CN104117373B - Mixed metal oxide catalyst of P Modification and its preparation method and application - Google Patents
Mixed metal oxide catalyst of P Modification and its preparation method and application Download PDFInfo
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- CN104117373B CN104117373B CN201310152768.6A CN201310152768A CN104117373B CN 104117373 B CN104117373 B CN 104117373B CN 201310152768 A CN201310152768 A CN 201310152768A CN 104117373 B CN104117373 B CN 104117373B
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Abstract
The present invention provides the mixed metal oxide catalyst of a kind of P Modification, and it is P that described catalyzer comprises general formulax-LiaLabZnFecOdActive ingredient and optional adhesion component, the value of wherein a is 0.02��0.2, b be 0.05��0.3, c to be 2.4��3.2, x be 0.8��1.2, d meets the requirement of other element valence. Present invention also offers the preparation method of described catalyzer. Present invention also offers and use the method for described catalyzer by preparing butadiene with butylene oxo-dehydrogenation. The catalyzer of the present invention improves physical strength and divinyl product yield, and the life-span of catalyzer is improved, and coking phenomenon is suppressed.
Description
Technical field
The invention belongs to catalysis technical field, it relates to a kind of Catalysts and its preparation method and purposes, particularly relate to a kind of mixed metal oxide catalyst of P Modification for carrying out Oxidative Dehydrogenation of Butene into Butadiene and its production and use.
Background technology
The fast development of rubber and resin industry causes the day by day vigorous of the divinyl market requirement, and by naphtha cracking obtains 1,3-divinyl can account for the 90% of total divinyl output, and the proportion that following Middle East light crude accounts for world's output is also improving gradually, and its derived product heaviness component (comprising divinyl) also has remarkable minimizing before comparing. Simultaneously due to the restriction of domestic petroleum naphtha amount and cracker, required divinyl breach can only be obtained by butylene oxidation-dehydrogenation.
The synthesis of current plant-scale divinyl can be produced by butylene dehydrogenation or oxydehydrogenation. And butylene direct dehydrogenation is strong endothermic reaction, it is necessary to high-temperature low-pressure condition, lower being difficult to of receipts rate is suitable for commercialization. And the product of butylene oxidation-dehydrogenation is divinyl and water, belong to strong exothermal reaction, it is possible to suitably reduce temperature of reaction.
C4H8��C4H6+H2��H298K,1MPa=113.6kJ.mol-1
C4H8+1/2O2��C4H6+H2O-��H298K,1MPa=127.9kJ.mol-1
The production of industrial divinyl is by making to comprise C4The mixed gas of raw material, water vapour, air is reacted by the fixed bed or fluidized-bed reactor being filled with catalyzer, thus produces divinyl. When adopting fixed-bed reactor, owing to butylene oxidation-dehydrogenation belongs to strong exothermal reaction, and fixed-bed reactor heat transfer property is poor, is unfavorable for temperature control, often causes the reaction bed temperature of local or entirety too high. In general, the entrance for the conventional fixed bed reactor of butylene oxidation-dehydrogenation has 150��250 �� of C with the outlet temperature difference, and needs to adopt two reactors one to open for one simultaneously, is used alternatingly.
In order to solve the problem of fixed-bed reactor thermal conduction difference, fluidized-bed is a kind of very desirable selection. In fluidized-bed reactor butylene oxidation-dehydrogenation move thermal capacitance easily, isothermal operation can be realized, the extending catalyst life-span, and improve catalyst utilization, and structure of reactor is relatively simple, manufactures easy to process, is easy to industry amplification. But commercial fixed bed butylene oxidation-dehydrogenation catalyst is due to reasons such as shape, physical strength and wear resistancies and is not suitable for fluidized-bed. How to synthesize a kind of butylene oxidation-dehydrogenation catalyst being suitable for fluidized-bed, and make it have resistance to wear, the characteristic such as high reactivity and long-time running stability, be that people wish the problem that solves always for a long time.
CN1184705A and CN1072110A discloses a kind of Fe-series catalyst for Oxidative Dehydrogenation of Butene into Butadiene reaction, and this catalyzer is used for shelf fluidized bed. Although this catalyzer have certain activity or (with) selectivity, but due to catalyzer be that irregular shape and particle diameter are relatively big, cause that butadiene yield is on the low side and catalyst attrition is more serious. Fig. 1 shows the stereoscan photograph that this kind has the catalyzer of irregular shape.
CN101674883 discloses one and utilizes iron acid zinc catalyst to prepare 1, the method of 3-divinyl, described catalyzer is the combination of simple zinc ferrite, it is difficult to reach desirable catalytic effect, and this catalyzer is applicable to fixed-bed reactor, beds temperature rise is serious, and energy consumption height, can not solve the wear problem of catalyzer on fluidized-bed reactor equally.
