CN102580749B - Preparation technology of butadiene catalyst by oxidative dehydrogenation of butene - Google Patents
Preparation technology of butadiene catalyst by oxidative dehydrogenation of butene Download PDFInfo
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Abstract
The invention provides a preparation technology of butadiene catalyst by oxidative dehydrogenation of butane, which comprises the following steps of: dissolving an iron sheet by dilute nitric acid to prepare ferric nitrate solution, adding mixed serous fluid of calcium chloride, calcium hydroxide and zinc oxide, taking ammonia water as precipitator to gelatinize ferric nitrate solution, adding binder and activated carbon to age, cooling to be room temperature, filtering and washing, and retaining a filter cake; performing spray granulation for the filter cake; and activating in a rotary kiln in a roasting way, and screening out catalyst spherical particles with the particle size from 40 mu m to 200 mu m by a vibrating screen after roasting. The catalyst prepared by the preparation technology is high in yield, even in particle size, hard to smash, and good in wear resistance, so that the loss of the catalyst can be reduced, the use quantity of the catalyst can be saved, and the economic benefit can be improved.
Description
Technical field
The present invention relates to a kind of production technology of butadiene catalyst made by butylene oxidation dehydrogen, particularly a kind of production technology that is used for shelf fluidized bed butylene oxidation-dehydrogenation system butadiene iron system spinel composite oxide catalysts.
Background technology
Butadiene is a kind of important petrochemical industry basic organic material, is to produce elastomeric primary raw material, also is widely used aspect engineering plastics and organic chemical industry's product synthetic.At present, the source of butadiene mainly contains two kinds, and a kind of is from oil plant C4(normal butane and n-butene) the cut dehydrogenation obtains; Another is that extracting obtains from the hybrid C 4 cut of ethylene cracker by-product.Because it is cheap that method for extracting prepares butadiene, become the main method of butadiene production; In recent years, along with the feasible sharp increase of rapid development of automobile industry to the rubber demand, market is all in rising trend for successive years to the demand of butadiene and rubber, the butadiene of being produced by cracking ethylene preparation by-product C 4 fraction extraction process has not satisfied the demand in market, therefore, the industrial route that adopts butylene oxidation-dehydrogenation to produce butadiene becomes the optimization utilization of resources, produces the important process route of butadiene.
Industrial at present, the method that butadiene catalyst made by butylene oxidation dehydrogen adopts is a roasting press forming method, promptly adopts roasting, cooling, pulverizing, press forming.Its shortcoming is a complex process, and energy consumption, cost height, gained catalyst particle size inequality, and the fragment of moulding and smalls are not more, and catalyst finished product yield is not high.
CN96113127 discloses a kind of " iron group catalyst for producing butadiene by oxidative dehydrogenation of bytylene ", its technical scheme is: adopt coprecipitation method, make precipitating reagent with ammoniacal liquor, determine the precipitation terminal point by the pH value, the colloid of post precipitation wears out, colloid filtration washing after aging is kept filter cake, with filtration cakes torrefaction and activation.The Fe-series catalyst that this method makes has the catalytic activity height, purpose selectivity of product advantages of higher; Adopt the sesbania powder as binding agent, make catalyst under the fluidised operation of fluid bed, easily pulverizing, loss, bad mechanical strength, the catalyst consumption is big, and catalyst fines easily causes the obstruction of system.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of production technology of butadiene catalyst made by butylene oxidation dehydrogen, the catalyst finished product yield height that this method makes, catalyst particle size is even, difficult to be pulverized, has good wear resistance, can reduce the loss of catalyst, the save catalyst consumption reduces production costs.
