CN112742486A - Oil column catalyst forming device and forming method - Google Patents
Oil column catalyst forming device and forming method Download PDFInfo
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- CN112742486A CN112742486A CN201911037362.7A CN201911037362A CN112742486A CN 112742486 A CN112742486 A CN 112742486A CN 201911037362 A CN201911037362 A CN 201911037362A CN 112742486 A CN112742486 A CN 112742486A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000001816 cooling Methods 0.000 claims abstract description 98
- 239000002002 slurry Substances 0.000 claims abstract description 69
- 239000007921 spray Substances 0.000 claims abstract description 51
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000003921 oil Substances 0.000 claims description 191
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- 229940057995 liquid paraffin Drugs 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002808 molecular sieve Substances 0.000 claims description 11
- 239000005662 Paraffin oil Substances 0.000 claims description 10
- 239000003502 gasoline Substances 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000010687 lubricating oil Substances 0.000 claims description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 10
- 239000008188 pellet Substances 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004533 oil dispersion Substances 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000002826 coolant Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 5
- 239000012798 spherical particle Substances 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003349 gelling agent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 206010039101 Rhinorrhoea Diseases 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 208000010753 nasal discharge Diseases 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalyst forming, and particularly provides an oil column catalyst forming device and a catalyst forming method, wherein the forming device comprises: the spray gun comprises a spray gun and a hot oil column, wherein the hot oil column is used for receiving slurry from the spray gun and solidifying and forming the slurry into spherical particles; wherein the lance comprises a nozzle body and a nozzle cooling jacket; the nozzle body comprises a cavity, a slurry feeding hole and a bottom nozzle, wherein the slurry feeding hole and the bottom nozzle are communicated with the cavity; the nozzle cooling sleeve is sleeved on the outer wall of the nozzle main body. The invention overcomes the defect that slurry is gelled and stuck when encountering ammonia in the air, and simultaneously prevents the slurry in the nozzle from gelling and solidifying due to the contact with a hot oil column, so that the forming device can stably produce the small ball catalyst with the particle size of 0.2-0.5 mm for a long period.
Description
Technical Field
The invention relates to the field of oil column molding, in particular to a molding method of a spherical catalyst, and particularly relates to an oil column catalyst molding device and an oil column catalyst molding method.
Background
Industrial catalysts require catalyst particles of suitable shape, size and good mechanical strength to be able to match the corresponding catalytic reaction and reactor to participate in the reaction, depending on the reaction process. The molding step is the main process of catalyst preparation, and has great influence on the morphology, size, mechanical strength, activity, service life and the like of the catalyst.
The existing forming method of the spherical catalyst comprises the following steps: the dropping ball forming method can be used for preparing a small ball catalyst with the diameter of 0.5-30 mm; the rotation forming method can be used for preparing a spherical catalyst with the diameter of 0.6-30 mm; the spray drying method can be used for preparing the microsphere catalyst with the particle size of 20-200 mu m. In recent years, with the development of slurry beds and microreactors, spherical catalysts with diameters of 200-500 mu m are increasingly required.
The oil column molding method is a common method for preparing pellets of alumina, silica-alumina, etc. The method comprises the steps of reacting metal aluminum with a hydrochloric acid solution to prepare aluminum sol, fully stirring the aluminum sol and a gelling agent (urea or hexamethylenetetramine solution) to obtain an aluminum sol mixture with proper viscosity and solid content, and dripping the aluminum sol mixture into a hot oil column device filled with oil. The sol is contracted into spherical shape by surface tension after entering oil layer, at the same time the gelatinizer is heated to decompose ammonia gas to make the sol be solidified and formed, after the formation the sol is further aged in hot oil bath to raise its strength, and its bulk density and pore structure are optimized, and finally the above-mentioned material is passed through the processes ofThe finished product of gamma-Al is obtained by washing, drying and roasting2O3And (4) a small ball. When the dropping ball device is matched with an oil column to produce small balls, the dropping ball device adopts a dropping head dropping mode, namely colloid liquid drops are separated from the dropping head and fall under the action of gravity or external force, so that small liquid drops with the diameter of less than 500 mu m are difficult to drop. And the dripper of the dripping ball device is directly exposed in the production environment and often contacts with ammonia gas volatilized to the environment in the oil column, so that the dripper generates a 'nasal discharge' phenomenon, and the uniformity and the sphericity of the produced particles are directly influenced. In the general production process, the viscous slurry of the drippers needs to be cleaned timely and continuously, which not only seriously influences the continuity and scale of the production of the spherical carrier, but also reduces the product quality.
