CN102451730A - Preparation method for catalytic cracking catalyst - Google Patents
Preparation method for catalytic cracking catalyst Download PDFInfo
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- CN102451730A CN102451730A CN2010105152375A CN201010515237A CN102451730A CN 102451730 A CN102451730 A CN 102451730A CN 2010105152375 A CN2010105152375 A CN 2010105152375A CN 201010515237 A CN201010515237 A CN 201010515237A CN 102451730 A CN102451730 A CN 102451730A
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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, also is 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.It is required generally to be considered to catalytic cracking catalyst such as the molecular sieve of high silica alumina ratio.
Aspect the molecular sieve of preparation 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 (being also referred to as the chemical method aluminium-eliminating and silicon-replenishing) mainly is to use the 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 that forms in the dealumination process
3Influence hydrothermal stability with residual fluosilicate, also pollute the environment.
Hydro-thermal method is still the method that generally adopts in the present industry; But benefit silicon is untimely after in water-heat process, having dealuminzation, is prone to cause lattice to subside, and non-framework aluminum clogged with fragments duct; This has not only influenced the accessibility in activated centre, also influences the further raising of its heat endurance.
The characteristics of gas chemistry method aluminium-eliminating and silicon-replenishing are that dealuminzation is even, and it is timely to mend silicon, and product crystallization reservation degree is high, Heat stability is good, and the duct is unimpeded.For example; CN1057977C discloses a kind of preparation method who contains the carbon monoxide-olefin polymeric of rich silicon ultra stabilization Y zeolite; The drying and moulding thing that it comprises silicon tetrachloride gas that water content is carried less than the dry air of 900ppm 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; Particle diameter is that the particle of 35-125 micron accounts for more than 80% of total particle number in the said drying and moulding thing, and the weight ratio of NaY zeolite and heat-resistant inorganic oxide is 1: 0.2-1.0, the silica alumina ratio of NaY zeolite are 3-6.The used article shaped good fluidity of this method has avoided being agglomerated into piece and phenomenon of blocking, is easy to realize serialization large-scale production.
CN1121903C discloses a kind of preparation method of rare-earth type high-silicon gamma-zeolite, and this method comprises carries out dried with the y-type zeolite that contains rare earth, make its water content be lower than 10 weight % after; According to silicon tetrachloride: Y zeolite=0.1-0.9: 1 weight ratio feeds the silicon tetrachloride gas that dry air carries, under temperature 150-600 ℃; Reacted 10 minutes to 6 hours; After the reaction, purged 5 minutes to 2 hours, remove Na remaining in the zeolite with the decationized Y sieve water washing with dry air
+, Cl
-, Al
3+Etc. the solubility accessory substance.This method is simpler than 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 the balance lattice constant is at least 0.985 with the ratio of initial lattice constant.This prepare zeolite method comprises and contacting with silicon tetrachloride containing rare earth Y type zeolite that said contact is carried out in a consersion unit, this equipment is as shown in Figure 1; Comprise an agitated reactor (1), a charging aperture (2) and a gas outlet (3) also comprise an agitator (4) in the inside of agitated reactor (1); A gas-solid separator (5) is installed on the gas outlet (3); The bore dia of gas-solid separator (5) contained hole and porosity guarantee gas can through and the zeolitic solid particle can not pass through, the puddler of agitator (4) stretches out outside the agitated reactor (1), under the stirring of agitator (4); The said y-type zeolite that contains rare earth contacts with carbon tetrachloride gas; The temperature of contact is 100-500 ℃, and the time of contact is 5 minutes to 10 hours, and containing the y-type zeolite of rare earth and the weight ratio of carbon tetrachloride is 1: 0.05-0.5; The said silica alumina ratio that contains the y-type zeolite of rare earth is 3-8, and lattice constant is 2.45-2.48nm.This method makes silicon tetrachloride gas and molecular sieve solid particle haptoreaction more even; Avoid the phenomenon that is agglomerated into the compact massive thing between the molecular sieve solid particle, can reduce labour intensity, can reduce environmental pollution; Reduce production cost significantly, be easy to carry out large-scale industrial application.
Obviously, above said method generally all long required time of contact, need several hours; Add the discharging after charging and reaction before the reaction finishes, can only carry out once above-mentioned dealumination complement silicon reaction a general day shift at the most, even if adopt the operating type of break tour also can only carry out twice above-mentioned dealumination complement silicon reaction; And owing to need in the agitated reactor to stir, so agitated reactor also can not be infinitely great, based on present level; The production capacity of agitated reactor that can be used for the maximum of above-mentioned dealumination complement silicon reaction is 600kg; Continue the augmenting response still, then be difficult in the agitated reactor guarantee fully to stir, therefore; Adopt the mode of aforesaid reaction vessel, can obtain the molecular sieve of 1200kg in one day at the most.And in the method for above-mentioned prior art, the high silicon content for the molecular sieve that guarantees to obtain generally all makes SiCl
4Excessive far away, excessive SiCl
4Use increased production cost and expenses of environmental protection undoubtedly.On the other hand; Said method all needs very numerous and diverse manually-operated; Such as: hand charging, manual cleaning reach needs long blow line etc. after reaction is accomplished, these not only bring hand labor intensity big, 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 ultra steady technology of the gas phase of above-mentioned still formula is difficult to carry out suitability for industrialized production.