US8003840B2 discloses a kind of method utilizing bismuth molybdate catalysts to prepare 1,3-divinyl, and this catalyst series is for fixed-bed reactor, it does not have solve resistance to wearing and the problem such as high workability of catalyzer, and catalytic activity is general.
Accordingly, it is desirable to a kind of new catalyzer can be developed, overcome above-mentioned various defects.
Summary of the invention
For this area Problems existing, this invention exploits the catalyzer of a kind of novelty, zinc ferrite system is carried out modification by this catalyzer phosphorus, lithium and lanthanum, and the mode adopting spray drying granulation obtains. Compared with the catalyzer of traditional method manufacture, the catalyzer of the present invention shows wear resistance (physical strength) and the divinyl product yield of improvement, and in long period operating process, there is not coking and inactivation, therefore without the need to catalyzer is regenerated frequently, it is possible to meet in modern industrialization fluidized-bed system the performance demand of the catalyzer synthesized for divinyl.
In the first aspect of the invention, described catalyzer is the mixed metal oxide catalyst of a kind of P Modification, and it is P that described catalyzer comprises general formulax-LiaLabZnFecOdActive ingredient and optional adhesion component, wherein a is 0.02��0.2, b is 0.05��0.3, the value of c to be 2.4��3.2, x be 0.8��1.2, d meets the requirement of other element valence, counting by benchmark of the gross weight of described catalyzer, the content of described adhesion component is 0��10 weight %. Preferably, c is 2.8��3.1, x is 0.9��1.
The second aspect of the invention provides the method for the mixed metal oxide catalyst of a kind of P Modification preparing the present invention, it is characterised in that, the method comprises the following steps:
(1) by the presoma of Li, La, Zn, Fe, phosphorus source, tensio-active agent and water mixing, form aqueous mixture, in this aqueous mixture, add alkaline conditioner, form solid sediment;
(2) described solid sediment is mixed with binding agent and water, form raw slurry;
(3) described raw slurry is carried out spray drying granulation, form microspheres with solid;
(4) described microspheres with solid is dried and roasting, forms the mixed metal oxide catalyst of described P Modification.
In an embodiment of the invention, the presoma of described Li, La, Zn, Fe is selected from the nitrate of Li, La, Zn, Fe, vitriol, muriate, and their mixture; Described phosphorus source is selected from phosphoric acid, tetra-sodium, primary ammonium phosphate, ammonium hydrogen phosphate and combination thereof; Described tensio-active agent is selected from arginine, citric acid, ethylenediamine tetraacetic acid (EDTA), and combination; Described alkaline conditioner is selected from sodium hydroxide, potassium hydroxide, volatile salt, ammoniacal liquor and combination thereof; Described binding agent is selected from silica gel, methylcellulose gum, polyvinyl alcohol, dextran, and combination.
In an embodiment of the invention, for step (1), the volumetric molar concentration of various metal in described aqueous mixture is respectively: the content of Li is 0.01-0.3mol/L, the content of La is 0.03-0.4mol/L, the content of Zn is 0.8-1.2mol/L, the content of Fe is the content of 2.0-4.0mol/L, P is 0.8-1.2mol/L; Counting by benchmark of the gross weight of described aqueous mixture, the content of described tensio-active agent is 1 weight %��3 weight %.
In yet another embodiment of the present invention, for step (2), counting by benchmark of the gross weight of described raw slurry, in this raw slurry, the total content of all components in addition to water is 10��50 weight %, it is preferable that 20��45 weight %; Counting by benchmark of the gross weight of described raw slurry, the content of described binding agent is 2 weight %��5 weight %.
In yet another embodiment of the present invention, in step (1), by the presoma of Li, La, Zn, Fe, phosphorus source, tensio-active agent and water mixing, form aqueous mixture, alkaline conditioner is added in this aqueous mixture, the pH value making this aqueous mixture is 6��10, obtains solid sediment, is then filtered by this solid sediment and washs to pH value as neutral.
In yet another embodiment of the present invention, in step (3), use spraying drying granulating equipment that described raw slurry is carried out spray drying granulation, it is 100-500ml/min that slurries input the feeding rate of described spray-dryer, the opening for feed temperature of described spraying drying granulating equipment is 200 DEG C��400 DEG C, it is preferable that 220 DEG C��350 DEG C, and discharge port temperature is 100 DEG C��160 DEG C, preferably 110 DEG C��150 DEG C, the particle diameter of obtained microspheres with solid is 40 microns��300 microns; In step (4), described microspheres with solid at the 80 DEG C��temperature of 200 DEG C, preferably 80 DEG C��180 DEG C dry 1��24 hour, preferably 4��16 hours, the 500 DEG C��roasting temperature of 900 DEG C, preferably 520 DEG C��820 DEG C 4��24 hours, it is preferable that 4��18 hours.
