CN109701443B - Method for forming dropping ball - Google Patents
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- CN109701443B CN109701443B CN201711016151.6A CN201711016151A CN109701443B CN 109701443 B CN109701443 B CN 109701443B CN 201711016151 A CN201711016151 A CN 201711016151A CN 109701443 B CN109701443 B CN 109701443B
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Abstract
The invention relates to the field of dropping ball forming and discloses a dropping ball forming method. The method comprises the following steps: dropping the slurry containing oxide particles into balls to form small drops, wrapping the small drops with protective oil to form slurry wet balls, and forming the slurry wet balls into spherical particles through an oil-ammonia column; wherein the oxide is selected from at least one of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve; the protective oil is selected from at least one of hexane, heptane, octane, nonane, toluene, gasoline, kerosene and petroleum ether. The method solves the problems of slurry sticking or blocking at the dripper during the oil ammonia column forming process and oil phase loss during the forming process, can facilitate dripper replacement, and can continuously produce spherical particles in large scale.
Description
Technical Field
The invention relates to the field of oil ammonia column molding, in particular to a method for forming dropping balls.
Background
The oil ammonia column forming method is a common method for preparing small balls of aluminum oxide, silicon aluminum and the like. The method comprises dropping sol (such as aluminum sol, silica sol, etc.) into oil ammonia column to make sol particles form spheres in oil phase at upper layer of the oil ammonia column and gel in ammonia water at lower layer. And aging the gelled particles, drying and roasting to obtain spherical solid particles. The pellet prepared by the method has uniform structure, low abrasion and high strength, and can be widely used as a fixed bed and moving bed catalyst, a catalyst carrier, an adsorbent and the like.
Industrial catalysts have different shapes and sizes according to the process operation requirements, and thus the molding operation is a main step of catalyst preparation, which has a great influence on the mechanical strength, activity, life, etc. of the catalyst. Some catalysts are broken and pulverized due to poor compressive strength or abraded due to poor wear resistance, so that pipelines are blocked, and normal operation is influenced. For the moving bed process, in order to facilitate the circulation of the catalyst and reduce the mechanical abrasion of the catalyst, the carrier must be made into small balls with the inner diameter of 1-2 mm. For the solid-liquid fluidized bed process, in order to facilitate the fluidization of the catalyst, the carrier is required to be made into small balls with the inner diameter of 0.5-1 mm.
The dropping ball device of the oil ammonia column forming method mainly has three types: (1) the ball dropping device is used for carrying out variable-speed linear reciprocating motion on the ball dropping disc; (2) the ball dropping disc is a ball dropping device which rotates at a constant speed; (3) a dropping ball device with a static dropping ball disc. When the three ball dropping devices are matched with the oil ammonia column to produce the balls, the dropping heads of the ball dropping devices are directly exposed in the production environment and often contacted with ammonia gas volatilized into the environment in the oil ammonia column, so that the phenomenon of 'nasal discharge' of the dropping heads is caused, and the size and the sphericity of the produced balls 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.
CN101632909A discloses a ball dropper for oxide ball dropping, including ball dropper casing and ball dropper press from both sides the cover, ball dropper casing upper portion be equipped with air inlet and material import, it has the dripper jack to open on the casing bottom plate, the dripper is fixed in the dripper jack, ball dropper press from both sides the cover and is located the lower part of ball dropper casing, the lower extreme of dripper stretches into in the clamp and corresponds with the vent that sets up on the ball dropper press from both sides the cover bottom plate, ball dropper press from both sides the wall middle part and is equipped with gas inlet and gas outlet. Although this ball dropper can effectively avoid sticking the phenomenon of hanging because of the dripper that contacts the ammonia and produce, nevertheless because the dripper is overlapped by the clamp, when single dripper takes place to block up, can't in time change the dripper, cause production efficiency to descend. In addition, although the gas is used in the jacket, the liquid drops and the ammonia gas can be separated by wind, the wind inevitably disturbs the liquid drops, and the upper oil in the oil ammonia pool is volatilized by the wind, so that the using amount of the oil in the forming process is consumed too quickly.
US4628040 discloses a method for preparing uniform catalyst pellet particles by placing a liquid to be dropped into a capillary tube, placing the other end of the capillary tube at the throat of a "venturi" tube, and blowing off the dropped droplets by gas or ammonia passing through the capillary tube, thereby producing a uniform-sized spherical catalyst and carrier. However, since the drippers are wrapped by the venturi tube, the drippers cannot be replaced in time when a single dripper is blocked, and the production efficiency is reduced.
Therefore, a method capable of solving the defects of blockage of the dropping ball device, slurry sticking at the position of the dropping head and excessive loss of oil phase in the oil ammonia pool in the prior art and more flexibly replacing the dropping head is needed.
Disclosure of Invention
The invention aims to overcome the problems that a ball dropper of an oil ammonia column forming device in the prior art is easy to block, slurry is stuck at a dripper, and an oil layer of an oil ammonia pool of the oil ammonia column forming device is consumed too fast, and provides a method for forming the dripper.
In order to achieve the above object, the present invention provides a method of forming a dropping ball, comprising:
dropping the slurry containing oxide particles into balls to form small drops, wrapping the small drops with protective oil to form slurry wet balls, and forming the slurry wet balls into spherical particles through an oil-ammonia column; wherein the content of the first and second substances,
the oxide is selected from at least one of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve; the protective oil is selected from at least one of hexane, heptane, octane, nonane, toluene, gasoline, kerosene and petroleum ether.
Preferably, the solid content of the slurry is 10-30 wt%.
Preferably, the slurry also contains 0.001-1 wt% of surfactant based on the dry basis of the slurry; the surfactant is selected from dioctyl sodium sulfosuccinate, sodium p-methoxyfatty amido benzene sulfonate, coconut oil diethanolamide, cetearyl alcohol polyoxyethylene ether, and C6-C8At least one of alkyl polyglucosides.
