CN102451729B - Method for preparing catalytic cracking catalyst - Google Patents

Abstract

The invention relates to a method for a catalytic cracking catalyst, which comprises the following steps: a molecular sieve and gas containing gas phase SiCl4 to form mixed flow, the gas containing gas phase SiCl4 is gas phase SiC4 or a mixed gas of gas phase SiCl4 and inert carrier gas, the molecular sieve in the mixed flow flows with gas, and is contacted with gas phase SiCl4 under a flowing state, wherein the contact time of the molecular sieve and the gas phase SiCl4 is 10 seconds to 100 minutes, then the obtained reactant is contacted with mixed with the molecular sieve contacted with gas phase SiCl4, a binder, clay and water, and granulated to obtain the catalytic cracking catalyst. The preparation method has the advantages that the continuous contact reaction of the molecular sieveand SiCl4 can be realized, the contact time of the molecular sieve and SiCl4 can be controlled by controlling the velocity of the mixed gas and the length of a tubular reactor, so that the contact reaction of the molecular sieve and SiCl4 can be fully carried out in the tubular reactor.

Description

A kind of preparation method of catalytic cracking catalyst

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, the degree of crystallinity height of the molecular sieve of acquisition, and Si/Al is the heat endurance height when, 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 at present industrial method that generally adopts, but benefit silicon is untimely have dealuminzation in water-heat process after, easily causes 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, product crystallization reservation degree height, and Heat stability is good, 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 described drying and moulding thing, 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, this method comprises that the y-type zeolite that will contain rare earth carries out drying and handles, after making its water content be lower than 10 weight %, 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 with dry air, remove Na remaining in the zeolite with the decationized Y sieve water washing ⁺, 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, described contact is carried out in a consersion unit, this equipment as shown in Figure 1, comprise a reactor (1), a charging aperture (2) and a gas outlet (3), also comprise an agitator (4) in the inside of reactor (1), a gas-solid separator (5) is installed on the gas outlet (3), the bore dia of gas-solid separator (5) contained hole and porosity guarantee gas can by and the zeolitic solid particle can not pass through, the puddler of agitator (4) stretches out outside the reactor (1), under the stirring of agitator (4), the described y-type zeolite that contains rare earth contacts with carbon tetrachloride gas, the temperature of contact is 100-500 ℃, the time of contact is 5 minutes to 10 hours, containing the y-type zeolite of rare earth and the weight ratio of carbon tetrachloride is 1: 0.05-0.5, and the described silica alumina ratio that contains the y-type zeolite of rare earth is 3-8, 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 described method generally all long required time of contact, need a few hours, add charging and the discharging of reaction after finishing before the reaction, 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 reactor to stir, therefore reactor also can not be infinitely great, based on present level, energy is 600kg for the production capacity of the reactor of the maximum of above-mentioned dealumination complement silicon reaction, continue the augmenting response still, then be difficult in the 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 and after reaction is finished, need long blow line etc., these not only bring hand labor intensity big, the problem that production efficiency is very low, and, the molecular sieve dust when charging and discharging and excessive SiCl ₄Also cause serious environmental pollution and serious harm operating personnel's health.Therefore, the super steady technology of the gas phase of above-mentioned still formula is difficult to carry out suitability for industrialized production.

Summary of the invention

At the critical defect that the super 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 described 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 molecular sieve and gas phase SiCl ₄Time of contact be 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 with molecular sieve with contain SiCl ₄And the mixed gas flow of inert carrier gas carries down, and molecular sieve is flowed with mist, and with gas phase SiCl ₄Under flow regime, contact, then with gained and gas phase SiCl ₄Molecular sieve after the contact mixes making beating and granulation with binding agent, clay and water.This shows that the method for preparing catalytic cracking catalyst provided by the invention can realize molecular sieve and SiCl ₄Haptoreaction carry out continuously, by the control flow velocity of carrier gas and the length of tubular reactor, can control molecular sieve and SiCl ₄The time of contact, thus can make molecular sieve and SiCl ₄Haptoreaction carry out fully, thereby obtain to contain the catalytic cracking catalyst of high-silica zeolite.The present invention is by making molecular sieve and containing gas phase SiCl ₄Gas evenly mix after reaction again, 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.