Summary of the invention
To the critical defect that the ultra steady technology of the gas phase of still formula exists, the objective of the invention is to develop and a kind ofly can reduce SiCl
4Consumption, reduce labour intensity and the preparation method of the catalytic cracking catalyst that is applicable to the serialization suitability for industrialized production of greatly enhancing productivity.
The invention provides a kind of preparation method of catalytic cracking catalyst, wherein, this method is included under the carrying of inert carrier gas flow, and molecular sieve is flowed with inert carrier gas, 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 is so that molecular sieve and gas phase SiCl
4The temperature of contact is 250-700 ℃, then with gained and gas phase SiCl
4Molecular sieve after the contact mixes making beating and granulation with binding agent, clay and water, obtain catalytic cracking catalyst.
The method for preparing catalyst provided by the invention is through making molecular sieve and gas phase SiCl
4Thereby contact can realize molecular sieve and SiCl under flow regime
4Haptoreaction carry out continuously; Through the flow velocity of control 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; Through in contact process to molecular sieve and gas phase SiCl
4The heating, make molecular sieve with gas phase SiCl
4Can under different temperature, contact, thereby can obtain the molecular sieve of Different Silicon aluminum ratio, molecular sieve obtains catalytic cracking catalyst through mix making beating and granulation with binding agent, clay and water.
Compare with the ultra steady technology of existing still formula gas phase; The method for preparing catalytic cracking catalyst provided by the invention can realize the ultra steady reaction of serialization gas phase; And operation can carry out in all automation serializations, and hand labor intensity is little, and production efficiency is high; Properties of product are stable, make the suitability for industrialized production of the ultra steady technology of molecular sieve serialization gas phase become a reality.Experiment showed, the disclosed still reaction method of CN1281493C that adopts, even if adopt the operating type of break tour; Also can produce the molecular sieve of 1200kg every day at the most; And adopt the said equipment provided by the invention, and per hour can produce the molecular sieve of 1000kg, 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, and this shows that the economic benefit of method of the present invention is very significant.
Description of drawings
Fig. 1 is the structural representation that vapor phase method prepares the equipment of molecular sieve that is used for of prior art;
Fig. 2 be the present invention relates to be used to prepare the equipment of catalytic cracking catalyst and the sketch map of method.
Fig. 3 is axis and the sketch map of the angle between the horizontal plane of first tilting section 131 of the tubular reactor 1 of equipment shown in Figure 2;
Fig. 4 is axis and the sketch map of the angle β between the horizontal plane of second tilting section 132 of the tubular reactor 1 of equipment shown in Figure 2.
The specific embodiment
Below in conjunction with accompanying drawing further explain method provided by the invention.
According to the preparation method of catalytic cracking catalyst provided by the invention, although as long as make said molecular sieve and gas phase SiCl
4Form contact with Continuous Flow is molecular sieve and SiCl
4The contact that suspends can realize the object of the invention, but under the preferable case, in order to guarantee that molecular sieve is suspended in inert carrier and SiCl
4Further reduce said SiCl under the situation of air-flow
4The consumption of gas, preferred said molecular sieve of the present invention and gas phase SiCl
4Contact in the presence of inert carrier gas flow, carry out.Said inert gas flow can be various not disturbing molecule sieves and gas phase SiCl
4The gas stream of reaction for example, can be one or more in the group 0 element gas stream in air stream, nitrogen stream and the periodic table of elements.Because SiCl
4To water sensitive, therefore, under the preferable case, above-mentioned inert carrier gas flow is dry inert carrier gas flow, and further the water content of preferred said inert carrier gas flow is no more than 100ppm.
The condition of said contact comprises that the solid content of molecular sieve is preferably greater than 98 weight %, and the solid content of said molecular sieve is that molecular sieve is through the weight after the high-temperature roasting and the weight ratio before the roasting, the i.e. water content of the solid content of molecular sieve=100%-molecular sieve; SiCl
4Be preferably 0.01-1 with the weight ratio of molecular sieve: 1, further be preferably 0.05-0.60: 1; Molecular sieve and gas phase SiCl
4The contact temperature be 250-700 ℃, further be preferably 300-650 ℃; The flow velocity of carrier gas makes SiCl
4With the time of staying of molecular sieve in reactor be 10 seconds to 100 minutes, be preferably 1 minute to 20 minutes; The flow velocity of inert carrier gas flow is preferably 0.015-3m/s, and more preferably 0.03-3m/s further is preferably 0.1-2.5m/s.With respect to diameter is that 0.01-1.5 rice, length are the tubular reactor of 50-95 rice, and the flow of molecular sieve is preferably 50-2000kg/ hour, further is preferably 100-1500kg/ hour, further is preferably 200-1200kg/ hour.The temperature of carrier gas stream is preferably 50-350 ℃, further is preferably 100-250 ℃.Under these conditions, molecular sieve and gas phase SiCl both can have been guaranteed
4Through tubular reactor, can guarantee molecular sieve and gas phase SiCl with continuous airflow pattern again
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 reduce gas phase SiCl greatly
4Consumption.
Pass through control molecular sieve and gas phase SiCl among the present invention
4Different contact temperature, and then can obtain the zeolite product of different dealumination depths.
