CN102452658B - Preparation method of molecular sieve - Google Patents
Preparation method of molecular sieve Download PDFInfo
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- CN102452658B CN102452658B CN201010515228.6A CN201010515228A CN102452658B CN 102452658 B CN102452658 B CN 102452658B CN 201010515228 A CN201010515228 A CN 201010515228A CN 102452658 B CN102452658 B CN 102452658B
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Abstract
A preparation method of a molecular sieve. According to the method, a molecular sieve and gas containing gas phase SiCl4 are mixed to form a mixture flow; the gas containing gas phase SiCl4 is gas phase SiCl4 or a mixed gas of gas phase SiCl4 and inertia carrying gas; and the molecular sieve in the mixture flow flows with the gas and contacts with the gas phase SiCl4 in the gas in a flowing state, at a contact temperature of 250-700 DEG C and with a contact time of 10 sec to 100 min. The preparation method of the molecular sieve provided by the invention can realize continuous contact reaction of molecular sieve and SiCl4; uniform mixing of the molecular sieve and the gas containing gas phase SiCl4 guarantees uniform and complete conduction of a silicon supplement reaction; accordingly, the prepared molecular sieve has higher degree of crystallization, more stable quality and better performance. According to control on different contact temperatures of the molecular sieve and the SiCl4, different reaction conditions and reaction degrees can be controlled, thereby obtaining molecular sieve products with different degrees of aluminium removal.
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, is also very important a kind of component simultaneously, and the performance of molecular sieve has directly had influence on the reactivity worth of catalytic cracking catalyst.According to different needs, can carry out different modifications to reach the requirement of use to molecular sieve.Such as the molecular sieve of high silica alumina ratio, to be generally considered to catalytic cracking catalyst required.
Preparing aspect the molecular sieve of high silica alumina ratio, mainly contain following several method: ammonium silicofluoride method aluminium-eliminating and silicon-replenishing, hydrothermal method aluminium-eliminating and silicon-replenishing and gas chemistry method aluminium-eliminating and silicon-replenishing.
Ammonium silicofluoride method aluminium-eliminating and silicon-replenishing (also referred to as chemical method aluminium-eliminating and silicon-replenishing) is mainly to use ammonium silicofluoride dealumination complement silicon, and the degree of crystallinity of the molecular sieve of acquisition is high, and Si/Al when thermostability is high, but the indissoluble thing AlF forming in dealumination process
3affect hydrothermal stability with residual silicofluoride, also pollute the environment.
Hydrothermal method is still the at present industrial method generally adopting, but mend silicon not in time there is dealuminzation in water-heat process after, easily cause lattice to subside, and non-framework aluminum clogged with fragments duct, this has not only affected the accessibility in active centre, also affects the further raising of its thermostability.
The feature of gas chemistry method aluminium-eliminating and silicon-replenishing is that dealuminzation is even, mends silicon timely, and product crystallization reservation degree is high, Heat stability is good, and duct is unimpeded.For example, CN1057977C discloses a kind of preparation method of the catalyst composition containing rich silicon ultra stabilization Y zeolite, it comprises that drying and moulding thing that water content is less than to silicon tetrachloride gas that the dry air of 900ppm carries and NaY zeolite and heat-resistant inorganic oxide is by silicon tetrachloride total amount: forming composition=0.1-0.8: 1 weight ratio, 150-550 ℃ of contact reacts 10 minutes to 5 hours, in described drying and moulding thing, particle diameter is that the particle of 35-125 micron accounts for the more than 80% of total particle number, the weight ratio of NaY zeolite and heat-resistant inorganic oxide is 1: 0.2-1.0, the silica alumina ratio of NaY zeolite is 3-6.The method forming composition good fluidity used, has avoided being agglomerated into the phenomenon of piece and obstruction, is easy to realize serialization scale operation.
CN1121903C discloses a kind of preparation method of rare-earth type high-silicon gamma-zeolite, the method comprises carries out drying treatment by the y-type zeolite containing rare earth, after making its water-content lower than 10 % by weight, according to silicon tetrachloride: Y zeolite=0.1-0.9: 1 weight ratio, passes into the silicon tetrachloride gas that dry air carries, at temperature 150-600 ℃, react 10 minutes to 6 hours, after reaction, with dry air, purge 5 minutes to 2 hours, with decationized Y sieve water washing, remove Na remaining in zeolite
+, Cl
-, Al
3+etc. solubility by product.The method is simpler compared with prior art, the saving energy and pollution-free.
