CN102451736A - Preparation method of catalytic cracking catalyst - Google Patents
Preparation method of catalytic cracking catalyst Download PDFInfo
- Publication number
- CN102451736A CN102451736A CN2010105154154A CN201010515415A CN102451736A CN 102451736 A CN102451736 A CN 102451736A CN 2010105154154 A CN2010105154154 A CN 2010105154154A CN 201010515415 A CN201010515415 A CN 201010515415A CN 102451736 A CN102451736 A CN 102451736A
- Authority
- CN
- China
- Prior art keywords
- gas
- molecular sieve
- sicl
- section
- gas phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
A preparation method of a catalytic cracking catalyst comprises the following steps: mixing a molecular sieve and gas containing gas-phase SiCl4 to form a mixture flow, allowing the molecular sieve and the gas-phase SiCl4 to contact at 250-700 DEG C for 10 seconds to 100 minutes, mixing the molecular sieve obtained after contacting with the gas-phase SiCl4 with a binder, clay and water, performing beating and granulation to obtain the catalytic cracking catalyst. The preparation method of the catalyst provided by the invention can realize the continuous proceeding of the contact reaction of the molecular sieve and SiCl4; by the uniform mixing of the molecular sieve and the gas containing gas-phase SiCl4, the silicon supplementing reaction is ensured to be performed uniformly and fully; therefore the prepared molecular sieve has a high crystallization degree, more stable quality, and better performance; by controlling the different contact temperatures of the molecular sieve and SiCl4, different reaction conditions and reaction degrees can be controlled; therefore molecular sieve products with different dealuminization degrees can be obtained, and the catalytic cracking catalyst can be obtained.
Description
Technical field
The invention relates to a kind of preparation method of molecular sieve.
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/Al 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 high-silica zeolite 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 comprises molecular sieve and contains gas phase SiCl
4Gas mix to form mix logistics, the said gas phase SiCl that contains
4Gas be gas phase SiCl
4Or gas phase SiCl
4With the mist of inert carrier gas, mix molecular sieve in the logistics with gas flow, and with gas in gas phase SiCl
4Under flow regime, contact, and logistics is heated with control molecular sieve and gas phase SiCl
4The contact temperature be that 250-700 ℃, time of contact are 10 seconds to 100 minutes, 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 preparation method of catalytic cracking catalyst provided by the invention through with molecular sieve with contain gas phase SiCl
4Gas mix to form mix logistics, mix molecular sieve and gas phase SiCl in the logistics
4Gas contacts under flow regime.This shows that the preparation method of molecular sieve provided by the invention can realize molecular sieve and SiCl
4Haptoreaction carry out continuously, through flow velocity and the length of tubular reactor of control carrier gas, can control molecular sieve and SiCl
4The time of contact, thus can make molecular sieve and SiCl
4Haptoreaction carry out fully, thereby obtain high-silica zeolite; Through making molecular sieve and containing gas phase SiCl
4Gas evenly mix, thereby guaranteed that the benefit pasc reaction can evenly and fully carry out, therefore the degree of crystallinity of the molecular sieve of preparation is higher, quality is more stable, performance is better; The present invention is through control molecular sieve and SiCl
4Different contact temperature in tubular reactor, thus the differential responses condition and the extent of reaction can be controlled, and then can obtain the zeolite product of different dealuminzation degree.Molecular sieve obtains having more highly active 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 preparation method of catalytic cracking catalyst provided by the invention can realize the ultra steady prepared in reaction high-silica zeolite 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 high-silica zeolite of 1200kg every day at the most; And adopt the said equipment provided by the invention, and per hour can produce the high-silica zeolite of 1000kg, can produce the high-silica zeolite of 24000kg every day; Its production efficiency is 20 times of the disclosed still reaction method of CN1281493C; And workman's labor operation intensity also greatly reduces, and this shows that the economic benefit of method provided by the 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 is be used to the prepare equipment of catalytic cracking catalyst and the sketch map of method provided by the invention.
