CN112742486B - Oil column catalyst forming device and forming method - Google Patents
Oil column catalyst forming device and forming method Download PDFInfo
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- CN112742486B CN112742486B CN201911037362.7A CN201911037362A CN112742486B CN 112742486 B CN112742486 B CN 112742486B CN 201911037362 A CN201911037362 A CN 201911037362A CN 112742486 B CN112742486 B CN 112742486B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000001816 cooling Methods 0.000 claims abstract description 97
- 239000002002 slurry Substances 0.000 claims abstract description 66
- 239000007921 spray Substances 0.000 claims abstract description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims description 202
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 239000002245 particle Substances 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 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008188 pellet Substances 0.000 claims description 12
- 229940057995 liquid paraffin Drugs 0.000 claims description 11
- 239000002808 molecular sieve 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
- 239000005662 Paraffin oil Substances 0.000 claims description 9
- 239000003350 kerosene Substances 0.000 claims description 9
- 239000010687 lubricating oil Substances 0.000 claims description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 239000003502 gasoline Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000003349 gelling agent Substances 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 5
- 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
- 230000007547 defect Effects 0.000 abstract description 4
- 239000012798 spherical particle Substances 0.000 abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000032683 aging 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
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007493 shaping process 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
- 206010039101 Rhinorrhoea Diseases 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001965 increasing effect Effects 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
- 208000010753 nasal discharge Diseases 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
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 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
- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- -1 petrol Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring 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, in particular to an oil column catalyst forming device and a catalyst forming method, wherein the forming device comprises the following components: the device comprises a spray gun and a hot oil column, wherein the hot oil column is used for receiving the slurry from the spray gun and solidifying 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 feed inlet and a bottom spout, wherein the slurry feed inlet and the bottom spout are communicated with the cavity, and the bottom spout is arranged below the liquid level of the oil phase in the oil column; 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 in the air by ammonia gas, and simultaneously prevents the slurry in the nozzle from gelling and solidifying due to contact with a hot oil column, so that the forming device can stably produce the small-ball catalyst with the grain diameter of 0.2-0.5 mm for a long period.
Description
Technical Field
The invention relates to the field of oil column forming, in particular to a forming method of a spherical catalyst, and particularly relates to an oil column catalyst forming device and an oil column catalyst forming method.
Background
According to the different reaction processes, the industrial catalyst needs to have catalyst particles with proper shape, size and excellent mechanical strength, which can be matched with the corresponding catalytic reaction and reactor to participate in the reaction. The shaping step is a main process for preparing the catalyst, and has great influence on the appearance, the size, the mechanical strength, the activity, the service life and the like of the catalyst.
The current forming method of the spherical catalyst comprises the following steps: the drop ball forming method can be used for preparing the small ball catalyst with the diameter of 0.5-30 mm; the rotational molding method can be used for preparing spherical catalysts with the diameter of 0.6-30 mm; spray drying can be used to prepare 20-200 μm microsphere catalysts. In recent years, with the development of slurry beds and microreactors, there has been an increasing demand for spherical catalysts having diameters of 200 to 500. Mu.m.
The oil column forming method is a common method for preparing small balls of alumina, silica, silicon aluminum and the like. The method comprises the steps of reacting metallic aluminum with hydrochloric acid solution to prepare aluminum sol, fully stirring the aluminum sol and gelatinizer (urea or hexamethylenetetramine solution) to obtain 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 a sphere by means of surface tension after entering an oil layer, simultaneously the gel is heated to decompose ammonia gas to solidify and shape the sol, the strength of the sol is further improved by aging treatment in a hot oil bath after the sol is shaped, the bulk density and pore structure of the sol are optimized, and finally the gamma-Al finished product is obtained by washing, drying and roasting 2 O 3 And (3) a small ball. When the device is matched with an oil column to produce small balls, the device adopts a mode that the dripper drips out, namely colloid liquid drops are separated from the dripper to fall down under the action of gravity or external force, so that the small liquid drops with the diameter smaller than 500 mu m are difficult to drip out. The dripper of the dripping ball device is directly exposed in the production environment and is often contacted with ammonia volatilized into the environment in an oil column, so that the dripper generates a phenomenon of 'nasal discharge flow', and the uniformity and sphericity of the produced particles are directly influenced. In the general production process, the sticking slurry of the dripper is cleaned timely and continuously, which not only seriously affects the continuity and scale of the production of the spherical carrier, but also reduces the quality of the product.