Preferably, the dropping ball speed of the dropping ball forming is 10-60 drops/cm2·min。
Preferably, the process of forming the oil ammonia column comprises the following steps: the slurry wet ball is dropped into the oil ammonia liquid, firstly passes through the upper oil phase and then enters the lower ammonia phase for gel forming, and gel particles are obtained through aging; and drying and roasting the gel particles taken out of the ammonia phase to obtain spherical particles.
Preferably, the falling position of the slurry wet ball drop is 1-20 cm, preferably 1-10 cm away from the oil ammonia liquid.
Preferably, the dropping ball forming process is to form the slurry into small liquid drops through a dropping ball machine; wherein, the ball dropping device includes: the device comprises a slurry chamber 3, an oil chamber 2 and a dripper 1, wherein the slurry chamber 3 is provided with a compressed gas inlet 4 and a slurry inlet 5, and a bottom plate of the slurry chamber 3 is provided with a plurality of slurry outlets 10 protruding to the outside of the slurry chamber 3; the oil chamber 2 is connected to the outside of the bottom plate of the slurry chamber 3, the lower end of the slurry outlet 10 extends into the oil chamber 2 and corresponds to a plurality of oil outlets 9 which extend to the outside of the oil chamber 2 and are arranged on the bottom plate of the oil chamber 2, and the oil chamber 2 is provided with an oil inlet 6; the dripper 1 is sleeved on the lower end of the slurry outlet 10, and the lower end of the dripper 1 extends out of an oil outlet 9 corresponding to the slurry outlet 10.
Preferably, the plurality of slurry outlets 10 are evenly distributed on the bottom plate of the slurry chamber 3, with a distance between adjacent slurry outlets 10 of more than 1 mm.
Preferably, the number of the slurry outlets 10 is 1-6/cm2Preferably 1 to 4/cm2。
Preferably, the length of the slurry outlet 10 protruding out of the bottom plate of the slurry chamber 3 is 5-20 mm, the slurry outlet 10 is a pipe with a circular or square cross section, and the inner diameter of the cross section of the slurry outlet 10 is 0.5-10 mm; preferably 1 to 5 mm.
Preferably, the length of the oil outlet 9 protruding out of the bottom plate of the oil chamber 2 is 5-20 mm, the oil outlet 9 is a pipe with a circular or square cross section, and the inner diameter of the cross section of the oil outlet 9 is 0.6-15 mm; preferably 1 to 10 mm.
Preferably, the dripper 1 is a reducing pipe, the wide end of the dripper 1 is sleeved on the lower end of the slurry outlet 10, and the tip of the dripper 1 extends out of the oil outlet 9 corresponding to the slurry outlet 10.
Preferably, the distance from the tip of the dripper 1 to the oil outlet 9 is 5 to 30mm, preferably 5 to 20 mm.
Preferably, the inner diameter of the wide end of the dripper 1 is 3-15 mm, preferably 3-10 mm; the inner diameter of the tip of the dripper 1 is 0.3-3 mm, preferably 0.5-1.5 mm.
Preferably, the inner diameter of the oil outlet 9 is larger than the outer diameter of the wide end of the dripper 1.
Preferably, the dripper further comprises an optional annular sleeve sleeved on the oil outlet 9.
According to the technical scheme, the slurry is wrapped with the protective oil and then subjected to oil-ammonia column forming, so that the problems of blockage of a dropping ball device, slurry sticking at a dripper and excessive consumption of an oil layer are solved. The method adopts the novel ball dripper, the slurry flowing out of the slurry outlet of the slurry chamber of the ball dripper can be dripped into liquid drops through the reducing dripper, and the oil flowing out of the oil outlet of the oil chamber and flowing down along the outside of the dripper can wrap the liquid drops, so that the slurry liquid drops are isolated from ammonia volatilized from the environment by the oil, and the problem of sticking, hanging and blocking of the slurry at the dripper is solved. The dripper is sleeved on the slurry outlet, and the size of the slurry outlet, the oil outlet and the dripper is set, so that the dripper can be conveniently replaced without stopping working. In addition, the change of the dripper can change with the gap between the oil outlet, so that the flow velocity of oil can be conveniently adjusted, and the continuous and large-scale production of spherical particles by the dripper forming is facilitated.
Drawings
FIG. 1 is a schematic diagram of a set of slurry outlets, drippers, and oil outlets of a ball dripper.
FIG. 2 is a schematic view of an oil ammonia column forming apparatus.
Description of the reference numerals
1. Dripper 2, oil chamber 3 and slurry chamber
4. Compressed gas inlet 5, slurry inlet 6 and oil inlet
7. Oil phase 8 of oil ammonia pool, ammonia phase 9 of oil ammonia pool, and oil outlet
10. Slurry outlet
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 up and down in the vertical direction, unless otherwise specified.
The invention provides a method for forming dropping balls, which comprises the following steps:
dropping the slurry containing oxide particles into balls to form small drops, wrapping the small drops with protective oil to form slurry wet balls, and forming the slurry wet balls into spherical particles through an oil-ammonia column; wherein the content of the first and second substances,
the oxide is selected from at least one of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve; the protective oil is selected from at least one of hexane, heptane, octane, nonane, toluene, gasoline, kerosene and petroleum ether.
The present invention can be used to produce various spherical oxide carriers or catalysts, and preferably, the oxide used for the dropping balls can be a single oxide or a mixture of oxides. The single oxide may preferably be alumina and the mixture of oxides may preferably be an alumina-molecular sieve mixture. The molecular sieve can be a sodium-type or hydrogen-type 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. Preferably, the weight ratio of alumina to molecular sieve is 1: (0.1 to 3).
In the invention, the solid content of the slurry determines the viscosity of the slurry, and the higher the viscosity is, the higher the pressure of the compressed air is required for carrying out the dropping ball. Preferably, the solid content of the slurry is 10-30 wt%.
In the invention, in order to better enable the oil flowing out of the oil outlet 9 to flow to the tip of the dripper 1 along the outer wall of the dripper 1 to wrap slurry liquid drops and fully play a role of isolating ammonia gas, the slurry preferably also contains 0.001-1 wt% of surfactant in the dry basis of the slurry.