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
Among the present invention, send in the reactor after can be directly gas phase silicon tetrachloride and molecular sieve being mixed and react; Can be that carrier gas mixes with the gas phase silicon tetrachloride with inert gas earlier also, form mist, send into after again this mist and molecular sieve being mixed and carry out haptoreaction in the reactor; Also can earlier inert gas be mixed with molecular sieve, molecular sieve is mixed with the gas phase silicon tetrachloride with flow regime under the drive of inert gas; Send in the reactor together after can also simultaneously inert gas, molecular sieve and gas phase silicon tetrachloride being mixed and react.Under the preferable case; Be that carrier gas mixes with the gas phase silicon tetrachloride with inert gas earlier; Form mist; Thereby the concentration that makes silicon tetrachloride obtains dilution, sends into after this mist and molecular sieve being mixed again and carries out haptoreaction in the reactor, thereby can reduce the unnecessary waste of silicon tetrachloride.
According to method for preparing catalyst provided by the invention, said inert carrier gas 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 in air, nitrogen and the periodic table of elements.Because SiCl
4To water sensitive, therefore, under the preferable case, above-mentioned inert carrier gas is dry inert carrier gas flow, and further the water content of preferred said inert carrier gas is no more than 100ppm.
Preparation method according to catalytic cracking catalyst provided by the invention; The condition of said contact comprises that the solid content of molecular sieve is preferably greater than 98 weight %; 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 that mixes logistics 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.Molecular sieve is preferably 0.015-3m/s with the flow velocity of gas flow in the mixing logistics, and more preferably 0.03-3m/s further is preferably 0.1-2.5m/s.With respect to diameter is that 0.1-1.4 rice, length are the tubular reactor of 50-95 rice, and the inlet amount of molecular sieve is preferably 50-2000kg/ hour, further is preferably 100-1500kg/ hour, further is preferably 200-1200kg/ hour.The temperature of inert carrier gas 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.
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 SiCl of the molecular sieve that gets into reactor
4Temperature do not have any requirement, can be molecular sieve, inert carrier gas and the SiCl of arbitrary temp
4, and the present invention passes through molecular sieve and gas phase SiCl
4The contact temperature control, thereby make that its longest limit to tubular reactor gas does not require, thereby can control molecular sieve and SiCl
4Time of contact, thereby can obtain better crystallinity degree, the molecular sieve of dealuminzation better effects if, and the present invention is through control molecular sieve and SiCl
4Different contact temperature in tubular reactor, thus the differential responses condition and the extent of reaction can be controlled, and then can obtain the zeolite product of different dealuminzation degree.
Although 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 do 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, thereby effectively utilize the length of tubular reactor, 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 through tubular reactor is combined with roaster when the reaction beginning, that is to say; Under the preferable case; The equipment of preparation molecular sieve provided by the invention preferably is communicated with roaster, and as the upstream device of roaster, can utilize the thermal source of the high temperature of molecular sieve after the roasting as the dealumination complement silicon reaction so on the one hand; Start the dealumination complement silicon reaction, thus energy savings; Can also practice thrift the time of heating molecular sieve on the other hand, be reflected in the short time and can fully carry out thereby make.In addition, although through making air and SiCl
4The temperature of gas raises also can reach the required temperature of reaction, and still, the inventive method more can guarantee fully carrying out of dealumination complement silicon reaction comparatively speaking.
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 a kind of preferred implementation, the method for preparing molecular sieve described in the present invention is carried out in equipment shown in Figure 2, and this equipment comprises tubular reactor 1, gas-solid separator 2, absorption tower 3 and raw material mixed cell 4, beater 5 and heater 6.