CN101912747 discloses a vibration crushing type granulating system and a granulating method for metal oxide particles, wherein sol forms a jet flow with a constant speed through a spray hole of a spray head under the action of a gear pump or a screw pump, and is crushed under the vibration of a vibration exciter and enters liquid paraffin on the upper part of a forming column, and then enters ammonia water on the lower part of the forming column to form spherical gel particles. The metal oxide pellets with the particle size of 0.2-5 mm can be produced through the design of the structure of the ball dropping device. However, when the technology is used for producing small balls (with the diameter of 0.2-1 mm), the small balls are influenced by interfacial tension when passing through the interface of liquid paraffin and ammonia water, so that elliptical small balls are formed or accumulated on a phase interface, a spray head of the technology is directly exposed in a production environment, sol at the position of the spray head is contacted with ammonia gas volatilized into the environment from an oil ammonia column, the phenomenon of 'nasal discharge' of a dripper is caused, and continuous production is influenced.
Disclosure of Invention
The invention aims to solve the problem that a dripper is easy to generate 'nasal discharge' when contacting with air when the existing oil column forming and oil ammonia forming device generates a small ball catalyst, provides an oil column catalyst forming device and a forming method, and can overcome the problem to continuously prepare spherical oxide with the particle size of 0.2-0.5 mm.
In order to achieve the above object, the present invention provides an oil column catalyst molding apparatus, comprising: the spray gun and the oil column are used for receiving the slurry from the spray gun and curing and forming the slurry into spherical gel pellets; wherein the lance comprises a nozzle body and a nozzle cooling jacket;
the nozzle body comprises a cavity, a slurry feeding hole and a bottom nozzle, wherein the slurry feeding hole and the bottom nozzle are communicated with the cavity;
the nozzle cooling sleeve is sleeved on the outer wall of the nozzle body and used for cooling the nozzle body, and the slurry in the nozzle body is prevented from being gelled and solidified due to heat from a hot oil column so as to block the nozzle.
Preferably, the outlet of the nozzle cooling jacket surrounds the nozzle orifice and the depth of the oil phase level deeper into the oil column is greater.
Preferably, the ratio of the cross-sectional area of the cooling jacket outlet to the cross-sectional area of the bottom nozzle is 50-200: 1.
preferably, the nozzle cooling jacket comprises:
the cooling oil distribution device comprises a cooling oil direct guide pipe sleeved on the outer wall of the cavity, and a cooling oil inlet and a cooling oil dispersion port which are arranged on the cooling oil direct guide pipe;
the cooling oil dispersing ports are uniformly distributed on a circular interface of the cooling oil direct guide pipe, so that the back mixing of the cooling oil in the sleeve is enhanced, and heat conducted from the nozzle is taken away to the maximum extent;
preferably, the number of the cooling oil dispersing openings is 2-12;
the fixing plate is connected with the cooling oil direct guide pipe;
a cooling oil guide pipe extending from the fixing plate to the bottom surface of the nozzle body;
and a gap between the cooling oil guide pipe and the bottom nozzle is formed as an outlet of the nozzle cooling sleeve.
Preferably, the cooling oil guide pipe is a 90-degree guide pipe.
Preferably, the hot oil column comprises: an oil column and a heating unit for heating the oil column.
Preferably, the heating unit includes: a heating belt wound outside the oil column and/or a heating plate arranged at the bottom of the oil column.
The invention provides a method for forming an oil column catalyst, which comprises the following steps: spraying the slurry containing oxide particles into the hot oil column through a spray gun, heating the gelatinizing agent in the small slurry droplets to decompose ammonia gas so as to solidify and form the small slurry droplets, and aging the small slurry droplets in a hot oil bath to improve the strength of the small slurry droplets. Cooling the spray gun by using cooling oil in the working process of the spray gun;
the oxide is selected from at least one of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve.
Preferably, during the operation of the spray gun, cooling the spray gun so that the temperature of the outlet of the spray gun is lower than 0-30 ℃, preferably lower than 0-20 ℃; wherein the cooling medium is one or more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
Preferably, the spray gun sprays the slurry directly into the oil column without contacting air.
The invention provides an oil column catalyst forming method, which is carried out in the oil column forming device and comprises the following steps: spraying the slurry containing oxide particles into the hot oil column via the spray gun, decomposing the gelatinizing agent in the small slurry drops into ammonia gas under heating to solidify and form the small slurry drops, aging in hot oil bath to raise their strength,
the oxide is selected from at least one of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve.
