Method of preparing catalyst

专利摘要:

公开号:SU1245253A3
申请号:SU823442101
申请日:1982-05-27
公开日:1986-07-15
发明作者:Арнтц Дитрих；Прешер Гюнтер；Буркхардт Вернер；Хайлос Йоханнес；Маннер Райнхардт
申请人:Дегусса Аг (Фирма)；
IPC主号:

专利说明:

The invention relates to methods for the preparation of catalysts for oxidation, laziness and oxidative ammonolysis, in particular to a method for the preparation of catalysts consisting of a surface rough inert carrier with a particle size of 0.5-6 mm and covering it with a fixed sheath by means of active catalytic material
The aim of the invention is to obtain a catalyst with increased abrasion resistance by fabricating the steps of the process under certain conditions,
The invention is illustrated by the following examples.
Example I, Co-Salt Mass for the preparation of the active phase of a catalyst is prepared as follows: 20 increase from a speed of 0.096 to a speed of 0.104 l / min to a solution of 32.3 kg of nickel nitrate,
Ni (NO.j) 2 6Н ,, 0, 1 kg of cobalt nitrate- After the spraying process is completed with Co (MOh) 2 and 4.5 kg of iron nitrate or with further rotation of the drum FefNOj j 9 into 38 kg of water the compacted phase is fixed in solution, with stirring, a solution of 0.3 kg of samarium oxide Sm 0 in 3.5 kg of 38% nitric acid is added,
5.8 kg Aerosil 200, 10.8 kg yontmo-. Rillonite, a solution of 23.4 kg of ammonium molybdate (NH) in 31.4 kg of 3.5% phosphoric acid and a solution of 5; 4 kg of bismuth nitrate Bi (NO) s 33 4.5 kg 7, nitric acid. The obtained suspension of the co-precipitated mass is dried on a roller dryer, calcined at 530 ° C in a rotating pipe and then crushed. The resulting powder of the initial mass of the catalytically active material has a particle size of 2-40 µm (90%) with max 1-gum KSi J m and thermal expansion coefficient at 400 ° C, equal to 81 ,.
By suspending 6.5 kg of this nopoiuKa - preparation in 4.7 kg of water with the addition of 0.5 kg of D-glucose as a link to the subsisting and 0.3 kg of pentaerythritol as a pore-forming agent, a suspension of an original material is prepared. shells, calcined steatite beads with a diameter of 4 mm, which are practically devoid of pores, have a rough surface (average roughness value of 25 mm by 4768/1) and their linear thermal expansion coefficient at 90 10 Vc as the carrier for this material.
35
25 minutes, 5 minutes and then during the 20-minute drying phase, only with a single turn of the drum per minute.
After drying on air overnight, the pore former is decomposed in a rotating tube at 400 ° C and an average residence time of 15 minutes. Aging of the catalyst after the process. they are kept at 550 ° C and also for 5 minutes in a rotating - with a pipe,
The resulting catalyst — a shell (a catalyst applied in the form of a shell) has a shell that is strong without cracking. Average diameter
(5 of the catalyst (sheath catalyst) obtained is 5.25 m with a standard deviation of 0.3 mm. Wear is determined in the freesawer through abrasion when rolling and paired at 20 rpm as wear less than 2 mm after 7 minutes. For calcined catalysis: the melt (catalyst - shell), it is less than 0.2 wt.%. After heat treatment with 100 cycles of heating and cooling, areni, in
50
which: catalyst for. 0, 5 h
review by circumstances 5 heat up
from 250 to and cooled again to
250 C, the wear value is insignificantj but rises and amounts to 0.2 ms,%.
. In the case of a drop test, the free fall of 100 ml of the catalyst through a 3.4 m long tube with 6 kg of carrier is introduced into the pan, and the base by blowing it at a speed of -2 preheated to air and rotating the drum.
at a speed of 20 rpm, it is brought into intensive mixing motion to flow, but in this way, the carrier set in motion is first sprinkled with a spray of 0.4 liters for 2 minutes
suspension using a double nozzle. Spraying by spraying the residual suspension through the temperature of the exhaust air is sent from the drum so that it is constantly observed
moisture preserving shell. At the same time, the temperature of the outgoing air ear drops Bt of the initial 48 to 39 ° C at the end of the suspension application (after 6 minutes) and the application of the suspension
 At the end of the spraying process, with further rotation of the drum, the compacted phase is fixed in the
35
25 minutes 5 minutes and then during the 20-minute drying phase only with a single turn of the drum per minute.