In the present invention, preferably, the added surfactant may be an ionic surfactant or/and a nonionic surfactant. More preferably, the surfactant is selected from dioctyl sodium sulfosuccinate, sodium p-methoxyfatty amidobenzene sulfonate, coconut oil diethanolamide, ceteareth, C6-C8At least one of alkyl polyglucosides.
In the invention, the protective oil is an organic solvent with proper viscosity, and the viscosity of the protective oil at 25 ℃ is preferably 0.1-2 centipoises, and more preferably 0.3-1.5 centipoises.
In the invention, the too high dropping ball speed of the dropping ball forming can cause more emulsion drops to be formed between oil and ammonia phases in the oil ammonia liquid used for oil ammonia column forming, and the oil and the water are not separated in time to form an emulsion layer. The presence of an emulsion layer affects the balling properties of the droplets. Therefore, in order to improve the quality of the balling, the formation of the emulsion layer should be minimized. Controlling the dropping ball speed within a proper range, preferably, the dropping ball speed of the dropping ball forming is 10-60 drops/cm2·min。
In the present invention, preferably, the process of forming the oil ammonia column comprises: the slurry wet ball is dropped into the oil ammonia liquid, firstly passes through the upper oil phase and then enters the lower ammonia phase for gel forming, and gel particles are obtained through aging; and drying and roasting the gel particles taken out of the ammonia phase to obtain spherical particles.
In the invention, the slurry wet bulb is dripped into the oil phase of the oil ammonia liquid from the upper part and enters the ammonia phase through the oil ammonia phase interface depending on the speed. Preferably, the falling position of the slurry wet ball drop is 1-20 cm, preferably 1-10 cm, away from the upper part of the oil ammonia liquid. The greater the distance, the faster the slurry wet bulb enters the oil phase, the greater the deformation that occurs upon contact with the oil phase surface, the shorter the residence time in the oil phase, and the corresponding increase in oil phase thickness is required to make the slurry wet bulb residence time in the oil phase greater than the contraction time. The height of the oil phase should not be too large to facilitate the slurry wet bulb to enter the ammonia phase smoothly to form gel particles at a proper speed. Too small a distance, the slurry wet bulb enters the oil phase too slowly, making it difficult for the slurry wet bulb to pass through the oil-water interface due to the resistance of the slurry wet bulb being greater than gravity.
In the oil ammonia phase, the oil phase is an organic solvent with appropriate viscosity, and preferably the viscosity of the oil phase at 25 ℃ is 0.1-2 centipoises, and more preferably 0.3-1.5 centipoises. Preferably, the oil phase is selected from at least one of hexane, heptane, octane, nonane, toluene, gasoline, kerosene, and petroleum ether. The depth of the oil phase is preferably 0.1-10 mm. The presence of the oil phase can cause the dropped slurry wet ball to shrink into a ball shape under the action of interfacial tension. Without the oil phase, the wet slurry globules would deform upon impact with the liquid surface, and this deformation would set in the ammonia phase. When the oil phase is present, the impacted slurry wet balls will shrink into a spherical shape under the action of interfacial tension. In the present invention, it is preferable that the protective oil and the oil phase are selected the same.
In the oil ammonia phase, the ammonia phase is an electrolyte solution phase and has a depth of 50-200 cm. The ammonia phase is an aqueous solution of ammonia water, ammonium sulfate or ammonium chloride, and the concentration of the ammonia phase is 3-15 wt%, preferably 5-10 wt%. Preferably an aqueous ammonia solution.
In the process of forming the oil ammonia column, the temperature of an ammonia phase is 10-30 ℃. The temperature is not easy to be too high, and the volatilization of electrolytes such as ammonia gas and the like and oil is aggravated.
In the oil ammonia column forming process, the aging time is preferably 0.5-12 h. The drying temperature is 40-120 ℃. The roasting temperature is 450-750 ℃, preferably 550-650 ℃.
In the invention, the process of forming the dropping ball is to form the slurry into small liquid drops through a dropping ball device; wherein, the ball dropping device includes: the device comprises a slurry chamber 3, an oil chamber 2 and a dripper 1, wherein the slurry chamber 3 is provided with a compressed gas inlet 4 and a slurry inlet 5, and a bottom plate of the slurry chamber 3 is provided with a plurality of slurry outlets 10 protruding to the outside of the slurry chamber 3; the oil chamber 2 is connected to the outside of the bottom plate of the slurry chamber 3, the lower end of the slurry outlet 10 extends into the oil chamber 2 and corresponds to a plurality of oil outlets 9 which extend to the outside of the oil chamber 2 and are arranged on the bottom plate of the oil chamber 2, and the oil chamber 2 is provided with an oil inlet 6; the dripper 1 is sleeved on the lower end of the slurry outlet 10, and the lower end of the dripper 1 extends out of an oil outlet 9 corresponding to the slurry outlet 10.
According to the invention, the oil chamber is additionally arranged below the slurry chamber 3 and is used for containing protective oil, so that slurry dropping liquid dripped by the dripper 1 can be wrapped by the oil which flows out of the oil chamber and flows down along the outer wall of the dripper 1, and the slurry dropping liquid is protected. Preferably, the oil in the oil chamber 2 corresponds to the oil used in the oil ammonia sump when the oil ammonia column is formed. Can overcome the influence of ammonia gas on the slurry dripped liquid at the dripper 1 in the existing oil ammonia column forming process. In the ball dropper of the present invention, the slurry chamber 3 is located above and the oil chamber 2 is located below. The lower end of the slurry outlet 10 is the end of the slurry outlet 10 protruding outside the slurry chamber 3, away from the slurry chamber 3.
In the invention, the dripper 1 can guide the slurry dripped from the slurry outlet 10. The slurry outlet 10 is connected with the dripper 1 in a way of easily replacing the dripper 1. Preferably, the dripper 1 is sleeved with the slurry outlet 10 in a threaded or socket connection. The dripper 1 can be conveniently replaced when blockage occurs in industrial production, and continuous production is ensured.