The third aspect of the invention provides a kind of method by preparing butadiene with butylene oxo-dehydrogenation, and the method comprises, at reaction conditions so that butylene, water vapour, oxygen contact with the catalyzer of the present invention, forms 1,3-divinyl. In one preferred embodiment, described reaction conditions is: react in a fluidized bed reactor, and temperature is 300��400 DEG C, pressure is normal pressure, the mol ratio of water vapour and butylene is 6��16, and the mol ratio of oxygen and butylene is 0.4��1.0, and the volume space velocity of butylene is 300��800h-1��
Accompanying drawing explanation
Fig. 1 is the SEM micrograph of the catalyzer with irregular shape of prior art;
The SEM micrograph of the catalyzer that Fig. 2 obtains according to an embodiment of the invention.
Embodiment
" scope " disclosed herein is with the form of lower limit and the upper limit. One or more lower limit can be respectively, and one or more upper limit. Given range is limited by a selected lower limit and a upper limit. Selected lower limit and the upper limit define the border of special scope. All scopes that can carry out by this way limiting comprise and may be combined with, and namely any lower limit can be combined to form a scope with any upper limit. Such as, the scope of 60-120 and 80-110 is listed for special parameter, it is to understand that for the scope of 60-110 and 80-120 is also expected in advance. In addition, if the minimum extent value listed 1 and 2, and if list maximum range value 3,4 and 5, then the scope below can all be expected in advance: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, numerical range " a-b " represents that the contraction table of any real combinings between a to b is shown, wherein a and b is real number. Such as numerical range " 0-5 " represents the whole real numbers all listing between " 0-5 " herein, and the contraction table that " 0-5 " is these combinations of values is shown.
If do not particularly not pointed out, this specification sheets term " two kinds " used refers to " at least two kinds ".
In the present invention, if do not illustrated especially, all enforcement modes mentioned in this article and preferred implementation can be combined to form new technical scheme mutually.
In the present invention, if do not illustrated especially, all technology features mentioned in this article and preferred feature can be combined to form new technical scheme mutually.
In the present invention, if do not illustrated especially, mentioned in this article can sequentially carry out in steps, it is also possible to carry out at random, but preferably order carries out. Such as, described method comprises step (a) and (b), represents that described method can comprise step (a) and (b) that order carries out, it is also possible to comprise step (b) and (a) that order carries out. Such as, described mention described method and also can comprise step (c), represent that step (c) random order can join described method, such as, described method can comprise step (a), (b) and (c), also step (a), (c) and (b) can be comprised, it is also possible to comprise step (c), (a) and (b) etc.
In the present invention, if do not illustrated especially, " comprising " mentioned in this article represents open, it is also possible to be closed. Such as, described " comprising " other elements that can also comprise and not list can be represented, it is also possible to only comprise the element listed.
The present invention makes metal and phosphorus form solid sediment first in the basic conditions, subsequently described solid sediment is carried out spray drying granulation, and then be dried and roasting by the microspheres with solid formed, thus form the mixed metal oxide catalyst of the P Modification of the present invention. The method of the present invention comprises the following steps:
(1) by the presoma of Li, La, Zn, Fe, phosphorus source, tensio-active agent and water mixing, form aqueous mixture, in this aqueous mixture, add alkaline conditioner, form solid sediment;
(2) described solid sediment is mixed with binding agent and water, form raw slurry;
(3) described raw slurry is carried out spray drying granulation, form microspheres with solid;
(4) described microspheres with solid is dried and roasting, forms the mixed metal oxide catalyst of described P Modification.
In step (1), first the presoma of Li, La, Zn and Fe, phosphorus source and tensio-active agent are dissolved in water, and then add alkaline conditioner wherein, so that metallic element and phosphoric form solid sediment. In order to guarantee that metallic element fully precipitates, it is preferable that the pH value making aqueous mixture by adding alkaline conditioner is 6��10, such as pH value can be 6,6.5,7,7.5,8,8.5,9,9.5 or 10. Then by conventional solid-liquid separation method, such as normal pressure filters, take out filter or centrifugation to collect solid sediment, and with water by the washing of this solid sediment to pH value in neutral.
The presoma of described Li, La, Zn, Fe is selected from the nitrate of Li, La, Zn, Fe, vitriol, muriate, and their mixture, it is also possible to be other water-soluble salt of these four kinds of elements. Described phosphorus source is selected from phosphoric acid, tetra-sodium, primary ammonium phosphate, ammonium hydrogen phosphate and combination thereof, it is also possible to be other water-soluble P contained compound. Described tensio-active agent is for promoting the full and uniform dispersion of various raw material in aqueous mixture.
In one preferred embodiment, described aqueous mixture is the aqueous solution. In another embodiment, described aqueous mixture is the form of colloid.
Described alkaline conditioner is selected from sodium hydroxide, potassium hydroxide, volatile salt, ammoniacal liquor and combination thereof. In time using the alkaline conditioner of solid form of sodium hydroxide, potassium hydroxide or volatile salt and so on, these alkaline conditioners can directly add in described aqueous mixture in solid form, but preferably it is dissolved in water, is added in form of an aqueous solutions in described aqueous mixture. In one preferred embodiment, the add-on of described alkaline conditioner makes the pH value of described aqueous mixture be 6-10, so that metallic element and phosphoric fully precipitate.