CN1281493C discloses Y type zeolites containing rare-earth and high content of silicon and preparation method thereof, and this zeolite contains rare earth, and the silica alumina ratio of this zeolite is 5-30, and initial lattice constant is 2.430-2.465nm, and balance lattice constant is at least 0.985 with the ratio of initial lattice constant.The preparation method of this zeolite comprises and will contact with silicon tetrachloride containing rare earth Y type zeolite, described contact is carried out in a conversion unit, this equipment as shown in Figure 1, comprise a reactor (1), an opening for feed (2) and an air outlet (3), in the inside of reactor (1), also comprise an agitator (4), a gas-solid separator (5) is installed on air outlet (3), the bore dia of gas-solid separator (5) contained hole and porosity guarantee gas can by and zeolitic solid particle can not pass through, the agitator arm of agitator (4) stretches out outside reactor (1), under the stirring of agitator (4), the described y-type zeolite containing rare earth contacts with carbon tetrachloride gas, the temperature of contact is 100-500 ℃, the time of contact is 5 minutes to 10 hours, containing the y-type zeolite of rare earth and the weight ratio of tetracol phenixin, be 1: 0.05-0.5, the silica alumina ratio of the described y-type zeolite containing rare earth is 3-8, lattice constant is 2.45-2.48nm.The method make silicon tetrachloride gas and molecular sieve solid particle contact reacts more even, avoid the phenomenon that is agglomerated into compact mass thing between molecular sieve solid particle, can reduce labour intensity, can reduce environmental pollution, reduce significantly production cost, be easy to carry out large-scale industrial application.
Obviously, above described method generally all long required duration of contact, need a few hours, add charging before reaction and discharging after completion of the reaction, can only carry out once at the most above-mentioned dealumination complement silicon reaction a general day shift, even if adopt the mode of operation of break tour also can only carry out twice above-mentioned dealumination complement silicon reaction, and owing to needing stirring in reactor, therefore reactor also can not be infinitely great, level based on current, the production capacity of the maximum reactor that can react for above-mentioned dealumination complement silicon is 600kg, continue augmenting response still, in reactor, be difficult to guarantee fully to stir, therefore, adopt the mode of aforesaid reaction vessel, within one day, can obtain at the most the high-silica zeolite of 1200kg.And, in the method for above-mentioned prior art, in order to guarantee the high silicon content of the molecular sieve of acquisition, generally all make SiCl
4excessive far away, excessive SiCl
4use increased undoubtedly production cost and expenses of environmental protection.On the other hand, aforesaid method all needs very numerous and diverse manual operation, such as: hand charging, manual cleaning and after reaction completes, need long scavenging line etc., these not only bring hand labor intensity large, the problem that production efficiency is very low, and, molecular sieve dust when charging and discharging and excessive SiCl
4also cause serious environmental pollution and serious harm operator's health.Therefore, the super steady technique of the gas phase of above-mentioned autoclave is difficult to carry out suitability for industrialized production.
Summary of the invention
The critical defect existing for the super steady technique of the gas phase of autoclave, the object of the invention is to develop and a kind ofly can reduce SiCl
4consumption, reduce labour intensity and the preparation method of the high-silica zeolite that is applicable to serialization suitability for industrialized production of greatly enhancing productivity.
The invention provides a kind of preparation method of molecular sieve, wherein, the method comprises molecular sieve and contains gas phase SiCl
4gas be mixed to form mixture flow, described in contain gas phase SiCl
4gas be gas phase SiCl
4or gas phase SiCl
4with the mixed gas of inert carrier gas, the molecular sieve in mixture flow is with gas flow, and with gas in gas phase SiCl
4under flow state, contact molecular sieve and gas phase SiCl
4contact Temperature be that 250-700 ℃, duration of contact are 10 seconds to 100 minutes.
The preparation method of molecular sieve provided by the invention passes through by molecular sieve and containing gas phase SiCl
4gas be mixed to form mixture flow, the molecular sieve in mixture flow and gas phase SiCl
4gas contacts under flow state.As can be seen here, the preparation method of molecular sieve provided by the invention can realize molecular sieve and SiCl
4contact reacts carry out continuously, by controlling the flow velocity of carrier gas and the length of tubular reactor, can control molecular sieve and SiCl
4the time of contact, thus can make molecular sieve and SiCl
4contact reacts carry out fully, thereby obtain high-silica zeolite; By making molecular sieve and containing gas phase SiCl
4gas uniform mix, thereby guaranteed that 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 by controlling molecular sieve and SiCl
4different Contact Temperature in tubular reactor, thus differential responses condition and level of response can be controlled, and then can obtain the zeolite product of different dealuminzation degree.