Said tubular reactor 1 comprises at least one charging aperture, discharging opening, body 13 and heater, and charging aperture in the said charging aperture and discharging opening lay respectively at two ends of said body 13; Said heater can be to said body heating, and said mixing logistics gets into from charging aperture carries out haptoreaction in the said body, and 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 13.Under the preferable case, among the present invention, said heater can be arranged on one or more in said body 13 outer walls 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 13 is divided into multistage, twines a heat tape respectively at the outer wall of every section body 13.So just can be respectively at the set inside temperature measuring equipment of body 13; The actual temperature that records this section body 13 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 body 13 outer walls through control, realize the control of the temperature in every section body 13.For example, the length of every section body 13 can be 2-20 rice, is preferably 5-10 rice.
Said gas-solid separator 2 is communicated with said tubular reactor 1 through said discharging opening; The top of said gas-solid separator 2 is communicated with said absorption tower 3, and the position that said gas-solid separator 2 is connected with the tubular reactor discharging opening is lower than the position that said gas-solid separator 2 is connected with said absorption tower 3.
Said raw material mixed cell 4 is used for different gas is mixed and/or gas is mixed with solid, and said raw material mixed cell 4 is communicated with said tubular reactor 1 through one in the said charging aperture.Said raw material mixed cell generally comprises gas-solid blender and/or gas mixer.
Under the optimum condition; The charging aperture of said tubular reactor is one; Said raw material mixed cell 4 comprises gas-solid blender and gas mixer, and gas mixer is communicated with the gas-solid blender, and the gas-solid blender is communicated with said tubular reactor 1 through the charging aperture of said tubular reactor 1.
Said gas mixer can be to well known to a person skilled in the art the various devices that can realize that the gas phase silicon tetrachloride mixes with carrier gas, for example, can be pipeline, and soon the gas phase silicon tetrachloride is sent in the pipeline simultaneously with carrier gas and mixed.Said gas-solid blender can be to well known to a person skilled in the art the various devices that gas phase silicon tetrachloride and/or carrier gas and molecular sieve are mixed that can be used in; For example said gas-solid blender can be cylinder mixer, and this cylinder mixer comprises cylindrical body and the grid that is positioned at cylindrical body.Said grid is preferably along the axial of cylindrical body and is fixed on the corrosion resistant plate on the cylindrical body inwall with spiralling mode; It is that gas phase silicon tetrachloride and molecular sieve are uniformly dispersed and increase time of contact of stock yard that grid is used to make raw material; The pitch of flase floor is preferably 0.1～1 meter; More preferably 0.2～0.7 meter, the width of flase floor (being grid from the inwall of cylindrical body) to the distance the axis of cylindrical body be preferably cylindrical body diameter 1/3rd to 2/3rds.Further preferred said gas mixer and gas-solid blender are cylinder type, and the cylinder of the two is structure as a whole.
The length of said tubular reactor 1 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 °, is preferably 30-80 °.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 ° (0 °＜α≤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 equipment provided by 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 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 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 equipment provided by 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 SiCl4 also 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.
Owing to produce the material deposition blocking pipeline that fluctuation causes, second tilting section also can be provided with gas feed with the position that vertical section is connected, and in order to send into inert carrier gas, blows afloat with the molecular sieve with deposition, prevents pipeline blockage in order to prevent the section of lifting; The carrier gas that said gas feed feeds can also comprise the gaseous state silicon tetrachloride, both can prevent that material from this sedimentation, can replenish silicon tetrachloride again.
According to method provided by the invention, will contact the back products therefrom and carry out gas solid separation, obtain solid high-silica zeolite product and gas component.
As shown in Figure 2, said gas solid separation is preferably carried out in gas-solid separator 2, and said gas-solid separator generally comprises charging aperture and top gas outlet.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 high-silica zeolite 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 to adopt equipment provided by the invention to prepare the workflow of high-silica zeolite.Temperature is 200-600 ℃ molecular sieve a, carrier gas c and gas phase SiCl
4After raw material b mixes in raw material mixed cell 4, send in the tubular reactor 1 from the charging aperture of tubular reactor, molecular sieve is with inert carrier gas and gas phase SiCl
4The mist contact of in tubular reactor 1, flowing, get into gas-solid separator 2 afterwards, in gas-solid separator 2, high-silica zeolite d is deposited in the bottom of gas-solid separator 2, directly or regularly discharges.Inert carrier gas 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 carrier gas (tail gas e) is overflowed 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.