In described aqueous mixture, the presoma of Li, La, Zn and Fe and the add-on in phosphorus source depend on the corresponding content of these elements in catalyzer to be prepared. Counting by benchmark of the gross weight of described aqueous mixture, wherein the total content of component in addition to water is 5-10 weight %. In an embodiment of the invention, the volumetric molar concentration of various metal in described aqueous mixture is respectively: the content of Li is 0.01-0.3mol/L, the content of La is 0.03-0.4mol/L, the content of Zn is 0.8-1.2mol/L, the content of Fe is the content of 2.0-4.0mol/L, P is 0.8-1.2mol/L. In addition, counting by benchmark of the gross weight of described aqueous mixture, the content of described tensio-active agent is 1-3 weight %.
In step (2), the solid sediment that step 1 is obtained is mixed with binding agent and water, form raw slurry. Described binding agent can improve homogeneity and the fluid property of this slurries system in slurry stage, also is conducive to improving the overall mechanical strength of final obtained catalyzer simultaneously, significantly improves its wear resistance. Described binding agent is selected from silica gel, methylcellulose gum, polyvinyl alcohol, dextran, and combination. Wherein silica gel represents the colloid that silica dioxide granule is formed in water, and the median size of described silica dioxide granule is 20��40 nanometers, and its pH scope is 9-10, and wherein silica containing molecular formula can be denoted as SiO2��nH2O, counts by benchmark of the gross weight of this silica gel, calculates in the form of an oxide, wherein comprises the silicon-dioxide of 15-40 weight %, the Na of 0.2-0.4 weight %2O, and the water of surplus. The viscosity (25 DEG C) of described silica gel is 2-2.5MPaS, and density (25 DEG C) is 1.1-1.3 gram per centimeter3. Counting by benchmark of the gross weight of described raw slurry, in this raw slurry, the total content of all components in addition to water is 10��50 weight %, it is preferable that 20��45 weight %; Counting by benchmark of the gross weight of described raw slurry, the content of described binding agent is 2 weight %��5 weight %. When the system that the binding agent used is moisture, time such as silica gel, the content of described binding agent represents the content of component in addition to water, i.e. the net content of binding agent.
One of the present invention preferred embodiment in, before carrying out step (3), it may also be useful to described raw slurry is carried out further homogenizing by disintegrating apparatus, so that the solid particulate in raw slurry is more even. In a preferred enforcement mode of the present invention, described disintegrating apparatus is colloidal mill.
In step (3), use spraying drying granulating equipment that described raw slurry is carried out spray drying granulation, it is 100-500ml/min that slurries input the feeding rate of described spray-dryer, such as 120, 150, 180, 200, 250, 300, 340, 350, 380, 400, 420, 450, 480, 500ml/min, the opening for feed temperature of described spraying drying granulating equipment is 200 DEG C��400 DEG C, preferably 220 DEG C��350 DEG C, discharge port temperature is 100 DEG C��160 DEG C, preferably 110 DEG C��150 DEG C, the particle diameter of obtained microspheres with solid is 40 microns��300 microns, such as 50 microns, 70 microns, 90 microns, 100 microns, 120 microns, 150 microns, 180 microns, 200 microns, 250 microns, 300 microns etc.
In step (4), described microspheres with solid puts into infrared baking box or forced ventilation convection oven, at the 80 DEG C��temperature of 200 DEG C, preferably 80 DEG C��180 DEG C, such as 80 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C, dry 1��24 hour, preferably 4��16 hours, such as 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours; Then transfer in retort furnace, in air atmosphere, at the 500 DEG C��temperature of 900 DEG C, preferably 520 DEG C��820 DEG C, such as 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C roastings 4��24 hours, preferably 4��18 hours, such as 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours.
Comprising general formula in the catalyzer that the method for the present invention is obtained is Px-LiaLabZnFecOdActive ingredient and optional adhesion component, wherein a is 0.02��0.2, b is 0.05��0.3, the value of c to be 2.4��3.2, x be 0.8��1.2, d meets the requirement of other element valence, counting by benchmark of the gross weight of described catalyzer, the content of described adhesion component is 0��10 weight %. In one preferred embodiment, c is 2.8��3.1, x is 0.9��1.
At this it is noted that when the binding agent used comprises silica gel, silica gel can be decomposed to form silicon-dioxide in the process of roasting, is included in final catalyzer. The cost of this provenance self-adhesive agent comprised in catalyzer is referred to as " adhesion component " by the present invention. When the binding agent used is selected from methylcellulose gum, polyvinyl alcohol, dextran, and when combination, these binder components can be burnouted completely in roasting process, and obtained catalyzer is only containing Px-LiaLabZnFecOdActive ingredient, and containing any adhesion component. One of the present invention preferred embodiment in, count by benchmark of the gross weight of described catalyzer, wherein the content of adhesion component is 0-10 weight %.
