CN102451730B - Preparation method for catalytic cracking catalyst - Google Patents
Preparation method for catalytic cracking catalyst Download PDFInfo
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- CN102451730B CN102451730B CN201010515237.5A CN201010515237A CN102451730B CN 102451730 B CN102451730 B CN 102451730B CN 201010515237 A CN201010515237 A CN 201010515237A CN 102451730 B CN102451730 B CN 102451730B
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Abstract
The invention relates to a preparation method for a catalytic cracking catalyst. The method is characterized in that: the method comprises that: with carrying by inert carrier gas flow, a molecular sieve flows along with the inert carrier gas flow, and contacts gas phase SiCl4 under a flowing state; the molecular sieve and the gas phase SiCl4 are heated during the contacting process, such that the contacting temperature of the molecular sieve and the gas phase SiCl4 is 250-700 DEG C; the resulting molecular sieve after contacting the gas phase SiCl4, a binder, clay and water are subjected to mixing, beating and pelletizing to obtain the catalytic cracking catalyst. With the method for preparing the catalyst, the contact reaction of the molecular sieve and the SiCl4 can be continuously performed; the molecular sieves with different silica alumina ratios can be obtained, and the catalytic cracking catalyst is obtained by carrying out treatments of mixing, beating and pelletizing for the molecular sieve, the binder, the clay and the water.
Description
Technical field
The invention relates to a kind of preparation method of catalytic cracking catalyst.
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/A1 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, purge 5 minutes to 2 hours with dry air, remove Na remaining in zeolite with decationized Y sieve water washing
+, 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), also comprise an agitator (4) in the inside of reactor (1), 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, be 1 containing the y-type zeolite of rare earth and the weight ratio of carbon tetrachloride: 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, described method is generally all long required time of contact above, 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, based on current level, the production capacity that can be used for the maximum reactor of above-mentioned dealumination complement silicon reaction 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 molecular sieve of 1200kg.And, in the method for above-mentioned prior art, in order to guarantee the high silicon content of the molecular sieve obtaining, 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 gas phase of autoclave, the object of the invention is to develop one and can reduce SiCl
4consumption, reduce the preparation method of labour intensity and the catalytic cracking catalyst that is applicable to serialization suitability for industrialized production of greatly enhancing productivity.
The invention provides a kind of preparation method of catalytic cracking catalyst, wherein, the method is included under the carrying of inert carrier gas flow, make molecular sieve with inert carrier gas flow, and with gas phase SiCl
4under flow regime, contact molecular sieve and gas phase SiCl
4time of contact be 10 seconds to 100 minutes, and in contact process to molecular sieve and gas phase SiCl
4heating, so that molecular sieve and gas phase SiCl
4the temperature of contact is 250-700 ℃, then by gained and gas phase SiCl
4molecular sieve after contact mixes making beating granulation with binding agent, clay and water, obtain catalytic cracking catalyst.
The method of Kaolinite Preparation of Catalyst provided by the invention is by making molecular sieve and gas phase SiCl
4thereby contact can realize molecular sieve and SiCl under flow regime
4haptoreaction carry out continuously; By controlling the flow velocity of carrier gas, 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 in contact process to molecular sieve and gas phase SiCl
4heating, make molecular sieve with gas phase SiCl
4can at different temperature, contact, thereby can obtain the molecular sieve of Different Silicon aluminum ratio, molecular sieve, by mix making beating granulation with binding agent, clay and water, obtains catalytic cracking catalyst.
Compared with the super steady technique of existing autoclave gas phase, the method of preparing catalytic cracking catalyst provided by the invention can realize 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 molecular sieve of 1200kg every day, and adopt the said equipment provided by the invention, the molecular sieve that can produce 1000kg per hour, can produce the molecular sieve 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 method of the present invention is very significant.
Accompanying drawing explanation
Fig. 1 be prior art prepare the structural representation of the equipment of molecular sieve for vapor phase method;
Fig. 2 be the present invention relates to for the preparation of the equipment of catalytic cracking catalyst and the schematic diagram of method.