Among the present invention because to molecular sieve and gas phase SiCl
4The contact temperature control, therefore to temperature, the temperature of inert carrier gas, the gas phase SiCl of molecular sieve
4Temperature can no requirement (NR), can be the molecular sieve of arbitrary temp, inert carrier gas, gas phase SiCl
4Although among the present invention because to molecular sieve and gas phase SiCl
4The contact temperature control, to temperature, the temperature of inert carrier gas, the SiCl of molecular sieve
4Temperature can not have any requirement, can be the molecular sieve of arbitrary temp, the temperature of inert carrier gas, but under the preferable case can be at molecular sieve and gas phase SiCl in order to make reaction
4Carry out fast after the contact, the temperature of the preferred said molecular sieve of the present invention is 200-600 ℃, SiCl
4Temperature be 60-150 ℃.Because the temperature of the molecular sieve after the roasting is generally more than 300 ℃; Therefore the temperature of above-mentioned molecular sieve can obtain by reactor is combined with roaster when the reaction beginning; That is to say; Under the preferable case; Said molecular sieve is the molecular sieve of just discharging from roaster; Can utilize the thermal source of the high temperature of molecular sieve after the roasting so on the one hand, start the dealumination complement silicon reaction as the dealumination complement silicon reaction, thus energy savings; Can also save the time of heating molecular sieve on the other hand, be reflected in the short time and can fully carry out thereby make.
The reaction of dealumination complement silicon described in the present invention can carried out in the reactor arbitrarily, as long as satisfy molecular sieve and gas phase SiCl among the present invention
4Contact conditions get final product, for example can in reactors such as fluid bed, fixed bed, tubular reactor, carry out, but under the preferable case, dealumination complement silicon according to the invention is reflected in the tubular reactor and carries out.
According to method provided by the invention, said tubular reactor generally comprises heater, body and is positioned at first charging aperture and the discharging opening at body two ends, and said heater can be to said body heating, said molecular sieve and gas phase SiCl
4Get into from first charging aperture and to carry out haptoreaction in the said body, the product after the haptoreaction is outside discharging opening is discharged said body.
Said heater can be various heaters, and according to the characteristics of different heaters itself, said heater can be arranged on the inside and/or the outside of body.
Adopt mode of heating commonly used to realize, for example can use Steam Heating through electric furnace heating wire, the reactor of reactor outer wall winding heating tape, the heating of reactor outer wall; The heating of inside reactor coil pipe; The heat radiation heating; Heating using microwave is heated.That is to say that under the preferable case, among the present invention, said heater can be arranged on one or more in said tube wall and/or inner heat tape, steam jacket, the spiral heater.
In order to control the temperature in the tubular reactor more accurately, under the preferable case, said heater is a heat tape, and said heat tape is many, simultaneously, body is divided into multistage, twines a heat tape respectively at the outer wall of every section body.So just can be respectively at the set inside temperature measuring equipment of body; The actual temperature that records this section body according to the temperature requirement and the temperature measuring equipment of aluminium-eliminating and silicon-replenishing reaction; Be wrapped in the heat tape electric current and the voltage of every section tube wall through control, realize the temperature in every section body is controlled.For example, the length of every section 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 material temperature in the tubular reactor, and can be according to the requirement to final aluminium-eliminating and silicon-replenishing molecular sieve, control realizes in the tubular reactor identical or different to discharging opening each several part temperature from charging aperture.
According to the present invention, wherein, the length of said tubular reactor is to guarantee said molecular sieve and SiCl
4Sufficient reacting get final product, specifically can confirm according to the requirement of aluminium-eliminating and silicon-replenishing reaction.That takes all factors into consideration reaction fully carries out, reacts required power and production efficiency; Inventor of the present invention finds; The length of said tubular reactor is preferable for 5-100 rice, and therefore, the length of the preferred said tubular reactor of the present invention is 5-100 rice; Further be preferably 7-95 rice, further be preferably 50-95 rice.The diameter of said tubular reactor is preferably 0.01-1.5 rice, further is preferably 0.02-1.4 rice, further is preferably 0.1-1.4 rice.
Although the pipeline of straight line also can be realized molecular sieve and SiCl
4The sufficient reacting purpose of carrying out; But, under the preferable case, for the flow backwards generation of the situation in the tubular reactor of the molecular sieve in the gas-solid separator that prevents in tubular reactor, to cause under the unsettled situation of air-flow; And further fully guarantee in short pipeline, to realize contacting more fully; As shown in Figure 2, said body 13 comprises first tilting section 131 and vertical section 132, and an end of said first tilting section 131 and said vertical section 132 end join; Said discharging opening is positioned at the other end of said first tilting section 131, and said first tilting section 131 is higher than the position that said discharging opening belongs to said vertical section 132 position that is connected.Under this preferable case, the setting of said first tilting section 131 can effectively prevent the generation of above-mentioned suck-back phenomenon, and said vertical section 132 make said tubular reactor be similar to riser reactor.Among the present invention, said vertical section is not that absolute vertical is in horizontal plane, as long as look like vertically up promptly by in this scope.