After drying on air for overnight, the pore former is expanded in a rotating tube at 400 ° C and an average residence time of 15 minutes. The catalyst is activated at 550 ° C and also for 5 minutes in a rotating tube.
The resulting catalyst — a shell (a catalyst applied in the form of a shell) has a shell that is strong without cracking. Average diameter
(5 of the catalyst (sheath catalyst) obtained is 5.25 m with a standard deviation of 0.3 mm. Wear is determined in the freesawer through abrasion when rolling and paired at 20 rpm as wear less than 2 mm after 7 minutes. For calcined catalysis: the melt (catalyst - shell), it is less than 0.2 wt.%. After heat treatment with 100 cycles of heating and cooling, areni, in
50
which: catalyst for. 0, 5 h
review by circumstances 5 heat up
from 250 to and cooled again to
250 C, the wear value is insignificantj but rises and amounts to 0.2 ms,%.
. In the case of a drop test, the free fall of a 100 ml catalyst through a 3.4 m long pipe with an internal diameter of 200 mm on a solid basis gives a fracture fraction of less than 2 mm, equal to 0.03 wt.%.
Comparative Example 1 A powdered catalyst is prepared as in Example 1, only the co-precipitated material dried on rollers is calcined at 410 ° C in a rotary tube. The coefficient of thermal expansion of the powder is 50–10 / C at 400 ° C. Using this poroptary initial mass of the catalyst. A catalyst prepared in the form of a shell (catalyst – shell) is prepared analogously to Example 1. In the case of both processes in a rotating tube, the blowing agent decomposes and the calcination causes a strong abrasion.
(approximately 5 wt.%). The shell is strongly cracked and its pieces partially flake off. Dp this catalyst, in which case the coefficient
124
thirty
thermal expansion of the powdered initial mass is not coordinated by appropriate thermal treatment with this indicator of the carrier; wear is 15 wt.%.
Comparative example 2. A powdered initial catalyst mass prepared according to example I is used to prepare a catalyst in a panning drum. To do this, 30 kg of steatite carrier used in example 1 is placed in a drum containing 50 kg of load and due to the rotation of drum 35 at 21 revolutions / When it is tilted by 20 °, stirring of 3 kg of the catalyst base mass of the catalyst together with 2.5 kg of D-glucose and 1.5 kg of pentaerythritol is suspended in 22 l of water. The surface of the viscous bulk material is exposed to heated to 90 ° C air passed through with a speed of 200 MV4. To obtain a shell with a slightly lower suspension flow rate of initially 0.5 to 0.48 l / min, an hour later it is sprayed by spraying through a double nozzle. After application (approximately 50–80 minutes), the shell is compacted for 10 more minutes spin the drum. The catalyst, deposited in the shell, is dried for 15 hours and 40 ° C, a porous separator is heated in a rotary pipe at 400 ° C and
25
calcining I5 min,
its there at 550 ° C flows
thirty
35 - 50 55
2452534
The resulting catalyst has the following physical properties: the average diameter is 5.3 mm with a standard deviation of 0.68 mm; wear for 5 scans and drops (20 rpm, 7 minutes of driving time) is 1 wt.% and after treatment at a variable temperature of 250 to (100 cycles for 50 hours), 10 means 1.2 wt. % In the 100 ml drop test (catalyst) through a 3.4 m long pipe with an internal diameter of 20 mm, the fraction to less than 2 mm is 0.2 wt.%.
t5 Example 2. The catalytic effect of the catalyst obtained in example 1 is tested in a technical tubular reactor with an internal diameter of 20.5 mm, which is outside cooled with a salt bath,
when the height of the loose mass of the catalyst is 2.7 m by the example of the conversion of propylene to acrolein.
about,. When feeding 5 mol / h of propylene,
25 40 mol / h of air and 10.1 mol / h of water at a salt bath temperature of 351 ° С conversion reaches 94%, the yield of acrolein is 79.2% and the total selectivity to acrolein and acrylic acid is 92.5%.
eight . When 5 mol / h of propylene, 38 mol / h of air and 29 mol / h of inverse flue gas (composition: 7% 0, 1% of propylene, 92% of inert gas, water) are applied at a salt bath temperature of 355 ° C, the conversion is 94.9%, the yield of acrolein is 79.5% and the selectivity to acrolein and acrylic acid is 92% ..
Example 3: The raw material of the catalytically active material is a raw powder catalyst, which is subjected to heat treatment for 8 hours. It has a composition, wt.%: Mooz67,1;
Ye.Oz
12.8; TiO 2 20.1. The main area (90%) of the particle size distribution is at 1-10 µm with a 50% value at 1.7 µm. The thermal conductivity of the catalytic material is.