Technical solution of the present invention is:
A kind of production technology of butadiene catalyst made by butylene oxidation dehydrogen, its concrete steps are:
1, making mass fraction with the dilute nitric acid dissolution iron plate is 28%~32% iron nitrate solution, the mixed aqueous solution that adds calcium chloride, calcium hydroxide and zinc oxide, wherein, the mol ratio of calcium chloride and iron is 14:500~15:500, the mol ratio of calcium hydroxide and iron is 23:500~29:500, the mol ratio of zinc oxide and iron is 125:500~500:500, makes solution become glue with ammoniacal liquor as precipitating reagent then, precipitation terminal point PH=8.3~8.4;
2, the colloid with post precipitation adds binding agent and active carbon, described binding agent is the mixture of sesbania powder or sesbania powder and component A, described component A is at least a in methylcellulose, the polyvinyl alcohol, wherein, the consumption of binding agent is 0.5%~3% of iron, calcium chloride, calcium hydroxide and a zinc oxide gross weight, and the consumption of active carbon is 0.5%~3% of iron, calcium chloride, calcium hydroxide and a zinc oxide gross weight;
3, the colloid that will add binding agent and active carbon wears out, and aging temperature is 70 ℃~80 ℃, and ageing time is 10min~60min, is cooled to room temperature, and filtration washing keeps filter cake;
4, filter cake is prepared into the spheric granules that particle diameter is 40 μ m~200 μ m by the mist projection granulating moulding;
5, the spheric granules after the moulding is carried out calcination activation at rotary kiln, sintering temperature activates by table 1 requirement; By reciprocating sieve, sifting out particle diameter is the spheric granules of 40 μ m~200 μ m, promptly makes catalyst after the roasting;
Corresponding curve of table 1 spheric granules activation temperature and time
Furnace temperature ℃ | 20~100 | 100 | 100~280 | 280 | 280~550 | 550 | 550~695 | 695 | 695~100 |
Time h | 2 | 2 | 5 | 4 | 4 | 2 | 3 | 14 | 11 |
The production technology of above-mentioned butadiene catalyst made by butylene oxidation dehydrogen, during with the dilute nitric acid dissolution iron plate, reaction temperature is 50 ℃~60 ℃, the reaction time is 1h~1.5h; In half an hour, be warming up to 100 ℃~105 ℃ then, constant temperature 30min~60min.
The production technology of above-mentioned butadiene catalyst made by butylene oxidation dehydrogen, described ammoniacal liquor rate of addition is 250ml/h~750ml/h.
The production technology of above-mentioned butadiene catalyst made by butylene oxidation dehydrogen during washing, with 40 ℃~50 ℃ ionized water, when the PH=7 of filtrate, stops washing.
The production technology of above-mentioned butadiene catalyst made by butylene oxidation dehydrogen, when the mist projection granulating moulding, it is 60%~75% catalyst pulp that filter cake is mixed with water content, catalyst pulp poured in the catalyst slurry batch can stir, send into high pressure nozzle, be injected in the granulation tower, send into catalyst pulp forth droplet at the granulation tower top, add hot-air simultaneously from the granulation tower top, make droplet be dried to spheric granules, spheric granules and not the catalyst dust of particle spherical in shape be settled down to the granulation tower discharging opening, enter into cyclone separator, catalyst dust is delivered to the catalyst slurry batch can through the air conveyer belt, and spheric granules is collected the catalyst gatherer by the cyclone separator discharging opening.
Above-mentioned mist projection granulating becomes, and described high-pressure fog mouth is sprayed onto catalyst pulp in the granulation tower under 1.0MPa~10.0MPa pressure, and the charging aperture temperature of granulation tower is 300 ℃~500 ℃, and the discharging opening temperature of granulation tower is 120 ℃~200 ℃.
Above-mentioned mist projection granulating moulding when catalyst dust is added to the catalyst slurry batch can, is regulated by adding deionized water, makes its water content with catalyst pulp identical.
The present invention generates iron nitrate solution with iron plate and dilute nitric acid reaction, adds the mixed aqueous solution of calcium chloride, zinc oxide and calcium hydroxide simultaneously; Become glue under the neutralization of precipitating reagent ammoniacal liquor, add binding agent and active carbon again, aging under steady temperature, filtering-depositing spends the deionised water filter cake; The mist projection granulating moulding, activation obtains iron system spinel composite oxide catalysts spheric granules.Its beneficial effect is:
1, catalyst does not contain the chromium element, has fundamentally avoided in Preparation of Catalyst and use because the secondary pollution that the existence of chromium causes; Adopted spray granulation to improve the mechanical strength of catalyst, made it to be difficult for pulverizing the scuff resistance height.