Fig. 3 is the schematic diagram of the angle α between axis and the horizontal plane of the first tilting section 131 of the tubular reactor 1 of equipment shown in Fig. 2;
Fig. 4 is the schematic diagram of the angle β between axis and the horizontal plane of the second tilting section 132 of the tubular reactor 1 of equipment shown in Fig. 2.
The specific embodiment
Further describe method provided by the invention below in conjunction with accompanying drawing.
According to the preparation method of catalytic cracking catalyst provided by the invention, although as long as make described molecular sieve and gas phase SiCl
4form contact with Continuous Flow is molecular sieve and SiCl
4the contact that suspends can realize object of the present invention, but under preferable case, in order to guarantee that molecular sieve is suspended in inert carrier and SiCl
4in the situation of air-flow, further reduce described SiCl
4the consumption of gas, the preferred described molecular sieve of the present invention and gas phase SiCl
4contact inert carrier gas flow exist under carry out.Described inert gas flow can be various not disturbing molecule sieves and gas phase SiCl
4the gas flow of reaction for example, can be one or more in group 0 element gas flow in air stream, nitrogen stream and the periodic table of elements.Due to SiCl
4to water sensitive, therefore, under preferable case, above-mentioned inert carrier gas flow is dry inert carrier gas flow, and further the water content of preferred described inert carrier gas flow is no more than 100ppm.
The condition of described contact comprises that the solid content of molecular sieve is preferably greater than 98 % by weight, and the solid content of described molecular sieve is the weight ratio before weight and the roasting of molecular sieve after high-temperature roasting, i.e. the water content of solid content=100%-molecular sieve of molecular sieve; SiCl
4be preferably 0.01-1 with the weight ratio of molecular sieve: 1, more preferably 0.05-0.60: 1; 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 reactor is 10 seconds to 100 minutes, is preferably 1 minute to 20 minutes; 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.Be that 0.01-1.5 rice, length are the tubular reactor of 50-95 rice with respect to diameter, 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 carrier gas stream is preferably 50-350 ℃, more preferably 100-250 ℃.Under these conditions, molecular sieve and gas phase SiCl both can have been guaranteed
4by tubular reactor, can guarantee again molecular sieve and gas phase SiCl with continuous airflow pattern
4contact can fully carry out.From above-mentioned gas phase SiCl
4can find out with the numerical value of the weight ratio of molecular sieve, adopt method provided by the invention can greatly reduce gas phase SiCl
4consumption.
In the present invention, pass through to control molecular sieve and gas phase SiCl
4different Contact Temperatures, and then can obtain the zeolite product of different dealumination depths.
In the present invention due to molecular sieve and gas phase SiCl
4contact Temperature control, the therefore temperature of the temperature to molecular sieve, inert carrier gas, gas phase SiCl
4temperature can no requirement (NR), can be the molecular sieve of arbitrary temp, inert carrier gas, gas phase SiCl
4.Although in the present invention due to molecular sieve and gas phase SiCl
4contact Temperature control, the temperature to molecular sieve, the temperature of inert carrier gas, SiCl
4temperature can be without any requirement, can be the molecular sieve of arbitrary temp, the temperature of inert carrier gas, but under preferable case, in order to make the reaction can be at molecular sieve and gas phase SiCl
4after contact, carry out fast, the temperature of the preferred described molecular sieve of the present invention is 200-600 ℃, SiCl
4temperature be 60-150 ℃.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 reactor to obtain with roaster in the time that reaction starts, that is to say, under preferable case, described molecular sieve is the molecular sieve of just discharging from 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.
The reaction of dealumination complement silicon described in the present invention can be carrying out in reactor arbitrarily, as long as meet molecular sieve and gas phase SiCl in the present invention
4contact conditions, for example can in the reactors such as fluid bed, fixed bed, tubular reactor, carry out, but under preferable case, dealumination complement silicon reaction of the present invention is carried out in tubular reactor.