Among the present invention, said molecular sieve can be various molecular sieves that can aluminium-eliminating and silicon-replenishing, for example can be the Y zeolite of different content of rare earth.
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 the method for preparing catalyst provided by the invention.Raw materials used is three kinds of Y zeolites that contain rare earth, is designated as raw material 1, raw material 2 and raw material 3 respectively, and its character is seen table 5.
Embodiment 1
Used thickness is that 3 millimeters the industrial trade mark is the equipment that the stainless steel of NiCr18Ti is made preparation molecular sieve shown in Figure 2, 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 °, and the axis of second tilting section 133 and the angle β between the horizontal plane are 65 °, and the port of second tilting section 133 is charging aperture (its position is higher than the position that second tilting section is connected with vertical section); 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; Raw material mixed cell 4 comprises that length is that 5 meters, diameter are 0.8 meter cylinder mixer; One end of cylinder mixer is communicated with charging aperture, is provided with the molecular sieve inlet along the axial position apart from 2.5 meters of charging apertures of cylinder mixer, and entering the mouth to this cylindrical section mixer inner walls of charging aperture from this molecular sieve is distributed with one group of spiralling stainless steel flase floor; The pitch of flase floor is 0.3 meter; The width of flase floor is 0.4 meter, and this cylinder mixer is divided into two parts thus, and first is as gas mixer; Second portion is provided with flase floor, thereby as the gas-solid blender.
According to shown in Figure 2, be the SiCl that 100 ℃ dry air and temperature is 90 ℃ with temperature
4After gas is sent into gas mixer in the raw material mixed cell 4 and is mixed; With get into from the molecular sieve of pipeline inlet, be that (this molecular sieve is a raw material 1 for 600 ℃ the Y zeolite that contains rare earth from the temperature of roaster; Its character is seen table 5) be to mix the back in the gas-solid blender to send into continuously in the body 13 of tubular reactor 1 in being provided with the pipeline of grid by charging aperture; Body 13 with tubular reactor is divided into 15 sections simultaneously, 5 meters of every segment lengths, and the outer wall on every section body twines a heat tape tubular reactor is heated; Make the temperature of each several part in the tubular reactor 1 be 400 ℃, get into the SiCl of raw material mixed cell 4
4Control and SiCl by mass flowmenter with the mixed gas flow of inert carrier gas
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 mist 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 1.
Embodiment 2
Used thickness is that 3 millimeters the industrial trade mark is the equipment that the stainless steel of NiCr18Ti is made preparation molecular sieve shown in Figure 2, 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 0.4 meter, and vertically the length of section 132 is 50 meters, and diameter is 0.4 meter; The length of second tilting section 133 is 20 meters; Diameter is 0.4 meter, and vertically section 132 is perpendicular to horizontal plane, and 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 are 55 ° (promptly the angle between second tilting section 133 and the vertical section 132 is 35 °); The port of second tilting section 133 is charging aperture (its position is higher than second tilting section and the vertical position that is connected of section), and the top of gas-solid separator 2 is that diameter is that 5 meters, height are 10 meters cylindrical, and the bottom is for having the opening taper; Cone angle is 35 °; And opening part is provided with valve, and discharging opening is positioned at apart from the gas-solid separator top 2 meters position, fills 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; Raw material mixed cell 4 comprises that length is that 5 meters, diameter are 0.8 meter cylinder mixer; One end of cylinder mixer is communicated with charging aperture, is provided with the molecular sieve inlet along the axial position apart from 2.5 meters of charging apertures of cylinder mixer, and entering the mouth to this cylindrical section mixer inner walls of charging aperture from this molecular sieve is distributed with one group of spiralling stainless steel flase floor; The pitch of flase floor is 0.3 meter; The width of flase floor is 0.4 meter, and this cylinder mixer is divided into two parts thus, and first is as gas mixer; Second portion is provided with flase floor, thereby as the gas-solid blender.