2 kg of this powder are suspended in 2 kg of water after the addition of 0.12 kg of urea (as a binder). As a carrier of this material, 6 kg of aluminum silicate with a specific surface of less than 1 is loaded into a panning drum, in which 90% of the pores have dazers 30–250 m, with a surface roughness according to DIN 4768/1 with an average roughness of 40 microns. with a diameter of 4.8 mm and a coefficient of thermal expansion of 6910 / ° C (at 400. C), by blowing at a speed of 4 m / min of air heated to 95 ° C and rotating the drum at 20 rpm, the carrier is put vigorous mixing and those
A slurry of the initial mass of the catalyst for 75 minutes is sprayed onto a liquefied carrier so that the temperature of the exhaust air drops from initially 50 to the end of the application. After an additional compaction phase for 5 minutes, with further liquefaction and drying the wet supported catalyst shell last 15 hours, dried in air and then calcined for 5 hours in a stream of air. The wear resistance in the standard dough (7 min, 20 rpm) is 0.3 masl.
5.180 g (approx. About 3,760 ml) of the finished coated catalyst are placed evenly in nine tubes (inner diameter 18.1 mm) of the tube bundle reactor. The height of the catalyst bed in tubes with side-mounted temperature probes is em 173 cm,,.
The tube bundle reactor is cooled by a circulating stream of molten salt. Salt bath temperature. A gas stream preheated to 290 300 ° C is fed to the reactor at a rate of 4.640 nl / h of the following composition, vol.%: Methanol 11, oxygen 12.85, the rest inert gases, mainly nitrogen, along with small amounts of water Foot steam (about 0.5% by volume). Maximum temperature in the catalyst bed, Z55 s. The gas leaving the reactor t is immediately cooled; Condensing products are then absorbed by water. After a balanced period of time (74 hours) with a conversion of 99% of the used methanol, 93.1% of formaldehyde is calculated based on the methanol used.
Example 4 Preparing a catalyst powder that contains spfm, molybdenum, vanadium and tungsten in a 5 molar ratio of 6: 12: 3: 1, 2, co-precipitated material dried on rollers further at 250 ° C by roasting in a rotating pipe t to oxides and then grind. The powder 10 has a particle size distribution with a main area (more than 90%) of 2-50 microns with a maximum of 4. 7 microns and a coefficient of thermal expansion at 400 ° C equal to / s.
 6.5 kg of this suspension-cosiness catalyst powder in 3.5 kg of water with 0.2 kg of glucose as a binder and in a dragee drum are sprayed onto 6 kg of steatitic carrier by spraying (as in Example 1) for 75 min. In this case, the carrier is blown up with preheated air and the drum is rotated to achieve intensive mixing of the content flow 5, the activating subsequent heat treatment is carried out in a rotating tube for a dwell time of .15 min. The wear resistance in the standard test 30 (7 min, 20 rpm) is 0.05 wt.%,
58 g of this supported catalyst shell is loaded into a tubular reactor with an internal diameter of 16 m, which is cooled from the outside with a salt melt. At the temperature of the salt bath, a gaseous stream consisting of 1.4 mol / h of air 40 0.5 mol / h of water and 0.16 mol / h of acrolein is passed through the catalyst, and a conversion of 98.8% and an output of acrylic acid 94 are obtained, 5% based on acrolein used.
Example 5 A catalyst base powder was prepared by precipitating 23.3 kg of antimony trioxide, 4.7 kg of ammonium metavanadate, 12.8 kg of titanium dioxide, 11.7 kg of montmorillonite and 5.8 kg of pyrogenic silicic acid; drying on rollers and heat treatment at 450 ° C for 0.3 hours. The obtained powder after grinding has a particle size of 1 µm (90%) with a maximum of 15 µm and a thermal expansion coefficient of 400 µr of C, equal to 65-10 / C,
in kg of this powder, the initial mass of catalyst is suspended in 6 kg during
Dyes with 0.4 kg of glucose as a binder and 0.6 kg of pentaerythritol and in a coating pan were sprayed on 6 kg of balls of aluminum silicate (as in Example 3) for 85 minutes. In this case, the carrier is fluidized due to the preheated air and the rotation of the drum, and the spraying process is adjusted so that the temperature of the outgoing air from the drum decreases from initially 47 to 37 ° C at the end.
After drying in air (15 hours), the coated catalyst was then heat treated by calcining successively for 3 hours at 550 ° C, 1 hour at 650 ° C, and 3 hours at 770 ° C in a muffle furnace. The weight loss of the finished coated catalyst in the standard test is 0.1% by weight.