The gelatinizing agent is added into the slurry, so that the gelatinizing agent in the small slurry drops can be heated in the hot oil column to decompose ammonia gas, and the small slurry drops are solidified and formed. The gelatinizer is preferably one or two of urea or hexamethylenetetramine, and the adding amount is 0.01-5%.
Preferably, the flow rate of the oil phase in the nozzle cooling jacket is such that the temperature at the nozzle orifice (2) is below 0-30 ℃, preferably below 0-20 ℃.
Preferably, the oil phase in the nozzle cooling jacket is one or more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
Preferably, the thickness of the oil phase within the oil column is from 80 to 300cm, preferably 150-300 cm.
Preferably, the temperature of the oil phase in the oil column is 70-100 deg.C, preferably 80-98 deg.C.
Preferably, the solids content of the slurry is 10-30 wt%.
The invention utilizes the spray gun with the cooling interlayer and the hot oil column to carry out catalyst molding, the nozzle of the spray gun is arranged below the oil layer of the oil column, and the cooling oil in the cooling interlayer prevents slurry in the spray gun from being heated, gelled and solidified, the molding method overcomes the defect that the slurry is gelled and hung when encountering ammonia in the air, and simultaneously prevents the slurry in the nozzle arranged in the oil phase of the hot oil column from being heated, gelled and solidified to block the nozzle, so that the molding device can realize the stable production of the small ball catalyst with the particle size of 0.2-0.5 mm in a long period.
Through the technical scheme, the spray gun with the cooling sleeve is combined with the hot oil column in the forming device, the preparation of the small ball catalyst with the particle size of 0.2-0.5 mm can be realized, meanwhile, the forming method overcomes the defect that slurry is stuck with a dripper, and the forming device can run for a long period.
Drawings
Fig. 1 is an oil column molding apparatus according to an embodiment of the present invention.
Description of the reference numerals
1 spray gun 2 nozzle
3 fixed plate 4 cooling oil guide pipe
5 cooling oil inlet 6 slurry feed inlet
7 cavity 8 cooling oil direct guide pipe
9 cooling oil dispersion opening 10 nozzle cooling sleeve outlet
11 hot oil column 12 heating belt
13 heating plate
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the use of the directional terms such as "upper" and "lower" generally means the vertical direction of the upper and lower parts, and the directional terms refer to the positional relationship of the drawings in detail.
The present invention will be described below with reference to the accompanying drawings, and in order to achieve the above object, the present invention provides an oil column catalyst forming apparatus, including: the spray gun comprises a spray gun 1 and a hot oil column 11, wherein the hot oil column 11 is used for receiving slurry from the spray gun and solidifying and forming the slurry into spherical particles;
wherein the lance 1 comprises a nozzle body and a nozzle cooling jacket;
the nozzle body comprises a cavity 7, a slurry feed inlet 6 and a bottom nozzle 2 which are communicated with the cavity 7, wherein the bottom nozzle 2 is arranged to be lower than the oil phase liquid level in the hot oil column 11;
the nozzle cooling sleeve is sleeved on the outer wall of the nozzle body and used for cooling the nozzle body, and the slurry in the nozzle body is prevented from being gelled and solidified due to the heat from the hot oil column.
In the invention, the nozzle 2 of the spray gun is arranged below the liquid level of the oil phase in the oil column, so that the phenomenon of sticking after the slurry is contacted with ammonia gas volatilized from air can be prevented, and the slurry liquid drops can be ensured not to grow up, thereby realizing the preparation of the small ball catalyst with the particle size of 0.2-0.5 mm.
According to the invention, preferably the outlet 10 of the nozzle cooling jacket surrounds the spout 2 and the depth of the oil phase level deeper into the hot oil column 11 is greater. Therefore, the cooling effect can be ensured, and the preparation of the small ball catalyst with the particle size of 0.2-0.5 mm can be realized.
Preferably, the ratio of the cross-sectional area of the outlet 10 to the cross-sectional area of the spout 2 is 50-200: 1.
according to a preferred embodiment of the present invention, as shown in fig. 1, preferably, the nozzle cooling jacket includes: a cooling oil direct guide pipe 8 sleeved on the outer wall of the cavity 7, and a cooling oil inlet 5 and a cooling oil dispersion port 9 which are arranged on the cooling oil direct guide pipe 8; the fixed plate 3 is connected with the cooling oil direct guide pipe 8; a cooling oil guide pipe 4 extending from the fixed plate 3 to the bottom surface of the nozzle body;
the gap between the cooling oil guide pipe 4 and the bottom nozzle 2 is formed as an outlet 10 of the nozzle cooling jacket. Thereby, the cooling oil enters the cooling oil direct guide pipe 8 through the cooling oil inlet 5 and then enters the cooling oil guide pipe 4 through the cooling oil dispersion port 9 to cool the lance.
