CN105457623B - The industrial production process of chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst - Google Patents

The industrial production process of chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst Download PDF

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CN105457623B
CN105457623B CN201510980445.5A CN201510980445A CN105457623B CN 105457623 B CN105457623 B CN 105457623B CN 201510980445 A CN201510980445 A CN 201510980445A CN 105457623 B CN105457623 B CN 105457623B
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catalyst
alumina support
roasting
fluid bed
chromium
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CN105457623A (en
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肖俊平
丑凌军
张韩
葛志勇
赵军
李立新
杨建�
宋焕玲
赵华华
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SHANGHAI HOTO ENGINEERING Inc
Jiangsu Yangzi Catalyst Co ltd
Lanzhou Institute of Chemical Physics LICP of CAS
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SHANGHAI HOTO ENGINEERING Inc
Jiangsu Yangzi Catalyst Co ltd
Lanzhou Institute of Chemical Physics LICP of CAS
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    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • C07C5/3335—Catalytic processes with metals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to a kind of industrial production process of chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst, it is characterised in that the processing step is：It is prepared by S1 carriers：After the water aluminum oxide of α mono- is beaten and is spray-dried, microspheric alumina support is obtained after roasting；S2 impregnates：Alumina support is placed in rotatory vacuum soak drying machine with chromium nitrate aqueous solution and impregnated；S3 is dried：Scattered drying is carried out to catalyst in above-mentioned steps using high velocity air drier；S4 is calcined：Heating roasting is carried out to catalyst using rotary kiln, temperature is 500 ~ 700 DEG C, roasting time 1 ~ 6 hour.In the present invention, alumina support mashing roasting is directly obtained into micro-ball gamma aluminum oxide carrier, alumina support uses quiet twice, dynamic bind impregnation method with maceration extract.Good using the catalyst carrier dipping effect of this method, without repeatedly dipping, efficiency high, then the catalyst activity component produced after drying, roasting are evenly distributed, good product quality.