Compare with the super steady technique of existing autoclave gas phase, the preparation method of molecular sieve provided by the invention can realize the super steady reaction of serialization gas phase and prepare high-silica zeolite, and operation can all automatization serializations carries out, hand labor intensity is little, and production efficiency is high, product performance are stable, and the suitability for industrialized production of the super steady technique of molecular sieve serialization gas phase is become a reality.Experimental results show that, adopt the disclosed still reaction method of CN1281493C, even if adopt the mode of operation of break tour, also can produce at the most the high-silica zeolite of 1200kg every day, and adopt aforesaid device provided by the invention, the high-silica zeolite that can produce 1000kg per hour, can produce the high-silica zeolite of 24000kg every day, its production efficiency is 20 times of the disclosed still reaction method of CN1281493C, and workman's labor operation intensity also greatly reduces, as can be seen here, the economic benefit of method of the present invention is very significant.
Accompanying drawing explanation
Fig. 1 be prior art for vapor phase process, prepare the structural representation of the equipment of molecular sieve;
Fig. 2 be the present invention relates to for vapor phase process, prepare the equipment of molecular sieve and the schematic diagram of method.
Fig. 3 is the axis of the first tilting section 131 and the schematic diagram of the angle α between horizontal plane of the tubular reactor 1 of Fig. 2 apparatus shown;
Fig. 4 is the axis of the second tilting section 132 and the schematic diagram of the angle β between horizontal plane of the tubular reactor 1 of Fig. 2 apparatus shown.
Embodiment
According to the method for preparing molecular sieve provided by the invention, after can directly gas phase silicon tetrachloride being mixed with molecular sieve, send in reactor and react; Also can by rare gas element, be first that carrier gas mixes with gas phase silicon tetrachloride, form mixed gas, then after this mixed gas is mixed with molecular sieve, send into and in reactor, carry out contact reacts; Also can first rare gas element be mixed with molecular sieve, molecular sieve is mixed with gas phase silicon tetrachloride with flow state under the drive of rare gas element; Together with after can also rare gas element, molecular sieve being mixed with gas phase silicon tetrachloride simultaneously, send in reactor and react.Under preferable case, by rare gas element, be first that carrier gas mixes with gas phase silicon tetrachloride, form mixed gas, thereby the concentration of silicon tetrachloride is diluted, after again this mixed gas being mixed with molecular sieve, send into and in reactor, carry out contact reacts, thereby can reduce the unnecessary waste of silicon tetrachloride.
Described rare gas element can be various not disturbing molecule sieves and gas phase SiCl
4the gas stream of reaction for example, can be one or more in neutral element gas in air, nitrogen and the periodic table of elements.Due to SiCl
4to water sensitive, therefore, under 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 % by weight, and the solid content of described molecular sieve is weight and weight ratio roasting before, the i.e. water content of the solid content=100%-molecular sieve of molecular sieve of molecular sieve after high-temperature roasting; SiCl
4be preferably 0.01-1 with the weight ratio of molecular sieve: 1,0.05-0.60 more preferably: 1; Molecular sieve and gas phase SiCl
4contact Temperature be 250-700 ℃, more preferably 300-650 ℃; The flow velocity of mixture flow makes SiCl
4the residence time with molecular sieve in reactor is 10 seconds to 100 minutes, is preferably 1 minute to 20 minutes.Molecular sieve in mixture flow is preferably 0.015-3m/s with the flow velocity of gas flow, more preferably 0.03-3m/s, more preferably 0.1-2.5m/s.With respect to diameter, be that 0.1-1.4 rice, length are the tubular reactor of 50-95 rice, the inlet amount of molecular sieve is preferably 50-2000kg/ hour, and more preferably 100-1500kg/ hour, is further preferably 200-1200kg/ hour.The temperature of inert carrier gas is preferably 50-350 ℃, more preferably 100-250 ℃.Under these conditions, molecular sieve and gas phase SiCl both can have been guaranteed
4with continuous airflow pattern, by tubular reactor, can guarantee again molecular sieve and gas phase SiCl
4contact can fully carry out.From above-mentioned gas phase SiCl
4can find out with the numerical value of the weight ratio of molecular sieve, adopt method provided by the invention can greatly reduce gas phase SiCl
4consumption.