The catalyzer that the present invention obtains may be used for carrying out in fluidized-bed system the reaction that butylene oxidation prepares divinyl. In an embodiment of the invention, the catalyzer of the present invention of appropriate amount is filled within fluidized-bed, then leads to the mixture into butylene, water vapour and oxygen, make this gaseous mixture react at reaction conditions, generate product 1,3-divinyl. The temperature of described fluidized-bed reactor can be 300-400 DEG C, it is preferable to 355 DEG C, and reaction pressure is a normal atmosphere, and the mol ratio of water vapour and butylene is the mol ratio of 6-16, oxygen and butylene is 0.4-1.0, and the volume space velocity of butylene is 300-800 hour-1��
Catalyzer prepared by the present invention has following useful effect: the catalyzer of (1) the present invention have employed phosphorus, zinc ferrite system is carried out modification by lithium and lanthanum, and the mode adopting spray drying granulation obtains, compared with the catalyzer that prior art is known, the granules of catalyst flowing property of the present invention is strong, even particle size distribution, there is higher wear resistance (physical strength) and higher butadiene yield, fit and coking and inactivation not easily occur in long-term operation process, do not need frequent regeneration, meet the performance demand of modern industrialization fluidized-bed synthesis butadiene catalyst, (2) catalyzer of the application of the invention carries out the reaction of Oxidative Dehydrogenation of Butene into Butadiene, and the receipts rate of product divinyl is higher, and catalyst life is longer, wear-resistant, utilization ratio height.
The present invention will describe the feature of the present invention in detail by embodiment.
In the examples below, the silica gel used is SiO2Colloid in water, wherein SiO2Content be 28 weight %. Unless otherwise indicated, all reagent used is commercially available analytical reagent.
Embodiment 1
3000ml beaker adds 1mol zinc nitrate, 2.8mol iron nitrate, 0.02mol lithium nitrate, 0.05mol lanthanum nitrate, 1mol phosphoric acid (phosphate aqueous solutions of 76 weight %) and arginine, wherein arginic consumption is 1 weight % of metal precursor mixture, then add 1400 ml deionized water mix and blends, form solution. Drip in this solution and add the ammoniacal liquor that concentration is 15 weight % so that the pH value of system is 7.5, continue to stir 2 hours. Then solid precipitation is filtered out in the way of taking out filter with B��chner funnel, and with deionized water wash, until the pH value of filtrate is to neutral. 1270 grams of gained filter cakes are mixed with 5.8 grams of polyvinyl alcohol (molecular weight 5000) and 1100 ml deionized water, obtained raw slurry. This raw slurry being carried out violent stirring, then uses JM-LB stainless steel colloidal mill to make the further homogenizing of the solid particulate in slurries, the filtering accuracy of described colloidal mill is set as 20 ��m. Then this raw slurry is sent in centrifugal spray shaping equipment with the speed of 250 ml/min and carry out granulation, and control opening for feed temperature 280 �� of C of spray shaping machine, discharge port temperature 150 �� of C, obtain microspheres with solid, described microspheres with solid is transferred in infrared dryer, at the dry 14h of 120 �� of C, then transfer in retort furnace, at the temperature of 700 �� of C, roasting 10h in air atmosphere, obtains catalyzer finished product. Being recorded by icp analysis, in catalyzer, the mol ratio of various element is P:Li:La:Zn:Fe=0.9:0.03:0.07:1:3.1.
Embodiment 2
3000ml beaker adds 1mol zinc sulfate, 1.4mol ferric sulfate, 0.09mol Lithium Sulphate, 0.25mol Lanthanum trichloride, 0.5mol tetra-sodium and citric acid, the consumption of citric acid is the 2wt% of metal precursor mixture, then 1300 ml deionized water mix and blends are added, to form solution, drip in described solution and add the aqueous sodium hydroxide solution that concentration is 14 weight %, pH value is adjusted to 8.5, continues to stir 2 hours. Then with B��chner funnel, material is filtered, with deionized water, the solid filtered out is washed, until the pH value of filtrate turns into neutrality. The filter cake of 1300 grams of gained and 7.4 grams of methylcellulose gum and 1200 ml deionized water are mixed, form raw slurry, this raw slurry is carried out violent stirring, then using JM-LB stainless steel colloidal mill to make the further homogenizing of the solid particulate in slurries, the filtering accuracy of described colloidal mill is set as 20 ��m. Then this raw slurry is sent in centrifugal spray shaping equipment with the speed of 300 ml/min and carry out granulation, and control opening for feed temperature 400 �� of C of spray shaping machine, discharge port temperature 110 �� of C, obtain microspheres with solid, described microspheres with solid is transferred in infrared dryer, at the dry 24h of 80 �� of C, then transfer in retort furnace, at the temperature of 900 �� of C, roasting 4h in air atmosphere, obtains catalyzer finished product. Being recorded by icp analysis, in catalyzer, the mol ratio of various element is P:Li:La:Zn:Fe=0.9:0.19:0.28:1:2.97.
