphere, preferred air atmosphere, the catalyzer naturally cooling after the roasting obtains the inert support kernel.
(2) preparation of coating ingredients slurries.At first, the preparation of solid ultrafine particle.Solid ingredient such as aluminum oxide, sieve particle can be controlled at its particle diameter below 20 microns by methods such as comminution by gas stream, ultrasonication, ball millings in the coating, in order to obtain ultrafine particle.It is more even that ultrafine particle is conducive to the coating coating on the one hand, can increase the specific surface area of coating simultaneously, is conducive to the dispersion of active ingredient.Then coating ingredients ultrafine particle, organic binder bond, mineral binder bond, tensio-active agent and deionized water are stirred, are mixed, ground according to required ratio, made slurries.In order to strengthen the firmness of coating, need to reduce particle size in the slurries, obtain that size of particles is little, the slurries of narrowly distributing.This can be undertaken by ball milled, colloidal grinding method, but is not limited to the method.Ball-milling Time is controlled at 30 minutes～and 5 hours, preferably be controlled at 1.5～3 hours, thereby the slurries particle diameter is controlled at below 20 microns, be combined firmly with matrix to guarantee the stable and coating of slurry.
(3) slurries are coated on the inert support kernel.Slurries form coating by the surface that sprays, the methods such as glue is coated with, dipping, dip-coating are coated on kernel, preferred spraying method.When the coated material of the kernel of lamellar composite carrier coated good after, 50～250 ℃ of dryings 1～24 hour, then 700～1200 ℃ of roastings 0.5～10 hour so that coating and the effective combination of carrier kernel, thereby obtain lamellar composite carrier.
(4) area load active ingredient.Adopt the area load method will contain the Solution Dispersion of active ingredient on the lamellar composite carrier coating.Catalyst activity component such as platinum metals, promotor and modifier can be dispersed on the lamellar composite carrier with any method that is suitable for obtaining surface impregnation.When preparation catalyzer of the present invention, can use any decomposable platinum family compound, such as halogenide, nitrate, oxide compound etc.: for example Platinic chloride, bromoplatinic acid, platinum dichloride, Tetrachloroplatinum, ammonium chloroplatinate, sodium platinous chloride, potassium chloroplatinite, dichloro four ammino platinum, dinitroso diammonia platinum, potassium platinichloride.Platinum-group component and modifier Li, K, Mg, Ba component can be combined with carrier with random order.Can flood platinum-group component on the lamellar composite carrier surface first, follow again one or more modifier components of surface impregnation, also can flood one or more modifier components at carrier surface first, then flood platinum-group component; Certainly flood simultaneously platinum-group component and the modifier component also can.The IVA promotor is tin preferably, and is wherein comparatively suitable with tin protochloride and tin tetrachloride; The group of the lanthanides promotor there is no special restriction to its source, and is comparatively suitable with nitrate, oxalate, oxide compound or muriate.Promotor can be dispersed in first in the aluminum oxide slurries, also can carry out surface impregnation after forming coating.Comparatively method commonly used is to spray the coating slurries that contain promotor at kernel first, after dry and roasting, according to method recited above carrier impregnation is prepared catalyzer in the solution that contains platinum and basic metal, alkaline earth metal compound.At last, the catalyzer that will contain active ingredient is first 100～150 ℃ of dryings 1～24 hour, and 200～700 ℃ of roastings 1～24 hour under hydrogen or other reductibility agent effects, in 400～700 ℃ of reduction 1～4 hour, namely make catalyzer at last.
Above-described catalyzer is generally used for the hydrogen selective combustion reactions that ethylbenzene dehydrogenation process produces.
In view of length is limit, do not exemplify among the embodiment in the platinum metals except platinum such as precious metals such as ruthenium, rhodium, palladium, osmium, iridium, but because the similarity of its character and platinum, thereby its performance and preparation method and platinum have same or similar part.