Description

The industrial production process of chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst
Technical field
The present invention relates to a kind of preparation method of catalyst, more particularly to a kind of chromium series microspheroidal fluid bed iso-butane takes off The industrial production process of hydrogen catalyst.
Background technology
Iso-butane is one of key component in catalytic cracking C-4-fraction, and its content may be up to 34%, for a long time, due to Only pay attention to the utilization of alkene, and alkane is burnt up as fuel mostly, cause huge waste.From nineteen nineties, With the raising of isolation technics, C-4-fraction is rapidly developed as the application of petrochemical materials, it is contemplated that, it will be after second The petrochemical materials that being likely to be obtained after alkene and propylene makes full use of.The chemical utilization rate of carbon four in the U.S., Japan and West Europe For 60-70%, and China only has 40%, and based on being utilized with alkene.Therefore, the chemical utilization technology of iso-butane is developed, is not only Alkene source provides supplement, and the competitiveness to lifting petrochemical industry relevant enterprise has important realistic meaning.
In recent years, with the continuous expansion of isobutene application field, existing ethylene by-product isobutene total amount has been difficult to full The growing demand of foot, dehydrogenation of isobutane are made for solve the problems, such as one of main competitive technologyL of isobutene, are provided in iso-butane The abundant area in source and enjoy favor.By the isobutene of dehydrogenation of isobutane production every year up to more than 300 ten thousand tons in world wide, and mesh Preceding China is also without industrialized technique and relevant device.Industrialized dehydrogenation of isobutane technique has Phillips companies Star techniques, joint catalysis and the Catofin techniques of Lu Musi companies, the Oleflex techniques of Uop Inc., Linde with The Linde techniques of Engelhard joint developments and Russian Yaroslavl research institute and Italian Snamprogetti FBD-4 fluid bed dehydrogenating technologies that engineering company develops jointly etc..
In dehydrogenation of isobutane reaction, the coking deactivation of catalyst is the main restricting factor of direct dehydrogenation technique, simultaneously The reaction is thermodynamically the endothermic reaction.In recent years, to solve the problems, such as the energy consumption problem of direct dehydrogenation method and catalyst carbon deposition, Using the oxidative dehydrogenation process of exothermic reaction, various catalyst are reported by numerous studies, but deep oxidation product COxIt is difficult to keep away Exempt from, up to the present, the once through yield of isobutene still is below 30%, it is difficult to competed with direct dehydrogenation method.Therefore, iso-butane is straight Connect dehydrogenation and be still most potential path for transformation, it is important to develop the catalyst of new high selectivity and anti-carbon deposit.Therefore open High activity, anti-carbon catalyst system are sent out, realizes that dehydrogenation of isobutane domesticizes, no matter to oil refining enterprise or petroleum chemical industry It is respectively provided with significance.In the area with iso-butane resource, the technical process will also be received much concern, and the success of key technology is opened Hair, its application prospect are very clear and definite.
Microspheroidal fluid bed dehydrogenation of isobutane catalyst, because the requirement of its performance is, it is necessary to which catalyst has appropriateness Size distribution, particle diameter is concentrated mainly on 20 --- 150 μm.Meanwhile the active component generally use of this catalyst Cr2O3, content is generally more than 14%.
The preparation method that foreign countries are currently known mainly has two kinds：When be beaten with alumina support and chromium nitrate solution, it Expansion drying is carried out after being sent into spray drying or filtering by conveying device afterwards, then high-temperature roasting.This method Task-size Controlling Difficulty is big, the high energy consumption of evaporation water timesharing, and drying process can change the particle diameter distribution of original carrier due to post forming.
Another method is with repeatedly saturation dipping, dry, the then high-temperature roasting of alumina support substep.In catalyst Dipping process in, due to the chromic nitrate very high concentrations of maceration extract, chromium nitrate solution runs into alumina support, easily crystallization analysis Go out, cause active component to be evenly distributed in the duct of alumina support.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of energy consumption is low, technique is easy to control and Active components distribution is uniform The industrial production process of chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst.
In order to solve the above technical problems, the technical scheme is that：A kind of chromium series microspheroidal fluid bed iso-butane takes off The industrial production process of hydrogen catalyst, its innovative point are that the processing step is：It is prepared by S1 carriers：By α-one water aluminum oxide Mashing, the liquid-solid ratio of water and α-one water aluminum oxide is 2 liters/kilogram, is then not less than 750 DEG C, spraying pressure in gas inlet temperature 5.0 ~ 8.0MPa of power, exhaust temperature are spray-dried under conditions of being 200 ~ 240 DEG C, obtain aluminum oxide dried pellet, then adopt Microspheric alumina support is obtained after being calcined 2 ~ 6 hours at 500 ~ 700 DEG C with rotary kiln；S2 impregnates：By alumina support It is placed in chromium nitrate aqueous solution in vacuum impregnation drying machine and carries out supersaturated dipping, the pre-preg 1 ~ 4 in vacuum impregnation drying machine Hour, temperature is 50 ~ 80 DEG C, and liquid-solid ratio during dipping is 1.0-2.0 liters/kilograms；Then toward the chuck of vacuum impregnation drying machine Thermal source is inside passed through, and the dipping inner cylinder of vacuum impregnation drying machine is vacuumized, realizes vacuum drying, until alumina support Lose bright water, the catalyst for introducing chromium is made；S3 is dried：It is more than the high velocity air drier pair of 15 meter per seconds using flow velocity Catalyst is disperseed, dried in above-mentioned steps, and the hot-wind inlet temperature of high velocity air drier is 80 ~ 180 DEG C；S4 is calcined： Heating roasting is carried out to catalyst using rotary kiln, temperature is 500 ~ 700 DEG C, roasting time 1 ~ 6 hour.
Preferably, described alumina support is microballoon of the particle diameter at 5 ~ 200 μm.
Preferably, ploughed in the vacuum impregnation drying machine used in above-mentioned steps S2, stirring of the inside equipped with rotation rate-controllable Knife and scattered fly cutter, during impregnation drying, the rotating speed for controlling stirring colter is 20 ~ 30 turns/min, disperses turning for fly cutter Speed is 100 ~ 200 turns/min.