According to a preferred embodiment of the present invention, the cooling oil dispersion port 9 includes a plurality of ports uniformly distributed on the circular cross section of the cooling oil guiding straight pipe end 8 after the fixing plate is disposed. The arrangement has the advantages of strengthening the back mixing of cooling oil in the sleeve and taking away heat conducted from the nozzle to the maximum extent.
According to a preferred embodiment of the present invention, the cooling oil guide tube 4 is a 90-degree guide tube.
According to a preferred embodiment of the present invention, said column of hot oil 11 comprises: an oil column and a heating unit for heating the oil column.
According to a preferred embodiment of the present invention, the heating unit comprises: a heating belt 12 wound around the outside of the oil column and/or a heating plate 13 disposed at the bottom of the oil column.
The forming process using the apparatus of the present invention is as follows: slurry from a slurry feed port 6 is conveyed to a spout 2 through a cavity 7 and dispersed into small droplets of 0.3-0.8 mm in an oil phase of a hot oil column 11 under the action of pressure; the small liquid drops slowly in the hot oil column, and is heated to decompose ammonia gas to make it self-gel, solidify and form. And the cooling oil from the cooling oil inlet 5 flows to the flowing cooling oil outlet 10 in the cooling oil guide pipe 4, so that the temperature of the nozzle is reduced in the forming process, and the slurry in the nozzle is prevented from being gelled and solidified by the heat from the hot oil column.
The invention provides a method for forming an oil column catalyst, which comprises the following steps: spraying slurry containing oxide particles into a hot oil column through a spray gun, and solidifying and forming the slurry into spherical particles through the oil column, wherein the spray gun is cooled in the working process of the spray gun; the oxide is selected from at least one of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve.
According to the invention, cooling is preferably carried out such that the lance outlet temperature is below 0-30 ℃, preferably below 0-20 ℃.
The invention can be used for producing various spherical oxide carriers or catalysts, and the oxide used for shaping can be a single oxide or a mixture of oxides. The oxide is at least one selected from alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve, preferably alumina, and the mixture of oxides is preferably one mixture of alumina-molecular sieve. The molecular sieve may be ZSM-5, ZSM-11, ZSM-13, ZSM-22, ZSM-32, ZSM-48, ZSM-50, SAPO-11, SAPO-34, MCM-22, MCM-44, X, Y, beta or MOR molecular sieve.
In the present invention, the oil layer mainly functions to shape the dropped slurry, and the oil phase is preferably one or a mixture of more selected from hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil, and petroleum ether. After the sol is pelletized, the sol can be further aged in an oil bath to improve the strength, optimize the bulk density and the pore structure, and finally, the finished product gamma-Al is obtained through washing, drying and roasting2O3And (4) a small ball.
The invention has no special requirements on the preparation of the catalyst slurry, and the preferable preparation process of the catalyst slurry comprises the following steps: the pseudo-boehmite is reacted with nitric acid solution to prepare aluminum sol, and the aluminum sol and gelling agent (urea or hexamethylenetetramine solution) are fully stirred to obtain an aluminum sol mixture with proper viscosity and solid content.
According to the invention, preferably, the spray gun is cooled during operation of the spray gun, and the oil phase is preferably one or a mixture of more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
According to the present invention, it is preferable that the cooling medium is the same as the oil phase in the hot oil column, and is one or more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil, and petroleum ether.
According to the invention, the spray gun preferably sprays the slurry directly into the oil column without contacting air. Therefore, the defect that the slurry meets ammonia gelation and sticking in the air can be avoided, and the forming device can realize long-period stable production.
According to the present invention, there is provided an oil column catalyst forming method which is carried out in the oil column forming apparatus according to the present invention, the method comprising: and spraying slurry containing oxide particles into a hot oil column through a spray gun, and solidifying and forming the slurry into spherical particles through the hot oil column, wherein the oxide is at least one selected from alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieves.
According to the invention, the flow rate of the oil phase in the nozzle cooling jacket is such that the temperature at the nozzle orifice (2) is below 0-30 ℃, preferably below 0-20 ℃.