The present invention when Kaolinite Preparation of Catalyst, on the one hand because to adopt at least a in lanthanum, cerium, praseodymium, the neodymium be auxiliary agent, its at high temperature with activated alumina and zeolite molecular sieve generation chemical reaction, the higher chemical substance of generation hydrothermal stability is such as CeAlO
3, LaAlO
3Deng, thereby the hydrothermal stability of raising catalyzer floating coat; On the other hand, by introducing nonmetal phosphorus, make the oh group reaction of itself and metal oxide surface, in case the sintering of block compound, gathering improve the hydrothermal stability of carrier, thereby obviously improve work-ing life.In addition, catalyst components synergy of the present invention, the performance of selective oxidation hydrogen significantly strengthens, thereby the rate of loss of aromatic hydrocarbons significantly reduces.
When using the inventive method to produce vinylbenzene for ethylbenzene dehydrogenation-hydrogen selective oxidation, at normal pressure, liquid air speed 3h
-1, 580 ℃ of temperature of reaction, its result is O
2Transformation efficiency＞99.5%, aromatic hydrocarbons rate of loss＜0.1%.Raw material after the oxidation carries out dehydrogenation again, and in the situation of identical selectivity of styrene, conversion of ethylbenzene can be increased to 80%.In addition, through 24 hours 800 ℃ of hydrothermal test, the catalyzer property indices was compared with reference catalyst, and performance is excellent.Above data declaration: the inventive method is because conversion of ethylbenzene improves, and catalyst selectivity is high, long service life, thereby can reduce the ethylbenzene internal circulating load, reduce power charge, improve the throughput of device, thereby its economy obviously is better than traditional technology, obtained preferably technique effect.
Description of drawings
Fig. 1 is the SEM photo of the catalyzer D of fresh preparation in 4 among the embodiment.
Fig. 2 be among the embodiment in 4 the catalyzer D of preparation in the SEM photo of 800 ℃ of steam treatment after 24 hours.
Fig. 3 is the SEM photo of live catalyst I in the comparative example 1.
Fig. 4 be in the comparative example 1 catalyst I in 24 hours SEM photos of 800 ℃ of steam treatment.
Fig. 5 is the SEM photo of live catalyst J in the comparative example 2.
Fig. 6 be in the comparative example 2 catalyzer J in 24 hours SEM photos of 800 ℃ of steam treatment.
Fig. 7 is the SEM photo of the catalyzer L of fresh preparation in the comparative example 4.
Fig. 8 be in the comparative example 4 preparation catalyzer L in the SEM photo of 800 ℃ of steam treatment after 24 hours.
Fig. 9 is the TEM photo of the catalyzer D of fresh preparation in 4 among the embodiment.
Figure 10 be among the embodiment in 4 the catalyzer D of preparation in the TEM photo of 800 ℃ of steam treatment after 24 hours.
Figure 11 is the TEM photo of the catalyzer L of fresh preparation in the comparative example 4.
Figure 12 be in the comparative example 4 preparation catalyzer L in the TEM photo of 800 ℃ of steam treatment after 24 hours.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Aluminum oxide, magnesium oxide are added in the kneader according to stoichiometric ratio, mix, then the rare nitric acid that adds concentration 2% (weight), mediate and form the bulk material, extruded moulding and pressure ball, room temperature are placed and to be spent the night, 150 ℃ of air dryings 2 hours, roasting is 5 hours in 1350 ℃ of air, makes diameter and be 4 millimeters spherical MgAl
2O
4Carrier.
Glycerine solution, 0.13 gram strong phosphoric acid, the 0.3 gram sorbester p17 of 40 gram alumina sols (aluminum oxide that contains 15% mass ratio), 60 grams 2% are made slurries.Then adding 0.6 gram potassium felspar sand, 40 gram particles directly are the γ-Al below 20 microns in this mixed solution
2O
3Powder (200 meters of specific surface areas
2/ g).Stir about adds 0.85 gram Ce after ten minutes
2O
3, 2.2 the gram barium oxide and 0.2 the gram germanium dioxide, the slurries that obtain at room temperature ball milling 5 hours so that Particle size control below 20 microns.Slurries spray to MgAl
2O
4On the bead, in 80 ℃ of dryings 2 hours, then be warming up to 100 ℃ dry 2 hours again, in 1200 ℃ of roastings 3 hours, obtain lamellar composite carrier at last.