Preferably, during the step S3 is dried, the high velocity air flow velocity is more than 15 meter per seconds, and the heat of drier enters one's intention as revealed in what one says Temperature is 90 ~ 140 DEG C.
Preferably, in the step S4 roastings, sintering temperature is 550 ~ 680 DEG C, and roasting time is 1 ~ 4 hour.
The advantage of the invention is that：In the present invention, alumina support mashing roasting is directly obtained into micro-ball gamma aluminum oxide and carried Body, alumina support use quiet twice, dynamic bind impregnation method with maceration extract：Maceration extract and alumina support are heated to After to a certain degree, pre-preg is carried out, good static dipping is carried out by pre-preg alumina support and maceration extract, is avoided Chromic nitrate crystallization in maceration extract separates out；Then carry out by rotatory vacuum soak drying machine vacuumizing drying again, in this process In realization dynamic be stirred by agitating device impregnated, be advantageous to active component being evenly dispersed to the hole of alumina support In road.It is good using the catalyst carrier dipping effect of this method, without repeatedly dipping, efficiency high, then made after drying, roasting The catalyst activity component gone out is evenly distributed, good product quality.
Embodiment
Embodiment one
To prepare Cr2O3Exemplified by content is 14% microspheroidal fluid bed dehydrogenation of isobutane catalyst, processing step is：
It is prepared by S1 carriers：α-one water aluminum oxide is beaten, the liquid-solid ratio of water and α-one water aluminum oxide is 2 liters/kilogram, so Enter under conditions of being afterwards 200 ~ 240 DEG C not less than 750 DEG C, 5.0 ~ 8.0MPa of atomisation pressure, exhaust temperature in gas inlet temperature Row spray drying, aluminum oxide dried pellet is obtained, then microballoon is obtained after being calcined 2 ~ 6 hours at 500 ~ 700 DEG C using rotary kiln The alumina support of shape, alumina support particle diameter is between 20 ~ 150 μm；
S2 impregnates：Alumina support and chromium nitrate aqueous solution are placed in vacuum impregnation drying machine and carry out supersaturated dipping, Pre-preg 1 hour in vacuum impregnation drying machine, temperature are 45 ~ 50 DEG C, and the liquid-solid ratio of maceration extract and alumina support is 1.0L/ kg；Then toward being passed through thermal source in the chuck of vacuum impregnation drying machine, and the dipping inner cylinder of vacuum impregnation drying machine take out true Sky, vacuum drying is realized, until alumina support loses bright water, the catalyst for introducing chromium is made；Used in this step Vacuum impregnation drying machine, stirring colter and scattered fly cutter of the inside equipped with rotation rate-controllable, during impregnation drying, control The rotating speed of system stirring colter is 20 turns/min, and the rotating speed for disperseing fly cutter is 100 turns/min；
S3 is dried：Catalyst in above-mentioned steps is disperseed using the high velocity air drier of the meter per second of flow velocity 16, done Dry, the hot-wind inlet temperature of high velocity air drier is 120 ~ 135 DEG C of EAT；
S4 is calcined：Heating roasting, roasting time 2.5 hours are carried out to catalyst using rotary kiln, sintering temperature is 560~600℃。
Cr in the present embodiment is prepared using two methods in method for preparing catalyst of the present invention and background technology2O3Content is The resulting reduced parameter of 14% catalyst is as follows：
Embodiment two
To prepare Cr2O3Exemplified by content is 14% microspheroidal fluid bed dehydrogenation of isobutane catalyst, processing step is：
It is prepared by S1 carriers：α-one water aluminum oxide is beaten, the liquid-solid ratio of water and α-one water aluminum oxide is 2 liters/kilogram, so Enter under conditions of being afterwards 200 ~ 240 DEG C not less than 750 DEG C, 5.0 ~ 8.0MPa of atomisation pressure, exhaust temperature in gas inlet temperature Row spray drying, aluminum oxide dried pellet is obtained, then microballoon is obtained after being calcined 2 ~ 6 hours at 500 ~ 700 DEG C using rotary kiln The alumina support of shape, alumina support particle diameter is between 20 ~ 150 μm；
S2 impregnates：Alumina support and chromium nitrate aqueous solution are placed in vacuum impregnation drying machine and carry out supersaturated dipping, Pre-preg 1 hour in vacuum impregnation drying machine, temperature are 45 ~ 50 DEG C, and the liquid-solid ratio of maceration extract and alumina support is 1.4L/ kg；Then toward being passed through thermal source in the chuck of vacuum impregnation drying machine, and the dipping inner cylinder of vacuum impregnation drying machine take out true Sky, vacuum drying is realized, until alumina support loses bright water, the catalyst for introducing chromium is made；Used in this step Vacuum impregnation drying machine, stirring colter and scattered fly cutter of the inside equipped with rotation rate-controllable, during impregnation drying, control The rotating speed of system stirring colter is 25 turns/min, and the rotating speed for disperseing fly cutter is 150 turns/min；
S3 is dried：Catalyst in above-mentioned steps is disperseed using the high velocity air drier of the meter per second of flow velocity 16, done Dry, the hot-wind inlet temperature of high velocity air drier is 120 ~ 135 DEG C of EAT；
S4 is calcined：Heating roasting, roasting time 2.5 hours are carried out to catalyst using rotary kiln, sintering temperature is 580~620℃。
Cr in the present embodiment is prepared using two methods in method for preparing catalyst of the present invention and background technology2O3Content is The resulting reduced parameter of 14% catalyst is as follows：
Embodiment three
The present embodiment uses the identical process conditions of embodiment one, prepares Cr2O3The microspheroidal fluid bed that content is 16% is different Butane dehydrogenation catalyst.
Cr in the present embodiment is prepared using two methods in method for preparing catalyst of the present invention and background technology2O3Content is The resulting reduced parameter of 16% catalyst is as follows：
Example IV
The present embodiment uses the identical process conditions of embodiment two, prepares Cr2O3The microspheroidal fluid bed that content is 16% is different Butane dehydrogenation catalyst.
Cr in the present embodiment is prepared using two methods in method for preparing catalyst of the present invention and background technology2O3Content is The resulting reduced parameter of 16% catalyst is as follows：
Conclusion：The chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst prepared using the inventive method, it compares biography Catalyst prepared by system method, Active components distribution is uniform, size distribution uniformity is good, and the activity and selectivity of catalyst is good.

Claims (4)

  1. A kind of 1. industrial production process of chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst, it is characterised in that the technique Step is：
    It is prepared by S1 carriers：α-one water aluminum oxide is beaten, the liquid-solid ratio of water and α-one water aluminum oxide is 2L/kg, then in air-flow Inlet temperature not less than 750 DEG C, 5.0 ~ 8.0MPa of atomisation pressure, exhaust temperature be 200 ~ 240 DEG C under conditions of to carry out spraying dry It is dry, aluminum oxide dried pellet is obtained, then microspheric oxidation is obtained after being calcined 2 ~ 6 hours at 500 ~ 700 DEG C using rotary kiln Alumina supporter；
    S2 impregnates：Alumina support and chromium nitrate aqueous solution are placed in vacuum impregnation drying machine and carry out supersaturated dipping, true Pre-preg 1 ~ 4 hour in empty soak drying machine, temperature are 50 ~ 80 DEG C, and liquid-solid ratio during dipping is 1.0-2.0 liters/kilograms；So Afterwards toward being passed through thermal source in the chuck of vacuum impregnation drying machine, and the dipping inner cylinder of vacuum impregnation drying machine is vacuumized, it is real Now it is dried in vacuo, until alumina support loses bright water, the catalyst for introducing chromium is made；In the Vaccum Permeating used in step S2 Stain drying machine, stirring colter and scattered fly cutter of the inside equipped with rotation rate-controllable, during impregnation drying, control stirring The rotating speed of colter is 20 ~ 30 turns/min, and the rotating speed for disperseing fly cutter is 100 ~ 200 turns/min；
    S3 is dried：Catalyst in above-mentioned steps is disperseed more than the high velocity air drier of 15 meter per seconds using flow velocity, done Dry, the hot-wind inlet temperature of high velocity air drier is 80 ~ 180 DEG C；
    S4 is calcined：Heating roasting is carried out to catalyst using rotary kiln, temperature is 500 ~ 700 DEG C, roasting time 1 ~ 6 hour.
  2. 2. the industrial production process of chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst according to claim 1, its It is characterised by：Described alumina support is microballoon of the particle diameter at 5 ~ 200 μm.
  3. 3. the industrial production process of chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst according to claim 1, its It is characterised by：During the step S3 is dried, the high velocity air flow velocity is more than 15 meter per seconds, and the hot entrance air temperature of drier is 90~140℃。
  4. 4. the industrial production process of chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst according to claim 1, its It is characterised by：In the step S4 roastings, sintering temperature is 550 ~ 680 DEG C, and roasting time is 1 ~ 4 hour.
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CN107488096B (en) * 2016-06-13 2020-08-07 中国石油天然气股份有限公司 Dehydrogenation process of low-carbon alkane circulating fluidized bed

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