CN101912747 discloses a metal oxide particle vibration crushing type granulating system and granulating method, wherein the sol forms a jet flow with constant speed through the spray hole of the 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 into liquid paraffin at the upper part of a forming column, and then enters into ammonia water at 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 ball dropping device structure. However, when the technology produces smaller pellets (with the diameter of 0.2-1 mm), the pellets are affected by interfacial tension when passing through the interface between liquid paraffin and ammonia water, so that oval pellets are formed or accumulated on a phase interface, and a spray nozzle of the technology is directly exposed in a production environment, and the sol at the nozzle opening contacts with ammonia volatilized into the environment in an oil ammonia column, so that a 'nasal discharge' phenomenon is generated by the dripper, and continuous production is affected.
Disclosure of Invention
The invention aims to solve the problem that a dripper is easy to generate 'snivel flow' when contacting air when the existing oil column forming and oil ammonia forming device generates a small ball catalyst, and provides an oil column catalyst forming device and an oil column catalyst forming method, which can 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 solidifying 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 feed inlet and a bottom spout, wherein the slurry feed inlet and the bottom spout are communicated with the cavity, and the bottom spout is arranged below the liquid level of the oil phase in the oil column;
the nozzle cooling sleeve is sleeved on the outer wall of the nozzle main body and used for cooling the nozzle main body, so that the slurry in the nozzle main body is prevented from being gelled and solidified by heat from the hot oil column, and the nozzle is prevented from being blocked.
Preferably, the outlet of the nozzle cooling jacket surrounds the spout and the depth of the oil phase level 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 direct guide pipe is sleeved on the outer wall of the cavity, and the cooling oil inlet and the cooling oil dispersing port are arranged on the cooling oil direct guide pipe;
the cooling oil dispersing openings are uniformly distributed on the circular interface of the cooling oil direct guide pipe, and the purpose of the cooling oil dispersing openings is to strengthen back mixing of the cooling oil in the sleeve and take away heat conducted by the nozzle to the greatest extent;
preferably, the number of cooling oil dispersing ports is 2-12;
a fixing plate connected with the cooling oil straight guide pipe;
a cooling oil guide pipe extending from the fixing plate to the bottom surface of the nozzle body;
the gap between the cooling oil guiding pipe and the bottom nozzle is formed as the outlet of the nozzle cooling jacket.
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 a hot oil column through a spray gun, heating a gelatinizing agent in slurry droplets to decompose ammonia gas to solidify and shape the slurry droplets, and further aging in a hot oil bath after shaping to improve the strength of the slurry droplets. During the working process of the spray gun, cooling the spray gun by using cooling oil;
the oxide is at least one selected from the group consisting of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieves.
Preferably, during operation of the lance, the lance is cooled 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.
Preferably, the lance injects the slurry directly into the column of oil without contact with air.
The invention provides a method for forming an oil column catalyst, which is carried out in the oil column forming device, and comprises the following steps: spraying the slurry containing oxide particles into a hot oil column through the spray gun, heating a gelatinizing agent in the slurry droplets to decompose ammonia gas to solidify and shape the slurry droplets, aging in a hot oil bath to improve the strength of the slurry droplets,
the oxide is at least one selected from the group consisting of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieves.
The gelling agent is added into the slurry, so that the gelling agent in the slurry droplets can be heated in a hot oil column to decompose ammonia gas, and the slurry droplets are solidified and molded. The gelatinizer is preferably one or two of urea and hexamethylenetetramine, and the addition 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 in the column is 80-300cm, preferably 150-300cm.
Preferably, the temperature of the oil phase in the column is 70-100deg.C, preferably 80-98deg.C.
Preferably, the slurry has a solids content of 10 to 30 wt.%.
The invention uses the spray gun with cooling interlayer and the hot oil column to mold the catalyst, the spray gun nozzle is arranged under the oil layer of the oil column, the cooling oil in the cooling interlayer prevents the slurry in the spray gun from being heated, gelled and solidified.