Platinic chloride is dissolved in the water, making its pH value with the HCl regulator solution is about 4, then this solution is heated to 80 ℃, be immersed on the lamellar composite carrier of having made, then in 150 ℃ of dryings 1 hour, then 700 ℃ of roastings 1 hour, at last reduction 4 hours in 400 ℃ of hydrogen atmospheres, then be cooled to room temperature, obtain catalyst A.
[embodiment 2]
The sesbania powder of a certain amount of dry powder pseudo-boehmite, alumina trihydrate (ratio 30: 70) and the aluminum oxide gross weight 5% of in bowling machine, packing into, start bowling machine, spray into rare nitric acid binding agent of 2% (weight), constantly stir and make dry powder and the abundant mixing of water, when the binding agent spraying finishes, alumina material rolls becomes the particle cluster of diameter 1～2mm, then constantly is sprinkled into equably dry powder and binding agent, makes particle reach 4mm.80 ℃ of vacuum-drying 24 hours, 300 ℃ of dry airs 2 hours, roasting is 10 hours in 1400 ℃ of oxygen atmospheres, makes spherical α-Al
2O
3Carrier.
With SnCl
2Reach praseodymium chloride and be dissolved at 1: 0.5 in the water according to mol ratio, mentioned solution is immersed in θ-Al
2O
3On (solid-to-liquid ratio 1: 2) powder, in 150 ℃ of dryings 2 hours, 400 ℃ of roastings 4 hours.Polyacrylamide solution, the 0.4 gram polyoxyethylene nonylphenol ether-5 of 40 gram alumina sols (containing 15% aluminum oxide), 0.28 gram ammonium hydrogen phosphate, 60 grams 3% are made slurries.Then the particle diameter that adds 0.3 gram Calucium Silicate powder, 40 gram process pre-soaked Sn, Pr in this mixed solution is the θ-Al below 15 microns
2O
3Powder.Stir about adds 2.0 gram 25%MgCl after ten minutes
2The aqueous solution, the slurries that obtain at room temperature adopted colloidal mill 30 minutes so that Particle size control below 15 microns.Slurries spray to the α-Al of 4 millimeters of particle diameters
2O
3On the bead, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours again, in 800 ℃ of roastings 10 hours, obtain lamellar composite carrier at last.
Lithium nitrate and Platinic chloride are dissolved in the water respectively, making its pH value with the HCl regulator solution is about 3, then this solution is heated to 75 ℃, be immersed on the lamellar composite carrier of having made, then in 100 ℃ of dryings 24 hours, then immerse the solution reduction 30 minutes that contains hydrazine hydrate, then drain, 500 ℃ of roastings 6 hours, then be cooled to room temperature, obtain catalyst B.
[embodiment 3]
The first powder of a certain amount of mullite of in bowling machine, packing into, start bowling machine, spray into aluminium sol adhesive, constantly stir and make dry powder and the abundant mixing of binding agent, when spraying finishes, the mullite material rolls becomes the particle cluster of diameter 1～2mm, then constantly is sprinkled into equably dry powder and binding agent, makes particle reach 3mm.Drying is 10 hours in 120 ℃ of air atmospheres, and roasting is 4 hours in 1100 ℃ of air atmospheres, makes spherical mullite carrier.
Cyclodextrin soln, 0.35 gram ammonium phosphate, the 1.0 gram tween-80s of 35 gram alumina sols (aluminum oxide that contains 25% mass ratio), 5 grams, 40% silicon sol, 60 grams 4% are made slurries.Then in this mixed solution, add 0.4 gram Calucium Silicate powder, 0.3 gram salt of wormwood, 0.4 gram plumbous oxide and 40 gram particles and directly be the δ-Al below 20 microns
2O
3Powder.Stir about adds 2.0 grams, 10% the Neodymium trichloride aqueous solution after ten minutes, the slurries that obtain at room temperature colloidal mill 2 hours so that Particle size control below 10 microns.Slurries spray on the mullite bead, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours again, in 900 ℃ of roastings 6 hours, obtain lamellar composite carrier at last.