Angle between said first tilting section 131 and the vertical section 132 can be 10-90 °; Be preferably 30-80 °; Promptly when said vertical section 132 during perpendicular to horizontal plane, as shown in Figure 3, the axis of said first tilting section 131 and the angle between the horizontal plane can be for greater than 0 ° to 80 °; Under the preferable case, the axis of said first tilting section 131 and the angle between the horizontal plane are 10 ° to 60 °.Under this preferable case, can make molecular sieve and SiCl
4Also can fully react at first tilting section 131, and unlikelyly get into fast in the gas-solid separator 2 because of the gravity effect.
According to the method for the invention, under the preferable case, the length of said first tilting section 131 and vertical section 132 is than being 0.1-10: 1, further be preferably 0.2-9: and 1, further preferred 0.4-0.6: 1.
A preferred embodiment of the invention, said body 13 also comprises second tilting section 133, and an end and said vertical section 132 other end of said second tilting section 133 join, and said first charging aperture is positioned at the other end of said second tilting section 133.Can avoid the flowing velocity of molecular sieve solid material under the effect of gravity too fast like this, increase the haptoreaction time between reaction mass.
Further under the preferable case; The position at said first charging aperture place is higher than said second tilting section 133 and said vertical section 132 position that is connected; So that the molecular sieve solid material can dependence itself the gravity effect directly get in second tilting section 133, can under the carrying of carrier gas, further carry then.
Angle between said second tilting section 133 and the vertical section 132 can be 10-90 °; Be preferably 30-80 °; Promptly, as shown in Figure 4 when said vertical section 132 during perpendicular to horizontal plane, according to the method for the invention; The axis of said second tilting section 133 and the angle β between the horizontal plane can be preferably 10 ° to 60 ° for greater than 0 ° to 80 °.Under this preferable case, can make molecular sieve and SiCl
4Also can fully react at first tilting section 131, and the unlikely end that gets into vertical section 132 because of the gravity effect fast.
Further under the preferable case, the length of said second tilting section 133 and vertical section 132 is than being 0.1-10: 1, and 0.2-9 more preferably: 1, further be preferably 0.3-9: 1.
Have only under the situation of a charging aperture at the used equipment of the present invention, 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 the preferable case, when producing continuously for the ease of industrialization with the cooperating of other devices; Said molecular sieve is generally the thermo-molecular sieve from roaster; That is to say that this charging aperture is communicated with roaster usually, therefore; Preferable case, said tubular reactor 1 comprises a plurality of charging apertures.When the number of said charging aperture is 2; Said charging aperture is respectively first charging aperture and second charging aperture; Said second charging aperture be positioned at body 13 the end and with the said first charging aperture position adjacent, said second charging aperture is the gas feed mouth, said first charging aperture is the feeding-in solid body mouth.In this case, carrier gas stream and gas phase SiCl
4Sent into by second charging aperture, molecular sieve is then sent into by said first charging aperture.
Further under the preferable case; The charging aperture number of said tubular reactor 1 is more than 3 or 3; For example, said tubular reactor also comprises the 3rd charging aperture on the basis of above-mentioned first charging aperture and second charging aperture; Said the 3rd charging aperture be positioned at body 13 the end and with the said first charging aperture position adjacent, said the 3rd charging aperture is the gas feed mouth.In this case, carrier gas stream and SiCl
4Can send into by different charging apertures respectively.Can independently control carrier gas and SiCl like this
4The amount of gas.
Further under the preferable case; Said the 3rd charging aperture be the position at charging aperture place of carrier gas stream compared to said second charging aperture further from said first charging aperture; The position of said in other words the 3rd charging aperture compared to the position of said second charging aperture more near said discharging opening; And carrier gas and SiCl in this case,
4Send into by second charging aperture and the 3rd charging aperture respectively, thus make carrier gas in advance to the molecular sieve solid material disperse after again with SiCl
4Haptoreaction is to avoid a large amount of SiCl
4The local reaction intensity that directly contacts with a large amount of molecular sieve materials simultaneously 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 the preferable case, this method also comprises carries out gas solid separation with contact back products therefrom, obtains solid molecular sieves product and gas component.
Said gas solid separation is preferably carried out in gas-solid separator, and said gas-solid separator generally comprises charging aperture and top gas outlet, and the other end of said first tilting section is communicated with through said charging aperture with said gas-solid separator.The other end of said first tilting section is communicated with said gas-solid separator, and the sectional area of said gas-solid separator is greater than the cross-sectional area of said tubular reactor body.Sectional area through making said gas-solid separator is greater than the cross-sectional area of said tubular reactor body, can realize making being suspended in SiCl originally
4Air-flow or SiCl
4The sedimentation of molecular sieve under the gravity effect in the mixed airflow of air-flow and carrier gas stream, thus realize gas solid separation.Further preferable case, the sectional area of said gas-solid separator is 2-10 with the ratio of the cross-sectional area of said tubular reactor body: 1, can fully realize the rapid subsidence of molecular sieve like this.In order to guarantee that further molecular sieve fully is deposited in the gas-solid separator, the present invention also height of preferred said gas-solid separator is not less than 5 meters, for example 5-10 rice.Further under the preferable case, the charging aperture of said gas-solid separator is positioned at the middle part of said gas-solid separator, can guarantee so on the one hand the molecular sieve that is deposited in the gas-solid separator bottom not to be produced to stir, and can also guarantee the sedimentation time fully on the other hand.