According to the invention, the oil phase in the nozzle cooling sleeve is one or a mixture of more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
The method can be used for preparing the spherical oxide with the particle size of 0.2-0.5 mm, the forming method overcomes the defect of slurry sticking, and the forming device can run for a long period.
In the present invention, the cooling oil introduced from the cooling oil inlet 5 may be introduced from the outside, or may be taken from the oil phase in the upper low-temperature region of the oil column, and is preferably introduced from the outside. The flow rate is not particularly limited, and the temperature at the nozzle 2 is ensured to be lower than 0-30 ℃, preferably lower than 0-20 ℃.
The oil phase and the cooling oil of the hot oil column used for forming by the method can be one or a mixture of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether. The height of the hot oil column oil phase is 80-300cm, preferably 150-300 cm. The slurry is sprayed into the oil phase of the hot oil column through the spray holes to form small balls, and the small balls form gel small balls in the falling process.
Preferably, the solid content of the slurry is 10-30 wt%.
The ratio of the cross-sectional area of the cooling oil outlet to the cross-sectional area of the material nozzle is 50-200: 1.
as shown in fig. 1, the hot oil column is used to hold the slurry droplets and the cooling oil from the spray gun. The oil phase in the oil column and the cooling oil are the same substance, but at different temperatures. The slurry liquid drops enter the oil column oil phase and contract into balls by virtue of surface tension, and the balls are gelled, solidified and formed after ammonia gas is decomposed by heating.
The present invention will be described in detail below by way of examples.
Example 1
The formation was carried out according to the apparatus shown in FIG. 1, and a catalyst slurry having a solid content of 30% by weight (containing 95% by weight of acidified pseudoboehmite and 5% by weight of the gelling agent hexamethylenetetramine) was introduced from a material inlet into a nozzle by a high-pressure pump, and the slurry was jetted from a nozzle to form a gob. The ratio of the cross-sectional area of the cooling oil outlet to the cross-sectional area of the material spout is 50: 1. the number of cooling oil dispersion ports was 6. The cooling oil flow was 20mL/min and the inlet temperature was 10 ℃. The height of the oil phase in the hot oil column is 200cm, and the temperature of the oil phase in the hot oil column is 90 ℃. After the sol is pelletized, the sol is further aged in a hot oil column for 5 hours, and a finished product gamma-Al is obtained after washing, drying at 120 ℃ and roasting at 550 DEG C2O3And (4) a small ball.
The particle size distribution of the prepared catalyst pellets was measured by a laser particle size analyzer, and the particle diameter of particles between 200 and 500 μm accounted for 90%, and the sphericity of the catalyst (measured by a sphericity analyzer, the same applies hereinafter) was measured to be 0.94.
In the whole balling process, the dripper has no sticking phenomenon and produces no small balls stuck together. The obtained alumina pellet has good sphericity, bulk density of 0.8g/ml, and crushing strength of 70N/mm2。
Example 2
The formation was carried out according to the apparatus shown in FIG. 1, and a catalyst slurry having a solid content of 30% by weight (containing 30% by weight of acidified pseudoboehmite, 65% by weight of Y-type molecular sieve and 5% by weight of a gelling agent hexamethylenetetramine) was introduced from a material inlet into a nozzle by a high-pressure pump, and the slurry was jetted from a nozzle to form a gob. The ratio of the cross-sectional area of the cooling oil outlet to the cross-sectional area of the material spout is 50: 1. the number of cooling oil dispersion ports was 6. The cooling oil flow was 30mL/min and the inlet temperature was 0 ℃. The height of the oil phase in the hot oil column is 200cm, and the temperature of the oil phase in the hot oil column is 98 ℃. After the sol is pelletized, the sol is further aged in a hot oil column for 5 hours, and a finished product gamma-Al is obtained after washing, drying at 120 ℃ and roasting at 550 DEG C2O3And (4) a small ball.
The particle size distribution of the catalyst pellets obtained was measured by a laser particle sizer, and the catalyst sphericity was measured to be 0.932, in which 89% of the particles having a particle diameter of 200-500. mu.m were present.
In the whole balling process, the dripper has no sticking phenomenon and produces no small balls stuck together. The prepared catalyst pellets have good sphericity, the bulk density of 0.65g/ml and the crushing strength of 20N/mm2。
Comparative example 1
The test procedure was the same as in example 1, except that the cooling oil flow rate was 0 mL/min.
After the test is started, the pressure of the spray head rises, and the spray head is blocked soon, so that the test cannot be continued.