2, by regulating adhesive kind and use amount, make the wear resistance of catalyst increase, active carbon has the pore-creating function, adds the specific area that active carbon helps increasing catalyst in preparation process, helps improving activity of such catalysts.
3, during the mist projection granulating moulding, utilize the hot-air of high speed hot-fluid in the tower, make hot-air can take away the moisture of catalyst granules fast, rate of drying is fast, and uniform drying.
When 4, catalyst prod was collected, catalyst dust was sent the catalyst slurry batch can back to through the air conveyer belt, made whole mist projection granulating process form a circulation, had reduced unnecessary waste.
5, the mist projection granulating forming technique is applied on the iron system spinel composite oxide catalysts of butylene oxidation-dehydrogenation system butadiene, make catalyst particle size even, the fragment of moulding and smalls are not less, thereby catalyst finished product yield is very high, produced the catalyst spherical particle effectively, mist projection granulating preparation technology is simple, and technological parameter is easy to control, be easy to the large-scale low-cost industrial production, thereby improved economic benefit.
When the catalyst spherical particle that 6, makes reacts at shelf fluidized bed catalyzing butene oxidative dehydrogenation system butadiene, have good wear resistance, reduce the loss of catalyst, the save catalyst cost.
Description of drawings
Fig. 1 is the structural representation that the present invention adopts the mist projection granulating system;
Among the figure: 1-high pressure nozzle, 2-granulation tower, 3-cyclone separator, 4-catalyst gatherer, 5-air conveyer belt, 6-catalyst slurry batch can, 7-dehvery pump.
The specific embodiment
Embodiment 1
Dilute nitric acid solution is joined in the container that iron plate is housed, at 50 ℃ of following reaction 1h, be warming up to 100 ℃ with 15min then, constant temperature 30min obtains mass fraction and is 28% iron nitrate solution; Add the mixed aqueous solution of calcium chloride, zinc oxide and calcium hydroxide, wherein, the mol ratio of calcium chloride and iron is 14:500, and the mol ratio of calcium hydroxide and iron is 23:500, and the mol ratio of zinc oxide and iron is 125:500; Make precipitating reagent with ammoniacal liquor then, to solution PH=8.3~8.4, make solution become glue with 250ml/h speed dropping ammonia.The colloid of post precipitation is added 0.5% sesbania powder binding agent and 0.5% active carbon (in iron, calcium chloride, calcium hydroxide and zinc oxide gross weight); The colloid that adds binding agent and active carbon at 70 ℃ of down aging 10min, is cooled to room temperature, filters and with 40 ℃ deionised water, when the PH=7 of filtrate, stop washing, the reservation filter cake.Filter cake is passed through the mist projection granulating moulding of mist projection granulating system, as shown in Figure 1, the mist projection granulating system is by granulation tower 2, the cyclone separator 3 that is connected with granulation tower 2 below discharging openings, the catalyst gatherer 4 that is positioned at cyclone separator 3 belows, the air conveyer belt 5 that is connected with cyclone separator 3, the catalyst slurry batch can 6 that is connected with air conveyer belt 5, form by the high pressure nozzle 1 that pipeline is connected with catalyst slurry batch can 6, described high pressure nozzle 1 is positioned at granulation tower 2 charging apertures, is provided with dehvery pump 7 between described catalyst slurry batch can 6 and the high pressure nozzle 1.During the mist projection granulating moulding, it is 60% catalyst pulp that filter cake is mixed with water content, catalyst pulp poured in the catalyst slurry batch can 6 stir, send into high pressure nozzle 1 by dehvery pump 7, under 1.0MPa pressure, catalyst pulp is sprayed onto in the granulation tower 2, send into catalyst pulp forth droplet at granulation tower 2 tops, add hot-air simultaneously from granulation tower 2 tops, the charging aperture temperature that makes granulation tower 2 is 300 ℃, droplet is dried to spheric granules, spheric granules and not the catalyst dust of particle spherical in shape be settled down to granulation tower 2 bottom discharge mouths (the discharging opening temperature is 120 ℃), enter into cyclone separator 3, catalyst dust is delivered to catalyst slurry batch can 6 through air conveyer belt 5, adding deionized water regulates, make its water content with catalyst pulp identical, continue the mist projection granulating moulding, spheric granules is collected catalyst gatherer 4 by cyclone separator 3 discharging openings.Spheric granules after the moulding carries out calcination activation in rotary kiln, the rotary kiln baking temperature activates by table 1 requirement temperature programming, and by reciprocating sieve, sifting out particle diameter is the spheric granules of 40 μ m~200 μ m, promptly gets catalyst after the roasting, and yield is 94%.