According to method provided by the invention, described tubular reactor generally comprises heater, body and is positioned at the first charging aperture and the discharging opening at body two ends, and described heater can be to described body heating, described molecular sieve and gas phase SiCl
4enter in described body and carry out haptoreaction from the first charging aperture, the product after haptoreaction is from discharging opening is discharged described body.
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.
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.That is to say, under preferable case, in the present invention, described heater can be arranged on one or more in described tube wall 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 is divided into multistage, is wound around respectively a heat tape at the outer wall of every section of body.So just can be respectively at the inside of body set temperature measurement mechanism, the temperature requirement reacting according to aluminium-eliminating and silicon-replenishing and temperature measuring equipment record the actual temperature of this section of body, be wrapped in heat tape electric current and the voltage of every section of tube wall by control, realize the temperature control in every section of body.For example, the length of every section of body can be 2-20 rice, is preferably 5-10 rice.
According to the present invention, because tubular reactor 1 comprises heater, therefore can easily control the temperature of material in tubular reactor, 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 present invention, wherein, the length of described tubular reactor 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.
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, angle α between axis and the horizontal plane of described the first tilting section 131 can be for being greater than 0 ° to 80 °, under preferable case, the angle between axis and the horizontal plane of described the first tilting section 131 is 10 ° to 60 °.Under this preferable case, can make molecular sieve and SiCl
4also can fully react at the first tilting section 131, and unlikelyly enter fast in gas-solid separator 2 because of Action of Gravity Field.
The method according to this invention, under preferable case, described the first tilting section 131 and the vertically Length Ratio of section 132 are 0.1-10: 1, more preferably 0.2-9: 1, further preferred 0.4-0.6: 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.Can avoid like this 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, the method according to this invention, angle β between axis and the horizontal plane of described the second tilting section 133 can, for being greater than 0 ° to 80 °, be preferably 10 ° to 60 °.Under this preferable case, can make molecular sieve and SiCl
4also can fully react at the first tilting section 131, 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 more preferably 0.2-9: 1, be further preferably 0.3-9: 1.
Only have a charging aperture at the present invention's equipment used, can make molecular sieve, carrier gas stream and gas phase SiCl
4send into by this charging aperture in the body of tubular reactor 1, but under preferable case, while production 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 comprises multiple charging apertures.In the time that the number of described charging aperture is 2, described charging aperture is respectively the first charging aperture and 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 stream and gas phase SiCl
4sent into by the second charging aperture, molecular sieve is sent into by described the first charging aperture.
Further under preferable case, the charging aperture number of described tubular reactor 1 is more than 3 or 3, for example, described tubular reactor is on the basis of above-mentioned the first charging aperture and the second charging aperture, also comprise 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 described the 3rd charging aperture is gas feed mouth.In this case, carrier gas stream and SiCl
4can be sent into by different charging apertures respectively.Can independently control like this carrier gas and SiCl
4the amount of gas.
Further under preferable case, described the 3rd charging aperture is that the position at charging aperture place of carrier gas stream is compared to described the second charging aperture further from described the first charging aperture, the position of described the 3rd charging aperture is compared to the more close described discharging opening in position of described the second charging aperture in other words, and carrier gas and SiCl in this case,
4sent into by the second charging aperture and the 3rd charging aperture 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 simultaneously directly contacting with a large amount of molecular sieve materials and cause is excessive, and then causes the loss of the degree of crystallinity of zeolite product.
According to method provided by the invention, under preferable case, the method also comprises carries out gas solid separation by products therefrom after contact, obtains solid molecular sieves product and gas component.
Described gas solid separation is preferably carried out in gas-solid separator, and described gas-solid separator generally comprises charging aperture and top gas outlet, and the other end of described the first tilting section is communicated with by described charging aperture with described gas-solid separator.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 the molecular sieve that is deposited in gas-solid separator bottom not to be produced to stirring, can also guarantee on the other hand the more sufficient sedimentation time.
Further, under preferable case, described gas-solid separator also comprises bottom solid outlet, separates for discharging the molecular sieve solid obtaining.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 to its shape can there is no particular limitation, for example, can be cylindric.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.