Example 6. 2 kg of the initial catalyst mass prepared in Example 1 are suspended in 1.9 kg of water with the addition of 0.05 kg of glucose as a bond; In the coating drum 6 kg of carrier from aluminum silicate with a specific surface of less than 1 m / g, with a diameter of 4.8 mm5 macroporosity at which 90% of the pores have sizes of 70-500 microns with a surface roughness according to DIN 4768/1 with an average a roughness value of 48 / m and a thermal expansion coefficient at 400 ° C of 72-10 U C are brought into a state of intensive mixing and flow by blowing at a speed of 2 heated to air and rotating the drum at a speed of 12 rpm and thus 35 minutes moving media is applied by spraying Penza, as in Example 1, so that the temperature of the exhaust air decreases from 43 to. After drying the crude catalyst, it is activated with a rotating tube. Wear is 0.2% by weight.
Example 7. The powder of the initial mass of the catalyst was prepared analogously to example 1, with the only difference that 0.4 kg of potassium nitrate was added to the samarium oxide solution. Calcined at 470 ° C
.
20
I eat 5 Yu
a25
-
55 30
40
50
On a pipe, the catalyst preform powder has a coefficient of thermal expansion. - 9 kg of this starting material of the catalyst are suspended in 5.3 kg of water together with 0.7 kg of pentaerythritol (a preformer) and 0.8 kg of glucose (a binder) and sprayed in a panning drum by spraying on 6 kg of intensively moving steatite carrier (as in example I). At the same time, with a speed of 2.5 m- / min, the intake air is heated to 85 ° C and for 95 minutes the sprayed suspension is metered in such a way that: the temperature of the exhaust air decreases from 51 to 42 ° s . After drying, decomposing the binder and binder at 400 ° C and. activation in a rotating pipe, the catalyst has a wear of 0.3 wt.% ..
Example 8. The powder of the initial mass of the catalyst was prepared analogously to example 1, with the only difference that in a solution of 6.7 kg of nickel nitrate Ni (NOj) - 6, 12.3 kg of cobalt nitrate Co (NOj), j -6Н, 0 and 6.9 kg of iron nitrate FeCNO ,,) 9 in 30.4 kg of water are successively added a solution of 18.4 kg of ammonium molybdate (, ij, x X 4HjO in 24.1 kg of 3.1% phosphoric acid, a solution of 7 kg of bismuth nitrate B1 (Shz) a in 7.0 kg of a 0.8% aqueous solution of nitric acid and 6 kg of pyrogenic silicic acid with stirring. The resulting coprecipitated material is dried on a roller dryer at 140 ° C and calcined at in a rotary tube and then crushed in a rod mill. The resulting powder has a particle size of 5-80 microns (90%) with a maximum of 30 microns and a coefficient of thermal expansion of 85 10 V C.
Out of 7.5 kg of this powder, the initial mass of the catalyst with the addition of 0.6 kg of glucose and 0.5 kg of pentaerythritol in 6.2 kg of water and 6 kg of steatite carrier is prepared in a coating pan according to an example of a wear-resistant, shell-coated catalyst. Wear is 0.25 wt.% With
Example 9. Catalyst powder is prepared as in Example 8, with only an additional 0.2 kg of KNO.,
9124525
to the first solution, crawling ... shock G Sheet granulometric composition of 3-70 microns (90%) with a maximum of 25 microns, and the coefficient of thermal expansion
8A-10 V ° C. From 5.5 kg of this powder, the initial mass of catalyst with 0.4 kg of glucose to 4.5 kg of water and 6 kg of steatite carrier in a coating pan is prepared analogously to Example I, a wear-resistant, coated catalyst . Wear is 0.3 May,%
Example 10.50 ml prepared in example
with t in a thermostat-controlled tubing outside with a salt bath; a reactor with an inner diameter of 16 mm. When filing within an hour 0.25 mol of propylene, 45 nl of air-. and 9 5 5 g of water - get a conversion of 92 5%, the yield of acrylic acid is 80.5% and the total selectivity is 95.8% based on the used prprilen.
L p m i m p 11, 50 ml of the catalyst prepared in Example 6 is introduced into a reactor that is thermostatically controlled outside with a salt bath and has an internal diameter of 1 b mm. When feeding into. within one hour, 0.15 mol of isobutylene, 35 nl of air and 10.5 kg of water receive a conversion of 91%, a methacroleic acid yield based on 74.1% used isobutylene, and a total methacrolein and methacrylic acid yield of 82.4%.