According to shown in Figure 2, be the SiCl that 200 ℃ dry air and temperature is 130 ℃ with temperature
4After gas is sent into gas mixer in the raw material mixed cell 4 and is mixed; With get into from the molecular sieve of pipeline inlet, be that (this molecular sieve is a raw material 2 for 500 ℃ the Y zeolite that contains rare earth from the temperature of roaster; Its character is seen table 5) be to mix the back in the gas-solid blender to send into continuously in the body 13 of tubular reactor 1 in being provided with the pipeline of grid by charging aperture; Body 13 with tubular reactor is divided into 9 sections simultaneously, 10 meters of every segment lengths, and the outer wall on every section body twines a heat tape tubular reactor is heated; Make the temperature of each several part in the tubular reactor 1 be 500 ℃, get into the SiCl of raw material mixed cell 4
4Control and SiCl by mass flowmenter with the mixed gas flow of inert carrier gas
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 mist 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 1.
Embodiment 3
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 15 meters; Diameter is 1.2 meters, and vertically the length of section 132 is 35 meters, and diameter is 1.2 meters; The length of second tilting section 133 is 30 meters; Diameter is 1.2 meters, and vertically section 132 is perpendicular to horizontal plane, and 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 are 45 ° (promptly the angle between second tilting section 133 and the vertical section 132 is 45 °); The port of second tilting section 133 is a charging aperture, and the top of gas-solid separator 2 is that diameter is that 9 meters, height are 12 meters cylindrical, and the bottom is for having the opening taper; Cone angle is 30 °; And opening part is provided with valve, and discharging opening is positioned at apart from the gas-solid separator top 4 meters position, fills 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; Raw material mixed cell 4 comprises that length is that 5 meters, diameter are 0.8 meter cylinder mixer; One end of cylinder mixer is communicated with charging aperture, is provided with the molecular sieve inlet along the axial position apart from 2.5 meters of charging apertures of cylinder mixer, and entering the mouth to this cylindrical section mixer inner walls of charging aperture from this molecular sieve is distributed with one group of spiralling stainless steel flase floor; The pitch of flase floor is 0.3 meter; The width of flase floor is 0.4 meter, and this cylinder mixer is divided into two parts thus, and first is as gas mixer; Second portion is provided with flase floor, thereby as the gas-solid blender.
According to shown in Figure 2, be the SiCl that 140 ℃ dry air and temperature is 80 ℃ with temperature
4After gas is sent into gas mixer in the raw material mixed cell 4 and is mixed; With get into from the molecular sieve of pipeline inlet, be that (this molecular sieve is a raw material 3 for 300 ℃ the Y zeolite that contains rare earth from the temperature of roaster; Its character is seen table 5) be to mix the back in the gas-solid blender to send into continuously in the body 13 of tubular reactor 1 in being provided with the pipeline of grid by charging aperture; Body 13 with tubular reactor is divided into 16 sections simultaneously, 5 meters of every segment lengths, and the outer wall on every section body twines a heat tape tubular reactor is heated; Make the temperature of each several part in the tubular reactor 1 be 300 ℃, get into the SiCl of raw material mixed cell 4
4Control and SiCl by mass flowmenter with the mixed gas flow of inert carrier gas
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 1.
Embodiment 4
Method according to embodiment 3 prepares high-silica zeolite, and different is that the length of tubular reactor 1 is 25 meters; Wherein the length of first tilting section 131 is 5 meters, and diameter is 1.2 meters, and vertically the length of section 132 is 10 meters; Diameter is 1.2 meters, and the length of second tilting section 133 is 10 meters, and diameter is 1.2 meters; Body 13 with tubular reactor is divided into 5 sections simultaneously, 5 meters of every segment lengths, and the outer wall on every section body twines a heat tape tubular reactor is heated; Make the temperature of each several part in the tubular reactor 1 be 300 ℃, the inlet amount of molecular sieve is 1000kg/ hour, and it was 30 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 the table 1.