Due to molecular sieve and SiCl
4haptoreaction in, conventionally SiCl
4have part excessive, therefore, in order to prevent SiCl
4environmental pollution, under preferable case, the method also comprises described gas component is contacted with absorbent, to remove the SiCl in gas component
4.
As shown in Figure 2, described absorption is preferably carried out in absorption tower, and absorbent is contained in described absorption tower, for absorbing excessive unreacted SiCl
4thereby, make air reach discharge standard.Described absorption tower 3 can be the conventional various absorption towers that use, 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 comprises 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 discharged 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 the multiple of series connection.Multiple absorption towers of series connection are to SiCl
4form multistage absorption.
According to the preferred embodiment of the present invention, bonding apparatus describe catalytic cracking catalyst provided by the invention preparation method process chart 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 tubular reactor 1 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, and in contact process to molecular sieve and gas phase SiCl
4heating, so that molecular sieve and gas phase SiCl
4the temperature of contact is 250-700 ℃, enters afterwards gas-solid separator 2, and in gas-solid separator 2, molecular sieve d is deposited in the bottom of gas-solid separator 2, directly or regularly discharges air and gas phase SiCl
4enter in absorption tower 3 by the outlet at gas-solid separator 2 tops, contact with the absorbent alkali lye in absorption tower 3, (tail gas e) overflows air from alkali lye, discharges SiCl from the outlet at 3 tops, absorption tower
4, with alkaline reaction, directly or regularly discharge waste water f by outlet at bottom afterwards.
Molecular sieve gas phase dealumination complement silicon method 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 can be 10-20 % by weight.
Because the present invention relates generally to the preparation method's of the molecular sieve used to catalytic cracking catalyst improvement, 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, the described gross weight take catalytic cracking catalyst is benchmark, and the content of molecular sieve is 5-50 % by weight, and take the content of oxide binding agent as 0.5-50 % by weight, 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 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 used for illustrating method 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 132 and the second tilting section 133 form, 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, angle α between axis and the horizontal plane of the first tilting section 131 is 75 ° (the angle between the first tilting section 131 and vertical section 132 is 15 °), angle β between axis and the horizontal plane of the second tilting section 133 is 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, be respectively arranged with the second charging aperture and the 3rd charging aperture with the first charging aperture at a distance of the position of 3 meters and 8 meters, 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, connect by conduit, conduit gos deep in sodium hydrate aqueous solution.
Shown in Fig. 2, by the temperature from roaster be 350 ℃ be the SiCl of 90 ℃ containing the Y zeolite (character is as shown in table 1) of rare earth, dry air that temperature is 100 ℃ and temperature
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 control 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 132 and the second tilting section 133 form, 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, angle α between axis and the horizontal plane of the first tilting section 131 is 55 ° (the angle between the first tilting section 131 and vertical section 132 is 35 °), angle β between axis and the horizontal plane of the second tilting section 133 is 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, be respectively arranged with the second charging aperture and the 3rd charging aperture with the first charging aperture at a distance of the position of 6 meters and 10 meters, 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, connect by conduit, conduit gos deep in sodium hydrate aqueous solution.
Shown in Fig. 2, by temperature be 500 ℃ be the SiCl of 130 ℃ containing the Y zeolite (character is as shown in table 1) of rare earth, dry air that temperature is 200 ℃ and temperature
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 control, 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 132 and the second tilting section 133 form, 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, angle α between axis and the horizontal plane of the first tilting section 131 is 45 ° (the angle between the first tilting section 131 and vertical section 132 is 45 °), angle β between axis and the horizontal plane of the second tilting section 133 is 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, be respectively arranged with the second charging aperture and the 3rd charging aperture with the first charging aperture at a distance of the position of 2 meters and 6 meters, 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, connect by conduit, conduit gos deep in sodium hydrate aqueous solution.
Shown in Fig. 2, by temperature be 300 ℃ be the SiCl of 80 ℃ containing the Y zeolite (character is as shown in table 1) of rare earth, dry air that temperature is 140 ℃ and temperature
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 control, 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.