Compare with the super steady technology of existing still formula gas phase, the preparation method of catalytic cracking catalyst provided by the invention can realize the super steady prepared in reaction high-silica zeolite of serialization gas phase, and operation can all automation serializations carries out, hand labor intensity is little, and production efficiency height, properties of product are stable, make the suitability for industrialized production of the super steady technology of molecular sieve serialization gas phase become a reality.Experimental results show that, adopt the disclosed still reaction method of CN1281493C, even if adopt the operating type of break tour, also can produce the high-silica zeolite of 1200kg every day at the most, and adopt the said equipment provided by the invention, 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, this shows that the economic benefit of equipment provided by the invention is very significant.

Description of drawings

Fig. 1 is the structural representation that vapor phase method prepares the equipment of high-silica zeolite that is used for of prior art;

Fig. 2 is the structural representation of the method device therefor for preparing catalytic cracking catalyst that the present invention relates to;

Fig. 3 is the axis of first tilting section 131 of tubular reactor 1 of equipment shown in Figure 2 and the schematic diagram of the angle α between the horizontal plane;

Fig. 4 is the axis of second tilting section 133 of tubular reactor 1 of equipment shown in Figure 2 and the schematic diagram of the angle β between the horizontal plane.

The specific embodiment

According to the preparation method of catalytic cracking catalyst provided by the invention, send in the reactor after can be directly gas phase silicon tetrachloride and molecular sieve being mixed and react; Also can be earlier that carrier gas mixes with the gas phase silicon tetrachloride with inert gas, 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, is that carrier gas mixes with the gas phase silicon tetrachloride with inert gas earlier, the formation mist is sent into after this mist and molecular sieve being mixed again and is carried out haptoreaction in the reactor.

Described inert 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 described inert carrier gas is no more than 100ppm.

The condition of described contact comprises that the solid content of molecular sieve is preferably greater than 98 weight %, and the solid content of described 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: 1,0.05-0.60 more preferably: 1, the flow velocity of mist 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 that mixes molecular sieve in the logistics is preferably 0.015-3m/s, more preferably 0.03-3m/s, more preferably 0.1-2.5m/s.Be that 0.01-1.5 rice, length are the tubular reactor of 50-95 rice with respect to diameter, the flow of molecular sieve is preferably 50-2000kg/ hour, more preferably 100-1500kg/ hour, further is preferably 200-1200kg/ hour.The temperature of carrier gas air is preferably 50-350 ℃, more preferably 100-250 ℃.Under these conditions, molecular sieve and gas phase SiCl both can have been guaranteed ₄By tubular reactor, can guarantee molecular sieve and gas phase SiCl with continuous airflow pattern again ₄Contact can fully carry out.From above-mentioned gas phase SiCl ₄With the numerical value of the weight ratio of molecular sieve as can be seen, adopt method provided by the invention can reduce gas phase SiCl greatly ₄Consumption.

Although as long as guarantee molecular sieve and gas phase SiCl ₄Catalytic temperature is common molecular sieve and gas phase SiCl ₄Catalytic temperature gets final product, 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 described molecular sieve of the present invention is 200-600 ℃, gas phase SiCl ₄Temperature be 60-150 ℃, the temperature of carrier gas such as air is 60-200 ℃.Under these conditions, need not reactor is arranged heater separately, can guarantee that the temperature in the reactor satisfies molecular sieve and gas phase SiCl ₄Catalytic needs.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, that is to say, under the preferable case, described molecular sieve is the molecular sieve of just discharging from roaster, can utilize the high temperature of molecular sieve after the roasting as the thermal source of dealumination complement silicon reaction so on the one hand, start 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.In addition, although by making air and SiCl ₄The temperature of gas raises also can reach the required temperature of reaction, and still, obviously extraneous heating can only make molecular sieve heating gradually from outside to inside, thereby more cannot say for sure to demonstrate,prove 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 of the present invention is reflected in the tubular reactor and carries out.