Example 12 50 ml of the catalyst prepared in Example 7 are placed in a reactor that is thermostatically controlled outside with a salt bath and has an internal diameter of 16 mm. When 0.15 mol of tert-butanol, 35 nl of air and 10.5 kg of water are fed in for an hour, a conversion of 92.8% is obtained, the yield of methacroleic acid per 75.2% used for tert-bz tanol, as well as the total the yield of methacrolein and methacrylic acid is 81, 9%. .
Example 13 .50 ml of the catalyst prepared in example 9 is tested as in example 11 at a salt bath temperature. Conversion is 93.6%, the yield of methacrolein calculated for the isobutylene used is 75.6%, and the total selectivity is methacrolein and - methacrylate acid 82.9%.
ten
. Example 14 80 ml of the catalyst prepared in example 5 are placed in a temperature-controlled outside reactor at 430 ° C with an internal diameter of 20.5 mm. With the supply of 0.12 mol of picoline, 80.5 nl of air, 16 nl of ammonia and 19 g of water within an hour, a conversion of 89.5% is obtained and the selectivity calculated for the used picoline to nicotinic acid nitrile is 79%,
Irimer 15, 2.5 kg of the catalyst obtained in a dialogical example, the catalyst is suspended in 3 kg of an extra-15 nol meta-catalyst from 0.25 kg of glucose and applied to r ",", steatite carrier with 4 air at a temperature also example 1, the duration of the application layer
20 110 min. Annealing in a rotary kiln with a catalyst has a wear of 0.5 wt.% In the La Rocher freeabilator.
Example 16. 4.5 kg of the obtained 25 according to the method of example 4, the catalyst powder is suspended in 8 kg of zoda with 0.2 kg of glucose. The suspension, by analogy with example 1, is applied to 6 kg of aluminosilicate balls for
30 45 minutes, and a purge of 2 nm / min heated to air is performed. After activation of the catalyst at 365 ° C in a rotary kiln, the wear is 0.2 wt.%
35 Example 17.3 kg of the obtained catalyst according to Example 5, which, after peremalshan has particles of 1-150 mm, is suspended in 3 kg of water with 0.2 kg of glucose. As a binder,
40 By analogy with Example 5, the suspension was applied by spraying 6 kg of aluminum silculate pellets with diameter O ,, 5 mm, and the carrier was fluidized by supplying 3.2 mVMHH air heated to 110 ° C and using the rotation of the drum. Coating time 30 min. The abrasion resistance after heating the catalyst at 770 ° C for 5 hours is
50 May 0.15%
Example 18. 4 kg of the catalyst powder obtained in accordance with Example 8 with the addition of 0.4 kg of glucose and 0.5 kg of pentazurritol sus-55 pendieroteR in 3.5 kg of water, after which the resulting suspension was sprayed onto 5 kg of steatite carrier with with a particle diameter of 6 mm, respectively, heated to 110 ° C, and using the rotation of the drum. Coating time 30 min. The abrasion resistance after heating the catalyst at 770 ° C for 5 hours is
50 May 0.15%
Example 18. 4 kg of the catalyst powder obtained in accordance with Example 8 with the addition of 0.4 kg of glucose and 0.5 kg of pentazurritol sus-55 pendieroteR in 3.5 kg of water, after which the resulting suspension was sprayed onto 5 kg of steatite carrier with diameter of particles is 6 mm in accordance with 11
In accordance with Example 1, an abrasion resistant coated catalyst is obtained. Abrasion is 0.1% by weight.
Example 19, 2-Methylpiraein, ammonia and air with a molar ratio of 1: 3.8: 9.6 are introduced into a reactor with a 55 cm long salt bath and an internal diameter of 21 mm, into which 80 ml of the catalyst described in Example 5 is loaded, and maintain the temperature. The fraction of 2-methylpyrazine introduced is 0.29 mol / h. The reaction gases are absorbed in water and then examined by gas chromatography. The conversion to 2-cyano pyrazine is 87.9%,
Example 20: 80 ml of catalyst prepared according to Example 5 are loaded prior to filling into the reactor.
45253 2
with an internal diameter of 20.5 mm while maintaining the outside temperature at 360 ° C. When 0.12 mol is introduced within an hour. 4-fluorotoluene, 80.5 ml of air, 16 ml of 5 ammonia and 19 g of water give 65% conversion and selectivity to 4-t}) torobenzonitrile 68% with respect to 4-fluorotoluene used,
Example 21. 80 ml of the catalyst prepared according to Example 5 were loaded before filling the reactor with an inner diameter of 20.5 mm while maintaining the outside temperature. When 0.12 mol of 5 2,6-dichlorotoluene, 80.5 nl of air, 16 nl of ammonia and 19 g of water are converted in 40 hours and the selectivity to 2,6-di-chlorobenzonitrile is 89% with respect to used 2,6-dichloro-toluene.