Embodiment 3
3000ml beaker adds 1mol zinc nitrate, 2.8mol iron(ic) chloride, 0.08mol Lithium Sulphate, 0.2mol Lanthanum trichloride, 1mol primary ammonium phosphate, 8.3 grams of ethylenediamine tetraacetic acid (EDTA)s, then 1400 ml deionized water mix and blends are added, to form solution, drip in described solution and add the potassium hydroxide aqueous solution that concentration is 18 weight %, pH value is adjusted to 6.5, continues to stir 2 hours. Then with B��chner funnel, material is filtered, with deionized water, the solid filtered out is washed, until the pH value of filtrate turns into neutrality. The filter cake of 1300 grams of gained and 7.8 grams of dextran (molecular weight 10000) and 1400 ml deionized water are mixed, form raw slurry, this raw slurry is carried out violent stirring, then using JM-LB stainless steel colloidal mill to make the further homogenizing of the solid particulate in slurries, the filtering accuracy of described colloidal mill is set as 20 ��m. Then this raw slurry is sent in press spray molding device with the speed of 280 ml/min and carry out granulation, and control opening for feed temperature 200 �� of C of spray shaping machine, discharge port temperature 160 �� of C, obtain microspheres with solid, described microspheres with solid is transferred in infrared dryer, at the dry 4h of 200 �� of C, then transfer in retort furnace, at the temperature of 500 �� of C, roasting 18h in air atmosphere, obtains catalyzer finished product. Being recorded by icp analysis, in catalyzer, the mol ratio of various element is P:Li:La:Zn:Fe=0.91:0.18:0.21:1:3.03.
Embodiment 4
3000ml beaker adds 1mol zinc nitrate, 2.8mol iron nitrate, 0.18mol lithium nitrate, 0.15mol lanthanum nitrate, 1mol ammonium hydrogen phosphate and arginine, arginic consumption is the 1.5wt% of metal precursor mixture, then 1300 ml deionized water mix and blends are added, to form solution, drip in described solution and add the ammonium carbonate solution that concentration is 14 weight %, pH value is adjusted to 10, continues to stir 2 hours. Then with B��chner funnel, material is filtered, with deionized water, the solid filtered out is washed, until the pH value of filtrate turns into neutrality. Silica gel and 1080 ml deionized water of the filter cake of 1320 grams of gained and 520 gram of 28 quality % are mixed, form raw slurry, this raw slurry is carried out violent stirring, then using JM-LB stainless steel colloidal mill to make the further homogenizing of the solid particulate in slurries, the filtering accuracy of described colloidal mill is set as 20 ��m. Then this raw slurry is sent in centrifugal spray shaping equipment with the speed of 350 ml/min and carry out granulation, and control opening for feed temperature 220 �� of C of spray shaping machine, discharge port temperature 100 �� of C, obtain microspheres with solid, described microspheres with solid is transferred in infrared dryer, at the dry 16h of 80 �� of C, then transfer in retort furnace, at the temperature of 820 �� of C, roasting 20h in air atmosphere, obtains catalyzer finished product. Being recorded by icp analysis, in catalyzer, the mol ratio of various metallic element is P:Li:La:Zn:Fe=0.92:0.19:0.18:1:2.95.
Embodiment 5
3000ml beaker adds 1mol zinc chloride, 2.8mol iron nitrate, 0.14mol lithium chloride, 0.18mol lanthanum nitrate, 1mol phosphoric acid (aqueous solution of 75 weight %) and citric acid, wherein the consumption of citric acid is the 2.5wt% of metal precursor mixture, then 1100 ml deionized water mix and blends are added, to form solution, drip in described solution and add the ammoniacal liquor that concentration is 13 weight %, pH value is adjusted to 9, continues to stir 2 hours. Then with B��chner funnel, material is filtered, with deionized water, the solid filtered out is washed, until the pH value of filtrate turns into neutrality. Silica gel and 1300 ml deionized water of the filter cake of 1270 grams of gained and 260 gram of 28 quality % are mixed, form raw slurry, this raw slurry is carried out violent stirring, then using JM-LB stainless steel colloidal mill to make the further homogenizing of the solid particulate in slurries, the filtering accuracy of described colloidal mill is set as 20 ��m. Then this raw slurry is sent in centrifugal spray shaping equipment with the speed of 400 ml/min and carry out granulation, and control opening for feed temperature 350 �� of C of spray shaping machine, discharge port temperature 120 �� of C, obtain microspheres with solid, described microspheres with solid is transferred in infrared dryer, at the dry 10h of 180 �� of C, then transfer in retort furnace, at the temperature of 520 �� of C, roasting 24h in air atmosphere, obtains catalyzer finished product. Being recorded by icp analysis, in catalyzer, the mol ratio of various metallic element is P:Li:La:Zn:Fe=0.9:0.17:0.21:1:2.95.