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 1
| Containing the Y zeolite of | Embodiment | 1 | |
|
| Lattice constant, nm | 2.466 | 2.466 | 2.466 | |
| Relative crystallinity, % | 54 | 52 | 49 | |
| Framework si-al ratio (SiO 2/Al 2O 3Mol ratio) | 5.11 | 5.11 | 5.11 | |
| Lattice avalanche temperature, ℃ | 975 | 972 | 970 | |
| Specific area, m 2/g | 673 | 665 | 648 | |
| Na 2O content, % by weight | 4.5 | 4.4 | 4.1 | |
| RE 2O 3Content, % by weight | 11.9 | 13.2 | 16.3 |
Table 2
From the results shown in Table 2, compared with industrial REY, adopting the framework si-al ratio of the molecular sieve that method of the present 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, compared with industrial REY, adopt relative crystallinity, lattice avalanche temperature and the specific area of the molecular sieve that method of the present invention makes obviously to improve, sodium oxide content obviously reduces, and shows the excellent performance of the molecular sieve that method of the present 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 publishes) light oil microactivity of assess sample, catalyst loading amount is 5.0g, reaction temperature is 460 ℃, and feedstock oil is the huge port light diesel fuel of boiling range 235-337 ℃, and product composition is by gas chromatographic analysis, calculate light oil microactivity according to product composition, result is in table 3.
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 method of the present 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, compared with reference catalyst CC-1, adopting the molecular sieve being made by method of the present invention is that catalyst prepared by active component has higher conversion ratio, higher yield of light oil and liquid yield, lower coke selectivity.
Claims (23)
1. a preparation method for catalytic cracking catalyst, is characterized in that, the method is included under the carrying of inert carrier gas flow, make molecular sieve with inert carrier gas flow, and with gas phase SiCl
4under flow regime, contact, described contact is carried out in tubular reactor, and the condition of described contact comprises: the solid content of molecular sieve is greater than 98 % by weight, SiCl
4with the weight ratio of molecular sieve be 0.01-1:1, the flow velocity of inert carrier gas flow is 0.015-3m/s, molecular sieve and gas phase SiCl
4time of contact be 10 seconds to 100 minutes, and in contact process to molecular sieve and gas phase SiCl
4heating, so that molecular sieve and gas phase SiCl
4the temperature of contact is 250-700 ℃, then by gained and gas phase SiCl
4molecular sieve after contact mixes making beating granulation with binding agent, clay and water, obtain catalytic cracking catalyst.
2. preparation method according to claim 1, wherein, described molecular sieve and gas phase SiCl
4contact Temperature be 300-650 ℃.
3. preparation method according to claim 1, wherein, the inlet amount of described molecular sieve is 50-2000 kg/hr.
4. according to the preparation method described in claim 1 or 3, wherein, described gas phase SiCl
4with the weight ratio of molecular sieve be 0.05-0.60:1, the inlet amount of described molecular sieve is 100-1500 kg/hr.
5. preparation method according to claim 1, wherein, the temperature of described molecular sieve is 200-600 ℃, described gas phase SiCl
4temperature be 60-150 ℃, the temperature of described carrier gas stream is 50-350 ℃.
6. preparation method according to claim 1, wherein, the length of tubular reactor is 5-100 rice, diameter is 0.01-1.5 rice.
7. according to the preparation method described in claim 1 or 6, wherein, described tubular reactor comprises heater, body and is positioned at the first charging aperture and the discharging opening at body two ends, and described heater can be to described body heating, described molecular sieve and gas phase SiCl
4enter in described body and carry out haptoreaction from the first charging aperture, the product after haptoreaction is from discharging opening is discharged described body.
8. preparation method according to claim 7, wherein, described heater is to be arranged on one or more in described tube wall and/or inner heat tape, steam jacket, spiral heater.
9. preparation method according to claim 8, wherein, described heater is heat tape, and described heat tape is many, and body is divided into multistage, is wound around respectively a heat tape at the outer wall of every section of body.