According to the technical scheme, the spray gun with the cooling sleeve is combined with the hot oil column in the forming device, so that the preparation of the small-ball catalyst with the particle size of 0.2-0.5 mm can be realized, meanwhile, the defect that slurry sticks to the dripper is overcome, 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 straight guide pipe
9 cooling oil dispersing port 10 outlet of nozzle cooling jacket
11 hot oil column 12 heating belt
13 heating plate
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, terms such as "upper and lower" are used to refer generally to the vertical directions of upper and lower, and the terms refer to the positional relationships of the drawings in detail.
The present invention is described below with reference to the accompanying drawings, and in order to achieve the above object, the present invention provides an oil column catalyst molding apparatus comprising: the spray gun 1 and the hot oil column 11, the hot oil column 11 is used for receiving the slurry from the spray gun, and solidifying the slurry into spherical particles;
wherein the spray gun 1 comprises a nozzle body and a nozzle cooling jacket;
the nozzle body comprises a cavity 7, a slurry feed port 6 and a bottom spout 2, wherein the slurry feed port 6 and the bottom spout 2 are communicated with the cavity 7, and the bottom spout 2 is arranged below the liquid level of oil phase in a hot oil column 11;
the nozzle cooling sleeve is sleeved on the outer wall of the nozzle main body and used for cooling the nozzle main body, so that the slurry in the nozzle main body is prevented from being gelled and solidified due to heat from the hot oil column.
According to 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 and hanging after the slurry contacts with the volatilized ammonia in the air can be prevented, and the slurry liquid drops are prevented from growing, so that the preparation of the small-ball catalyst with the particle size of 0.2-0.5 mm can be realized.
According to the invention, preferably the outlet 10 of the nozzle cooling jacket surrounds the spout 2 and is deeper into the oil phase level in the hot oil column 11. Thereby ensuring the cooling effect and realizing the preparation of the small-sphere catalyst with the particle diameter of 0.2-0.5 mm.
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 comprises: a cooling oil direct guide pipe 8 sleeved on the outer wall of the cavity 7, a cooling oil inlet 5 and a cooling oil dispersing port 9 arranged on the cooling oil direct guide pipe 8; a fixing plate 3 connected to the cooling oil direct pipe 8; a cooling oil guide pipe 4 extending from the fixing plate 3 to the bottom surface of the nozzle body;
the gap between the cooling oil guiding pipe 4 and the bottom nozzle 2 is formed as the outlet 10 of the nozzle cooling jacket. Thereby, the cooling oil enters the cooling oil straight guiding pipe 8 through the cooling oil inlet 5, and then enters the cooling oil guiding pipe 4 through the cooling oil dispersing port 9 to cool the spray gun.
According to a preferred embodiment of the invention, the cooling oil dispersing opening 9 comprises a plurality of cooling oil dispersing openings uniformly distributed over the circular cross section of the cooling oil straight guiding tube end 8 after the fixing plate is arranged. This arrangement has the advantage of enhancing back mixing of the cooling oil in the jacket, maximizing the removal of heat from the nozzle.
According to a preferred embodiment of the invention, the cooling oil guiding pipe 4 is a 90 degree guiding pipe.
According to a preferred embodiment of the present invention, the hot oil column 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 includes: a heating belt 12 wound around the outside of the oil column and/or a heating plate 13 provided at the bottom of the oil column.
The molding process using the apparatus of the present invention is as follows: the slurry from the slurry feed port 6 is conveyed to the nozzle 2 through the cavity 7, and dispersed into small droplets of 0.3-0.8 mm in the oil phase of the hot oil column 11 under the action of pressure; the small liquid drops slowly fall in the hot oil column and are heated to decompose ammonia gas to gel, solidify and form the self-body. 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 as to cool the nozzle during the forming process and prevent the slurry in the nozzle from being gelled and solidified due to 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 at least one selected from the group consisting of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieves.
According to the invention, it is preferred to cool down such that the lance outlet temperature is below 0-30 ℃, preferably below 0-20 ℃.
The invention can be used to produce a variety of spherical oxide supports or catalysts, and the oxides used for shaping can be single oxides or mixtures of oxides. The oxide is selected from at least one of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve, preferably alumina, and the mixture of the oxide is preferably a mixture of alumina and molecular sieve. The molecular sieve may be a 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 main function of the oil layer is to shape the slurry dropped, and the oil phase is preferably one or more selected from hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether. After the sol is formed into balls, the ball 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 roasting 2 O 3 And (3) a small ball.