权利要求:
Claims (2)
[1]
1. METHOD FOR PREPARING THE CATALYST FOR Oxidation of propylene, isobutylene, tert-butanol or methanol and oxidative ammonolysis of halogen-substituted toluene or methyl-substituted pyridine and pyrazine, which is a shell of a catalytically active component on the surface of an inert carrier, by spraying with a shear size 0 5-6 mm aqueous suspension of catalytically active material under the action of a gas stream at 25-
240 * C with simultaneous partial removal of the suspending agent and maintaining a constant residual moisture of the shell, followed by drying in the same gas stream and calcining, characterized in that., In order to obtain a catalyst with increased abrasion resistance, a loose carrier with an average roughness value of 25 -48 μm is set in motion by stirring while simultaneously supplying a gas stream from below with a specific flow rate of 22-24 nm / h per 1 liter of carrier, an aqueous suspension containing 50 is countercurrent to the gas stream -63% of a powdery catalytically active mass with a grain size of 1-150 μm and 1.3 - 5% glucose or urea as a binder, in an increasing amount with increasing shell density, the amount of suspended suspending agent is kept constant in relation to the amount of suspension applied, which is determined by the carrier and active mass used with certain coefficients of thermal expansion,. differing by no more than 15%, and the resulting coated shell is compacted before drying by stirring,
[2]
2, Method pop, 1, characterized in that the aqueous suspension contains 50-63 wt.%, Powdery catalytically active mass with a grain size of 1-150 microns, 1.3-5.0 wt.% Glucose or urea as binder and 2.3 to 4.0 wt.% pore former - pentaerythritol,
SU 1245253 AZ

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同族专利:

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公开号 | 公开日

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DE3125062A1|1983-01-13|

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US4621072A|1986-11-04|

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DE3125062C2|1984-11-22|

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EP0068192A2|1983-01-05|

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CA1182439A|1985-02-12|

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EP0068192B1|1986-08-13|

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DE3272561D1|1986-09-18|

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US4521618A|1985-06-04|

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ES8304448A1|1983-03-01|

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BR8203654A|1983-06-21|

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JPS583644A|1983-01-10|

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ES512341A0|1983-03-01|

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EP0068192A3|1984-08-29|

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US4539409A|1985-09-03|

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JPH0330419B2|1991-04-30|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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DE3125062A|DE3125062C2|1981-06-26|1981-06-26|Process for the production of abrasion-resistant coated catalysts and the use of a catalyst obtained in this way|

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