According to a kind of preferred embodiment, the method for preparing catalytic cracking catalyst provided by the invention is carried out in equipment shown in Figure 2.This equipment comprises raw material mixed cell 4, gas phase is mended the silicon unit, beater 5 and nodulizer, described gas phase is mended the silicon unit and is comprised tubular reactor 1, gas-solid separator 2, absorption tower 3, described tubular reactor 1 comprises at least one charging aperture, discharging opening and body 13, charging aperture in described at least one charging aperture and discharging opening lay respectively at two ends of described body 13, described gas-solid separator 2 is communicated with by the described tubular reactor 1 of described discharging opening, the upper and lower of described gas-solid separator 2 is communicated with described absorption tower 3 and beater 5 respectively, the position that described gas-solid separator 2 is connected with discharging opening is lower than the position that described gas-solid separator 2 is connected with described absorption tower 3, described raw material mixed cell 4 is used for different gas being mixed and/or gas being mixed with solid, described raw material mixed cell 4 is communicated with described tubular reactor 1 by one in the described charging aperture, and described nodulizer receives the material from beater 5.

That is, among the present invention, described dealumination complement silicon reaction is preferably carried out in tubular reactor 1, and the length of described tubular reactor 1 is to guarantee described molecular sieve and SiCl ₄Sufficient reacting get final product.Pipeline is too short, and deficiency is so that molecular sieve and SiCl ₄Sufficient reacting carry out or for guaranteeing molecular sieve and SiCl ₄Sufficient reacting carry out, production efficiency is too low.Although long pipeline is conducive to time of contact of providing longer, but pipeline is more long, the required power of raw materials such as required delivery of molecules sieve and gas is more big, requirement to device that power is provided accordingly is also just more high, and, reaction time is oversize, causes the degree of crystallinity of molecular sieve to reduce easily.Therefore, that takes all factors into consideration reaction fully carries out, reacts required power and production efficiency, the present inventor finds, the length of described tubular reactor 1 is preferable for 5-100 rice, therefore, the length of the preferred described tubular reactor 1 of the present invention is 5-100 rice, and more preferably 7-95 rice further is preferably 50-95 rice.The diameter of described tubular reactor 1 is preferably 0.01-1.5 rice, and more preferably 0.02-1.4 rice further is preferably 0.1-1.4 rice.

According to the present invention, 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, flow back to the generation of the situation in the tubular reactor 1 for the molecular sieve in the gas-solid separator 2 that prevents from tubular reactor 1, causing under the unsettled situation of air-flow, and further fully guarantee in short pipeline, to realize contacting more fully, as shown in Figure 2, described body 13 comprises first tilting section 131 and vertical section 132, one end of described first tilting section 131 and described vertical section 132 end join, described discharging opening is positioned at the other end of described first tilting section 131, and described first tilting section 131 and described vertical section 132 position that is connected are higher than the position at described discharging opening place.Under this preferable case, the setting of described first tilting section 131 can effectively prevent the generation of above-mentioned suck-back phenomenon, and described vertical section 132 make described tubular reactor be similar to riser reactor.Among the present invention, described vertical section is not that absolute vertical is in horizontal plane, as long as look like vertically up namely by in this scope.

Angle between described first tilting section 131 and the vertical section 132 can be 10-90 °, be preferably 30-80 °, namely when described vertical section 132 during perpendicular to horizontal plane, as shown in Figure 3, the axis of described first tilting section 131 and the angle α between the horizontal plane can be for greater than 0 ° to 80 °, under the preferable case, the axis of described 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 enter fast in the gas-solid separator 2 because of the gravity effect.

According to the present invention, under the preferable case, described first tilting section 131 and vertically the length of section 132 than being 0.1-10: 1,0.2-9 more preferably: 1, preferred 0.4-0.6 further: 1.

A preferred embodiment of the invention, described body 13 also comprises second tilting section 133, and an end of described second tilting section 133 and described vertical section 132 other end join, and described first charging aperture is positioned at the other end of described second tilting section 133.Arrange like this and can avoid the flowing velocity of molecular sieve solid material under the effect of gravity too fast, increase the haptoreaction time between reaction mass.

Further under the preferable case, the position at described charging aperture place is higher than described second tilting section 133 and described vertical section 132 position that is connected, so that material can fast, directly enter in second tilting section 133, further carries then.

Angle between described second tilting section 133 and the vertical section 132 can be 10-90 °, be preferably 30-80 °, namely when described vertical section 132 during perpendicular to horizontal plane, as shown in Figure 4, according to equipment provided by the invention, the axis of described 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 enters vertical section 132 because of the gravity effect fast.

Further under the preferable case, described second tilting section 133 and vertically the length of section 132 than being 0.1-10: 1,0.2-9 more preferably: 1, further be preferably 0.3-0.9: 1.

According to the present invention, described raw material mixed cell 4 comprises gas-solid blender and/or gas mixer, and described gas-solid blender and/or gas mixer are communicated with described tubular reactor 1 by one in the described charging aperture.

When described raw material mixed cell only comprises gas mixer and does not comprise the gas-solid blender, when producing continuously for the ease of industrialization with the cooperating of other devices, described tubular reactor 1 preferably includes two charging apertures, one of them charging aperture i.e. first charging aperture is the port of tubular reactor 1, and another charging aperture is positioned at and the described first charging aperture position adjacent.Wherein any one in two charging apertures is communicated with this gas-solid blender, and another charging aperture then is communicated with molecular sieve feeding unit (not shown).During use, described carrier gas air and gas phase SiCl ₄After in gas mixer, mixing, enter the body 13 of described tubular reactor 1 by the charging aperture that is communicated with described gas mixer, molecular sieve then enters the body 13 of described tubular reactor 1 from another charging aperture, thereby reacts in the body 13 of tubular reactor 1.Described molecular sieve feeding unit is preferably roaster, that is to say, another charging aperture of the equipment of preparation molecular sieve of the present invention is communicated with roaster usually.In order effectively to utilize the length of tubular reactor, preferred first charging aperture and second charging aperture are close as far as possible, but it is simultaneously also as far as possible little for the interference between the charging that guarantees two charging apertures, distance between preferred described first charging aperture and described second charging aperture is the 0.5-15% of the length of described tubular reactor 1, more preferably 1-10%.

Further under the preferable case, described charging aperture is one, described 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 described tubular reactor 1 by one in the described charging aperture.Described carrier gas air and gas phase SiCl ₄After in the gas mixer of raw material mixed cell 4, mixing, enter the gas-solid blender and carry out gas-solid with molecular sieve and mix, mix the back and enter in the tubular reactor 1 by charging aperture.

Described 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.Described 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 described gas-solid blender can be cylinder mixer, and this cylinder mixer comprises cylindrical body and is positioned at the grid of cylindrical body.Described grid is preferably and axially is fixed on corrosion resistant plate on the cylindrical body inwall in spiralling mode along cylindrical body, 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 for making raw material, the pitch of flase floor is preferably 0.1-1 rice, 0.2-0.7 rice more preferably, the width of flase floor (be grid from and 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 described gas mixer and gas-solid blender are cylinder type, and the cylinder of the two is structure as a whole.

Among the present invention, described gas-solid separator 2 is used for collecting and SiCl ₄Molecular sieve after the gas contact.In this gas-solid separator, solid molecular sieves is separated with gas, thereby obtain the high-silica zeolite product.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 for example can be for cylindric to its shape can there is no particular limitation.Further under the preferable case, the bottom of described gas-solid separator 2 has the taper of opening for the end.Thereby the high-silica zeolite that obtains can be discharged from described opening.

Described gas-solid separator 2 generally comprises charging aperture and top gas outlet.The other end of described first tilting section is communicated with described gas-solid separator, and the sectional area of described gas-solid separator is greater than the cross-sectional area of described tubular reactor body.Sectional area by making described gas-solid separator is greater than the cross-sectional area of described 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 described gas-solid separator is 2-10 with the ratio of the cross-sectional area of described 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 described gas-solid separator is not less than 5 meters, for example 5-10 rice.Further under the preferable case, the charging aperture of described gas-solid separator is positioned at the middle part of described gas-solid separator, can guarantee so on the one hand the molecular sieve that is deposited in 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, described gas-solid separator also comprises the bottom solid outlet, is used for discharging the molecular sieve solid that separation obtains.Further under the preferable case, described gas-solid separator also comprises the valve of opening and closing for the described bottom of control solid outlet, thereby the molecular sieve solid with collecting in the gas-solid separator that can be in good time is discharged.

In order to make gas component in the post reaction mixture enter the absorption tower as far as possible and not discharge from above-mentioned opening, under the preferable case, the position that described gas-solid separator 2 is connected with tubular reactor 1 discharging opening is higher than the original position of described taper.Further under the preferable case, the position that described gas-solid separator 2 is connected with tubular reactor 1 discharging opening is positioned at the middle and upper part of described gas-solid separator 2, and gas-solid separator 2 is communicated with described absorption tower 3 by its top gas outlet.

Described absorption tower 3 is used for absorbing excessive unreacted SiCl ₄Thereby the gas that gas-solid separator is come out reaches discharge standard.Described 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, described absorption tower 3 preferably includes two entrances and two outlets, one of them described entrance is communicated with gas-solid separator 2, be preferably placed at the middle and upper part on described absorption tower, another entrance is used for adding alkali lye, and this entrance preferably also is positioned at the middle and upper part on described absorption tower.Described two outlets lay respectively at top and the bottom on described absorption tower, are respectively applied to emission gases (air) and absorb waste liquid.For SiCl in the air that guarantees to discharge ₄Content is enough low, and under the preferable case, described absorption tower is a plurality of for series connection.A plurality of absorption towers of series connection are to SiCl ₄Form multistage absorption.

According to preferred embodiment of the present invention, adopt workflow that the said equipment prepares catalytic cracking catalyst as shown in Figure 2.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 charging aperture, molecular sieve is with carrier gas and gas phase SiCl ₄The mist contact of in tubular reactor 1, flowing, enter gas-solid separator 2 afterwards, in gas-solid separator 2, molecular sieve d is deposited in the bottom of gas-solid separator 2, directly or regularly be expelled to beater 5, in beater 5, send into after the making beating and carry out granulation in the nodulizer (not shown), obtain catalytic cracking catalyst.Inert carrier gas and gas phase SiCl ₄Then the outlet by gas-solid separator 2 tops enters in the absorption tower 3, contacts with absorbent alkali lye in the absorption tower 3, and carrier gas (tail gas e) is overflowed from alkali lye, and SiCl is discharged in the outlet at 3 tops from the absorption tower ₄Then with alkaline reaction, directly or regularly discharge waste water f by outlet at bottom afterwards.

Among the present invention, described molecular sieve can be the various molecular sieves that need aluminium-eliminating and silicon-replenishing, can be the Y zeolite of different content of rare earth for example, with RE ₂O ₃Meter, described Y zeolite middle rare earth content is preferably 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, described gross weight with catalytic cracking catalyst is 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 %.Described 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 described clay can be in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite one or more.Described 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 does not repeat them here.

The following examples will give further instruction to the present invention, but not thereby limiting the invention.

Embodiment 1-5 is used for the explanation method for preparing catalytic cracking catalyst provided by the invention.

Embodiment 1

Used thickness is that 3 millimeters the industrial trade mark is the stainless steel making molecular sieve gas phase benefit silicon equipment shown in Figure 2 of NiCr18Ti, wherein the body 13 of tubular reactor 1 is by first tilting section 131, vertically section 132 and second tilting section 133 constitutes, the length of first tilting section 131 is 20 meters, diameter is 0.8 meter, vertically the length of section 132 is 40 meters, diameter is 0.8 meter, the length of second tilting section 133 is 15 meters, diameter is 0.8 meter, vertically section 132 is perpendicular to horizontal plane, the axis of first tilting section 131 and the angle α between the horizontal plane are 75 ° (namely 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 are 65 ° (namely the angle between second tilting section 133 and the vertical section 132 is 25 °), the port of second tilting section 133 is charging aperture, raw material mixed cell 4 comprises that length is 5 meters, diameter is 0.8 meter cylinder mixer, one end of cylinder mixer is communicated with charging aperture, axial position apart from 2.5 meters of charging apertures along cylinder mixer is provided with the molecular sieve entrance, this cylindrical section mixer inner walls from this molecular sieve entrance to charging aperture 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, this cylinder mixer is divided into two parts thus, first is as gas mixer, second portion is provided with flase floor, thereby as the gas-solid blender; 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, 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 by 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 100 ℃ dry air and temperature are 90 ℃ with temperature ₄After gas is sent into gas mixer in the raw material mixed cell 4 and is mixed, enter with molecular sieve entrance from pipeline, be that 350 ℃ the Y zeolite that contains rare earth (character is as shown in table 1) is to mix the back the gas-solid blender to be sent into continuously in the body 13 of tubular reactor 1 by charging aperture in being provided with the pipeline of grid from the temperature of roaster, enter the SiCl of raw material mixed cell 4 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 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 drying, obtain high-silica zeolite A in 120 ℃ of baking ovens, its main character is listed in the table 2.

According to (material butt) molecular sieve: kaolin: boehmite: aluminium colloidal sol=38: 30: 22: 10 part by weight is with above-mentioned mixing of materials, making beating, send into then in the spray dryer 450 ℃ of following spray-dryings, carry out granulation, obtain spherical catalytic cracking catalyst C-1, its main character is listed in the table 3.

Embodiment 2

Used thickness is that 3 millimeters the industrial trade mark is the stainless steel making molecular sieve gas phase benefit silicon equipment shown in Figure 2 of NiCr18Ti, wherein the body 13 of tubular reactor 1 is by first tilting section 131, vertically section 132 and second tilting section 133 constitutes, the length of first tilting section 131 is 25 meters, diameter is 0.4 meter, vertically the length of section 132 is 45 meters, diameter is 0.4 meter, the length of second tilting section 133 is 25 meters, diameter is 0.4 meter, vertically section 132 is perpendicular to horizontal plane, the axis of first tilting section 131 and the angle α between the horizontal plane are 55 ° (namely 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 ° (namely the angle between second tilting section 133 and the vertical section 132 is 35 °), the port of second tilting section 133 is charging aperture, raw material mixed cell 4 comprises that length is 5 meters, diameter is 0.8 meter cylinder mixer, one end of cylinder mixer is communicated with charging aperture, axial position apart from 2.5 meters of charging apertures along cylinder mixer is provided with the molecular sieve entrance, this cylindrical section mixer inner walls from this molecular sieve entrance to charging aperture 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, this cylinder mixer is divided into two parts thus, first is as gas mixer, second portion is provided with flase floor, thereby as the gas-solid blender; 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, 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 by 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 200 ℃ dry air and temperature are 130 ℃ with temperature ₄After gas is sent into and is mixed in the gas mixer in the raw material mixed cell 4, enter with molecular sieve entrance from pipeline, be that 350 ℃ the Y zeolite that contains rare earth (character is as shown in table 1) is to mix the back the gas-solid blender to be sent in the body 13 of tubular reactor 1 SiCl continuously by charging aperture in being provided with the pipeline of grid from the temperature of roaster ₄Flow controlled 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 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 drying, obtain high-silica zeolite B in 120 ℃ of baking ovens, its main character is listed in the table 2.

According to (material butt) molecular sieve: kaolin: boehmite: aluminium colloidal sol=38: 30: 22: 10 part by weight is with above-mentioned mixing of materials, making beating, send into then in the spray dryer 450 ℃ of following spray-dryings, carry out granulation, obtain spherical catalytic cracking catalyst C-2, its main character is listed in the table 3.

Embodiment 3

Used thickness is that 3 millimeters the industrial trade mark is the stainless steel making molecular sieve gas phase benefit silicon equipment shown in Figure 2 of NiCr18Ti, wherein the body 13 of tubular reactor 1 is by first tilting section 131, vertically section 132 and second tilting section 133 constitutes, the length of first tilting section 131 is 15 meters, diameter is 1.2 meters, vertically the length of section 132 is 35 meters, diameter is 1.2 meters, the length of second tilting section 133 is 30 meters, diameter is 1.2 meters, vertically section 132 is perpendicular to horizontal plane, the axis of first tilting section 131 and the angle α between the horizontal plane are 45 ° (namely 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 ° (namely the angle between second tilting section 133 and the vertical section 132 is 45 °), the port of second tilting section 133 is charging aperture, raw material mixed cell 4 comprises that length is 5 meters, diameter is 0.8 meter cylinder mixer, one end of cylinder mixer is communicated with charging aperture, axial position apart from 2.5 meters of charging apertures along cylinder mixer is provided with the molecular sieve entrance, this cylindrical section mixer inner walls from this molecular sieve entrance to charging aperture 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, this cylinder mixer is divided into two parts thus, first is as gas mixer, second portion is provided with flase floor, thereby as the gas-solid blender; 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, 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 by 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 140 ℃ dry air and temperature are 80 ℃ with temperature ₄After gas is sent into and is mixed in the gas mixer in the raw material mixed cell 4, enter with molecular sieve entrance from pipeline, be that 350 ℃ the Y zeolite that contains rare earth (character is as shown in table 1) is to mix the back the gas-solid blender to be sent in the body 13 of tubular reactor 1 SiCl continuously by charging aperture in being provided with the pipeline of grid from the temperature of roaster 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 drying, obtain high-silica zeolite C in 120 ℃ of baking ovens, its main character is listed in the table 2.

According to (material butt) molecular sieve: kaolin: boehmite: aluminium colloidal sol=38: 30: 22: 10 part by weight is with above-mentioned mixing of materials, making beating, send into then in the spray dryer 450 ℃ of following spray-dryings, carry out granulation, obtain spherical catalytic cracking catalyst C-3, its main character is listed in the table 3.

Embodiment 4

Method according to embodiment 3 prepares high-silica zeolite, different is, the length of tubular reactor 1 is 25 meters, wherein the length of first tilting section 131 is 4.7 meters, diameter is 1.2 meters, vertically the length of section 132 is 10.9 meters, diameter is 1.2 meters, the length of second tilting section 133 is 9.4 meters, diameter is 1.2 meters, and 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 2.

According to (material butt) molecular sieve: kaolin: boehmite: aluminium colloidal sol=38: 30: 22: 10 part by weight is with above-mentioned mixing of materials, making beating, send into then in the spray dryer 450 ℃ of following spray-dryings, carry out granulation, obtain spherical catalytic cracking catalyst C-4, its main character is listed in the table 3.

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 2.

According to (material butt) molecular sieve: kaolin: boehmite: aluminium colloidal sol=38: 30: 22: 10 part by weight is with above-mentioned mixing of materials, making beating, send into then in the spray dryer 450 ℃ of following spray-dryings, carry out granulation, obtain spherical catalytic cracking catalyst C-5, its main character is listed in the table 3.

Table 1

The Y zeolite that contains rare earth	Embodiment	1	Embodiment 2	Embodiment 3
					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

From the result of table 2 as can be seen, compare with industrial REY, adopting the framework si-al ratio of the molecular sieve that method provided by the invention makes is SiO ₂/ Al ₂O ₃Mol ratio improves greatly, shows that dealumination complement silicon is effective.In addition, from the result of table 2 as can be seen, compare with industrial REY, the molecular sieve that adopts method provided by the invention to make has better relative crystallinity, higher lattice avalanche temperature, and specific area obviously improves, and sodium oxide content reduces greatly, shows the excellent performance of the molecular sieve that equipment provided by the invention makes.

Comparative Examples 1

The method for preparing catalyst according to embodiment 1 adopts industrial REY type molecular sieve (main character is listed in the table 2) preparation catalyst, and the gained catalyst is designated as reference catalyst CC-1, and its main character is listed in the table 3.

Table 3

From the result of table 3 as can be seen, when adopting the molecular sieve that is made by method provided by the invention to prepare catalyst, the sodium oxide content of gained catalyst significantly reduces, and pore volume and specific area obviously increase, and micro-activity obviously improves.

The catalytic cracking performance test of catalyst

Light oil microactivity is estimated: adopt the standard method of RIPP92-90 (to see volumes such as " petrochemical industry analytical method " (RIPP test method) Yang Cuiding, Science Press, the nineteen ninety publication) light oil microactivity of assess sample, 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 5.

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 at ACE (fixed fluidized bed) device then, and feedstock oil is military three heavy oil (character sees 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=yield of liquefied gas+yield of gasoline+diesel yield

Coke selectivity=coking yield/conversion ratio

Estimate the catalytic cracking performance of the catalyst of embodiment 1-5 and Comparative Examples 1 preparation according to the method described above respectively, the results are shown in table 5.

Table 4

Table 5

Catalyst	C-1	C-2	C-3	C-4	C-5	CC-1
							Product distributes, weight %
Dry gas	1.17	1.19	1.13	1.21	1.2	1.23
							Liquefied gas	13.11	13.69	13.08	14.29	14.62	13.01
Coke	5.14	5.37	5.18	5.41	5.31	5.75
							Gasoline	54.75	56.05	55.09	51.76	50.83	47.17
Diesel oil	17.85	17.28	17.81	17.95	18.28	19.91
							Heavy oil	7.98	6.42	7.71	9.38	9.76	12.93
Add up to	100	100	100	100	100	100
							Conversion ratio, weight %	74.17	76.3	74.48	72.67	71.96	67.16
Coke selectivity, weight %	6.93	7.04	6.95	7.44	7.38	8.56
							Yield of light oil, weight %	72.6	73.33	72.9	69.71	69.11	67.08
Liquid yield, weight %	85.71	87.02	85.98	84	83.73	80.09

From the result of table 5 as can be seen, CC-1 compares with reference catalyst, and adopting the molecular sieve that is made by equipment provided by the invention is that the catalyst of active component preparation has higher conversion ratio, higher liquid yield, higher yield of light oil and lower coke selectivity.

Claims (22)

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 described 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 molecular sieve and gas phase SiCl ₄Time of contact be 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.

2. method according to claim 1, wherein, the molecular sieve in the described mixing logistics is 0.015-3m/s with the flow velocity of gas flow.

3. method according to claim 1 and 2, wherein, described gas is gas phase SiCl ₄Mist with inert carrier gas.

4. method according to claim 1 and 2, wherein, described gas phase SiCl ₄With the weight ratio of molecular sieve be 0.01-1: 1, the inlet amount of described molecular sieve be the 50-2000 kilogram/hour.

5. method according to claim 4, wherein, described gas phase SiCl ₄With the weight ratio of molecular sieve be 0.05-0.6: 1, the inlet amount of described molecular sieve be the 100-1500 kilogram/hour.

6. according to any described method in the claim 1,2 and 5, wherein, the temperature of described molecular sieve is 200-600 ℃, the described SiCl that contains ₄The temperature of gas be 60-200 ℃.

7. method according to claim 6, wherein, described contact is carried out in tubular reactor,, the method that forms described mixing logistics for molecular sieve with contain SiCl ₄Gas mix by a raw material mixed cell earlier before entering the contact of described tubular reactor.

8. method according to claim 7, wherein, described raw material mixed cell comprises gas-solid blender and/or gas mixer.

9. method according to claim 8, wherein, described charging aperture is one, described raw material mixed cell (4) comprises gas-solid blender and gas mixer, gas mixer is communicated with the gas-solid blender, and the gas-solid blender is communicated with described tubular reactor (1) by one in the described charging aperture.

10. method according to claim 7, wherein, the length of tubular reactor is 5-100 rice, diameter is 0.01-1.5 rice.

11. according to any described method among the claim 7-10, wherein, described tubular reactor comprises body and is positioned at least one charging aperture and the discharging opening at body two ends, described mixing logistics from described charging aperture enters and carries out haptoreaction in the described body, product after the haptoreaction is outside discharging opening is discharged described body, and described tubular reactor is connected with the raw material mixed cell by one in the described charging aperture.

12. method according to claim 11, wherein, described body comprises first tilting section and vertical section, one end of described first tilting section and a described vertical section end join, described discharging opening is positioned at the other end of described first tilting section, and described first tilting section and described vertical section position that is connected are higher than the position at described discharging opening place.

13. method according to claim 12, wherein, the angle between described first tilting section and the vertical section is greater than 10 ° to 90 °.

14. method according to claim 13, wherein, the angle between described first tilting section and the vertical section is greater than 30 ° to 80 °.

15. method according to claim 12, wherein, the length of described first tilting section and vertical section is than being 0.1-10: 1.

16. method according to claim 12, wherein, described body also comprises second tilting section, and an end of described second tilting section and the described vertical section other end join, and described charging aperture is positioned at the other end of described second tilting section.

17. method according to claim 16, wherein, the position at described charging aperture place is higher than described second tilting section and described vertical section position that is connected.

18. method according to claim 16, wherein, the angle between described second tilting section and the vertical section is greater than 10 ° to 90 °.

19. method according to claim 18, wherein, the angle between described second tilting section and the vertical section is greater than 30 ° to 80 °.

20. according to any described method among the claim 16-19, wherein, the length of described second tilting section and vertical section is than being 0.1-10: 1.

21. 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.

22. method according to claim 21, wherein, this method also comprises described gas component is contacted with absorbent, to remove the SiCl in the gas component ₄

Images