The invention has no special requirement on the preparation of the catalyst slurry, and the preparation process of the catalyst slurry preferably comprises the following steps: the pseudo-boehmite reacts with nitric acid solution to prepare alumina sol, and the alumina sol is fully stirred with a gelling agent (urea or hexamethylenetetramine solution) to obtain an alumina sol mixture with proper viscosity and solid content.
According to the invention, it is preferred that the lance is cooled during operation of the lance, the oil phase is preferably selected from one or more of hexane, heptane, octane, nonane, toluene, petrol, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
According to the invention, preferably the cooling medium is the same as the oil phase in the hot oil column, being one or more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
According to the invention, it is preferred that the lance sprays the slurry directly into the column of oil in the oil without contact with air. Therefore, the defect that the slurry is gelled and stuck by ammonia gas in the air can be avoided, and the forming device can realize long-period stable production.
According to the present invention, there is provided a method for molding an oil column catalyst, which is carried out in the oil column molding apparatus of the present invention, the method comprising: 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 of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve.
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 jacket is one or more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
The invention can prepare spherical oxide with the grain diameter of 0.2-0.5 mm, the forming method overcomes the defect of slurry sticking and hanging, 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, preferably, from the outside. The flow rate is not particularly limited, and the temperature at the nozzle 2 is ensured to be lower than 0 to 30 ℃, preferably lower than 0 to 20 ℃.
The oil phase and the cooling oil of the hot oil column formed by the method can be one or more 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 150-300cm. 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 slurry has a solids content of 10 to 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, a column of hot oil is used to hold the slurry droplets and cooling oil from the spray gun. The oil phase and the cooling oil in the oil column are the same substance, but the temperatures are different. The slurry liquid drops enter an oil column oil phase to shrink into balls by surface tension, and are gelled, solidified and formed after being heated to decompose ammonia.
The present invention will be described in detail by examples.
Example 1
The apparatus shown in fig. 1 was used for molding, and a catalyst slurry having a solid content of 30% by weight (containing 95% by weight of acidified pseudo-boehmite and 5% by weight of a gelling agent hexamethylenetetramine) was introduced from the inlet into the nozzle by a high-pressure pump, and the slurry was ejected from the 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 nozzle is 50:1. the number of cooling oil dispersing ports was 6. The flow rate of the cooling oil is 20mL/min, and the temperature at the inlet is 10 ℃. The height of the oil phase of the hot oil column is 200cm, and the temperature of the oil phase of the hot oil column is 90 ℃. After the sol is formed into balls, the balls are further aged in a hot oil column for 5 hours, and the products of gamma-Al are obtained after washing, drying at 120 ℃ and roasting at 550 DEG C 2 O 3 And (3) a small ball.
The particle size distribution of the catalyst pellets obtained was measured by a laser particle sizer, and the particle diameter of the pellets was 90% in the range of 200 to 500. Mu.m, and the sphericity (measured by a sphericity meter, the same applies hereinafter) of the catalyst was 0.94.
In the whole balling process, the dripper does not have the phenomenon of sticking and does not have the small balls adhered together. The prepared alumina pellets have good sphericity, bulk density of 0.8g/ml and crushing strength of 70N/mm 2 。
Example 2
The apparatus shown in fig. 1 was used for molding, and a catalyst slurry having a solid content of 30 wt% (containing 30 wt% of acidified pseudo-boehmite, 65 wt% of Y-type molecular sieve, and 5 wt% of a gelling agent hexamethylenetetramine) was introduced from the inlet into the nozzle by a high-pressure pump, and the slurry was ejected from the 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 nozzle is 50:1. the number of cooling oil dispersing ports was 6. The flow rate of the cooling oil is 30mL/min, and the temperature at the inlet is 0 ℃. The height of the oil phase of the hot oil column is 200cm, and the temperature of the oil phase of the hot oil column is 98 ℃. After the sol is formed into balls, the balls are further aged in a hot oil column for 5 hours, and the products of gamma-Al are obtained after washing, drying at 120 ℃ and roasting at 550 DEG C 2 O 3 And (3) a small ball.