In the present invention due to molecular sieve and gas phase SiCl
4contact Temperature control, therefore to the temperature of the temperature of molecular sieve, inert carrier gas, SiCl
4any requirement of temperature, can be the molecular sieve of arbitrary temp, inert carrier gas, SiCl
4, and the present invention passes through molecular sieve and gas phase SiCl
4contact Temperature control, thereby make, its longest limit to tubular reactor does not require, can the longer the better, thereby can increase molecular sieve and SiCl
4duration of contact, thereby it is better to obtain degree of crystallinity, the molecular sieve of dealuminzation better effects if, and the present invention is by controlling molecular sieve and SiCl
4different Contact Temperature in tubular reactor, thus differential responses condition and level of response can be controlled, and then can obtain the zeolite product of different dealuminzation degree.
Although in the present invention due to molecular sieve and gas phase SiCl
4contact Temperature control, to the temperature of the temperature of molecular sieve, inert carrier gas, SiCl
4temperature without any requirement, can be the molecular sieve of arbitrary temp, inert carrier gas, but under preferable case, in order to make the reaction can be at molecular sieve and gas phase SiCl
4after contact, carry out fast, thereby effectively utilize the length of tubular reactor, the temperature of the preferred described molecular sieve of the present invention is 200-600 ℃, SiCl
4temperature be 60-150 ℃.Because the temperature of the molecular sieve after roasting is generally more than 300 ℃, therefore the temperature of above-mentioned molecular sieve can be by combining tubular reactor to obtain with stoving oven, that is to say, under preferable case, described molecular sieve is the molecular sieve of just discharging from stoving oven, can utilize so on the one hand the high temperature of molecular sieve after roasting as the thermal source of dealumination complement silicon reaction, start dealumination complement silicon reaction, thus save energy; Can also save on the other hand the time of heating molecular sieve, thereby reaction can fully be carried out in the short period of time.
The reaction of dealumination complement silicon described in the present invention can carried out in reactor arbitrarily, as long as meet molecular sieve and gas phase SiCl in the present invention
4contact conditions, such as carrying out in the reactors such as fluidized-bed, fixed bed, tubular reactor, but under preferable case, dealumination complement silicon reaction of the present invention is carried out in tubular reactor.
According to a kind of preferred implementation, described in the present invention, to prepare the method for molecular sieve and carry out in the equipment shown in Fig. 2, this equipment comprises tubular reactor 1, gas-solid separator 2, absorption tower 3 and raw material mixed cell 4,
Described tubular reactor 1 comprises at least one opening for feed, discharge port, body 13 and well heater, and opening for feed in described opening for feed and discharge port lay respectively at two ends of described body 13; Described well heater can be to described body heating, and described mixture flow enters in described body and carries out contact reacts from opening for feed, and the product after contact reacts is from discharge port is discharged described body.
Described well heater can be various well heaters, and according to the feature of different well heater itself, described well heater can be arranged on inside and/or the outside of body 13.Under preferable case, in the present invention, described well heater can be arranged on one or more in described body 13 outer walls and/or inner heat tape, steam jacket, spiral heater.
In order to control more accurately the temperature in tubular reactor, under preferable case, described well heater is heat tape, and described heat tape is many, meanwhile, body 13 is divided into multistage, at the outer wall of every section of body 13, is wound around respectively a heat tape.So just can be respectively at the inside of body 13 set temperature measuring apparatus, the actual temperature that the temperature requirement reacting according to aluminium-eliminating and silicon-replenishing and temperature measuring equipment record this section of body 13, by control, be wrapped in heat tape electric current and the voltage of every section of body 13 outer walls, realize the temperature in every section of body 13 is controlled.For example, the length of every section of body 13 can be 2-20 rice, is preferably 5-10 rice.
Described gas-solid separator 2 is communicated with described tubular reactor 1 by described discharge port, the top of described gas-solid separator 2 is communicated with described absorption tower 3, the position that the position that described gas-solid separator 2 is connected with discharge port is connected with described absorption tower 3 lower than described gas-solid separator 2.
Described raw material mixed cell 4 is for mixing different gas and/or by gas and solids mixing, described raw material mixed cell 4 is communicated with described tubular reactor 1 by one in described opening for feed.Described raw material mixed cell generally comprises gas-solid mixer and/or gas mixer.