Lithium nitrate and sodium platinous chloride are dissolved in the water respectively, be mixed with mixing solutions, making its pH value with the HCl regulator solution is about 4, then this solution is heated to 80 ℃, is immersed on the lamellar composite carrier of having made, then in 120 ℃ of dryings 8 hours, then 200 ℃ of vacuum bakings 24 hours, then 700 ℃ of hydrogen reducings are 1 hour, are cooled at last room temperature in air atmosphere, obtain catalyzer C.
[embodiment 4]
Aluminum oxide, silicon sol, magnesium oxide are added in the kneader according to proportioning, mix, then the rare nitric acid that adds concentration 2% (weight), mediate and form the bulk material, extruded moulding and pressure ball, 150 ℃ of air dryings 6 hours, roasting is 4 hours in 1350 ℃ of air, makes diameter and be 6 millimeters spherical cordierite carrier.
Cyclodextrin soln, the 1.0 gram oleylamide Soxylat A 25-7s-6 of 38 gram alumina sols (aluminum oxide that contains 20% mass ratio), 1.2 grams, 5% phosphoric acid, 4 gram lanthanum nitrates, 60 grams 4% are made slurries.Then in this mixed solution, add 0.2 gram Calucium Silicate powder, 40 grams through pretreated δ-Al below 15 microns
2O
3Powder.The slurries that obtain at room temperature ball milling 3 hours so that Particle size control below 10 microns.On the slurries sprayings trichroite bead, in 50 ℃ of vacuum-dryings 2 hours, then be warming up to 250 ℃ dry 2 hours again, in 1000 ℃ of roastings 5 hours, obtain lamellar composite carrier at last.
Lithium nitrate is dissolved in the water, and vacuum impregnation is on the lamellar composite carrier of having made, then in 150 ℃ of dryings 2 hours.With SnCl
4And sodium platinous chloride is dissolved in the ethanolic soln, again be immersed on the carrier, and 100 ℃ of dryings 2 hours, then 550 ℃ of roastings 2 hours, reductase 12 hour in 600 ℃ of hydrogen atmospheres then is cooled to room temperature, obtains catalyzer D.
[embodiment 5]
α-Al
2O
3The preparation method of ball type carrier is with embodiment 2.
Hydroxypropyl cellulose solution, the 1.0 gram diethanolamine of 38 grams, 12% alumina sol, 1.2 grams, 5% phosphoric acid, 4 gram lanthanum nitrates, 60 grams 1% are made slurries.Then in this mixed solution, add 0.2 gram inorganic clay, 0.1 gram germanium dioxide, 0.4 gram plumbous oxide and 40 grams through pretreated ZSM5 (silica alumina ratio 22) powder below 10 microns.The slurries that obtain at room temperature colloidal mill 1.5 hours so that Particle size control below 10 microns.Slurries are sprayed to the α-Al of 4 millimeters of particle diameters
2O
3On the spheroid, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours again, in 700 ℃ of roastings 30 minutes, obtain lamellar composite carrier at last.
Then flood lithium nitrate, Platinic chloride, method obtains catalyzer E with embodiment 2.
[embodiment 6]
The preparation method of spherical trichroite kernel is with embodiment 4.
Walocel MT 20.000PV solution, 3 grams, 30% water glass, the 1.0 gram P123 of 38 grams, 10% alumina sol, 1.2 grams, 5% phosphoric acid, 60 grams 4% are made slurries.Then the 50% tin tetrachloride solution and the lanthanum nitrate, 40 that add 0.2 gram Calucium Silicate powder, requirement in this mixed solution restrain through pretreated δ-Al below 10 microns
2O
3Powder.The slurries that obtain at room temperature ball milling 4 hours so that Particle size control below 10 microns.Slurries spray on the trichroite spheroid of 4 millimeters of particle diameters, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours again, in 1100 ℃ of roastings 4 hours, obtain lamellar composite carrier at last.
Then flood lithium nitrate, Platinic chloride, method obtains catalyzer F with embodiment 2.
[embodiment 7]
Spherical MgAl
2O
4The preparation method of kernel is with embodiment 1.