Comparative example
Preparing catalyzer according to the step described in embodiment 1, difference is in the preparation process of catalyzer do not add phosphorus source, lithium salt and lanthanum salt. Being recorded by icp analysis, in catalyzer, the mol ratio of various element is Zn:Fe=1:3.1.
Embodiment 6: catalyst performance evaluation is tested
Take in the embodiment 1-5 of 360 grams the catalyzer of preparation respectively and catalyzer prepared by comparative example, load in high 100 centimetres, in the DN50 fluidized-bed reactor of diameter 50 centimetres, lead to the mixed gas into butylene, oxygen and water vapour wherein, carry out butylene oxidation-dehydrogenation reaction at the following reaction conditions: butylene volume space velocity 350h-1, in feed gas, the mol ratio of oxygen and butylene is 0.67, and the mol ratio of water vapour and butylene is 12, and temperature of reaction 360 �� of C, pressure is normal pressure. A sample is got, it may also be useful to the composition of the GC9560 type gas chromatograph detection product that Shanghai Hua Ai chromatogram company limited produces, calculates the transformation efficiency of raw material butylene and the receipts rate of product divinyl every 2h. Result is the mean value of each sampling inspection results, in table 1. It is benchmark with butadiene yield time initial, taking time that butadiene yield reduces by 20% as the inactivation moment, it is designated as one way working time. Catalyzer in the reaction system in this moment is taken out, it is carried out thermogravimetric analysis, thus records the coking amount on catalyzer, be denoted as one way cycle of operation coking amount.
The each catalyst test result of table 1
| Butadiene yield (%) | Butene conversion (%) | One way working time (h) | One way cycle of operation coking amount (%) | |
| Embodiment 1 | 84.7 | 89.2 | 2100 | 0.12 |
| Embodiment 2 | 86.5 | 93.1 | 2300 | 0.06 |
| Embodiment 3 | 85.1 | 92.2 | 1920 | 0.17 |
| Embodiment 4 | 87.2 | 93.5 | 1680 | 0.24 |
| Embodiment 5 | 82.4 | 90.4 | 1700 | 0.18 |
| Comparative example | 81.2 | 86.4 | 900 | 1.1 |
Can see from the data of table 1, compared with comparative example, the catalyzer of the present invention all obtains significant raising in butene conversion and butadiene yield, in addition, the life-span of the catalyzer of the present invention extends more than twice, and coking amount is more notable decreases more than 80%.
In addition, Fig. 2 shows the SEM micrograph of the catalyzer of 1 preparation according to embodiments of the present invention. As we can see from the figure, the present invention has the uniform particle size being less than 100 microns and regular shape substantially spherical in shape by catalyzer prepared by precipitation-drying process with atomizing. Therefore the catalyzer of the present invention not easily causes fragmentation and inactivation due to violent friction in for fluidized-bed system. The catalyzer of the present invention shown in table 1 has the life-span reaching at most more than 2,000 hours. By comparison, Fig. 1 shows the SEM micrograph of catalyzer prepared by art methods, and wherein not only granularity is relatively big for granules of catalyst, and shape is irregular, and size-grade distribution is also uneven, thus it is easy in fluidized-bed reaction process owing to being worn and rapid deactivation.
Claims (12)
1. a mixed metal oxide catalyst for P Modification, it is P that described catalyzer comprises general formulax-LiaLabZnFecOdActive ingredient and optional adhesion component, wherein a is 0.02��0.2, b is 0.05��0.3, the value of c to be 2.4��3.2, x be 0.8��1.2, d meets the requirement of other element valence, counting by benchmark of the gross weight of described catalyzer, the content of described adhesion component is 0��10 weight %.
2. the mixed metal oxide catalyst of P Modification as claimed in claim 1, it is characterised in that, c is 2.8��3.1, x is 0.9��1.
3. prepare the method for the mixed metal oxide catalyst of P Modification as claimed in claim 1 or 2 for one kind, it is characterised in that, the method comprises the following steps:
(1) by the presoma of Li, La, Zn, Fe, phosphorus source, tensio-active agent and water mixing, form aqueous mixture, in this aqueous mixture, add alkaline conditioner, form solid sediment;
(2) described solid sediment is mixed with binding agent and water, form raw slurry;
(3) described raw slurry is carried out spray drying granulation, form microspheres with solid;
(4) described microspheres with solid is dried and roasting, forms the mixed metal oxide catalyst of described P Modification.
4. method as claimed in claim 3, it is characterised in that, the presoma of described Li, La, Zn, Fe is selected from the nitrate of Li, La, Zn, Fe, vitriol, muriate, and their mixture; Described phosphorus source is selected from phosphoric acid, tetra-sodium, primary ammonium phosphate, ammonium hydrogen phosphate and combination thereof; Described tensio-active agent is selected from arginine, citric acid, ethylenediamine tetraacetic acid (EDTA), and combination; Described alkaline conditioner is selected from sodium hydroxide, potassium hydroxide, volatile salt, ammoniacal liquor and combination thereof; Described binding agent is selected from silica gel, methylcellulose gum, polyvinyl alcohol, dextran, and combination.