Embodiment 5
Method according to embodiment 3 prepares high-silica zeolite, and different is, it is 40 minutes that the flow of mist 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 1.
Table 1
Can find out that from the result of table 1 compare with industrial REY, adopting the framework si-al ratio of the molecular sieve that makes of equipment provided by the invention is SiO
2/ Al
2O
3Mol ratio improves greatly, shows that dealumination complement silicon is effective.In addition; Can find out from the result of table 1, compare, adopt relative crystallinity, lattice avalanche temperature and the specific area of the molecular sieve that equipment provided by the invention makes obviously to improve with industrial REY; Sodium oxide content obviously reduces, and shows the excellent performance of the molecular sieve that equipment provided by the invention makes.
Embodiment 6-11 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, A-5 respectively, and its main character is listed in the table 2.
Comparative Examples 1
Adopt industrial REY type molecular sieve (main character is listed in the table 1) preparation catalyst according to the method described above, the gained catalyst is designated as CC-1, and its main character is listed in the table 2.
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 2.
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 3) 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 6-11 and Comparative Examples 1 preparation according to the method described above respectively, the result lists in table 4.
Table 2
Can find out that from the result of table 2 adopt the pore volume and the specific area of the catalyst that is prepared by equipment provided by the invention obviously to increase, micro-activity obviously improves.
Table 3
Table 4
| Catalyst | A-1 | A-2 | A-3 | A-4 | A-5 | CC-1 |
| Product distributes, weight % | ||||||
| Dry gas | 1.12 | 1.11 | 1.13 | 1.17 | 1.15 | 1.23 |
| Liquefied gas | 13.19 | 13.69 | 13.08 | 14.29 | 14.45 | 13.01 |
| Coke | 4.91 | 4.85 | 5.01 | 5.11 | 5.15 | 5.75 |
| Gasoline | 55.69 | 57.31 | 55.78 | 53.17 | 52.29 | 47.17 |
| Diesel oil | 17.69 | 17.03 | 17.79 | 17.97 | 18.15 | 19.91 |
| Heavy oil | 7.4 | 6.01 | 7.21 | 8.29 | 8.81 | 12.93 |
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 |
| Conversion ratio, weight % | 74.91 | 76.96 | 75 | 73.74 | 73.04 | 67.16 |
| Coke selectivity, weight % | 6.55 | 6.30 | 6.68 | 6.93 | 7.05 | 8.56 |
| Yield of light oil, weight % | 73.38 | 74.34 | 73.57 | 71.14 | 70.44 | 67.08 |
| Liquid yield, weight % | 86.57 | 88.03 | 86.65 | 85.43 | 84.89 | 80.09 |
Can find out that from the result of table 4 CC-1 compares with reference catalyst, adopting the molecular sieve that is made by equipment provided by the invention is that the catalyst that active component prepares has higher conversion ratio, higher liquid yield and yield of light oil, lower coke selectivity.
Table 5
Claims (26)
1. the preparation method of a catalytic cracking catalyst is characterized in that, this method comprises molecular sieve and contains gas phase SiCl
4Gas mix to form mix logistics, the said gas phase SiCl that contains
4Gas be gas phase SiCl
4/ or gas phase SiCl
4With the mist of inert carrier gas, mix molecular sieve in the logistics with gas flow, and with gas in gas phase SiCl
4Contact is 10 seconds to 100 minutes under flow regime; 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 molecular sieve in the said mixing logistics is 0.015-3m/s with the flow velocity of gas flow.
3. method according to claim 1, wherein, said molecular sieve and gas phase SiCl
4The contact temperature be 300-650 ℃.
4. method according to claim 1, wherein, the said gas phase SiCl that contains
4Gas be gas phase SiCl
4Mist with inert carrier gas.
5. method according to claim 2, 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.
6. method according to claim 5, 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.