10. preparation method according to claim 9, wherein, the length of every section of body is 2-20 rice.
11. preparation methods according to claim 7, wherein, described body comprises the first tilting section and vertical section, one end of one end of described the first tilting section and described vertical section joins, described discharging opening is positioned at the other end of described the first tilting section, and described the first tilting section and the position of the described vertical section of position being connected higher than described discharging opening place.
12. preparation methods according to claim 11, wherein, described the first tilting section and the vertically angle between section are 10 ° to 90 °.
13. preparation methods according to claim 12, wherein, described the first tilting section and the vertically angle between section are 30 ° to 80 °.
14. preparation methods according to claim 11, wherein, described the first tilting section and the vertically Length Ratio of section are 0.1-10:1.
15. preparation methods according to claim 11, wherein, described body also comprises the second tilting section, and the other end of one end of described the second tilting section and described vertical section joins, and described the first charging aperture is positioned at the other end of described the second tilting section.
16. preparation methods according to claim 15, wherein, the position at described the first charging aperture place is higher than described the second tilting section and the described vertical section of position being connected.
17. preparation methods according to claim 16, wherein, described the second tilting section and the vertically angle between section are 10 ° to 90 °.
18. preparation methods according to claim 17, wherein, described the second tilting section and the vertically angle between section are 30 ° to 80 °.
19. preparation methods according to claim 15, wherein, described the second tilting section and the vertically Length Ratio of section are 0.1-10:1.
20. according to the preparation method described in claim 1 or 6, wherein, described tubular reactor comprises heater, body and is positioned at the first charging aperture and the discharging opening at body two ends, described heater can be to described body heating, described tubular reactor also comprises the second charging aperture, described the second charging aperture is positioned at the end of body and the position adjacent with described the first charging aperture, described inert carrier gas and described gas phase SiCl
4enter from described the second charging aperture, described molecular sieve enters from described the first charging aperture.
21. according to the preparation method described in claim 1 or 6, wherein, described tubular reactor comprises heater, body and the first charging aperture and the discharging opening that are positioned at body two ends, described heater can be to described body heating, described tubular reactor also comprises the second charging aperture, described the second charging aperture is positioned at the end of body and the position adjacent with described the first charging aperture, described tubular reactor also comprises the 3rd charging aperture, described the 3rd charging aperture is positioned at the end of body 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, described gas phase SiCl
4enter from described the 3rd charging aperture, described inert carrier gas enters from described the second charging aperture, and described molecular sieve enters from described the first charging aperture.
22. preparation methods according to claim 1, wherein, the method also comprises carries out gas solid separation by products therefrom after contact, obtains and gas phase SiCl
4molecular sieve after contact and gas component.
23. preparation methods according to claim 22, wherein, the method also comprises described gas component is contacted with absorbent, to remove the SiCl in gas component
4.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5318696A (en) * | 1992-12-11 | 1994-06-07 | Mobil Oil Corporation | Catalytic conversion with improved catalyst catalytic cracking with a catalyst comprising a large-pore molecular sieve component and a ZSM-5 component |
| CN1493656A (en) * | 2002-10-28 | 2004-05-05 | �й�ʯ�ͻ����ɷ�����˾ | Petroleum hydrocarbon cracking catalyst containing rare earthy type zeolite and its preparation method |
| CN1683245A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | High silicon Y-type zeolite containing rare-earth and its preparing method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5318696A (en) * | 1992-12-11 | 1994-06-07 | Mobil Oil Corporation | Catalytic conversion with improved catalyst catalytic cracking with a catalyst comprising a large-pore molecular sieve component and a ZSM-5 component |
| CN1493656A (en) * | 2002-10-28 | 2004-05-05 | �й�ʯ�ͻ����ɷ�����˾ | Petroleum hydrocarbon cracking catalyst containing rare earthy type zeolite and its preparation method |
| CN1683245A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | High silicon Y-type zeolite containing rare-earth and its preparing method |
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