Carboxyethyl cellulose solution, the 1.0 gram trolamines of 38 grams, 10% alumina sol, 1.2 grams, 5% phosphoric acid, 60 grams 4% are made slurries.Then the 50% tin tetrachloride solution, the pretreated δ-Al below 20 microns of 40 gram processes that in this mixed solution, add 0.2 gram Calucium Silicate powder, 5.3 gram cerium oxide, metering
2O
3Powder.The slurries that obtain at room temperature ball milling 4 hours so that Particle size control below 10 microns.Slurries spray to the MgAl of 4 millimeters of particle diameters
2O
4On the spheroid, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours again, in 900 ℃ of roastings 4 hours, obtain lamellar composite carrier at last.
Then flood lithium nitrate, Platinic chloride, method obtains catalyzer G with embodiment 2.
[embodiment 8]
The preparation method of spherical trichroite kernel is with embodiment 4.
Polyvinyl alcohol-20000 solution, the 1.0 gram polyoxyethylene octylphenol ethers-4 of 38 grams, 10% alumina sol, 2.4 grams, 5% phosphoric acid, 0.21 gram lead nitrate, 60 grams 5% are made slurries.Then in this mixed solution, add 0.2 gram Calucium Silicate powder, 2.0 gram lanthanum trioxides, 0.17 gram cerium oxide, 40 grams through pretreated δ-Al below 15 microns
2O
3Powder.The slurries that obtain at room temperature ball milling 4 hours so that Particle size control below 10 microns.Slurries spray on the trichroite spheroid of 4 millimeters of particle diameters, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours again, in 1200 ℃ of roastings 2 hours, obtain lamellar composite carrier at last.
Then flood lithium nitrate, Platinic chloride, method obtains catalyzer H with embodiment 2.
[comparative example 1]
The preparation method of lamellar composite carrier and catalyzer does not just introduce La with embodiment 4 in the preparation of lamellar composite carrier, catalyzer is marked as I.
[comparative example 2]
The preparation method of lamellar composite carrier and catalyzer does not just introduce P with embodiment 4 in the preparation of lamellar composite carrier, catalyzer is marked as J.
[comparative example 3]
The preparation of this oxide catalyst is shown in the embodiment 6 in the Chinese patent CN1479649A that mentions in the bibliography of front.Catalyzer is marked as K.
[comparative example 4]
The preparation of this oxide catalyst is shown in the embodiment 3 of 6858769 li of the US Patent No. mentioned in the bibliography of front.Catalyzer is marked as L.
[embodiment 9]
The catalyzer of embodiment and comparative example preparation is carried out 24 hours water vapour burin-in process in 800 ℃, and catalyst property sees Table 2.
Table 2 catalyzer physicochemical property
As seen from table, catalyzer and the reference catalyst of present method preparation are carried out 24 hours water vapour burin-in process in 800 ℃, decline in various degree all appears in specific surface area, but the carrier specific surface area fall of present method preparation is less, substantially below 5%, and without reference carrier K, the L specific surface area fall about 7～9% of present method preparation.As a comparison, the carrier D of embodiment 4 preparations and the comparative example carrier I, the J that do not introduce La or P (comparative example 1, comparative example 2) preparation, specific surface area changes obviously less.
Figure below is catalyzer D and the fresh preparation of reference catalyst and the SEM photo of 800 ℃ of steam treatment after 24 hours of the inventive method preparation.
The result shows that the lamellar composite carrier of present method preparation has no cracking phenomena through the hydrothermal treatment consists coating, and slight crack appears in the reference carrier coating, shows that the lamellar composite carrier of the inventive method preparation has the better advantage of hydrothermal stability.
[embodiment 10]
H 2 selective oxidation carries out in-built 30 milliliters of catalyzer in the ethylbenzene dehydrogenation process in internal diameter is 25 millimeters stainless steel reaction pipe.Reaction pressure is normal pressure, liquid air speed 3h
-1, 580 ℃ of temperature of reaction, reactant forms such as table 3.
The raw material of H 2 selective oxidation forms in table 3 ethylbenzene dehydrogenation process
| Raw material | Vinylbenzene | Ethylbenzene | Benzene and toluene | H 2 | O 2 | N 2 | Water |
| Content (molar percentage) | 2.4 | 5.4 | 0.08 | 2.4 | 1.1 | 0.11 | 88.51 |
The results are shown in Table 4 for the activity and selectivity of catalyzer.As can be seen from the table, the catalyzer of present method preparation is compared with reference catalyst and is had higher oxygen combustion selectivity and lower aromatic hydrocarbons rate of loss.