Under optimum condition, the opening for feed of described tubular reactor is one, described raw material mixed cell 4 comprises gas-solid mixer and gas mixer, and gas mixer is communicated with gas-solid mixer, and gas-solid mixer is communicated with described tubular reactor 1 by the opening for feed of described tubular reactor 1.
Described gas mixer can be to well known to a person skilled in the art variously can realize the device that gas phase silicon tetrachloride mixes with carrier gas, for example, can be pipeline, is about to gas phase silicon tetrachloride and sends in pipeline and mix simultaneously with carrier gas.Described gas-solid mixer can be to well known to a person skilled in the art the various devices that gas phase silicon tetrachloride and/or carrier gas are mixed with molecular sieve that can be used in, for example described gas-solid mixer can be cylinder mixer, and this cylinder mixer comprises cylindrical body and is positioned at the grid of cylindrical body.Described grid is preferably along the axial of cylindrical body and is fixed on the stainless steel plate on cylindrical body inwall in spiralling mode, grid is that gas phase silicon tetrachloride and molecular sieve are uniformly dispersed and increase duration of contact of stock yard for making 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 (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 mixer are round tube type, and the cylinder of the two is structure as a whole.
The length of described tubular reactor 1 is to guarantee described molecular sieve and SiCl
4sufficient reacting, specifically can determine according to the requirement of aluminium-eliminating and silicon-replenishing reaction.What consider reaction fully carries out, reacts required power and production efficiency, the present inventor finds, the length of described tubular reactor is that 5-100 rice is preferably, therefore, the length of the preferred described tubular reactor of the present invention is 5-100 rice, more preferably 7-95 rice, is further preferably 50-95 rice.The diameter of described tubular reactor is preferably 0.01-1.5 rice, and more preferably 0.02-1.4 rice, is further preferably 0.1-1.4 rice.
Although the pipeline of straight line also can be realized molecular sieve and SiCl
4the sufficient reacting object of carrying out, but, under preferable case, for the molecular sieve in the gas-solid separator that prevents from causing in the unsettled situation of air-flow in tubular reactor flows back to the generation of the situation in tubular reactor, and further fully guarantee to realize more fully and contacting in shorter pipeline, as shown in Figure 2, described body 13 comprises the first tilting section 131 and vertical section 132, one end of one end of described the first tilting section 131 and described vertical section 132 joins, described discharge port is positioned at the other end of described the first tilting section 131, and described the first tilting section 131 and the position of described vertical section 132 position being connected higher than described discharge port place.Under this preferable case, the setting of described the first tilting section 131 can effectively prevent the generation of above-mentioned suck-back phenomenon, and described vertical section 132 make described tubular reactor be similar to riser reactor.In the present invention, described vertical section and nisi perpendicular to horizontal plane, as long as look like vertically upward by within the scope of this.
Described the first tilting section 131 and the vertically angle between section 132 can be 10-90 °, be preferably 30-80 °, when described vertical section 132 during perpendicular to horizontal plane, as shown in Figure 3, the axis of described the first tilting section 131 and the angle α between horizontal plane can be for being greater than 0 ° to 80 °, under preferable case, the axis of described the first tilting section 131 and the angle between horizontal plane are 10 ° to 60 °.Under this preferable case, can make molecular sieve and SiCl
4at the first tilting section 131, also can fully react, and unlikelyly enter fast in gas-solid separator 2 because of action of gravity.
The method according to this invention, under preferable case, described the first tilting section 131 and the vertically Length Ratio of section 132 are 0.1-10: 1,0.2-9 more preferably: 1, preferred 0.4-0.6 further: 1.
A preferred embodiment of the invention, described body 13 also comprises the second tilting section 133, and the other end of one end of described the second tilting section 133 and described vertical section 132 joins, and described opening for feed is positioned at the other end of described the second tilting section 133.Can avoid like this velocity of flow of molecular sieve solid material under the effect of gravity too fast, increase the contact reacts time between reaction mass.
Further under preferable case, the position at described opening for feed place is higher than described the second tilting section 133 and described vertical section 132 position being connected, so that molecular sieve solid material can dependence itself action of gravity directly enter in the second tilting section 133, then can further conveying under the carrying of carrier gas.
Described the second tilting section 133 and the vertically angle between section 132 can be 10-90 °, be preferably 30-80 °, when described vertical section 132 during perpendicular to horizontal plane, as shown in Figure 4, according to the present invention, the axis of described the second tilting section 133 and the angle β between horizontal plane can, for being greater than 0 ° to 80 °, be preferably 10 ° to 60 °.Under this preferable case, can make molecular sieve and SiCl
4at the first tilting section 131, also can fully react, and unlikelyly enter fast the end of vertical section 132 because of action of gravity.