In the invention, the ball dropping device can be provided with a plurality of slurry outlets according to the forming requirement of the ball dropping device. Preferably, the plurality of slurry outlets 10 are evenly distributed on the bottom plate of the slurry chamber 3, with a distance between adjacent slurry outlets 10 of more than 1 mm.
In the invention, the number of the plurality of slurry outlets can be set according to the requirement of drop ball forming. Preferably, the number of the slurry outlets 10 is 1-6/cm2(ii) a Preferably 1 to 4/cm2。
In the present invention, it is preferable that the length of the slurry outlet 10 protruding from the bottom plate of the slurry chamber 3 may be 10 to 20 mm. The slurry for balling in the slurry chamber 3 is led out, and the convenient sleeve joint with the dripper 1 is only needed.
In the invention, preferably, the slurry outlet 10 is a pipe with a circular or square cross section, and the inner diameter of the cross section of the slurry outlet 10 is 0.5-10 mm; preferably 1 to 5 mm. The size of the slurry outlet 10 is such that the slurry can be smoothly pelletized. The wall thickness of thick liquids export 10 can be 1 ~ 5mm, can have the structure that realizes cup jointing with dripper 1, for example external screw thread or cup joint the buckle. Correspondingly, the end of the dripper 1 sleeved with the slurry outlet 10 has a structure for realizing the sleeving, such as an internal thread or a sleeving interface.
In the present invention, the oil chamber 2 and the slurry chamber 3 are preferably connected by a screw connection, a flange connection, a ferrule connection, or a nested fixation. The disassembly and the overhaul of the two can be convenient. Preferably, a sealing gasket is provided between the oil chamber 2 and the slurry chamber 3.
In the invention, preferably, the length of the oil outlet 9 protruding out of the bottom plate of the oil chamber 2 is 10-20 mm, the oil outlet 2 is a pipe with a circular or square cross section, and the inner diameter of the cross section of the oil outlet 9 is 0.6-15 mm; preferably 1 to 10 mm. Preferably, the number of oil outlets 9 corresponds to the number of slurry outlets 10, and there is a one-to-one correspondence. For example, may be coaxially disposed between the respective slurry outlet 10 and the oil outlet 9. The number of the oil outlets 9 is 1-6/cm2(ii) a Preferably 1 to 4/cm2。
In the present invention, the dripper 1 is used to draw the slurry in the slurry chamber 3 through the oil chamber 2 and drip droplets out of the oil outlet 9. Preferably, the dripper 1 is a reducing pipe, the wide end of the dripper 1 is sleeved on the lower end of the slurry outlet 10, and the tip of the dripper 1 extends out of the oil outlet 9 corresponding to the slurry outlet 10. Preferably, the dripper 1 may be a needle. The dripper 1 is a reducing pipe, i.e. the diameter of one end of the dripper 1 is larger than that of the other end. The end with the large diameter is a wide end, and the end with the small diameter is a tip. The wide end is used for sleeving the slurry outlet 10, and the tip is used for finally dripping slurry into a liquid drop with a required diameter. Generally, the dripper 1 is installed with the wide end on top and the sharp end on the bottom.
In the invention, the size of the wide end of the dripper 1 meets the connection with the slurry outlet 10, and the size of the tip of the dripper 1 meets the size requirement of a slurry droplet forming pellet. Preferably, the inner diameter of the wide end of the dripper 1 is 3-15 mm, preferably 3-10 mm; the inner diameter of the tip of the dripper 1 is 0.3-3 mm, preferably 0.5-1.5 mm.
In the present invention, it is preferable that the inner diameter of the oil outlet 9 is larger than the outer diameter of the wide end of the dripper 1. The convenient replacement of the dripper 1 can be satisfied.
In the invention, the distance that the dripper 1 extends out of the oil outlet 9 can realize the effect of oil coating liquid drops. The axial length of the dripper 1 may satisfy the distance. Preferably, the distance from the tip of the dripper 1 to the oil outlet 9 is 5-30 mm; preferably 5 to 20 mm. The distance here is the distance between the end of the tip of the drip emitter 1 and the end of the oil outlet 9 protruding out of the oil chamber 2.
In the present invention, the ball dropping device preferably further comprises an optional annular sleeve sleeved on the oil outlet 9. The lower end of the oil outlet 9 can be provided with an external thread, and one end of the annular sleeve can be provided with an internal thread for connecting the oil outlet 9; meanwhile, the other end of the annular sleeve can be provided with an external thread for being connected with another annular sleeve. The provision of the annular sleeve can extend the length of the projection of the oil outlet 9. Set up a plurality of connections the distance that oil export lower extreme and dripper 1's pointed end can be adjusted to the ring conduit, and is a plurality of the internal diameter of ring conduit is different, the space between the pointed end of ring conduit and dripper 1 also can be adjusted, can play control oil and follow the volume and the speed that the space flowed out, the speed of cooperation thick liquids dropping liquid. The axial length of the annular sleeve is sufficient to ensure that the distance from the tip of the dripper 1 satisfies the above-defined distance that the tip of the dripper 1 protrudes beyond the oil outlet 9. This distance is now the distance of the end of the annular sleeve from the tip of the dripper 1. The annular sleeve can be variable-diameter or non-variable-diameter, the inner diameter is not particularly limited, the connection between the annular sleeve and an oil outlet and between different annular sleeves can be realized, and the pore between the annular sleeve and the tip of the dripper 1 can be adjusted.
In the present invention, the oil flow rate at the oil outlet 9 is preferably 0.001 to 1L/min, and more preferably 0.001 to 0.5L/min. A flow variation can be achieved by means of the above-mentioned annular sleeve to be adapted to the drops of said slurry dripped by the dripper 1.