Further under the preferable case, said gas-solid separator also comprises the bottom solid outlet, is used to discharge the molecular sieve solid that separation obtains.Further under the preferable case, said gas-solid separator also comprises and is used to control the valve that said bottom solid outlet is opened and closed, thus can be in good time the molecular sieve solid of collecting in the gas-solid separator is discharged.
The various containers of above-mentioned purpose of can realizing all can be used as gas-solid separator 2 of the present invention, and the present invention can not have special qualification to its shape, for example can be for cylindric.Further under the preferable case, the bottom of said gas-solid separator 2 has the taper of opening for the end.Thereby the molecular sieve that obtains can be discharged from said opening.
In order to make gas component in the post reaction mixture get into the absorption tower as far as possible and not discharge from above-mentioned opening, under the preferable case, the position that said gas-solid separator 2 is connected with discharging opening is higher than the original position of said taper.Further under the preferable case, the position that said gas-solid separator 2 is connected with discharging opening is positioned at the middle and upper part of said gas-solid separator 2, and the absorption tower 3 that gas-solid separator 2 will be described through its open top and hereinafter is communicated with.
Because molecular sieve and SiCl
4Haptoreaction in, common SiCl
4It is excessive to have part, therefore, and in order to prevent SiCl
4Environmental pollution, under the preferable case, this method also comprises said gas component is contacted with absorbent, to remove the SiCl in the gas component
4
As shown in Figure 2, said absorption is preferably carried out in the absorption tower, and absorbent is contained in the said absorption tower, is used to absorb excessive unreacted SiCl
4Thereby, make air reach discharge standard.Said absorption tower 3 can be conventional various absorption towers of using, this area, as long as can absorb SiCl
4Get final product.General alkali lye such as the sodium hydrate aqueous solution of using absorbs SiCl
4Therefore, among the present invention, said absorption tower 3 comprises an inlet and two outlets, and said inlet is communicated with gas-solid separator 2, is preferably placed at the middle and upper part on said absorption tower.Said two outlets lay respectively at the top and the bottom on said absorption tower, are respectively applied for discharged air and absorb waste liquid.For SiCl in the air that guarantees to discharge
4Content is enough low, and under the preferable case, said 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 preferred implementation of the present invention, it is as shown in Figure 2 that bonding apparatus is described preparation method's the process chart of catalytic cracking catalyst provided by the invention.Temperature is 200-600 ℃ molecular sieve a, air c and gas phase SiCl
4Raw material b sends in the tubular reactor 1 from first charging aperture, second charging aperture and the 3rd charging aperture respectively, and molecular sieve is with air and gas phase SiCl
4The contact of in tubular reactor 1, flowing, and in contact process to molecular sieve and gas phase SiCl
4Heating is so that molecular sieve and gas phase SiCl
4The temperature of contact is 250-700 ℃, gets into gas-solid separator 2 afterwards, 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
4Then the outlet through gas-solid separator 2 tops gets in the absorption tower 3, contact with absorbent alkali lye in the absorption tower 3, and air (tail gas e) overflows from alkali lye, the outlet at the 3 tops discharge from the absorption tower, SiCl
4Then, directly or regularly discharge waste water f through outlet at bottom afterwards with alkaline reaction.
Molecular sieve gas phase dealumination complement silicon method provided by the invention can be used for various molecular sieves are carried out the gas phase dealumination complement silicon, and for example said molecular sieve can be the Y zeolite of different content of rare earth, with RE
2O
3Meter, said Y zeolite middle rare earth content can be 10-20 weight %.
Because the present invention relates generally to the improvement to the preparation method of the used molecular sieve of catalytic cracking catalyst, therefore, used other raw material and the method for operating of preparation catalytic cracking catalyst can adopt technology well known in the art to carry out.For example, said gross weight with catalytic cracking catalyst is a benchmark, and the content of molecular sieve is 5-50 weight %, is 0.5-50 weight % in the content of oxide binding agent, and the content of clay is 5-90 weight %.Said binding agent can be in aluminium oxide, hydrated alumina, aluminium colloidal sol, Ludox, silica-alumina gel, silicon-aluminum sol and their precursor one or more, and said clay can be in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite one or more.Said making beating and process for granulating all can adopt conventional making beating and the process for granulating of using in this area, and the present invention repeats no more at this.
Following embodiment will further explain the present invention, but therefore not limit the present invention.
Embodiment 1-5 is used to explain method provided by the invention.
Used thickness is that 3 millimeters the industrial trade mark is that the stainless steel of NiCr18Ti is made molecular sieve gas phase shown in Figure 2 and mended silicon equipment, and wherein the body 13 of tubular reactor 1 is by first tilting section 131, vertically section 132 and second tilting section 133 constitutes, and the length of first tilting section 131 is 20 meters; Diameter is 0.8 meter, and vertically the length of section 132 is 40 meters, and diameter is 0.8 meter; The length of second tilting section 133 is 15 meters, and diameter is 0.8 meter, and vertically section 132 is perpendicular to horizontal plane; The axis of first tilting section 131 and the angle between the horizontal plane are 75 ° (promptly the angle between first tilting section 131 and the vertical section 132 is 15 °); The axis of second tilting section 133 and the angle β between the horizontal plane be 65 ° (promptly second tilting section 133 and vertically the angle between the section 132 are 25 °), the port of second tilting section 133 is first charging aperture, is respectively arranged with second charging aperture and the 3rd charging aperture with 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 that 6 meters, height are 14 meters cylindrical; The bottom is for having the opening taper, and cone angle is 45 °, and opening part is provided with valve; Discharging opening is positioned at apart from the gas-solid separator top 1 meter position; Fill the sodium hydrate aqueous solution that concentration is 10 mol in the absorption tower 3, connect through conduit between absorption tower 3 and the gas-solid separator 2, conduit gos deep in the sodium hydrate aqueous solution.