The reactivity worth of table 4 catalyzer
[embodiment 11]
The H 2 selective oxidation condition is with embodiment 10 in the ethylbenzene dehydrogenation process, and just temperature is different, the results are shown in Table 5.As seen from table, along with the rising of temperature of reaction, O
2Transformation efficiency substantially do not change H
2Transformation efficiency, O
2Selectivity then obviously reduce, the rate of loss of aromatic hydrocarbons then presents ascendant trend.As seen from table, when temperature of reaction during 520～650 ℃ of scopes, H
2Transformation efficiency＞77%, aromatic hydrocarbons rate of loss＜0.3%.But the hydrogen selective oxide catalyst is preferably than the low reaction temperatures section operation, and effect is better.
Table 5 temperature of reaction is on the impact of catalyst performance
| Temperature of reaction/℃ | H 2Transformation efficiency % | O 2Transformation efficiency % | O 2Selectivity % | Aromatic hydrocarbons rate of loss % |
| 520 | 87.62 | 99.45 | 96.38 | 0.09 |
| 540 | 86.58 | 99.48 | 96.21 | 0.08 |
| 560 | 85.46 | 99.52 | 95.64 | 0.08 |
| 580 | 83.49 | 99.88 | 94.39 | 0.09 |
| 600 | 81.19 | 99.62 | 92.20 | 0.12 |
| 620 | 79.27 | 99.71 | 88.54 | 0.17 |
| 650 | 77.97 | 99.77 | 84.51 | 0.23 |
[embodiment 12]
The H 2 selective oxidation condition is with embodiment 10 in the ethylbenzene dehydrogenation process, and just pressure is different, the results are shown in Table 6.As seen from table, low pressure is slightly favourable for reaction, but difference is little on the whole.
Table 6 reaction pressure is on the impact of catalyst performance
| Reaction pressure/Kpa | H 2Transformation efficiency % | O 2Transformation efficiency % | O 2Selectivity % | Aromatic hydrocarbons rate of |
| 20 | 81.95 | 99.76 | 94.16 | 0.09 |
| 60 | 82.53 | 99.72 | 94.11 | 0.09 |
| 100 | 83.49 | 99.88 | 94.39 | 0.09 |
| 150 | 84.12 | 99.60 | 93.66 | 0.10 |
| 200 | 83.89 | 99.66 | 93.28 | 0.11 |
[embodiment 13]
The H 2 selective oxidation condition is with embodiment 10 in the ethylbenzene dehydrogenation process, and just air speed is different, the results are shown in Table 7.As seen from table, at liquid air speed 0.1～10h
-1In the scope, catalyst reaction performance generation considerable change, air speed height then performance is better, shows that the catalyzer that the present invention develops has comparatively wide in range material processing power.
Table 7 reaction velocity is on the impact of catalyst performance
| Liquid air speed/h -1 | H 2Transformation efficiency % | O 2Transformation efficiency % | O 2Selectivity % | Aromatic hydrocarbons rate of loss % |
| 0.1 | 64.60 | 99.99 | 76.52 | 0.40 |
| 0.3 | 76.12 | 99.92 | 85.72 | 0.23 |
| 1 | 81.65 | 99.89 | 89.30 | 0.17 |
| 3 | 83.49 | 99.88 | 94.39 | 0.09 |
| 6 | 82.62 | 99.74 | 94.22 | 0.09 |
| 10 | 81.19 | 99.71 | 94.82 | 0.08 |
[embodiment 14]
The H 2 selective oxidation condition is with embodiment 10 in the ethylbenzene dehydrogenation process, and just oxygen is different from the hydrogen mol ratio, the results are shown in Table 8.The result shows that the oxygen content in the unstripped gas has certain impact to the performance of catalyzer, and oxygen content is high, and the transformation efficiency of hydrogen raises, and the selectivity of oxidizes hydrogen gas can descend to some extent, but in the scope of studying, fall is little.