In the present invention, the slurry inlet provided at the upper portion of the slurry chamber may be in the form of a straight pipe or a bent pipe, preferably a bent pipe. The elbow is that the front end of inserting the indoor thick liquids import of thick liquids buries below the indoor thick liquids liquid level of thick liquids, prevents that raw materials thick liquids from directly falling into the thick liquids pond, causes the thick liquids to stir violently, and then influences the quality of spherical granule product.
The method of the invention can use an oil ammonia column forming device which comprises the ball dropping device provided by the invention and an oil ammonia pool arranged below the ball dropping device. As shown in figure 2, the oil ammonia tank is used for containing slurry drops which are dripped by the ball dripping device and wrapped with oil phase. The upper layer of the oil ammonia pool is an oil phase 7 of the oil ammonia pool, and the lower layer is an ammonia phase 8 of the oil ammonia pool. The slurry liquid drops wrapped with the oil phase enter an oil phase 7 of the oil ammonia pool to shrink into balls by surface tension, and then enter an ammonia phase 8 of the oil ammonia pool to be solidified and molded.
The working process of the dropping ball device for dropping ball forming and the oil ammonia column forming device of the invention is described with reference to fig. 1 and 2: the slurry enters the slurry chamber 3 through the feed inlet 5 and is dripped out of the dripper 1 through the slurry outlet 10 under the pressure action of the compressed gas inlet 4; meanwhile, the oil in the oil chamber 2 flows out from the oil outlet 9 and flows to the tip of the dripper 1 along the outer wall of the dripper 1 to wrap and drip the slurry droplets into the oil phase 7 of the oil ammonia column, the slurry droplets are contracted into small balls by virtue of the surface tension of the oil phase, the slurry small balls remove the wrapped oil and are deposited into the ammonia phase 8 of the oil ammonia pool under the action of gravity to be solidified, and finally, the oil is formed.
The present invention will be described in detail below by way of examples.
Example 1
The method provided by the invention is used for producing the alumina carrier spheres.
With the ball dropping device shown in figure 1 of the invention, 6 slurry outlets (2/cm) are uniformly arranged on the bottom plate of the slurry chamber2) 6 drippers are installed, and the distance between slurry outlets is 10 mm. The protruding length of the slurry outlet is 15 mm; the cross section is circular, and the cross section internal diameter is 5mm, and thick liquids export wall thickness is 2 mm. The inner diameter of the tip of the dripper is 0.8mm, and the inner diameter of the wide end of the dripper is 9 mm. The oil chamber bottom plate is connected with 6 oil outlets with the inner diameter of 10mm, the oil outlets are 5mm long, and each oil outlet corresponds to one dripper and is coaxial with the dripper. The distance between the tip of the dripper and the annular sleeve on the oil outlet is 20 mm.
The height of the oil ammonia pool is 1m, and the inner diameter of the column is 9 cm. The protective oil and oil phase were n-heptane (viscosity 0.41 cps at 25 deg.C), the oil layer was 20mm high, and the ammonia phase (7 wt% ammonia) was 78cm high.
The tip of the dropper is 3cm from the oil surface. Dropping ball rate of 30 drops/cm2Min. The oil flow rate at each oil outlet was 10 ml/min.
SB powder (pseudo-boehmite) produced by German Sasol company is peptized for 5 hours at 70 ℃, and the SB powder, deionized water and nitric acid are mixed according to the mass ratio of 70: 140: 2.5 to form slurry. The slurry had a solid content of 30% by weight, and 0.05% by weight of C was added to the slurry6-C8Alkyl polyglucosides (surfactants). The raw material slurry is introduced into a slurry chamber of a ball dropping device from a slurry inlet, the slurry drops out from a slurry outlet, passes through a dropping head, is wrapped by n-heptane flowing out from an oil outlet, enters an oil phase of an oil ammonia pool to form balls, and the small balls smoothly pass through an oil-ammonia water interface, enter an ammonia phase and are gelled and solidified. Aging the gelled pellets in ammonia water for 3h, taking out, drying at 60 ℃ for 12h, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain the alumina pellets.
In the whole dropping process, the dropping head has no sticking phenomenon and no small balls stuck together. The prepared alumina pellets have good sphericity and uniform particle size, the particle size of the pellets is about 1.6mm, the bulk density is 0.7g/ml, and the crushing strength is 150 newtons per pellet.
Example 2
The method provided by the invention is used for producing the alumina carrier spheres.
With the ball dropping device shown in figure 1 of the invention, 10 slurry outlets (4/cm) are uniformly arranged on the bottom plate of the slurry chamber2) And 10 drippers are installed, and the distance between slurry outlets is 8 mm. The protruding length of the slurry outlet is 5 mm; the cross section is circular, and the cross section internal diameter is 1mm, and thick liquids export wall thickness is 1 mm. The inner diameter of the tip end of the dripper is 0.5mm, and the inner diameter of the wide end of the dripper is 3 mm. The oil chamber bottom plate is connected with 10 oil outlets with the inner diameter of 3mm, the oil outlets are 10mm long, and each oil outlet corresponds to one dripper and is coaxial with the dripper. The distance between the tip of the dripper and the annular sleeve on the oil outlet is 10 mm.
The height of the oil-ammonia pool is 1m, the inner diameter of the column is 9cm, the protective oil and the oil phase are n-heptane (the viscosity at 25 ℃ is 0.41 centipoise), the height of the oil layer is 20mm, and the height of the ammonia phase (7 wt% ammonia water) is 78 cm.
The tip of the dropper is 4cm from the oil surface. Dropping ball rate of 40 drops/cm2Min. The oil flow rate at each oil outlet was 15 ml/min.
SB powder (pseudo-boehmite) produced by German Sasol company is peptized for 5 hours at 70 ℃, and the SB powder, deionized water and nitric acid are mixed according to the mass ratio of 70: 140: 2.5 to form slurry. The slurry had a solid content of 20 wt%, and 0.001 wt% dioctyl sodium sulfosuccinate (surfactant) was added to the slurry. The raw material slurry is introduced into a slurry chamber of a ball dropping device from a slurry inlet, the slurry drops out from a slurry outlet, passes through a dropping head, is wrapped by n-heptane flowing out from an oil outlet, enters an oil phase of an oil ammonia pool to form balls, and the small balls smoothly pass through an oil-ammonia water interface, enter an ammonia phase and are gelled and solidified. Aging the gelled pellets in ammonia water for 3h, taking out, drying at 60 ℃ for 12h, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain the alumina pellets.
In the whole dropping process, the dropping head has no sticking phenomenon and no small balls stuck together. The prepared alumina pellets have good sphericity and uniform particle size, the particle size of the pellets is about 1.2mm, the bulk density is 0.7g/ml, and the crushing strength is 120N/pellet.
Example 3
The method provided by the invention is used for producing the alumina carrier spheres.
With the ball dropping device shown in figure 1 of the invention, 3 slurry outlets (1/cm) are uniformly arranged on the bottom plate of the slurry chamber2) And 3 drippers are installed, and the distance between slurry outlets is 15 mm. The protruding length of the slurry outlet is 15 mm; the cross section is square, and the cross section internal diameter is 4mm, and thick liquids export wall thickness is 5 mm. The inner diameter of the tip of the dripper is 1.5mm, and the inner diameter of the wide end of the dripper is 10 mm. The oil chamber bottom plate is connected with 3 oil outlets with the inner diameter of 5mm, the oil outlets are 20mm long, and each oil outlet corresponds to one dripper and is coaxial with the dripper. The distance between the tip of the dripper and the annular sleeve on the oil outlet is 5 mm.
The height of the oil-ammonia pool is 1m, the inner diameter of the column is 9cm, the protective oil and the oil phase are n-heptane (the viscosity at 25 ℃ is 0.41 centipoise), the height of the oil layer is 20mm, and the height of the ammonia phase (7 wt% ammonia water) is 78 cm.
The tip of the dripper is 5cm away from the oil surface. Dropping ball rate of 60 drops/cm2Min. Each oil outletThe oil flow was 10 ml/min.
SB powder (pseudo-boehmite) produced by German Sasol company is peptized for 5 hours at 70 ℃, and the SB powder, deionized water and nitric acid are mixed according to the mass ratio of 70: 140: 2.5 to form slurry. The slurry had a solids content of 10 wt.% and 1 wt.% cetearyl polyoxyethylene ether (surfactant) was added to the slurry. The raw material slurry is introduced into a slurry chamber of a ball dropping device from a slurry inlet, the slurry drops out from a slurry outlet, passes through a dropping head, is wrapped by n-heptane flowing out from an oil outlet, enters an oil phase of an oil ammonia pool to form balls, and the small balls smoothly pass through an oil-ammonia water interface, enter an ammonia phase and are gelled and solidified. Aging the gelled pellets in ammonia water for 3h, taking out, drying at 60 ℃ for 12h, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain the alumina pellets.
In the whole dropping process, the dropping head has no sticking phenomenon and no small balls stuck together. The prepared alumina pellet has good sphericity and uniform particle size, the particle size of the pellet is about 2.3mm, the bulk density is 0.6g/ml, and the crushing strength is 160N/pellet.
Example 4
The method provided by the invention is used for producing the molecular sieve-alumina spheres.
With the ball dropping device shown in figure 1 of the invention, 10 slurry outlets (4/cm) are uniformly arranged on the bottom plate of the slurry chamber2) And 10 drippers are installed, and the distance between slurry outlets is 10 mm. The protruding length of the slurry outlet is 5 mm; the cross section is square, and the internal diameter of the cross section is 1 mm. The inner diameter of the tip of the dripper is 0.5mm, and the inner diameter of the wide end of the dripper is 3 mm. The oil chamber bottom plate is connected with 10 oil outlets with the inner diameter of 5mm, the oil outlets are 10mm long, annular sleeves with the inner diameter of 5mm are sleeved on the oil outlets, and each oil outlet corresponds to one dripper and is coaxial with the dripper. The distance between the tip of the dripper and the oil outlet was 10 mm.
The height of the oil-ammonia pool is 1m, the inner diameter of the column is 9cm, the protective oil and the oil phase are n-heptane (the viscosity at 25 ℃ is 0.41 centipoise), the height of the oil layer is 20mm, and the height of the ammonia phase (7 wt% ammonia water) is 78 cm.
The tip of the dropper is 4cm from the oil surface. Dropping ball rate of 40 drops/cm2Min. The oil flow rate at each oil outlet was 15 ml/min.
Using HY molecular sieve and aluminium sol as raw materialContinuously producing HY-alumina pellets by using raw materials, wherein the HY solid content in the raw materials is 35 wt%, the aluminum sol solid content is 30 wt%, mixing a molecular sieve and the aluminum oxide sol in a mass ratio of 1:1 to form slurry, wherein the slurry solid content is 25 wt%, and 0.05 wt% of C is added into the slurry6-C8Alkyl polyglucosides (surfactants). The raw material slurry is introduced into a slurry chamber of a ball dropping device from a slurry inlet, the slurry drops out from a slurry outlet, passes through a dropping head, is wrapped by n-heptane flowing out from an oil outlet, enters an oil phase of an oil ammonia pool to form balls, and the small balls smoothly pass through an oil-ammonia water interface, enter an ammonia phase and are gelled and solidified. Aging the gelled pellets in ammonia water for 3h, taking out, drying at 60 ℃ for 12h, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain HY-alumina pellets (the weight ratio of alumina to HY is 1: 1).
In the whole dropping process, the dropping head has no sticking phenomenon and no small balls stuck together. The prepared HY-alumina pellet has good sphericity and uniform particle size of about 1.2mm, bulk density of 0.6g/ml and crushing strength of 70N/pellet.
Example 5
The method provided by the invention is used for producing the alumina carrier spheres.
With the ball dropping device shown in figure 1 of the invention, 6 slurry outlets (2/cm) are uniformly arranged on the bottom plate of the slurry chamber2) 6 drippers are installed, and the distance between slurry outlets is 10 mm. The protruding length of the slurry outlet is 15 mm; the cross section is circular, and the cross section internal diameter is 5mm, and thick liquids export wall thickness is 2 mm. The inner diameter of the tip of the dripper is 0.8mm, and the inner diameter of the wide end of the dripper is 9 mm. The oil chamber bottom plate is connected with 6 oil outlets with the inner diameter of 10mm, the oil outlets are 5mm long, and each oil outlet corresponds to one dripper and is coaxial with the dripper. The distance between the tip of the dripper and the annular sleeve on the oil outlet is 20 mm.
The height of the oil-ammonia pool is 1m, the inner diameter of the column is 9cm, the protective oil and the oil phase are n-heptane (the viscosity at 25 ℃ is 0.41 centipoises), the height of the oil layer is 20mm, and the height of the ammonia phase (7 wt% ammonia water) is 78 cm.
The tip of the dropper is 3cm from the oil surface. Dropping ball rate of 30 drops/cm2Min. The oil flow rate at each oil outlet was 10 ml/min.
SB powder (pseudo-boehmite) produced by German Sasol company is peptized for 5 hours at 70 ℃, and the SB powder, deionized water and nitric acid are mixed according to the mass ratio of 70: 140: 2.5 to form slurry. The solid content of the slurry is 30 wt%, the raw material slurry is introduced into a slurry chamber of a ball dropping device from a slurry inlet, the slurry is dropped out from a slurry outlet, passes through a dropping head and is wrapped by n-heptane flowing out from an oil outlet, enters an oil phase of an oil ammonia pool to form balls, and the balls smoothly pass through an oil-ammonia water interface and enter an ammonia phase to be gelled and solidified. Aging the gelled pellets in ammonia water for 3h, taking out, drying at 60 ℃ for 12h, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain the alumina pellets.
In the whole dropping process, the dropping head has no sticking phenomenon and no small balls stuck together, but the protective oil does not completely wrap the slurry drops. The prepared alumina pellet has good sphericity and uniform particle size, the particle size of the pellet is about 1.8mm, the bulk density is 0.7g/ml, and the crushing strength is 150N/pellet.
Example 6
The method provided by the invention is used for producing the molecular sieve-alumina pellets.
With the ball dropping device shown in figure 1 of the invention, 10 slurry outlets (4/cm) are uniformly arranged on the bottom plate of the slurry chamber2) And 10 drippers are installed, and the distance between slurry outlets is 10 mm. The protruding length of the slurry outlet is 5 mm; the cross section is square, and the internal diameter of the cross section is 1 mm. The inner diameter of the tip of the dripper is 0.5mm, and the inner diameter of the wide end of the dripper is 3 mm. The oil chamber bottom plate is connected with 10 oil outlets with the inner diameter of 5mm, the oil outlets are 10mm long, annular sleeves with the inner diameter of 5mm are sleeved on the oil outlets, and each oil outlet corresponds to one dripper and is coaxial with the dripper. The distance between the tip of the dripper and the oil outlet was 10 mm.
The height of the oil-ammonia pool is 1m, the inner diameter of the column is 9cm, the protective oil and the oil phase are n-heptane (the viscosity at 25 ℃ is 0.41 centipoise), the height of the oil layer is 20mm, and the height of the ammonia phase (7 wt% ammonia water) is 78 cm.
The tip of the dropper is 4cm from the oil surface. Dropping ball rate of 40 drops/cm2Min. The oil flow rate at each oil outlet was 15 ml/min.
HY-alumina globule is continuously produced by taking an HY molecular sieve and alumina sol as raw materials, wherein the HY solid content in the raw materials is 35 wt%, the alumina sol solid content is 30 wt%, and the molecular sieve and the alumina sol are mixed according to the mass ratio of 1:1 to form slurry, wherein the slurry solid content is 25 wt%. The raw material slurry is introduced into a slurry chamber of a ball dropping device from a slurry inlet, the slurry drops out from a slurry outlet, passes through a dropping head, is wrapped by n-heptane flowing out from an oil outlet, enters an oil phase of an oil ammonia pool to form balls, and the small balls smoothly pass through an oil-ammonia water interface, enter an ammonia phase and are gelled and solidified. Aging the gelled pellets in ammonia water for 3h, taking out, drying at 60 ℃ for 12h, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain HY-alumina pellets (the weight ratio of alumina to HY is 1: 1).
In the whole dropping process, the dropping head has no sticking phenomenon and no small balls stuck together, but the protective oil does not completely wrap the slurry drops. The prepared HY-alumina pellet has good sphericity and uniform particle size of about 1.2mm, bulk density of 0.6g/ml and crushing strength of 70N/pellet.
Comparative example 1
The procedure is as in example 1, except that the oil in the oil chamber is replaced by air, the flow rate is 10ml/min and the pressure is 0.11 MPa.
In the whole dropping process, the dropping head has no sticking phenomenon and no small balls stuck together. The prepared alumina pellets have good sphericity and uniform particle size, the particle size of the pellets is about 1.6mm, the bulk density is 0.7g/ml, and the crushing strength is 150 newtons per pellet. However, the air in the jacket increases the volatilization loss of oil in the oil layer, and the oil phase needs to be supplemented regularly.
It can be seen from the results of the examples and the comparative examples that, by adopting the method provided by the invention, the dripped slurry is wrapped by the protective oil flowing out from the oil outlet and then enters the oil ammonia pool for oil ammonia column forming, so that the ball forming can be smoothly realized, and the ball forming effect is good. In the forming process, the dripper is not stuck and hung, and the continuous operation of industrial production is ensured. The embodiment under the preferable conditions can protect the oil to be wrapped better. Furthermore, the examples were not protected by air and there was no loss of oil from the oil phase.
In contrast, in comparative example 1, the air is used for protecting the slurry droplets, although continuous production can be ensured, air is continuously blown to an oil layer in an oil ammonia pool in the production process, the volatilization loss of oil in the oil ammonia pool is accelerated, the oil phase needs to be supplemented regularly, and the operation in the production process and the loss cost of the oil are increased.
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 (19)
1. A method of drop ball molding, comprising:
dropping the slurry containing oxide particles into balls to form small drops, wrapping the small drops with protective oil to form slurry wet balls, and forming the slurry wet balls into spherical particles through an oil-ammonia column; wherein the content of the first and second substances,
the oxide is selected from at least one of alumina, alumina sol, silica sol, zirconia, magnesia, silica and molecular sieve; the protective oil is selected from at least one of hexane, heptane, octane, nonane, toluene, gasoline, kerosene and petroleum ether;
the dropping ball forming process is to form the slurry into small drops through a dropping ball device; the ball dropping device consists of a slurry chamber (3), an oil chamber (2), a dropping head (1) and an optional annular sleeve which is sleeved on an oil outlet (9),
wherein, a compressed gas inlet (4) and a slurry inlet (5) are arranged on the slurry chamber (3), and a plurality of slurry outlets (10) which extend to the outside of the slurry chamber (3) are arranged on the bottom plate of the slurry chamber (3);
the oil chamber (2) is connected to the outside of the bottom plate of the slurry chamber (3), the lower end of the slurry outlet (10) extends into the oil chamber (2) and corresponds to a plurality of oil outlets (9) which are arranged on the bottom plate of the oil chamber (2) and extend to the outside of the oil chamber (2), and the oil chamber (2) is provided with an oil inlet (6);
the dripper (1) is a reducing pipe, the wide end of the dripper (1) is sleeved on the lower end of the slurry outlet (10), and the tip of the dripper (1) extends out of an oil outlet (9) corresponding to the slurry outlet (10).
2. The method of claim 1, wherein the slurry has a solids content of 10 to 30 wt%.
3. The method according to claim 2, wherein the slurry further comprises 0.001-1 wt% of a surfactant on a dry basis of the slurry; the surfactant is selected from dioctyl sodium sulfosuccinate, sodium p-methoxyfatty amido benzene sulfonate, coconut oil diethanolamide, cetearyl alcohol polyoxyethylene ether, and C6-C8At least one of alkyl polyglucosides.
4. The method according to any one of claims 1 to 3, wherein the dropping ball forming has a dropping ball rate of 10 to 60 drops/cm2·min。
5. The method according to any one of claims 1 to 3, wherein the oil ammonia column forming process comprises: the slurry wet ball is dropped into the oil ammonia liquid, firstly passes through the upper oil phase and then enters the lower ammonia phase for gel forming, and gel particles are obtained through aging; and drying and roasting the gel particles taken out of the ammonia phase to obtain spherical particles.
6. The method according to claim 5, wherein the position of the drop of the slurry wet ball drop is 1-20 cm above the oil ammonia liquid.
7. The method according to claim 6, wherein the position of the drop of the slurry wet ball drop is 1-10 cm above the oil ammonia liquid.
8. A method according to claim 1, wherein the plurality of slurry outlets (10) are evenly distributed on the floor of the slurry chamber (3) with a distance of more than 1mm between adjacent slurry outlets (10).
9. The method of claim 8The method, wherein the number of the slurry outlets (10) is 1-6/cm2。
10. The method according to claim 8, wherein the number of slurry outlets (10) is 1-4/cm2。
11. The method according to claim 1, wherein the length of the slurry outlet (10) protruding from the bottom plate of the slurry chamber (3) is 5-20 mm, the slurry outlet (10) is a pipe with a circular or square cross section, and the inner diameter of the cross section of the slurry outlet (10) is 0.5-10 mm.
12. A method according to claim 11, wherein the slurry outlet (10) has a cross-section with an inner diameter of 1-5 mm.
13. The method according to claim 1, wherein the length of the oil outlet (9) protruding from the bottom plate of the oil chamber (2) is 5-20 mm, the oil outlet (9) is a tube with a circular or square cross section, and the inner diameter of the cross section of the oil outlet (9) is 0.6-15 mm.
14. A method according to claim 13, wherein the oil outlet (9) has a cross-section with an inner diameter of 1-10 mm.
15. A method according to claim 1, wherein the tip of the dripper (1) protrudes beyond the oil outlet (9) by a distance of 5-30 mm.
16. A method according to claim 15, wherein the tip of the dripper (1) protrudes beyond the oil outlet (9) by a distance of 5-20 mm.
17. The method according to claim 1, wherein the inner diameter of the wide end of the dripper (1) is 3-15 mm; the inner diameter of the tip of the dripper (1) is 0.3-3 mm.
18. The method according to claim 17, wherein the inner diameter of the wide end of the dripper (1) is 3-10 mm; the inner diameter of the tip of the dripper (1) is 0.5-1.5 mm.
19. A method according to claim 1, wherein the inner diameter of the oil outlet (9) is larger than the outer diameter of the wide end of the dripper (1).
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| CN114505010B (en) * | 2020-10-28 | 2023-07-14 | 中国石油化工股份有限公司 | Catalyst oil ammonia forming method |
| CN114308139B (en) * | 2021-12-31 | 2023-10-24 | 中触媒新材料股份有限公司 | Continuous production device for spherical catalyst particles and application method thereof |
| CN115069230B (en) * | 2022-07-15 | 2023-10-10 | 西北化工研究院有限公司 | Powder molding preparation method of metal organic porous adsorbent |
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| JPS6111139A (en) * | 1984-06-27 | 1986-01-18 | Snow Brand Milk Prod Co Ltd | Capsule body encapsulating instable functional substance and its manufacture |
| CN101632909A (en) * | 2008-07-24 | 2010-01-27 | 中国石油化工股份有限公司 | Ball dropper used for drop ball forming of oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6111139A (en) * | 1984-06-27 | 1986-01-18 | Snow Brand Milk Prod Co Ltd | Capsule body encapsulating instable functional substance and its manufacture |
| CN101632909A (en) * | 2008-07-24 | 2010-01-27 | 中国石油化工股份有限公司 | Ball dropper used for drop ball forming of oxide |
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