The catalyst pellets obtained were measured for particle size distribution by a laser particle sizer, and the catalyst sphericity was measured to be 0.932 with particles having a particle diameter of 200 to 500 μm accounting for 89%.
In the whole balling process, the dripper does not have the phenomenon of sticking and does not have the small balls adhered together. The prepared catalyst pellets have good sphericity, bulk density of 0.65g/ml and crushing strength of 20N/mm 2 。
Comparative example 1
The test procedure was the same as in example 1, except that the cooling oil flow was 0mL/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 surface of the hot oil column.
After the test is started, the nozzle is stained and hung, the generated liquid drops are gradually increased, and the liquid drops can not 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.
As can be seen from the results of examples and comparative examples, according to the examples of the molding device or the catalyst molding method of the present invention, the cooling oil is added to prevent the dripper from clogging and sticking during the molding process, thereby ensuring continuous operation of 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, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (13)
1. An oil column catalyst molding apparatus, the molding apparatus comprising: the spray gun (1) and the hot oil column (11), the hot oil column (11) is used for receiving the slurry from the spray gun, and solidifying 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 feed port (6) communicated with the cavity (7) and a bottom spout (2), wherein the bottom spout (2) is arranged below the liquid level of the oil phase in the hot oil column (11);
the nozzle cooling sleeve is sleeved on the outer wall of the nozzle main body and used for cooling the nozzle main body, so that the slurry in the nozzle main body is prevented from being gelled and solidified due to 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 is deeper into the oil phase level in the hot oil column (11).
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. a device according to any one 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), a cooling oil inlet (5) and a cooling oil dispersing port (9) which are arranged on the cooling oil direct guide pipe (8);
a fixed plate (3) connected to the cooling oil direct pipe (8);
a cooling oil guide pipe (4) extending from the fixing plate (3) to the bottom surface of the nozzle body;
the gap between the cooling oil guiding pipe (4) and the bottom nozzle (2) is formed as an outlet (10) of the nozzle cooling jacket.
5. The device according to claim 4, wherein the cooling oil guiding tube (4) is a 90 degree guiding tube.
6. A 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 of forming an oil column catalyst, carried out in the oil column catalyst forming apparatus according to any one of claims 1 to 7, the method comprising: spraying the slurry containing oxide particles into a hot oil column through the spray gun, solidifying and forming gel pellets through the hot oil column, wherein,
the oxide is at least one selected from alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve;
the slurry contains the gelatinizer, so that the gelatinizer in the slurry droplets can be heated in a hot oil column to decompose ammonia gas, and the slurry droplets are solidified and molded.
9. The molding method according to claim 8, wherein the gelling agent is one or both of urea and hexamethylenetetramine and is added in an amount of 0.01 to 5% by weight.
10. The forming method according to claim 8, wherein the flow rate of the oil phase in the nozzle cooling jacket is such that the temperature at the nozzle (2) is below 0-30 ℃; and/or
The oil phase in the nozzle cooling sleeve is one or more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
11. A forming process according to claim 10, wherein the flow rate of the oil phase in the nozzle cooling jacket is such that the temperature at the nozzle orifice (2) is below 0-20 ℃.
12. The molding method according to any one of claims 8 to 11, wherein,
the thickness of the oil phase in the hot oil column is 80-300cm; and/or
The temperature of the oil phase in the hot oil column is 80-100 ℃; and/or
The slurry has a solids content of 10 to 30% by weight.
13. The molding method according to claim 12, wherein,
the thickness of the oil phase in the hot oil column is 150-300cm; and/or
The temperature of the oil phase in the hot oil column is 90-98 ℃; and/or
The oil phase is one or more of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, lubricating oil, liquid paraffin oil and petroleum ether.
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| GB645133A (en) * | 1943-06-19 | 1950-10-25 | Socony Vacuum Oil Co Inc | Improvements in or relating to inorganic oxide gels of spheroidal shape |
| US4392987A (en) * | 1981-12-30 | 1983-07-12 | W. R. Grace & Co. | Alumina spheroids with controlled small particle size and a process for producing them |
| DE10120612A1 (en) * | 2001-04-26 | 2002-11-21 | Omg Ag & Co Kg | Method and device for producing spherical metal particles |
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| CN105502447B (en) * | 2014-10-16 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of method that hot forming oil column prepares alumina globule |
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