According to shown in Figure 2, will be the SiCl that 350 ℃ the Y zeolite that contains rare earth (character is as shown in table 1), dry air that temperature is 100 ℃ and temperature are 90 ℃ from the temperature of roaster
4Gas is sent in the body 13 of tubular reactor 1 by first charging aperture, second charging aperture and the 3rd charging aperture respectively continuously; Body 13 with tubular reactor is divided into 15 sections simultaneously; 5 meters of every segment lengths; Outer wall on every section body twines a heat tape tubular reactor is heated, and makes the temperature of each several part in the tubular reactor 1 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.After reaction is carried out 1 hour, gas-solid separator 2 interior molecular sieves are discharged from the opening of conical lower portion, after pulling an oar, wash, filter with decationized Y sieve water afterwards and in 120 ℃ of baking ovens, drying, obtain high-silica zeolite A, its main character is listed in the table 2.
Used thickness is that 3 millimeters the industrial trade mark is that the stainless steel of NiCr18Ti is made molecular sieve gas phase shown in Figure 2 and mended silicon equipment, and wherein the body 13 of tubular reactor 1 is by first tilting section 131, vertically section 132 and second tilting section 133 constitutes, and the length of first tilting section 131 is 25 meters; Diameter is 0.4 meter, and vertically the length of section 132 is 45 meters, and diameter is 0.4 meter; The length of second tilting section 133 is 25 meters, and diameter is 0.4 meter, and vertically section 132 is perpendicular to horizontal plane; The axis of first tilting section 131 and the angle between the horizontal plane are 55 ° (promptly the angle between first tilting section 131 and the vertical section 132 is 35 °); The axis of second tilting section 133 and the angle β between the horizontal plane be 55 ° (promptly second tilting section 133 and vertically the angle between the section 132 are 35 °), the port of second tilting section 133 is first charging aperture, is respectively arranged with second charging aperture and the 3rd charging aperture with 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 that 5 meters, height are 10 meters cylindrical; The bottom is for having the opening taper, and cone angle is 35 °, and opening part is provided with valve; Discharging opening is positioned at apart from the gas-solid separator top 2 meters position; Fill the sodium hydrate aqueous solution that concentration is 1 mol in the absorption tower 3, connect through conduit between absorption tower 3 and the gas-solid separator 2, conduit gos deep in the sodium hydrate aqueous solution.
According to shown in Figure 2, be the SiCl that 500 ℃ the Y zeolite that contains rare earth (character is as shown in table 1), dry air that temperature is 200 ℃ and temperature are 130 ℃ with temperature
4Gas is sent in the body 13 of tubular reactor 1 by first charging aperture, second charging aperture and the 3rd charging aperture respectively continuously; Body 13 with tubular reactor is divided into 19 sections simultaneously; 5 meters of every segment lengths; Outer wall on every section body twines a heat tape tubular reactor is heated, and makes the temperature of each several part in the tubular reactor 1 be 500 ℃, SiCl
4Flow control and SiCl by mass flowmenter
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.After reaction is carried out 2 hours, gas-solid separator 2 interior molecular sieves are discharged from the opening of conical lower portion, after pulling an oar, wash, filter with decationized Y sieve water afterwards and in 120 ℃ of baking ovens, drying, obtain high-silica zeolite B, its main character is listed in the table 2.
Used thickness is that 3 millimeters the industrial trade mark is that the stainless steel of NiCr18Ti is made molecular sieve gas phase shown in Figure 2 and mended silicon equipment, and wherein the body 13 of tubular reactor 1 is by first tilting section 131, vertically section 132 and second tilting section 133 constitutes, and the length of first tilting section 131 is 16 meters; Diameter is 1.2 meters, and vertically the length of section 132 is 32 meters, and diameter is 1.2 meters; The length of second tilting section 133 is 32 meters, and diameter is 1.2 meters, and vertically section 132 is perpendicular to horizontal plane; The axis of first tilting section 131 and the angle between the horizontal plane are 45 ° (promptly the angle between first tilting section 131 and the vertical section 132 is 45 °); The axis of second tilting section 133 and the angle β between the horizontal plane be 45 ° (promptly second tilting section 133 and vertically the angle between the section 132 are 45 °), the port of second tilting section 133 is first charging aperture, is respectively arranged with second charging aperture and the 3rd charging aperture with 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 that 9 meters, height are 12 meters cylindrical; The bottom is for having the opening taper, and cone angle is 30 °, and opening part is provided with valve; Discharging opening is positioned at apart from the gas-solid separator top 4 meters position; Fill the sodium hydrate aqueous solution that concentration is 1 mol in the absorption tower 3, connect through conduit between absorption tower 3 and the gas-solid separator 2, conduit gos deep in the sodium hydrate aqueous solution.