7. according to any described method in the claim 1,5 and 6, wherein, the temperature of said molecular sieve is 200-600 ℃, said gas phase SiCl
4Temperature be 60-150 ℃, the temperature of said inert carrier gas is 50-350 ℃.
8. method according to claim 7, wherein, said contact is carried out in tubular reactor, the method for said formation mixing logistics can through molecular sieve with contain SiCl
4Gas mix through a raw material mixed cell earlier before getting into the contact of said tubular reactor.
9. method according to claim 8, wherein, said raw material mixed cell comprises gas-solid blender and/or gas mixer.
10. method according to claim 9; Wherein, said charging aperture is one, and said raw material mixed cell comprises gas-solid blender and gas mixer; Gas mixer is communicated with the gas-solid blender, and the gas-solid blender is communicated with said tubular reactor through one in the said charging aperture.
11. method according to claim 8, wherein, the length of tubular reactor is 5-100 rice, and diameter is a 0.01-1.5 rice.
12. according to Claim 8 or 11 described methods; Wherein, Said tubular reactor comprises heater, body and is positioned at the charging aperture and the discharging opening at body two ends; Said heater can be to said body heating, and said mixing logistics gets into from charging aperture carries out haptoreaction in the said body, and the product after the haptoreaction is outside discharging opening is discharged said body.
13. method according to claim 12, wherein, said heater is to be arranged in said tube wall and/or inner heat tape, steam jacket, the spiral heater one or more.
14. method according to claim 13, 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.
15. method according to claim 14, wherein, the length of every section body is 2-20 rice.
16. method according to claim 12; 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.
17. method according to claim 16, wherein, the angle between said first tilting section and the vertical section is greater than 10 ° to 90 °.
18. method according to claim 17, wherein, the angle between said first tilting section and the vertical section is 30 ° to 80 °.
19. method according to claim 16, wherein, the length of said first tilting section and vertical section is than being 0.1-10: 1.
20. method according to claim 16, 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 charging aperture is positioned at the other end of said second tilting section.
21. method according to claim 20, wherein, the position at said charging aperture place is higher than said second tilting section and said vertical section position that is connected.
22. method according to claim 21, wherein, the angle between said second tilting section and the vertical section is greater than 10 ° to 90 °.
23. method according to claim 22, wherein, the angle between said second tilting section and the vertical section is 30 ° to 80 °.
24. according to any described method among the claim 21-23, wherein, the length of said second tilting section and vertical section is than being 0.1-10: 1.
25. method according to claim 1, wherein, this method also comprises carries out gas solid separation with contact back products therefrom, obtains solid high-silica zeolite product and gas component.
26. method according to claim 25, wherein, this method also comprises said gas component is contacted with absorbent, to remove the SiCl in the gas component
4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010515415.4A CN102451736B (en) | 2010-10-22 | 2010-10-22 | Preparation method of catalytic cracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010515415.4A CN102451736B (en) | 2010-10-22 | 2010-10-22 | Preparation method of catalytic cracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102451736A true CN102451736A (en) | 2012-05-16 |
| CN102451736B CN102451736B (en) | 2014-03-12 |
Family
ID=46035663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010515415.4A Active CN102451736B (en) | 2010-10-22 | 2010-10-22 | Preparation method of catalytic cracking catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102451736B (en) |
Cited By (8)
| 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 |
| CN103769193A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing a catalytic cracking catalyst |
| CN103785436A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Device for preparing catalytic cracking catalyst |
| CN103787352A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Method for preparing molecular sieve |
| CN103785437A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Catalytic cracking catalyst production method |
| CN103785438A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Catalytic cracking catalyst production apparatus |
| CN104549445A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking promoter |