Butylene oxidation-dehydrogenation system butadiene: with butylene vaporization and be heated to 100 ℃, be mixed into blender with 0.4MPa raw water steam and 0.3MPa air then, oxygen alkene mol ratio is 0.65:1, and water alkene mol ratio is 9, butylene air speed (GHSV) 320 h
-1, enter into the shelf fluidized bed reactor that catalyst is housed again, at absolute pressure 0.2MPa, carry out the reaction of butylene oxidation-dehydrogenation system butadiene under the condition that temperature is 365 ℃.Butene conversion 80.2%, butadiene yield 78.5%, butadiene selectivity 91.3%.
Embodiment 2
Dilute nitric acid solution is joined in the container that iron plate is housed, at 55 ℃ of following reaction 1.3h, be warming up to 102 ℃ with 20min then, constant temperature 45min obtains mass fraction and is 30% iron nitrate solution; Add the mixed aqueous solution of calcium chloride solution, zinc oxide and calcium hydroxide, wherein, the mol ratio of calcium chloride and iron is 14:500, and the mol ratio of calcium hydroxide and iron is 25:500, and the mol ratio of zinc oxide and iron is 250:500; Make precipitating reagent with ammoniacal liquor then, to solution PH=8.3~8.4, make solution become glue with 500ml/h speed dropping ammonia; It is 1% sesbania powder and the methylcellulose mixture (in iron, calcium chloride, calcium hydroxide and zinc oxide gross weight) of 0.5 % that the colloid of post precipitation is added binding agent, adds 1% active carbon (in iron, calcium chloride, calcium hydroxide and zinc oxide gross weight) simultaneously; The colloid that adds binding agent and active carbon at 75 ℃ of down aging 35min, is cooled to room temperature, filters and with 45 ℃ deionised water, when the PH=7 of filtrate, stop washing, the reservation filter cake; It is 65% catalyst pulp that filter cake is mixed with water content, catalyst pulp poured in the catalyst slurry batch can 6 stir, send into high pressure nozzle 1 by dehvery pump 7, under 3.0MPa pressure, catalyst pulp is sprayed onto in the granulation tower 2, send into catalyst pulp forth droplet at granulation tower 2 tops, add hot-air simultaneously from granulation tower 2 tops, the charging aperture temperature that makes granulation tower 2 is 400 ℃, droplet is dried to spheric granules, spheric granules and not the catalyst dust of particle spherical in shape be settled down to granulation tower 2 bottom discharge mouths (the discharging opening temperature is 150 ℃), enter into cyclone separator 3, catalyst dust is delivered to catalyst slurry batch can 6 through air conveyer belt 5, adding deionized water regulates, make its water content identical with catalyst pulp, continue the mist projection granulating moulding, spheric granules is collected catalyst gatherer 4 by cyclone separator 3 discharging openings; Spheric granules after the moulding carries out calcination activation in rotary kiln, the rotary kiln baking temperature activates by table 1 requirement temperature programming, and by reciprocating sieve, sifting out particle diameter is the spheric granules of 40 μ m-200 μ m, promptly gets catalyst after the roasting, and yield is 95%.