According to shown in Figure 2, be the SiCl that 300 ℃ the Y zeolite that contains rare earth (character is as shown in table 1), dry air that temperature is 140 ℃ and temperature are 80 ℃ with temperature
4Gas is sent in the body 13 of tubular reactor 1 by first charging aperture, second charging aperture and the 3rd charging aperture respectively continuously; Body 13 with tubular reactor is divided into 10 sections simultaneously; 8 meters of every segment lengths; Outer wall on every section body twines a heat tape tubular reactor is heated, and makes the temperature of each several part in the tubular reactor 1 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.After reaction is carried out 1 hour, gas-solid separator 2 interior molecular sieves are discharged from the opening of conical lower portion, after pulling an oar, wash, filter with decationized Y sieve water afterwards and in 120 ℃ of baking ovens, drying, obtain high-silica zeolite C, its main character is listed in the table 2.
Method according to embodiment 3 prepares high-silica zeolite, and different is, the length of tubular reactor 1 is 40 meters, and wherein the length of first tilting section 131 is 8 meters; Diameter is 1.2 meters, and vertically the length of section 132 is 16 meters, and diameter is 1.2 meters; The length of second tilting section 133 is 16 meters, and diameter is 1.2 meters, and the body 13 with tubular reactor is divided into 5 sections simultaneously; 8 meters of every segment lengths make the temperature of each several part in the tubular reactor 1 be 300 ℃, and 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, obtained high-silica zeolite D, and its main character is listed in the table 2.
Method according to embodiment 3 prepares high-silica zeolite, and different is, 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 the table 2.
Table 1
| The Y zeolite that contains | 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, weight % | 4.5 | 4.4 | 4.1 | |
| RE 2O 3Content, weight % | 11.9 | 13.2 | 16.3 |
Table 2
Can find out from the result of table 2, compare that adopting the framework si-al ratio of the molecular sieve that method of the present invention makes is SiO with industrial REY
2/ Al
2O
3Mol ratio improves greatly, shows that dealumination complement silicon is effective.In addition; Can find out from the result of table 2, compare, adopt relative crystallinity, lattice avalanche temperature and the specific area of the molecular sieve that method of the present invention makes obviously to improve with industrial REY; 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 used to explain that the high-silica zeolite that adopts embodiment 1-5 to make prepares catalyst.
According to (material butt) molecular sieve: kaolin: boehmite: aluminium colloidal sol=38: 30: 22: 10 part by weight 450 ℃ of following spray-dryings, obtains spherical catalytic cracking catalyst then with above-mentioned mixing of materials, making beating.High-silica zeolite A, B, C, D and E that molecular sieve selects for use embodiment 1-5 to make respectively obtain catalyst A-1, A-2, A-3, A-4 and A-5 respectively, and its main character is listed in the table 3.
Comparative Examples 1
Adopt industrial REY type molecular sieve (main character is listed in the table 2) preparation catalyst according to the method described above, the gained catalyst is counted reference catalyst CC-1, and its main character is listed in the table 3.
The catalytic cracking performance test of catalyst
Light oil microactivity is estimated: the light oil microactivity that adopts standard method (seeing volumes such as " petrochemical industry analytical method " (RIPP test method) Yang Cuiding, Science Press, the nineteen ninety publication) assess sample of RIPP92-90; The catalyst loading amount is 5.0g; Reaction temperature is 460 ℃, and feedstock oil is boiling range 235-337 ℃ huge port light diesel fuel, and product is made up of gas chromatographic analysis; Calculate light oil microactivity according to the product composition, the result is in table 3.
Light oil microactivity (MA)=(being lower than gasoline output+gas yield+coke output of 216 ℃ in the product)/charging total amount * 100%
Residual oil cracking performance evaluation condition: catalyst is earlier at 800 ℃, and 100% steam aging 12 hours is estimated on ACE (fixed fluidized bed) device then, and feedstock oil is military three heavy oil (character is seen table 4) that mix, 500 ℃ of reaction temperatures, and 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
Estimate the catalytic cracking performance of the catalyst of embodiment 6-10 and Comparative Examples 1 preparation according to the method described above respectively, the result lists in table 5.
Table 3
Can find out that from the result of table 3 when adopting the molecular sieve that is made by method of the present invention to prepare catalyst, the pore volume and the specific area of gained catalyst obviously increase, micro-activity obviously improves.
Table 4
Table 5
| Catalyst | A-1 | A-2 | A-3 | A-4 | A-5 | CC-1 |
| Product distributes, 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, weight % | 74.64 | 76.72 | 74.67 | 73.25 | 72.17 | 67.16 |
| Coke selectivity, weight % | 6.85 | 6.63 | 7.07 | 7.37 | 7.23 | 8.56 |
| Yield of light oil, weight % | 72.85 | 73.8 | 72.97 | 70.32 | 69.33 | 67.08 |
| Liquefied gas+gasoline+diesel oil, weight % | 86.06 | 87.49 | 86.05 | 84.61 | 83.95 | 80.09 |
Can find out that from the result of table 5 CC-1 compares with reference catalyst, adopting the molecular sieve that is made by method of the present invention is that the catalyst that active component prepares has higher conversion ratio, higher yield of light oil and liquid yield, lower coke selectivity.