Comparative example 2
The test procedure was the same as in example 2, except that the spray head was not placed in the hot oil column, and the lowest end of the spray head was 10cm from the oil level of the hot oil column.
After the test is started, the spray head is attached, the generated liquid drops are gradually increased, and the liquid drops cannot smoothly pass through the interface between the air and the oil phase and are continuously accumulated at the interface. The molding process cannot be continued.
It can be seen from the results of the examples and comparative examples that, by using the example of the forming apparatus or the catalyst forming method of the present invention, the clogging and sticking of the dripper during the forming process can be prevented by adding the cooling oil, thereby ensuring the continuous operation of the industrial production.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. An oil column catalyst molding apparatus, comprising: the spray gun comprises a spray gun (1) and a hot oil column (11), wherein the hot oil column (11) is used for receiving slurry from the spray gun and curing and forming the slurry into gel pellets;
wherein the lance (1) comprises a nozzle body and a nozzle cooling jacket;
the nozzle body comprises a cavity (7), a slurry feeding hole (6) and a bottom nozzle (2) which are communicated with the cavity (7), wherein the bottom nozzle (2) is arranged to be lower than the oil phase liquid level in the hot oil column (11);
the nozzle cooling sleeve is sleeved on the outer wall of the nozzle body and used for cooling the nozzle body, and the slurry in the nozzle body is prevented from being gelled and solidified due to the heat from the hot oil column.
2. The device according to claim 1, wherein the outlet (10) of the nozzle cooling jacket surrounds the bottom spout (2) and the depth of the oil phase level deeper into the hot oil column (11) is deeper.
3. The device according to claim 2, wherein the ratio of the cross-sectional area of the outlet (10) of the cooling jacket to the cross-sectional area of the bottom nozzle (2) is 50-200: 1.
4. the apparatus of any of claims 1-3, wherein the nozzle cooling jacket comprises:
a cooling oil direct guide pipe (8) sleeved on the outer wall of the cavity (7), and a cooling oil inlet (5) and a cooling oil dispersion port (9) which are arranged on the cooling oil direct guide pipe (8);
the fixing plate (3) is connected with the cooling oil direct guide pipe (8);
a cooling oil guide pipe (4) extending from the fixed plate (3) to the bottom surface of the nozzle body;
the gap between the cooling oil guide pipe (4) and the bottom nozzle (2) is formed as an outlet (10) of the nozzle cooling sleeve.
5. The device according to claim 4, wherein the cooling oil guide tube (4) is a 90 degree guide tube.
6. The device according to any one of claims 1-3, wherein the hot oil column (11) comprises: an oil column and a heating unit for heating the oil column.
7. The apparatus of claim 6, wherein the heating unit comprises: a heating belt (12) wound outside the oil column and/or a heating plate (13) arranged at the bottom of the oil column.
8. A method for forming an oil column catalyst, comprising: spraying slurry containing oxide particles into a hot oil column through a spray gun, and solidifying and forming the slurry into gel pellets through the oil column, wherein the spray gun is cooled in the working process of the spray gun;
the oxide is selected from at least one of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve.
9. The molding process according to claim 8, wherein the cooling is such that the lance outlet temperature is below 0-30 ℃, preferably below 0-20 ℃; wherein the cooling medium is one or more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
10. The molding method according to claim 8, wherein the spray gun sprays the slurry directly into the hot oil column without contacting air.
11. A method for forming an oil column catalyst, which is carried out in the oil column forming apparatus according to any one of claims 1 to 7, comprising: spraying the slurry containing oxide particles into a hot oil column through the spray gun, and curing and forming the slurry into gel pellets through the hot oil column, wherein,
the oxide is selected from at least one of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve;
the slurry contains gelatinizer, which is preferably one or two of urea and hexamethylenetetramine and added in 0.01-5 wt%.
12. The molding process according to claim 11, wherein the flow rate of the oil phase inside the nozzle cooling jacket is such that the temperature at the nozzle orifice (2) is lower than 0-30 ℃, preferably lower than 0-20 ℃; and/or
The oil phase in the nozzle cooling sleeve is one or a mixture of more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
13. The molding method according to any one of claims 8 to 12,
the thickness of the oil phase in the hot oil column is 80-300cm, preferably 150-300 cm; and/or
The temperature of the oil phase in the hot oil column is 80-100 ℃, and preferably 90-98 ℃; and/or
The solid content of the slurry is 10-30 wt%; and/or
The oil phase is preferably selected from one or more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
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