Butylene oxidation-dehydrogenation system butadiene: with butylene vaporization and be heated to 100 ℃, be mixed into blender with 0.4MPa raw water steam and 0.3MPa air then, oxygen alkene mol ratio is 0.65:1, and water alkene mol ratio is 9, butylene air speed (GHSV) 320 h
-1, enter into the shelf fluidized bed reactor that catalyst is housed again, at absolute pressure 0.2MPa, carry out the reaction of butylene oxidation-dehydrogenation system butadiene under the condition that temperature is 365 ℃.Butene conversion 90%, butadiene yield 87.3%, butadiene selectivity 94.5%.
Dilute nitric acid solution is joined in the container that iron plate is housed, react 1.5h down at 60 ℃, be warming up to 105 ℃ with 30min then, constant temperature 60min obtains mass fraction and is 32% iron nitrate solution, adds the mixed aqueous solution of calcium chloride, zinc oxide and calcium hydroxide, wherein, the mol ratio of calcium chloride and iron is 15:500, and the mol ratio of calcium hydroxide and iron is 27:500, and the mol ratio of zinc oxide and iron is 375:500; Make precipitating reagent with ammoniacal liquor then, to solution PH=8.3~8.4, make solution become glue with 750ml/h speed dropping ammonia; It is 2% sesbania powder and 1% polyvinyl alcohol mixture (in iron, calcium chloride, calcium hydroxide and zinc oxide gross weight) that the colloid of post precipitation is added binding agent, adds 2% active carbon (in iron, calcium chloride, calcium hydroxide and zinc oxide gross weight) simultaneously; The colloid that adds binding agent and active carbon at 80 ℃ of down aging 60min, is cooled to room temperature, filters and with 50 ℃ deionised water, when the PH=7 of filtrate, stop washing, the reservation filter cake; It is 70% catalyst pulp that filter cake is mixed with water content, catalyst pulp poured in the catalyst slurry batch can 6 stir, send into high pressure nozzle 1 by dehvery pump 7, under 7.0MPa pressure, catalyst pulp is sprayed onto in the granulation tower 2, send into catalyst pulp forth droplet at granulation tower 2 tops, add hot-air simultaneously from granulation tower 2 tops, the charging aperture temperature that makes granulation tower 2 is 500 ℃, droplet is dried to spheric granules, spheric granules and not the catalyst dust of particle spherical in shape be settled down to granulation tower 2 bottom discharge mouths (the discharging opening temperature is 170 ℃), enter into cyclone separator 3, catalyst dust is delivered to catalyst slurry batch can 6 through air conveyer belt 5, adding deionized water regulates, make its water content identical with catalyst pulp, continue the mist projection granulating moulding, spheric granules is collected catalyst gatherer 4 by cyclone separator 3 discharging openings; Spheric granules after the moulding carries out calcination activation in rotary kiln, the rotary kiln baking temperature activates by table 1 requirement temperature programming, and by reciprocating sieve, sifting out particle diameter is the spheric granules of 40 μ m-200 μ m, promptly gets catalyst after the roasting, and yield is 93%.
Butylene oxidation-dehydrogenation system butadiene: with butylene vaporization and be heated to 100 ℃, be mixed into blender with 0.4MPa raw water steam and 0.3MPa air then, oxygen alkene mol ratio is 0.65:1, and water alkene mol ratio is 9, butylene air speed (GHSV) 320 h
-1, enter into the shelf fluidized bed reactor that catalyst is housed again, at absolute pressure 0.2MPa, carry out the reaction of butylene oxidation-dehydrogenation system butadiene under the condition that temperature is 365 ℃.Butene conversion 81.8%, butadiene yield 75%, butadiene selectivity 90.6%.
Embodiment 4
Dilute nitric acid solution is joined in the middle of the container that iron plate is housed, react 1.5h down at 60 ℃, be warming up to 105 ℃ with 30min then, constant temperature 60min obtains mass fraction and is 32% iron nitrate solution, adds the mixed aqueous solution of calcium chloride, zinc oxide and calcium hydroxide, wherein, the mol ratio of calcium chloride and iron is 15:500, and the mol ratio of calcium hydroxide and iron is 29:500, and the mol ratio of zinc oxide and iron is 500:500; Make precipitating reagent with ammoniacal liquor then, to solution PH=8.3~8.4, make solution become glue with 750ml/h speed dropping ammonia; It is 1% sesbania powder, 1% methylcellulose and 1% polyvinyl alcohol mixture (in iron, calcium chloride, calcium hydroxide and zinc oxide gross weight) that the colloid of post precipitation is added binding agent, adds 3% active carbon (in iron, calcium chloride, calcium hydroxide and zinc oxide gross weight) simultaneously; The colloid that adds binding agent and active carbon at 80 ℃ of down aging 60min, is cooled to room temperature, filters and with 50 ℃ deionised water, when the PH=7 of filtrate, stop washing, the reservation filter cake; It is 75% catalyst pulp that filter cake is mixed with water content, catalyst pulp poured in the catalyst slurry batch can 6 stir, send into high pressure nozzle 1 by dehvery pump 7, under 10.0MPa pressure, catalyst pulp is sprayed onto in the granulation tower 2, send into catalyst pulp forth droplet at granulation tower 2 tops, add hot-air simultaneously from granulation tower 2 tops, the charging aperture temperature that makes granulation tower 2 is 500 ℃, droplet is dried to spheric granules, spheric granules and not the catalyst powder grit of particle spherical in shape be settled down to granulation tower 2 bottom discharge mouths (the discharging opening temperature is 200 ℃), enter into cyclone separator 3, catalyst dust is delivered to catalyst slurry batch can 6 through air conveyer belt 5, adding deionized water regulates, make its water content identical with catalyst pulp, continue the mist projection granulating moulding, spheric granules is collected catalyst gatherer 4 by cyclone separator 3 discharging openings; Spheric granules after the moulding carries out calcination activation in rotary kiln, the rotary kiln baking temperature activates by table 1 requirement temperature programming, and by reciprocating sieve, sifting out particle diameter is the spheric granules of 40 μ m-200 μ m, promptly gets catalyst after the roasting, and yield is 90%.
Butylene oxidation-dehydrogenation system butadiene: with butylene vaporization and be heated to 100 ℃, be mixed into blender with 0.4MPa raw water steam and 0.3MPa air then, oxygen alkene mol ratio is 0.65:1, and water alkene mol ratio is 9, butylene air speed (GHSV) 320 h
-1, enter into the shelf fluidized bed reactor that catalyst is housed again, at absolute pressure 0.2MPa, carry out the reaction of butylene oxidation-dehydrogenation system butadiene under the condition that temperature is 365 ℃.Butene conversion 78.4%, butadiene yield 70.4%, butadiene selectivity 89.8%.
Claims (7)
1. the production technology of a butadiene catalyst made by butylene oxidation dehydrogen is characterized in that:
1.1 making mass percent with the dilute nitric acid dissolution iron plate is 28%~32% iron nitrate solution, the mixed aqueous solution that adds calcium chloride, calcium hydroxide and zinc oxide, wherein, the mol ratio of calcium chloride and iron is 14:500~15:500, the mol ratio of calcium hydroxide and iron is 23:500~29:500, the mol ratio of zinc oxide and iron is 125:500~500:500, makes solution become glue with ammoniacal liquor as precipitating reagent then, precipitation terminal point pH=8.3~8.4;
1.2 the colloid of post precipitation is added binding agent and active carbon, described binding agent is the mixture of sesbania powder or sesbania powder and component A, described component A is that methylcellulose, polyvinyl alcohol are at least a, wherein, the consumption of binding agent is 0.5%~3% of iron, calcium chloride, calcium hydroxide and a zinc oxide gross weight, and the consumption of active carbon is 0. 5%~3% of iron, calcium chloride, calcium hydroxide and a zinc oxide gross weight;
Wear out 1.3 will add the colloid of binding agent and active carbon, aging temperature is 70 ℃~80 ℃, and ageing time is 10min~60min, is cooled to room temperature, and filtration washing keeps filter cake;
1.4 filter cake is prepared into the spheric granules that particle diameter is 40 μ m~200 μ m by the mist projection granulating moulding;
1.5 the spheric granules after the moulding is carried out calcination activation at rotary kiln, and sintering temperature activates by table 1 requirement; By reciprocating sieve, sifting out particle diameter is the spheric granules of 40 μ m~200 μ m, promptly makes catalyst after the roasting;
Corresponding curve of table 1 spheric granules activation temperature and time
。
2. the production technology of butadiene catalyst made by butylene oxidation dehydrogen according to claim 1 is characterized in that: during with the dilute nitric acid dissolution iron plate, reaction temperature is 50 ℃~60 ℃, and the reaction time is 1h~1.5h; In half an hour, be warming up to 100 ℃~105 ℃ then, constant temperature 30min~60min.
3. the production technology of butadiene catalyst made by butylene oxidation dehydrogen according to claim 1, it is characterized in that: described ammoniacal liquor rate of addition is 250mL/h~750mL/h.
4. the production technology of butadiene catalyst made by butylene oxidation dehydrogen according to claim 1 is characterized in that: during washing, with 40 ℃~50 ℃ deionized water, when the pH=7 of filtrate, stop washing.
5. the production technology of butadiene catalyst made by butylene oxidation dehydrogen according to claim 1, it is characterized in that: when the mist projection granulating moulding, it is 60%~75% catalyst pulp that filter cake is mixed with water content, catalyst pulp poured in the catalyst slurry batch can stir, send into high pressure nozzle, be injected in the granulation tower, send into catalyst pulp forth droplet at the granulation tower top, add hot-air simultaneously from the granulation tower top, make droplet be dried to spheric granules, spheric granules and not the catalyst dust of particle spherical in shape be settled down to the granulation tower discharging opening, enter into cyclone separator, catalyst dust is delivered to the catalyst slurry batch can through the air conveyer belt, and spheric granules is collected the catalyst gatherer by the cyclone separator discharging opening.
6. the production technology of butadiene catalyst made by butylene oxidation dehydrogen according to claim 5, it is characterized in that: when the mist projection granulating moulding, described high pressure nozzle is sprayed onto catalyst pulp in the granulation tower under the pressure of 1.0 MPa~10.0MPa, the charging aperture temperature of granulation tower is 300 ℃~500 ℃, and the discharging opening temperature of granulation tower is 120 ℃~200 ℃.
7. the production technology of butadiene catalyst made by butylene oxidation dehydrogen according to claim 5 is characterized in that: when catalyst dust is added to the catalyst slurry batch can, regulate by adding deionized water, make its water content with catalyst pulp identical.
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CN1072110A (en) * | 1991-11-01 | 1993-05-19 | 中国科学院兰州化学物理研究所 | Butylene oxidation dehydrogenation catalyst for fluidized bed |
CN1074631A (en) * | 1992-01-24 | 1993-07-28 | 北京大学 | Loading type butadiene catalyst made by butylene oxidation dehydrogen |
CN1184705A (en) * | 1996-09-25 | 1998-06-17 | 中国科学院兰州化学物理研究所 | Iron group catalyst for producing butadiene by oxidative dehydrogenation of bytylene |
EP2343124A2 (en) * | 2001-11-08 | 2011-07-13 | Mitsubishi Chemical Corporation | Method for preparation of a composite oxide catalyst |
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CN1072110A (en) * | 1991-11-01 | 1993-05-19 | 中国科学院兰州化学物理研究所 | Butylene oxidation dehydrogenation catalyst for fluidized bed |
CN1074631A (en) * | 1992-01-24 | 1993-07-28 | 北京大学 | Loading type butadiene catalyst made by butylene oxidation dehydrogen |
CN1184705A (en) * | 1996-09-25 | 1998-06-17 | 中国科学院兰州化学物理研究所 | Iron group catalyst for producing butadiene by oxidative dehydrogenation of bytylene |
EP2343124A2 (en) * | 2001-11-08 | 2011-07-13 | Mitsubishi Chemical Corporation | Method for preparation of a composite oxide catalyst |
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