Table 8 oxygen and hydrogen mol ratio are on the impact of catalyst performance
| O 2With H 2Mol ratio | H 2Transformation efficiency % | O 2Transformation efficiency % | O 2Selectivity % | Aromatic hydrocarbons rate of loss % |
| 0.5∶1 | 81.00 | 99.74 | 94.13 | 0.09 |
| 1∶1 | 84.22 | 99.83 | 93.58 | 0.10 |
| 2∶1 | 85.54 | 99.77 | 93.65 | 0.10 |
[embodiment 15]
The H 2 selective oxidation condition is with embodiment 10 in the ethylbenzene dehydrogenation process, and just styrene content is different in the raw material, the results are shown in Table 9.As seen from table, when styrene content changed in 20～45% scopes, catalyst performance was substantially unaffected, showed that oxide catalyst can use in different ethylbenzene dehydrogenation transformation efficiency situations.
Table 9 styrene content is on the impact of catalyst performance
| Styrene content/% | H 2Transformation efficiency % | O 2Transformation efficiency % | O 2Selectivity % | Aromatic hydrocarbons rate of |
| 20 | 90.21 | 99.57 | 94.10 | 0.09 |
| 25 | 90.90 | 99.59 | 94.36 | 0.09 |
| 30 | 91.12 | 99.58 | 94.81 | 0.08 |
| 35 | 91.64 | 99.55 | 94.55 | 0.08 |
| 40 | 90.63 | 99.62 | 94.22 | 0.09 |
| 45 | 90.87 | 99.72 | 94.29 | 0.09 |
[embodiment 16]
Oxide catalyst with reference to the ZL03150720 ethyl benzene dehydrogenation preparation of styrene prepares dehydrogenation catalyst.With ethylbenzene dehydrogenation-again dehydrogenation coupling of hydrogen selective oxidation-ethylbenzene, investigate ethylbenzene dehydrogenation-hydrogen selective oxidation and produce vinylbenzene technique.
Three reactors are 2 inches of internal diameters, long 2 meters stainless steel adiabatic reactor reactor.First reactor charge dehydrogenation catalyst, the second reactor charge oxide catalyst D, the 3rd reactor still loads dehydrogenation catalyst.Three reactors are contacted in order.Loaded catalyst 750mL, 620 ℃ of temperature of reaction, air speed 1.0h
-1, pressure is 75KPa, the mass ratio of water vapor and ethylbenzene is 2.0.Wherein in H 2 selective oxidation, introduce high-concentration oxygen (90% oxygen and 10% nitrogen), mix with the product from the first dehydrogenation reactor, under the effect of oxide catalyst, make by-product hydrogen partial oxidation, the heat that produces heats up reactant flow, continue to enter the 3rd dehydrogenation catalyst layer and carry out ethylbenzene dehydrogenation reaction, reaction result sees Table 10.As seen from table, compare with traditional catalytic dehydrogenation, this technique has reduced the consumption of dilution steam generation, and the vinylbenzene per pass conversion is increased to 82.5% from 70%, and steam and oil fuel consumption significantly reduce.
Table 10 ethylbenzene dehydrogenation traditional technology and dehydrogenation-oxidation-dehydrogenating technology technology relatively
| Reaction conditions and result | Traditional technology | Dehydrogenation-oxidation-dehydrogenation |
| Conversion of ethylbenzene % | 69.8 | 82.5 |
| Selectivity of styrene % | 96.05 | 96.05 |
| Steam consumption (tt -1) | 2.3 | 1.3 |
| Oil fuel consumption/(kgt -1) | 114.0 | 68.3 |
[embodiment 17]
In order further to investigate the stability with the catalyzer of present method preparation, catalyzer D to embodiment 4 preparations carries out 24 hours water vapour burin-in process in 800 ℃, TEM result shows that the fresh and aging rear Pt particle diameter of catalyzer of the present invention is respectively 1～2 nanometer, have no obvious increase, and be respectively 1～2 nanometer and 2～3 nanometers after the fresh and weathering test of the Pt particle diameter of catalyzer in the comparative example, agglomeration obviously occurs.Catalyzer after aging and reference catalyst be loaded into again carry out performance evaluation in the reactor, it is identical with embodiment 10 to estimate processing condition, the results are shown in Table 11.As seen from table, reference catalyst significantly descends through weathering test rear catalyst performance, and catalyst performance of the present invention decline is less, shows to adopt the catalyzer of carrier preparation of the present invention to have especially good thermostability.