| JP2015532260A (en) * | 2012-10-26 | 2015-11-09 | 中国石油化工股▲ふん▼有限公司 | Method and apparatus for making zeolite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN2797341Y (en) * | 2002-04-30 | 2006-07-19 | 中国科学院过程工程研究所 | Device for preparing titanium tatrachloride by chlorization of titanium containing mineral |
-
2010
- 2010-10-22 CN CN201010515415.4A patent/CN102451736B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2797341Y (en) * | 2002-04-30 | 2006-07-19 | 中国科学院过程工程研究所 | Device for preparing titanium tatrachloride by chlorization of titanium containing mineral |
| 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 |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US9993811B2 (en) | 2012-10-26 | 2018-06-12 | China Petroleum & Chemical Corporation | Process and apparatus for preparing a molecular sieve and a catalytic cracking catalyst |
| 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 |
| CN103787352A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Method for preparing molecular sieve |
| CN103785437A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Catalytic cracking catalyst production method |
| CN103785438A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Catalytic cracking catalyst production apparatus |
| GB2527200A (en) * | 2012-10-26 | 2015-12-16 | China Petroleum & Chemical | Catalytic cracking catalyst preparation method |
| JP2015532260A (en) * | 2012-10-26 | 2015-11-09 | 中国石油化工股▲ふん▼有限公司 | Method and apparatus for making zeolite |
| CN103785436A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Device for preparing catalytic cracking catalyst |
| CN103769193A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing a catalytic cracking catalyst |
| CN103785437B (en) * | 2012-10-26 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of method preparing catalytic cracking catalyst |
| CN103785438B (en) * | 2012-10-26 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of equipment preparing catalytic cracking catalyst |
| CN103785436B (en) * | 2012-10-26 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of equipment preparing catalytic cracking catalyst |
| CN103769193B (en) * | 2012-10-26 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of method preparing catalytic cracking catalyst |
| CN103787352B (en) * | 2012-10-26 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of method of preparing molecular sieve |
| TWI579047B (en) * | 2012-10-26 | 2017-04-21 | China Petrochemical Technology Co Ltd | Methods and apparatus for preparing molecular sieves and catalyst for catalytic cracking |
| 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 |
| CN104549445A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking promoter |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102451736B (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102451736B (en) | Preparation method of catalytic cracking catalyst | |
| CN102050459B (en) | Method for preparing high silicon molecular sieve | |
| CN103787352B (en) | A kind of method of preparing molecular sieve | |
| CN102050460B (en) | Equipment for preparing molecular sieve | |
| CN102049315B (en) | Method for preparing catalytic cracking catalyst | |
| CN103785438B (en) | A kind of equipment preparing catalytic cracking catalyst | |
| TW201434748A (en) | Method and apparatus for preparing zeolite | |
| CN103787353B (en) | A kind of equipment preparing molecular sieve | |
| CN103785436B (en) | A kind of equipment preparing catalytic cracking catalyst | |
| CN104556132B (en) | A kind of preparation method of the molecular sieves of high silica alumina ratio ZSM 5 | |
| CN102451655B (en) | Equipment for preparing molecular sieve | |
| CN102452661B (en) | Method for preparing molecular sieve | |
| CN102451657B (en) | Device for preparing a molecular sieve | |
| CN102452660B (en) | Method for preparing molecular sieve | |
| CN102049316B (en) | Equipment for preparing catalytic cracking catalyst | |
| CN102451730B (en) | Preparation method for catalytic cracking catalyst | |
| CN102451658B (en) | Equipment for preparing catalytic cracking catalysts | |
| CN102451729B (en) | Method for preparing catalytic cracking catalyst | |
| CN102452658B (en) | Preparation method of molecular sieve | |
| CN102451732B (en) | Equipment for preparing catalytic cracking catalyst | |
| CN102452657B (en) | Equipment for preparing molecular sieve | |
| CN102451656B (en) | Device for preparing catalytic cracking catalyst | |
| CN104549445B (en) | A kind of preparation method of assistant for calalytic cracking | |
| CN103769193B (en) | A kind of method preparing catalytic cracking catalyst | |
| TWI579047B (en) | Methods and apparatus for preparing molecular sieves and catalyst for catalytic cracking |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |