CN102451655B - Equipment for preparing molecular sieve - Google Patents
Equipment for preparing molecular sieve Download PDFInfo
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- CN102451655B CN102451655B CN201010515191.7A CN201010515191A CN102451655B CN 102451655 B CN102451655 B CN 102451655B CN 201010515191 A CN201010515191 A CN 201010515191A CN 102451655 B CN102451655 B CN 102451655B
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Abstract
The invention provides equipment for preparing a molecular sieve. The equipment is characterized in that: the equipment comprises a tubular reactor, a gas-solid separator and an absorbing tower. The tubular reactor comprises a heater, a first feeding port, a discharging port and a tube body. The heater can be used for heating the tube body. With the molecular sieve preparing equipment provided by the invention, a contact reaction of the molecular sieve and SiCl4 can be continuously carried out. With the controlling over the length of the tubular reactor, the contact time of the molecular sieve and SiCl4 can be controlled, such that the contact reaction of the molecular sieve and SiCl4 can be sufficiently carried out in the tubular reactor. With the tubular reactor with the heating function, different reaction temperatures can be controlled, such that different reaction conditions and reaction degrees can be controlled. Therefore, molecular sieve products with different dealuminization depths can be obtained according to different requirements.
Description
Technical field
The present invention relates to a kind of equipment of preparing molecular sieve.
Background technology
In catalytic cracking catalyst, molecular sieve is a kind of application material very widely, is also very important a kind of component simultaneously, and the performance of molecular sieve has directly had influence on the reactivity worth of catalytic cracking catalyst.According to different needs, can carry out different modifications to reach the requirement of use to molecular sieve.Such as the molecular sieve of high silica alumina ratio, to be generally considered to catalytic cracking catalyst required.
Preparing aspect the molecular sieve of high silica alumina ratio, mainly contain following several method: ammonium fluosilicate method aluminium-eliminating and silicon-replenishing, hydro-thermal method aluminium-eliminating and silicon-replenishing and gas chemistry method aluminium-eliminating and silicon-replenishing.
Ammonium fluosilicate method aluminium-eliminating and silicon-replenishing (also referred to as chemical method aluminium-eliminating and silicon-replenishing) is mainly to use ammonium fluosilicate dealumination complement silicon, and the degree of crystallinity of the molecular sieve of acquisition is high, and Si/Al when heat endurance is high, but the indissoluble thing AlF forming in dealumination process
3affect hydrothermal stability with residual fluosilicate, also pollute the environment.
Hydro-thermal method is still the at present industrial method generally adopting, but mend silicon not in time there is dealuminzation in water-heat process after, easily cause lattice to subside, and non-framework aluminum clogged with fragments duct, this has not only affected the accessibility in activated centre, also affects the further raising of its heat endurance.
The feature of gas chemistry method aluminium-eliminating and silicon-replenishing is that dealuminzation is even, mends silicon timely, and product crystallization reservation degree is high, Heat stability is good, and duct is unimpeded.For example, CN1057977C discloses a kind of preparation method of the carbon monoxide-olefin polymeric containing rich silicon ultra stabilization Y zeolite, it comprises that drying and moulding thing that water content is less than to silicon tetrachloride gas that the dry air of 900ppm carries and NaY zeolite and heat-resistant inorganic oxide is by silicon tetrachloride total amount: article shaped=0.1-0.8: 1 weight ratio, 150-550 ℃ of haptoreaction 10 minutes to 5 hours, in described drying and moulding thing, particle diameter is that the particle of 35-125 micron accounts for the more than 80% of total particle number, the weight ratio of NaY zeolite and heat-resistant inorganic oxide is 1: 0.2-1.0, the silica alumina ratio of NaY zeolite is 3-6.The method article shaped good fluidity used, has avoided being agglomerated into the phenomenon of piece and obstruction, is easy to realize serialization large-scale production.
CN1121903C discloses a kind of preparation method of rare-earth type high-silicon gamma-zeolite, the method comprises and will be dried processing containing the y-type zeolite of rare earth, after making its water content lower than 10 % by weight, according to silicon tetrachloride: Y zeolite=0.1-0.9: 1 weight ratio, passes into the silicon tetrachloride gas that dry air carries, at temperature 150-600 ℃, react 10 minutes to 6 hours, after reaction, with dry air, purge 5 minutes to 2 hours, with decationized Y sieve water washing, remove Na remaining in zeolite
+, Cl
-, Al
3+etc. solubility accessory substance.The method is simpler compared with prior art, the saving energy and pollution-free.
CN1281493C discloses Y type zeolites containing rare-earth and high content of silicon and preparation method thereof, and this zeolite contains rare earth, and the silica alumina ratio of this zeolite is 5-30, and initial lattice constant is 2.430-2.465nm, and balance lattice constant is at least 0.985 with the ratio of initial lattice constant.The preparation method of this zeolite comprises and will contact with silicon tetrachloride containing rare earth Y type zeolite, described contact is carried out in a consersion unit, this equipment as shown in Figure 1, comprise a reactor (1), a charging aperture (2) and a gas outlet (3), in the inside of reactor (1), also comprise an agitator (4), a gas-solid separator (5) is installed on gas outlet (3), the bore dia of gas-solid separator (5) contained hole and porosity guarantee gas can by and zeolitic solid particle can not pass through, the puddler of agitator (4) stretches out outside reactor (1), under the stirring of agitator (4), the described y-type zeolite containing rare earth contacts with carbon tetrachloride gas, the temperature of contact is 100-500 ℃, the time of contact is 5 minutes to 10 hours, containing the y-type zeolite of rare earth and the weight ratio of carbon tetrachloride, be 1: 0.05-0.5, the silica alumina ratio of the described y-type zeolite containing rare earth is 3-8, lattice constant is 2.45-2.48nm.The method make silicon tetrachloride gas and molecular sieve solid particle haptoreaction more even, avoid the phenomenon that is agglomerated into compact massive thing between molecular sieve solid particle, can reduce labour intensity, can reduce environmental pollution, reduce significantly production cost, be easy to carry out large-scale industrial application.
Obviously, above described method generally all long required time of contact, need a few hours, add charging before reaction and discharging after completion of the reaction, can only carry out once at the most above-mentioned dealumination complement silicon reaction a general day shift, even if adopt the operating type of break tour also can only carry out twice above-mentioned dealumination complement silicon reaction, and owing to needing stirring in reactor, therefore reactor also can not be infinitely great, level based on current, the production capacity of the maximum reactor that can react for above-mentioned dealumination complement silicon is 600kg, continue augmenting response still, in reactor, be difficult to guarantee fully to stir, therefore, adopt the mode of aforesaid reaction vessel, within one day, can obtain at the most the high-silica zeolite of 1200kg.And, in the method for above-mentioned prior art, in order to guarantee the high silicon content of the molecular sieve of acquisition, generally all make SiCl
4excessive far away, excessive SiCl
4use increased undoubtedly production cost and expenses of environmental protection.On the other hand, said method all needs very numerous and diverse manual operation, such as: hand charging, manual cleaning and after reaction completes, need long blow line etc., these not only bring hand labor intensity large, the problem that production efficiency is very low, and, molecular sieve dust when charging and discharging and excessive SiCl
4also cause serious environmental pollution and serious harm operating personnel's health.Therefore, the super steady technique of the gas phase of above-mentioned autoclave is difficult to carry out suitability for industrialized production.
Summary of the invention
The critical defect existing for the super steady technique of the gas phase of autoclave, the object of the invention is to develop and a kind ofly can reduce SiCl
4consumption, the equipment of preparing molecular sieve that is applicable to serialization suitability for industrialized production that reduces labour intensity and greatly enhance productivity.
The invention provides a kind of equipment of preparing molecular sieve, this equipment comprises tubular reactor, gas-solid separator and absorption tower, described tubular reactor comprises heater, the first charging aperture, discharging opening and body, described heater can heat body, described the first charging aperture and discharging opening lay respectively at two ends of described body, described tubular reactor is communicated with described gas-solid separator by described discharging opening, the top of described gas-solid separator is communicated with described absorption tower, the position that the position that described gas-solid separator is connected with discharging opening is connected with described absorption tower lower than described gas-solid separator.
The equipment of preparing molecular sieve provided by the invention passes through molecular sieve and SiCl
4and carrier gas air is sent in the tubular reactor that is provided with heater from the charging aperture of tubular reactor, in tubular reactor, fully after reaction, from discharging opening, be expelled to gas-solid separator again, solid is stayed in gas-solid separator, and gaseous component enters absorption tower, sponges a small amount of excessive SiCl
4after air can directly discharge.As can be seen here, the equipment of preparing molecular sieve provided by the invention is by making molecular sieve and SiCl
4contact in tubular reactor, carry out, thereby can realize molecular sieve and SiCl
4haptoreaction carry out continuously; By controlling the flow velocity of carrier gas and the length of tubular reactor, can control molecular sieve and SiCl
4the time of contact, thus can make molecular sieve and SiCl
4haptoreaction in tubular reactor, carry out fully; By use, be provided with the tubular reactor of heater, can control different reaction temperatures, thereby can control differential responses condition and the extent of reaction, and then can obtain the zeolite product of different dealumination depths.
Compare with the super steady technique of existing autoclave gas phase, the equipment of preparing molecular sieve provided by the invention can be realized the super steady reaction of serialization gas phase, and operation can all automation serializations carries out, hand labor intensity is little, and production efficiency is high, properties of product are stable, and the suitability for industrialized production of the super steady technique of molecular sieve serialization gas phase is become a reality.Experimental results show that, adopt the disclosed still reaction method of CN1281493C, even if adopt the operating type of break tour, also can produce at the most the high-silica zeolite of 1200kg every day, and adopt the said equipment provided by the invention, the high-silica zeolite that can produce 1000kg per hour, can produce the high-silica zeolite of 24000kg every day, its production efficiency is 20 times of the disclosed still reaction method of CN1281493C, and workman's labor operation intensity also greatly reduces, as can be seen here, the economic benefit of equipment provided by the invention is very significant.
Accompanying drawing explanation
Fig. 1 is the structural representation of the equipment for the preparation of molecular sieve of prior art;
Fig. 2 is the structural representation of the equipment for the preparation of molecular sieve provided by the invention.
Fig. 3 is the axis of the first tilting section 131 and the schematic diagram of the angle α between horizontal plane of the tubular reactor 1 of Fig. 2 apparatus shown;
Fig. 4 is the axis of the second tilting section 132 and the schematic diagram of the angle β between horizontal plane of the tubular reactor 1 of Fig. 2 apparatus shown.
The specific embodiment
Below in conjunction with accompanying drawing, further describe equipment provided by the invention.
As shown in Figure 2, according to the equipment for the preparation of molecular sieve provided by the invention, wherein, this equipment comprises heater (not shown), described heater can heat body 13, therefore, the temperature in tubular reactor can be controlled easily, and then the zeolite product of different dealumination depths can be obtained.
Described heater can be various heaters, and according to the feature of different heater itself, described heater can be arranged on inside and/or the outside of body 13.
Can adopt conventional mode of heating to realize, for example, can be wound around heating tape, the electric furnace heating wire of reactor outer wall heating, reactor Steam Heating by reactor outer wall; The heating of inside reactor coil pipe; Heat radiation heating; Heating using microwave is heated.Under preferable case, in the present invention, described heater can be arranged on one or more in described body 13 outer walls and/or inner heat tape, steam jacket, spiral heater.
In order to control more accurately the temperature in tubular reactor, under preferable case, described heater is heat tape, and described heat tape is many, meanwhile, body 13 is divided into multistage, at the outer wall of every section of body 13, is wound around respectively a heat tape.So just can be respectively at the inside of body 13 set temperature measurement mechanism, the actual temperature that the temperature requirement reacting according to aluminium-eliminating and silicon-replenishing and temperature measuring equipment record this section of body 13, by control, be wrapped in heat tape electric current and the voltage of every section of body 13 outer walls, realize the temperature in every section of body 13 is controlled.For example, the length of every section of body 13 can be 2-20 rice, is preferably 5-10 rice.
In the present invention because tubular reactor 1 comprises heater, therefore can easily control the temperature of material in tubular reactor, thus the requirement of molecular sieve feeding temperature is reduced, and can be according to the requirement to final aluminium-eliminating and silicon-replenishing molecular sieve, control realizes in tubular reactor identical or different to discharging opening each several part temperature from charging aperture.
According to the equipment for the preparation of molecular sieve provided by the invention, wherein, the length of described tubular reactor 1 is to guarantee described molecular sieve and SiCl
4sufficient reacting, specifically can determine according to the requirement of aluminium-eliminating and silicon-replenishing reaction.What consider reaction fully carries out, reacts required power and production efficiency, the present inventor finds, the length of described tubular reactor is that 5-100 rice is preferably, therefore, the length of the preferred described tubular reactor of the present invention is 5-100 rice, more preferably 7-95 rice, is further preferably 50-95 rice.The diameter of described tubular reactor is preferably 0.01-1.5 rice, and more preferably 0.02-1.4 rice, is further preferably 0.1-1.4 rice.
According to equipment provided by the invention, although the pipeline of straight line also can be realized molecular sieve and SiCl
4the sufficient reacting object of carrying out, but, under preferable case, for the molecular sieve in the gas-solid separator that prevents from causing in the unsettled situation of air-flow in tubular reactor flows back to the generation of the situation in tubular reactor, and further fully guarantee to realize more fully and contacting in shorter pipeline, as shown in Figure 2, described body 13 comprises the first tilting section 131 and vertical section 132, one end of one end of described the first tilting section 131 and described vertical section 132 joins, described discharging opening is positioned at the other end of described the first tilting section 131, and described the first tilting section 131 and the position of described vertical section 132 position being connected higher than described discharging opening place.Under this preferable case, the setting of described the first tilting section 131 can effectively prevent the generation of above-mentioned suck-back phenomenon, and described vertical section 132 make described tubular reactor be similar to riser reactor.In the present invention, described vertical section and nisi perpendicular to horizontal plane, as long as look like vertically upward by within the scope of this.
Described the first tilting section 131 and the vertically angle between section 132 can be 10-90 °, be preferably 30-80 °, when described vertical section 132 during perpendicular to horizontal plane, as shown in Figure 3, the axis of described the first tilting section 131 and the angle α between horizontal plane can be for being greater than 0 ° to 80 °, under preferable case, the axis of described the first tilting section 131 and the angle between horizontal plane are 10 ° to 60 °.Under this preferable case, can make molecular sieve and SiCl
4at the first tilting section 131, also can fully react, and unlikelyly enter fast in gas-solid separator 2 because of Action of Gravity Field.
According to equipment provided by the invention, under preferable case, described the first tilting section 131 and the vertically Length Ratio of section 132 are 0.1-10: 1, and 0.2-9 more preferably: 1, preferred 0.4-0.6 further: 1.
A preferred embodiment of the invention, described body 13 also comprises the second tilting section 133, and the other end of one end of described the second tilting section 133 and described vertical section 132 joins, and described the first charging aperture is positioned at the other end of described the second tilting section 133.Arrange like this and can avoid the flowing velocity of molecular sieve solid material under the effect of gravity too fast, increase the haptoreaction time between reaction mass.
Further under preferable case, the position at described the first charging aperture place is higher than described the second tilting section 133 and described vertical section 132 position being connected, so that molecular sieve solid material can dependence itself Action of Gravity Field directly enter in the second tilting section 133, then can further conveying under the carrying of carrier gas.
Described the second tilting section 133 and the vertically angle between section 132 can be 10-90 °, be preferably 30-80 °, when described vertical section 132 during perpendicular to horizontal plane, as shown in Figure 4, according to equipment provided by the invention, the axis of described the second tilting section 133 and the angle β between horizontal plane can, for being greater than 0 ° to 80 °, be preferably 10 ° to 60 °.Under this preferable case, can make molecular sieve and SiCl
4at the first tilting section 131, also can fully react, and unlikelyly enter fast the end of vertical section 132 because of Action of Gravity Field.
Further, under preferable case, described the second tilting section 133 and the vertically Length Ratio of section 132 are 0.1-10: 1, and 0.2-9 more preferably: 1, be further preferably 0.3-9: 1.
In the situation that equipment provided by the invention only has a charging aperture, can make molecular sieve, carrier gas and SiCl
4by this charging aperture, send in the body of tubular reactor 1, but under preferable case, while producing continuously for the ease of industrialization with the coordinating of other devices, described molecular sieve is generally the thermo-molecular sieve from roaster, that is to say, this charging aperture is communicated with roaster conventionally, therefore, preferable case, described tubular reactor 1 also comprises the second charging aperture, described the second charging aperture is positioned at the end of body 13 and the position adjacent with described the first charging aperture, and described the second charging aperture is gas feed mouth, and described the first charging aperture is feeding-in solid body mouth.In this case, carrier gas and gas phase SiCl
4by the second charging aperture, sent into, molecular sieve is sent into by described the first charging aperture.
Further, under preferable case, described tubular reactor 1 also comprises the 3rd charging aperture, and described the 3rd charging aperture is positioned at the end of body 13 and the position adjacent with described the first charging aperture, and described the 3rd charging aperture is gas feed mouth.In this case, carrier gas and SiCl
4can by different charging apertures, be sent into respectively.Can independently control carrier gas and SiCl like this
4the amount of gas.
Further under preferable case, the position at described the 3rd charging aperture place is compared to described the second charging aperture further from described the first charging aperture, and in this case, carrier gas and SiCl
4by the second charging aperture and the 3rd charging aperture, sent into respectively, thus make carrier gas in advance to molecular sieve solid material disperse after again with SiCl
4haptoreaction, to avoid a large amount of SiCl
4the local reaction intensity that directly contacts with a large amount of molecular sieve material simultaneously and cause is excessive, and then causes the loss of the degree of crystallinity of zeolite product.
In the present invention, described gas-solid separator 2 is for collecting and SiCl
4molecular sieve after gas contact.In this gas-solid separator, solid molecular sieves and gas are carried out separated, thereby obtain high-silica zeolite product.Described gas-solid separator 2 generally comprises charging aperture and top gas outlet.The other end of described the first tilting section is communicated with described gas-solid separator, and the sectional area of described gas-solid separator is greater than the cross-sectional area of described tubular reactor body.By making the sectional area of described gas-solid separator be greater than the cross-sectional area of described tubular reactor body, can realize and make to be originally suspended in SiCl
4air-flow or SiCl
4the sedimentation of molecular sieve in the mixed airflow of air-flow and carrier gas stream under Action of Gravity Field, thus realize gas solid separation.Further preferable case, the sectional area of described gas-solid separator is 2-10 with the ratio of the cross-sectional area of described tubular reactor body: 1, can fully realize like this rapid subsidence of molecular sieve.In order further to guarantee that molecular sieve is fully deposited in gas-solid separator, the present invention also height of preferred described gas-solid separator is not less than 5 meters, for example 5-10 rice.Further, under preferable case, the charging aperture of described gas-solid separator is positioned at the middle part of described gas-solid separator, can guarantee so on the one hand to being deposited in the molecular sieve of gas-solid separator bottom, not produce stirring, can also guarantee the more sufficient sedimentation time on the other hand.
Further, under preferable case, described gas-solid separator also comprises bottom solid outlet, the molecular sieve solid obtaining for discharging separation.Further, under preferable case, described gas-solid separator also comprises the valve of opening and closing for controlling described bottom solid outlet, thus can be in good time the molecular sieve solid collected in gas-solid separator is discharged.
The various containers that can realize above-mentioned purpose all can be used as gas-solid separator 2 of the present invention, and the present invention, for example can be for cylindric to its shape can there is no particular limitation.Further, under preferable case, the bottom of described gas-solid separator 2 is the taper that end has opening.Thereby the molecular sieve obtaining can be discharged from described opening.
In order to make the gas component in reacted mixture enter as far as possible absorption tower and not discharge from above-mentioned opening, under preferable case, the position that described gas-solid separator 2 is connected with discharging opening is higher than the original position of described taper.Further, under preferable case, the position that described gas-solid separator 2 is connected with discharging opening is positioned at the middle and upper part of described gas-solid separator 2, and gas-solid separator 2 is communicated with the absorption tower 3 that below will describe by its open top.
Described absorption tower 3 is for absorbing excessive unreacted SiCl
4thereby, make gas-solid separator gas out reach discharge standard.Described absorption tower 3 can be conventional various absorption towers of using, this area, as long as can absorb SiCl
4.The general alkali lye that uses absorbs SiCl as sodium hydrate aqueous solution
4.Therefore, in the present invention, described absorption tower 3 preferably includes an entrance and two outlets, and described entrance is communicated with gas-solid separator 2, is preferably placed at the middle and upper part on described absorption tower.Described two outlets lay respectively at top and the bottom on described absorption tower, are respectively used to emission gases (air) and absorb waste liquid.For SiCl in the air that guarantees to discharge
4content is enough low, and under preferable case, described absorption tower is a plurality of for series connection.A plurality of absorption towers of series connection are to SiCl
4form multistage absorption.
According to the preferred embodiment of the present invention, adopt workflow that equipment provided by the invention prepares molecular sieve as shown in Figure 2.Temperature is molecular sieve a, air c and the gas phase SiCl of 200-600 ℃
4raw material b sends in the tubular reactor 1 that is provided with heater from the first charging aperture, the second charging aperture and the 3rd charging aperture respectively, and molecular sieve is with air and gas phase SiCl
4in the interior mobile contact of tubular reactor 1, by being arranged on the heater of body 13 outer walls and/or inside, tubular reactor 1 is heated, take and guarantee that the reaction temperature in tubular reactor 1 is 250-700 ℃, enter afterwards gas-solid separator 2, in gas-solid separator 2, high-silica zeolite d is deposited in the bottom of gas-solid separator 2, directly or regularly discharges air and gas phase SiCl
4the outlet by gas-solid separator 2 tops enters in absorption tower 3, contacts with the absorbent alkali lye in absorption tower 3, and air (tail gas e) overflows from alkali lye, and from absorption tower, the outlet at 3 tops is discharged, SiCl
4, with alkaline reaction, by outlet at bottom, directly or regularly discharge waste water f afterwards.
While adopting molecular sieve gas phase dealumination complement silicon equipment provided by the invention to carry out gas phase dealumination complement silicon to molecular sieve, the condition of described gas phase dealumination complement silicon comprises that the solid content of molecular sieve is preferably greater than 98 % by weight, the solid content of described molecular sieve is weight and weight ratio roasting before, the i.e. water content of the solid content=100%-molecular sieve of molecular sieve of molecular sieve after high-temperature roasting; The temperature of molecular sieve is 200-600 ℃, SiCl
4temperature be 60-150 ℃, SiCl
4be preferably 0.01-1 with the weight ratio of molecular sieve, 0.05-0.60 more preferably, molecular sieve and gas phase SiCl
4contact Temperature be 250-700 ℃, more preferably 300-650 ℃; The flow velocity of carrier gas makes SiCl
4the time of staying with molecular sieve in tubular reactor is 10 seconds to 100 minutes, is preferably 1 minute to 20 minutes, and the length that the time of staying of molecular sieve in tubular reactor is tubular reactor is divided by the value of the flow velocity gained of molecular sieve.Because molecular sieve is by carrier gas and SiCl in tubular reactor
4gas jointly carries and in tubular reactor, is fluidisation state, so the flow velocity of molecular sieve equals carrier gas and SiCl
4the flow velocity of gas gaseous mixture.The flow velocity of inert carrier gas flow is preferably 0.015-3m/s, more preferably 0.03-3m/s, more preferably 0.1-2.5m/s.With respect to diameter, be that 0.01-1.5 rice, length are the tubular reactor of 50-95 rice, the flow of molecular sieve is preferably 50-2000kg/ hour, and more preferably 100-1500kg/ hour, is further preferably 200-1200kg/ hour.The temperature of air is preferably 50-350 ℃, more preferably 100-250 ℃.Because the temperature of the molecular sieve after roasting is generally more than 300 ℃, therefore the temperature of above-mentioned molecular sieve can be by combining tubular reactor to obtain with roaster when reaction starts, that is to say, under preferable case, the equipment of preparing molecular sieve provided by the invention is preferably communicated with roaster, and as the upstream device of roaster, can utilize so on the one hand the high temperature of molecular sieve after roasting as the thermal source of dealumination complement silicon reaction, start dealumination complement silicon reaction, thereby save the energy; Can also save on the other hand the time of heating molecular sieve, thereby reaction can fully be carried out in the short period of time.But, only depend on the requirement that can not meet the degree of further raising dealumination complement silicon reaction from the heat of roaster.The present invention is provided with the tubular reactor of heater by use, therefore in course of reaction, can in time the material in tubular reactor be heated by the heater of tubular reactor, thereby in assurance tubular reactor, the reaction temperature of pipeline section also can improve the carrying out that reaction temperature meets the aluminium-eliminating and silicon-replenishing reaction of higher degree, and then can obtain the more better product of stability of high silica alumina ratio.
The equipment of preparing molecular sieve provided by the invention can be for carrying out gas phase dealumination complement silicon to various molecular sieves, and for example described molecular sieve can be the Y zeolite of different content of rare earth, with RE
2o
3meter, described Y zeolite Rare-Earth Content is preferably 10-20 % by weight.
Because the present invention relates generally to preparing the improvement of the equipment of molecular sieve, therefore, prepare catalytic cracking catalyst other raw material used and method of operating and can adopt technology well known in the art to carry out.For example, described gross weight of take catalytic cracking catalyst is benchmark, and the content of molecular sieve is 5-50 % by weight, and the content of oxide binding agent of take is 0.5-50 % by weight, and the content of clay is 5-90 % by weight.Described binding agent can be one or more in aluminium oxide, hydrated alumina, aluminium colloidal sol, Ludox, silica-alumina gel, silicon-aluminum sol and their precursor, and described clay can be one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite.The method of described making beating and granulation all can adopt the conventional making beating of using in this area and the method for granulation, and the present invention does not repeat them here.
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1-5 is for illustrating the equipment of preparing molecular sieve provided by the invention.
Used thickness is that the industrial trade mark of 3 millimeters is NiCr18Ti the molecular sieve gas phase shown in stainless steel construction drawing 2 is mended silicon equipment, wherein the body 13 of tubular reactor 1 is by the first tilting section 131, vertically section the 132 and second tilting section 133 forms, the length of the first tilting section 131 is 20 meters, diameter is 0.8 meter, vertically the length of section 132 is 40 meters, diameter is 0.8 meter, the length of the second tilting section 133 is 15 meters, diameter is 0.8 meter, vertically section 132 is perpendicular to horizontal plane, the axis of the first tilting section 131 and the angle α between horizontal plane are 75 ° (the angle between the first tilting section 131 and vertical section 132 is 15 °), the axis of the second tilting section 133 and the angle β between horizontal plane are 65 ° (the angle between the second tilting section 133 and vertical section 132 is 25 °), the port of the second tilting section 133 is the first charging aperture, at a distance of the position of 3 meters and 8 meters, be respectively arranged with the second charging aperture and the 3rd charging aperture with the first charging aperture, the top of gas-solid separator 2 is that diameter is 6 meters, height is 14 meters cylindrical, bottom is for having opening taper, cone angle is 45 °, and opening part is provided with valve, discharging opening is positioned at apart from gas-solid separator top the position of 1 meter, in absorption tower 3, fill the sodium hydrate aqueous solution that concentration is 10 mol/L, between absorption tower 3 and gas-solid separator 2, by conduit, connect, conduit gos deep in sodium hydrate aqueous solution.
Shown in Fig. 2, by the temperature from roaster, be the SiCl that is 90 ℃ containing the Y zeolite (character is as shown in table 1) of rare earth, dry air that temperature is 100 ℃ and temperature of 350 ℃
4gas is sent in the body 13 of tubular reactor 1 continuously by the first charging aperture, the second charging aperture and the 3rd charging aperture respectively, the body of tubular reactor 13 is divided into 15 sections simultaneously, 5 meters of every segment lengths, outer wall on every section of body is wound around a heat tape tubular reactor is heated, make the temperature of tubular reactor 1 interior each several part be 400 ℃, SiCl
4flow by mass flowmenter, controlled and SiCl
4with the weight ratio of molecular sieve be 0.30, the inlet amount of molecular sieve is 800kg/ hour, it is 10 minutes that the flow of dry air makes the time of staying of molecular sieve in tubular reactor 1.Reaction was carried out after 1 hour, and the molecular sieve in gas-solid separator 2 is discharged from the opening of conical lower portion, after pulling an oar, wash, filter afterwards and drying in 120 ℃ of baking ovens, obtained high-silica zeolite A with decationized Y sieve water, and its main character is listed in table 2.
Used thickness is that the industrial trade mark of 3 millimeters is NiCr18Ti the molecular sieve gas phase shown in stainless steel construction drawing 2 is mended silicon equipment, wherein the body 13 of tubular reactor 1 is by the first tilting section 131, vertically section the 132 and second tilting section 133 forms, the length of the first tilting section 131 is 25 meters, diameter is 0.4 meter, vertically the length of section 132 is 45 meters, diameter is 0.4 meter, the length of the second tilting section 133 is 25 meters, diameter is 0.4 meter, vertically section 132 is perpendicular to horizontal plane, the axis of the first tilting section 131 and the angle α between horizontal plane are 55 ° (the angle between the first tilting section 131 and vertical section 132 is 35 °), the axis of the second tilting section 133 and the angle β between horizontal plane are 55 ° (the angle between the second tilting section 133 and vertical section 132 is 35 °), the port of the second tilting section 133 is the first charging aperture, at a distance of the position of 6 meters and 10 meters, be respectively arranged with the second charging aperture and the 3rd charging aperture with the first charging aperture, the top of gas-solid separator 2 is that diameter is 5 meters, height is 10 meters cylindrical, bottom is for having opening taper, cone angle is 35 °, and opening part is provided with valve, discharging opening is positioned at apart from gas-solid separator top the position of 2 meters, in absorption tower 3, fill the sodium hydrate aqueous solution that concentration is 1 mol/L, between absorption tower 3 and gas-solid separator 2, by conduit, connect, conduit gos deep in sodium hydrate aqueous solution.
Shown in Fig. 2, by temperature, be the SiCl that is 130 ℃ containing the Y zeolite (character is as shown in table 1) of rare earth, dry air that temperature is 200 ℃ and temperature of 500 ℃
4gas is sent in the body 13 of tubular reactor 1 continuously by the first charging aperture, the second charging aperture and the 3rd charging aperture respectively, the body of tubular reactor 13 is divided into 19 sections simultaneously, 5 meters of every segment lengths, outer wall on every section of body is wound around a heat tape tubular reactor is heated, make the temperature of tubular reactor 1 interior each several part be 500 ℃, SiCl
4flow by mass flowmenter, controlled, and SiCl
4with the weight ratio of molecular sieve be 0.55, the inlet amount of molecular sieve is 700kg/ hour, it is 15 minutes that the flow of dry air makes the time of staying of molecular sieve in tubular reactor.Reaction was carried out after 2 hours, and the molecular sieve in gas-solid separator 2 is discharged from the opening of conical lower portion, after pulling an oar, wash, filter afterwards and drying in 120 ℃ of baking ovens, obtained high-silica zeolite B with decationized Y sieve water, and its main character is listed in table 2.
Used thickness is that the industrial trade mark of 3 millimeters is NiCr18Ti the molecular sieve gas phase shown in stainless steel construction drawing 2 is mended silicon equipment, wherein the body 13 of tubular reactor 1 is by the first tilting section 131, vertically section the 132 and second tilting section 133 forms, the length of the first tilting section 131 is 16 meters, diameter is 1.2 meters, vertically the length of section 132 is 32 meters, diameter is 1.2 meters, the length of the second tilting section 133 is 32 meters, diameter is 1.2 meters, vertically section 132 is perpendicular to horizontal plane, the axis of the first tilting section 131 and the angle α between horizontal plane are 45 ° (the angle between the first tilting section 131 and vertical section 132 is 45 °), the axis of the second tilting section 133 and the angle β between horizontal plane are 45 ° (the angle between the second tilting section 133 and vertical section 132 is 45 °), the port of the second tilting section 133 is the first charging aperture, at a distance of the position of 2 meters and 6 meters, be respectively arranged with the second charging aperture and the 3rd charging aperture with the first charging aperture, the top of gas-solid separator 2 is that diameter is 9 meters, height is 12 meters cylindrical, bottom is for having opening taper, cone angle is 30 °, and opening part is provided with valve, discharging opening is positioned at apart from gas-solid separator top the position of 4 meters, in absorption tower 3, fill the sodium hydrate aqueous solution that concentration is 1 mol/L, between absorption tower 3 and gas-solid separator 2, by conduit, connect, conduit gos deep in sodium hydrate aqueous solution.
Shown in Fig. 2, by temperature, be the SiCl that is 80 ℃ containing the Y zeolite (character is as shown in table 1) of rare earth, dry air that temperature is 140 ℃ and temperature of 300 ℃
4gas is sent in the body 13 of tubular reactor 1 continuously by the first charging aperture, the second charging aperture and the 3rd charging aperture respectively, the body of tubular reactor 13 is divided into 10 sections simultaneously, 8 meters of every segment lengths, outer wall on every section of body is wound around a heat tape tubular reactor is heated, make the temperature of tubular reactor 1 interior each several part be 300 ℃, SiCl
4flow by mass flow agent, controlled, and SiCl
4with the weight ratio of molecular sieve be 0.05, the inlet amount of molecular sieve is 1000kg/ hour, it is 1 minute that the flow of dry air makes the time of staying of molecular sieve in tubular reactor.Reaction was carried out after 1 hour, and the molecular sieve in gas-solid separator 2 is discharged from the opening of conical lower portion, after pulling an oar, wash, filter afterwards and drying in 120 ℃ of baking ovens, obtained high-silica zeolite C with decationized Y sieve water, and its main character is listed in table 2.
Embodiment 4
Method according to embodiment 3 is prepared high-silica zeolite, different is, the length of tubular reactor 1 is 40 meters, wherein the length of the first tilting section 131 is 8 meters, diameter is 1.2 meters, vertically the length of section 132 is 16 meters, diameter is 1.2 meters, the length of the second tilting section 133 is 16 meters, diameter is 1.2 meters, the body of tubular reactor 13 is divided into 5 sections simultaneously, 8 meters of every segment lengths, make the temperature of tubular reactor 1 interior each several part be 300 ℃, the inlet amount of molecular sieve is 1000kg/ hour, it was 40 seconds that the flow of dry air makes the time of staying of molecular sieve in tubular reactor, obtain high-silica zeolite D, its main character is listed in table 2.
Method according to embodiment 3 is prepared high-silica zeolite, different, and it is 40 minutes that the flow of dry air makes the time of staying of molecular sieve in tubular reactor, obtains high-silica zeolite E, and its main character is listed in table 2.
Table 2
From the results shown in Table 2, compare with industrial REY, adopting the framework si-al ratio of the molecular sieve that equipment provided by the invention makes is SiO
2/ Al
2o
3mol ratio improves greatly, shows that dealumination complement silicon is effective.In addition, from the results shown in Table 2, compare with industrial REY, adopt relative crystallinity, lattice avalanche temperature and the specific area of the molecular sieve that equipment provided by the invention makes obviously to improve, sodium oxide content obviously reduces, and shows the excellent performance of the molecular sieve that equipment provided by the invention makes.
Embodiment 6-10 is for illustrating the high-silica zeolite Kaolinite Preparation of Catalyst that adopts embodiment 1-5 to make.
According to (material butt) molecular sieve: kaolin: boehmite: aluminium colloidal sol=38: the part by weight of 30: 22: 10 is by above-mentioned mixing of materials, making beating, and then at 450 ℃, spraying is dry, obtains spherical catalytic cracking catalyst.High-silica zeolite A, B, C, D and E that molecular sieve selects respectively embodiment 1-5 to make, obtain respectively catalyst A-1, A-2, A-3, A-4 and A-5, and its main character is listed in table 3.
Comparative example 1
Adopt according to the method described above industrial REY type molecular sieve (main character is listed in table 2) Kaolinite Preparation of Catalyst, gained catalyst is counted reference catalyst CC-1, and its main character is listed in table 3.
The Catalytic Cracking Performance test of catalyst
Light oil microactivity is evaluated: adopt the standard method of RIPP92-90 (to see the volumes such as < < Petrochemical Engineering Analysis method > > (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publication) light oil microactivity of assess sample, catalyst loading amount is 5.0g, reaction temperature is 460 ℃, feedstock oil is the huge port light diesel fuel of boiling range 235-337 ℃, product composition is by gas chromatographic analysis, according to product composition, calculate light oil microactivity, result is in table 2.
Light oil microactivity (the MA)=gasoline output+gas yield+coke output of 216 ℃ (in the product lower than)/charging total amount * 100%
Residual oil cracking performance evaluation condition: catalyst is first at 800 ℃, 100% steam aging 12 hours is then evaluated on ACE (fixed fluidized bed) device, and feedstock oil is military mixed three heavy oil (character is in Table 4), 500 ℃ of reaction temperatures, agent weight of oil ratio is 4.
Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield
Yield of light oil=yield of gasoline+diesel yield
Liquid yield=liquefied gas+gasoline+diesel oil
Coke selectivity=coke yield/conversion ratio
The Catalytic Cracking Performance of the catalyst that respectively prepared by Evaluation operation example 6-10 and comparative example 1 according to the method described above, the results are shown in table 5.
Table 3
From the results shown in Table 3, while adopting the molecular sieve catalyst being made by equipment provided by the invention, pore volume and the specific area of gained catalyst obviously increase, and micro-activity obviously improves.
Table 4
Table 5
| Catalyst | A-1 | A-2 | A-3 | A-4 | A-5 | CC-1 |
| Product distributes, % by weight | ||||||
| Dry gas | 1.14 | 1.15 | 1.13 | 1.19 | 1.18 | 1.23 |
| Liquefied gas | 13.21 | 13.69 | 13.08 | 14.29 | 14.62 | 13.01 |
| Coke | 5.11 | 5.09 | 5.28 | 5.4 | 5.22 | 5.75 |
| Gasoline | 55.18 | 56.79 | 55.18 | 52.37 | 51.15 | 47.17 |
| Diesel oil | 17.67 | 17.01 | 17.79 | 17.95 | 18.18 | 19.91 |
| Heavy oil | 7.69 | 6.27 | 7.54 | 8.8 | 9.65 | 12.93 |
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 |
| Conversion ratio, % by weight | 74.64 | 76.72 | 74.67 | 73.25 | 72.17 | 67.16 |
| Coke selectivity, % by weight | 6.85 | 6.63 | 7.07 | 7.37 | 7.23 | 8.56 |
| Yield of light oil, % by weight | 72.85 | 73.8 | 72.97 | 70.32 | 69.33 | 67.08 |
| Liquefied gas+gasoline+diesel oil, % by weight | 86.06 | 87.49 | 86.05 | 84.61 | 83.95 | 80.09 |
From the results shown in Table 5, CC-1 compares with reference catalyst, and adopting the molecular sieve being made by equipment provided by the invention is that catalyst prepared by active component has higher conversion ratio, higher yield of light oil and liquid yield, lower coke selectivity.
Claims (17)
1. an equipment of preparing molecular sieve, it is characterized in that, this equipment comprises tubular reactor (1), gas-solid separator (2) and absorption tower (3), described tubular reactor (1) comprises heater, the first charging aperture, discharging opening and body (13), described heater can heat body (13), described the first charging aperture and discharging opening lay respectively at two ends of described body (13), described body (13) comprises the first tilting section (131) and vertical section (132), one end of described the first tilting section (131) and the one end of described vertical section (132) join, described discharging opening is positioned at the other end of described the first tilting section (131), and the position that described the first tilting section (131) is connected with described vertical section (132) is higher than the position at described discharging opening place, described tubular reactor (1) is communicated with described gas-solid separator (2) by described discharging opening, the top of described gas-solid separator (2) is communicated with described absorption tower (3), the position that the position that described gas-solid separator (2) is connected with discharging opening is connected with described absorption tower (3) lower than described gas-solid separator (2).
2. equipment according to claim 1, wherein, the length of described tubular reactor (1) is 5-100 rice, diameter is 0.01-1.5 rice.
3. equipment according to claim 1, wherein, described the first tilting section (131) and the vertically angle between section (132) are for being greater than 10 ° to being less than or equal to 90 °.
4. equipment according to claim 3, wherein, described the first tilting section (131) and the vertically angle between section (132) are 30 ° to 80 °.
5. equipment according to claim 1, wherein, described the first tilting section (131) and the vertically Length Ratio of section (132) are 0.1-10:1.
6. equipment according to claim 1, wherein, described body (13) also comprises the second tilting section (133), and one end of described the second tilting section (133) and the other end of described vertical section (132) join, and described the first charging aperture is positioned at the other end of described the second tilting section (133).
7. equipment according to claim 6, wherein, the position at described the first charging aperture place is higher than described the second tilting section (133) and the described vertical section of position that (132) are connected.
8. equipment according to claim 7, wherein, described the second tilting section (133) and the vertically angle between section (132) are for being greater than 10 ° to being less than or equal to 90 °.
9. equipment according to claim 8, wherein, described the second tilting section (133) and the vertically angle between section (132) are 30 ° to 80 °.
10. according to the equipment described in claim 6 or 7, wherein, described the second tilting section (133) and the vertically Length Ratio of section (132) are 0.1-10:1.
11. according to the equipment described in claim 1 or 6, and wherein, described tubular reactor (1) also comprises the second charging aperture, and described the second charging aperture is positioned at the end of body (13) and the position adjacent with described the first charging aperture.
12. equipment according to claim 11, wherein, described tubular reactor (1) also comprises the 3rd charging aperture, described the 3rd charging aperture is positioned at the end of body (13) and the position adjacent with described the first charging aperture, and the position at described the 3rd charging aperture place is compared to described the second charging aperture further from described the first charging aperture.
13. equipment according to claim 1, wherein, described heater is for being arranged on one or more in described body (13) outer wall and/or inner heat tape, steam jacket, spiral heater.
14. equipment according to claim 13, wherein, described heater is heat tape, and described heat tape is many, and body (13) is divided into multistage, at the outer wall of every section of body (13), is wound around respectively a heat tape.
15. equipment according to claim 14, wherein, the length of every section of body (13) is 2-20 rice.
16. equipment according to claim 1, wherein, the bottom of described gas-solid separator (2) is the taper that end has opening.
17. equipment according to claim 16, wherein, the position that described gas-solid separator (2) is connected with discharging opening is higher than the original position of described taper.
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| CN111977664B (en) * | 2020-08-21 | 2022-02-01 | 山东荣创催化新材料有限公司 | Molecular sieve material modification treatment equipment and use method thereof |
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| CN1683244A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | Gas phase aluminium extracting and silicon supplementing method of molecular sieve |
| CN2797341Y (en) * | 2002-04-30 | 2006-07-19 | 中国科学院过程工程研究所 | Device for preparing titanium tatrachloride by chlorization of titanium containing mineral |
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| CN2797341Y (en) * | 2002-04-30 | 2006-07-19 | 中国科学院过程工程研究所 | Device for preparing titanium tatrachloride by chlorization of titanium containing mineral |
| CN1683244A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | Gas phase aluminium extracting and silicon supplementing method of molecular sieve |
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| Title |
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| 张继光.加热器.《催化剂制备过程技术》.中国石化出版社,2004,第132页. * |
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