5. method as claimed in claim 3, it is characterized in that, for step (1), the volumetric molar concentration of various metal in described aqueous mixture is respectively: the content of Li is 0.01-0.3mol/L, the content of La is 0.03-0.4mol/L, the content of Zn is the content of 0.8-1.2mol/L, Fe be the content of 2.0-4.0mol/L, P is 0.8-1.2mol/L; Counting by benchmark of the gross weight of described aqueous mixture, the content of described tensio-active agent is 1 weight %��3 weight %.
6. method as claimed in claim 3, it is characterised in that, for step (2), to count by benchmark of the gross weight of described raw slurry, in this raw slurry, the total content of all components in addition to water is 10��50 weight %; Counting by benchmark of the gross weight of described raw slurry, the content of described binding agent is 2 weight %��5 weight %.
7. method as claimed in claim 3, it is characterised in that, for step (2), to count by benchmark of the gross weight of described raw slurry, in this raw slurry, the total content of all components in addition to water is 20��45 weight %; Counting by benchmark of the gross weight of described raw slurry, the content of described binding agent is 2 weight %��5 weight %.
8. method as claimed in claim 3, it is characterized in that, in step (1), by the presoma of Li, La, Zn, Fe, phosphorus source, tensio-active agent and water mixing, form aqueous mixture, in this aqueous mixture, add alkaline conditioner so that the pH value of this aqueous mixture is 6��10, obtain solid sediment, then this solid sediment is filtered and wash to pH value as neutral.
9. method as claimed in claim 3, it is characterized in that, in step (3), use spraying drying granulating equipment that described raw slurry is carried out spray drying granulation, it is 100-500ml/min that slurries input the feeding rate of described spraying drying granulating equipment, the opening for feed temperature of described spraying drying granulating equipment is 200 DEG C��400 DEG C, and discharge port temperature is 100 DEG C��160 DEG C, and the particle diameter of obtained microspheres with solid is 40 microns��300 microns; In step (4), described microspheres with solid at the temperature of 80 DEG C��200 DEG C dry 1��24 hour, at the roasting temperature 4��24 hours of 500 DEG C��900 DEG C.
10. method as claimed in claim 3, it is characterized in that, in step (3), use spraying drying granulating equipment that described raw slurry is carried out spray drying granulation, it is 100-500ml/min that slurries input the feeding rate of described spraying drying granulating equipment, the opening for feed temperature of described spraying drying granulating equipment is 220 DEG C��350 DEG C, and discharge port temperature is 110 DEG C��150 DEG C, and the particle diameter of obtained microspheres with solid is 40 microns��300 microns; In step (4), described microspheres with solid at the temperature of 80 DEG C��180 DEG C dry 4��16 hours, at the roasting temperature 4��18 hours of 520 DEG C��820 DEG C.
11. 1 kinds by the method for preparing butadiene with butylene oxo-dehydrogenation, the method comprises, at reaction conditions so that butylene, water vapour, oxygen contact with the catalyzer described in claim 1 or 2, formed 1,3-divinyl.
12. methods as described in claim requirement 10, it is characterized in that, described reaction conditions is: react in a fluidized bed reactor, temperature is 300��400 DEG C, pressure is normal pressure, the mol ratio of water vapour and butylene is 6��16, and the mol ratio of oxygen and butylene is 0.4��1.0, and the volume space velocity of butylene is 300��800h-1��
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| CN1201769A (en) * | 1998-04-13 | 1998-12-16 | 中国科学院固体物理研究所 | Zinc ferrite-titanium dioxide nino-sized composite material and manufacture thereof |
| CN102716754A (en) * | 2012-07-12 | 2012-10-10 | 上海碧科清洁能源技术有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butene in fluidized bed reactor and preparation method and application thereof |
| CN102824914A (en) * | 2012-09-18 | 2012-12-19 | 陕西煤业化工技术研究院有限责任公司 | Catalyst and method used for preparing 1,3-butadiene by oxidative dehydrogenation of n-butene |
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| CN1201769A (en) * | 1998-04-13 | 1998-12-16 | 中国科学院固体物理研究所 | Zinc ferrite-titanium dioxide nino-sized composite material and manufacture thereof |
| CN102716754A (en) * | 2012-07-12 | 2012-10-10 | 上海碧科清洁能源技术有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butene in fluidized bed reactor and preparation method and application thereof |
| CN102824914A (en) * | 2012-09-18 | 2012-12-19 | 陕西煤业化工技术研究院有限责任公司 | Catalyst and method used for preparing 1,3-butadiene by oxidative dehydrogenation of n-butene |
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