The hydrogen selective combustion reactions performance of the aging rear catalyst of table 11
Claims (8)
1. cinnamic method is produced in ethylbenzene dehydrogenation-hydrogen selective oxidation, take product and the oxygen of ethylbenzene catalytic dehydrogenation or the gas that contains oxygen as raw material, it is 0.01～100 hour at 400～800 ℃ of temperature of reaction, reaction pressure 1～1000KPa, liquid reactions air speed LHSV
-1Under the condition, reaction raw materials and oxide catalyst catalytic combustion hydrogen, promotion balance move material, thereby improve the transformation efficiency of ethylbenzene, generate vinylbenzene, used oxide catalyst wherein, by weight percentage, comprise 91.5～99% lamellar composite carrier, load on 0.001～1.0% platinum on the lamellar composite carrier, 0.01 IVA and the group of the lanthanides promotor component of～5.0% basic metal, alkaline-earth metal modifier and 0.001～2.5%, wherein lamellar composite carrier by weight percentage, comprises that 75～90% are selected from α-Al
2O
3, at least a inert support in trichroite, spinel or the mullite kernel and be combined in 8%～25% on the kernel, thickness is 50～250 microns, specific surface area is 10～200 meters
2/ gram is selected from γ-Al
2O
3, δ-Al
2O
3, θ-Al
2O
3Or at least a in the molecular sieve and 0.005～0.1% to be selected from the coating porous material of nonmetal P auxiliary agent outer, described nonmetal P is selected from high temperature decomposable ammonia salt of inorganic phosphorus acids, organophosphorus acids or its.
2. cinnamic method is produced in described ethylbenzene dehydrogenation-hydrogen selective oxidation according to claim 1, it is characterized in that temperature of reaction is 520～650 ℃.
3. cinnamic method is produced in described ethylbenzene dehydrogenation-hydrogen selective oxidation according to claim 1, it is characterized in that reaction pressure is 20～200KPa.
4. cinnamic method is produced in described ethylbenzene dehydrogenation-hydrogen selective oxidation according to claim 1, it is characterized in that the liquid reactions air speed is 0.1～10 hour
-1
5. cinnamic method is produced in described ethylbenzene dehydrogenation-hydrogen selective oxidation according to claim 1, and the mol ratio that it is characterized in that oxygen and hydrogen is 0.5: 1～2: 1.
6. cinnamic method is produced in described ethylbenzene dehydrogenation-hydrogen selective oxidation according to claim 1, and the consumption that it is characterized in that platinum is 0.01～0.5% of catalyst weight.
7. cinnamic method is produced in described ethylbenzene dehydrogenation-hydrogen selective oxidation according to claim 1, it is characterized in that at least a among the preferred Li of used oxide catalyst modifier, K, Mg, the Ba, and consumption is 0.05～2.0% of catalyst weight.
8. cinnamic method is produced in described ethylbenzene dehydrogenation-hydrogen selective oxidation according to claim 1, it is characterized in that promotor one IVA is selected from least a among Ge, Sn, the Pb, and consumption is 0.01～1.0% of catalyst weight; Promotor two group of the lanthanides are selected from least a among La, Ce, Pr, the Nd, and consumption is 0.005～0.5% of catalyst weight.
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| CN103623818B (en) * | 2012-08-23 | 2015-10-28 | 中国石油天然气股份有限公司 | A kind of thin shell shaped noble metal catalyst and preparation method thereof |
| CN103626623B (en) * | 2012-08-23 | 2015-05-13 | 中国石油天然气股份有限公司 | Ethylbenzene dehydrogenation-hydrogen selective oxidation method used for producing styrene |
| CN103908868B (en) * | 2014-04-15 | 2016-03-02 | 大连理工大学 | Remove the method for styrene and recover hydrogen in ethylbenzene dehydrogenation tail gas |
| CN114425409B (en) * | 2020-10-15 | 2024-05-03 | 中国石油化工股份有限公司 | Catalyst for producing unsaturated aromatic hydrocarbon by dehydrogenation of saturated aromatic hydrocarbon and application thereof |
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