Claims (25)
1. the preparation method of a catalytic cracking catalyst is characterized in that, this method is included under the carrying of inert carrier gas flow, and molecular sieve is flowed with inert carrier gas, 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 is so that molecular sieve and gas phase SiCl
4The temperature of contact is 250-700 ℃, then with gained and gas phase SiCl
4Molecular sieve after the contact mixes making beating and granulation with binding agent, clay and water, obtain catalytic cracking catalyst.
2. method according to claim 1, wherein, the flow velocity of said inert carrier gas flow is 0.015-3m/s.
3. method according to claim 1, wherein, said molecular sieve and gas phase SiCl
4The contact temperature be 300-650 ℃.
4. according to claim 1 or 3 described methods, wherein, said gas phase SiCl
4With the weight ratio of molecular sieve be 0.01-1: 1, the inlet amount of said molecular sieve be the 50-2000 kilogram/hour.
5. method according to claim 4, wherein, said gas phase SiCl
4With the weight ratio of molecular sieve be 0.05-0.60: 1, the inlet amount of said molecular sieve be the 100-1500 kilogram/hour.
6. according to any described method in the claim 1,4 and 5, wherein, the temperature of said molecular sieve is 200-600 ℃, said gas phase SiCl
4Temperature be 60-150 ℃, the temperature of said carrier gas stream is 50-350 ℃.
7. method according to claim 6, wherein, said contact is carried out in tubular reactor.
8. method according to claim 7, wherein, the length of tubular reactor is 5-100 rice, diameter is a 0.01-1.5 rice.
9. according to claim 7 or 8 described methods, wherein, said tubular reactor comprises heater, body and is positioned at first charging aperture and the discharging opening at body two ends that said heater can be to said body heating, said molecular sieve and gas phase SiCl
4Get into from first charging aperture and to carry out haptoreaction in the said body, the product after the haptoreaction is outside discharging opening is discharged said body.
10. method according to claim 9, wherein, said heater is to be arranged in said tube wall and/or inner heat tape, steam jacket, the spiral heater one or more.
11. method according to claim 10, wherein, said heater is a heat tape, and said heat tape is many, and body is divided into multistage, twines a heat tape respectively at the outer wall of every section body.
12. method according to claim 11, wherein, the length of every section body is 2-20 rice.
13. method according to claim 9; Wherein, Said body comprises first tilting section and vertical section; One end of said first tilting section and a said vertical section end join, and said discharging opening is positioned at the other end of said first tilting section, and said first tilting section is higher than the position that said discharging opening belongs to said vertical section position that is connected.
14. method according to claim 13, wherein, the angle between said first tilting section and the vertical section is greater than 10 ° to 90 °.
15. method according to claim 14, wherein, the angle between said first tilting section and the vertical section is 30 ° to 80 °.
16. method according to claim 13, wherein, the length of said first tilting section and vertical section is than being 0.1-10: 1.
17. method according to claim 13, wherein, said body also comprises second tilting section, and an end and the said vertical section other end of said second tilting section join, and said first charging aperture is positioned at the other end of said second tilting section.
18. method according to claim 17, wherein, the position at said first charging aperture place is higher than said second tilting section and said vertical section position that is connected.
19. method according to claim 18, wherein, the angle between said second tilting section and the vertical section is greater than 10 ° to 90 °.
20. method according to claim 19, wherein, the angle between said second tilting section and the vertical section is 30 ° to 80 °.
21. according to any described method among the claim 17-20, wherein, the length of said second tilting section and vertical section is than being 0.1-10: 1.
22. according to claim 9 or 17 described methods, wherein, said tubular reactor also comprises second charging aperture, said second charging aperture be positioned at body the end and with the said first charging aperture position adjacent, said inert carrier gas and said gas phase SiCl
4Get into from said second charging aperture, said molecular sieve gets into from said first charging aperture.
23. method according to claim 22; Wherein, Said tubular reactor also comprises the 3rd charging aperture; Said the 3rd charging aperture be positioned at body the end and with the said first charging aperture position adjacent, and the position at said the 3rd charging aperture place compared to said second charging aperture further from said first charging aperture, said gas phase SiCl
4Get into from said the 3rd charging aperture, said inert carrier gas gets into from said second charging aperture, and said molecular sieve gets into from said first charging aperture.
24. method according to claim 1, wherein, this method also comprises carries out gas solid separation with contact back products therefrom, obtains and gas phase SiCl
4Molecular sieve after the contact and gas component.
25. method according to claim 24, wherein, this method also comprises said gas component is contacted with absorbent, to remove the SiCl in the gas component
4
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| 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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014063445A1 (en) * | 2012-10-26 | 2014-05-01 | 中国石油化工股份有限公司 | Catalytic cracking catalyst preparation method |
| JP2015533644A (en) * | 2012-10-26 | 2015-11-26 | 中国石油化工股▲ふん▼有限公司 | Method for making catalytic cracking catalyst |
| GB2527200A (en) * | 2012-10-26 | 2015-12-16 | China Petroleum & Chemical | Catalytic cracking catalyst preparation method |
| US9895681B2 (en) | 2012-10-26 | 2018-02-20 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst preparation method |
| GB2527200B (en) * | 2012-10-26 | 2018-06-06 | China Petroleum & Chem Corp | Process and apparatus for preparing a molecular sieve and a catalytic cracking catalyst |
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