Further, under preferable case, described the second tilting section 133 and the vertically Length Ratio of section 132 are 0.1-10: 1, and 0.2-9 more preferably: 1, be further preferably 0.3-9: 1.
According to method provided by the invention, products therefrom after contact is carried out to gas solid separation, obtain solid high-silica zeolite product and gaseous fraction.
As shown in Figure 2, described gas solid separation is preferably carried out in gas-solid separator 2, and described gas-solid separator generally comprises opening for feed and top gas outlet.The other end of described the first tilting section is communicated with described gas-solid separator, and the sectional area of described gas-solid separator is greater than the cross-sectional area of described tubular reactor body.By making the sectional area of described gas-solid separator be greater than the cross-sectional area of described tubular reactor body, can realize and make to be originally suspended in SiCl
4air-flow or SiCl
4the sedimentation of molecular sieve in the mixed airflow of air-flow and carrier gas stream under action of gravity, thus realize gas solid separation.Further preferable case, the sectional area of described gas-solid separator is 2-10 with the ratio of the cross-sectional area of described tubular reactor body: 1, can fully realize like this rapid subsidence of molecular sieve.In order further to guarantee that molecular sieve is fully deposited in gas-solid separator, the present invention also height of preferred described gas-solid separator is not less than 5 meters, for example 5-10 rice.Further, under preferable case, the opening for feed of described gas-solid separator is positioned at the middle part of described gas-solid separator, can guarantee so on the one hand to being deposited in the molecular sieve of gas-solid separator bottom, not produce stirring, can also guarantee the more sufficient settling time on the other hand.
Further, under preferable case, described gas-solid separator also comprises bottom solid outlet, the molecular sieve solid obtaining for discharging separation.Further, under preferable case, described gas-solid separator also comprises the valve of opening and closing for controlling described bottom solid outlet, thus can be in good time the molecular sieve solid collected in gas-solid separator is discharged.
The various containers that can realize above-mentioned purpose all can be used as gas-solid separator 2 of the present invention, and the present invention, for example can be for cylindric to its shape can there is no particular limitation.Further, under preferable case, the bottom of described gas-solid separator 2 is the taper that end has opening.Thereby the high-silica zeolite obtaining can be discharged from described opening.
In order to make the gaseous fraction in reacted mixture enter as far as possible absorption tower and not discharge from above-mentioned opening, under preferable case, the position that described gas-solid separator 2 is connected with discharge port is higher than the zero position of described taper.Further, under preferable case, the position that described gas-solid separator 2 is connected with discharge port is positioned at the middle and upper part of described gas-solid separator 2, and gas-solid separator 2 is communicated with the absorption tower 3 that below will describe by its open top.
Due to molecular sieve and SiCl
4contact reacts in, common SiCl
4have part excessive, therefore, in order to prevent SiCl
4environmental pollution, under preferable case, the method also comprises described gaseous fraction is contacted with absorption agent, to remove the SiCl in gaseous fraction
4.
As shown in Figure 2, described absorption is preferably carried out in absorption tower, and absorption agent is contained in described absorption tower, for absorbing excessive unreacted SiCl
4thereby, make air reach emission standard.Described absorption tower 3 can be conventional various absorption towers of using, this area, as long as can absorb SiCl
4.The general alkali lye that uses absorbs SiCl as aqueous sodium hydroxide solution
4.Therefore, in the present invention, described absorption tower 3 comprises an entrance and two outlets, and described entrance is communicated with gas-solid separator 2, is preferably placed at the middle and upper part on described absorption tower.Described two outlets lay respectively at top and the bottom on described absorption tower, are respectively used to discharged air and absorb waste liquid.For SiCl in the air that guarantees to discharge
4content is enough low, and under preferable case, described absorption tower is a plurality of for series connection.A plurality of absorption towers of series connection are to SiCl
4form multistage absorption.
According to the preferred embodiment of the present invention, adopt workflow that method of the present invention prepares high-silica zeolite as shown in Figure 2.Temperature is molecular sieve a, carrier gas c and the gas phase SiCl of 200-600 ℃
4after raw material b mixes in raw material mixed cell 4, from the opening for feed of tubular reactor, send in tubular reactor 1, molecular sieve is with inert carrier gas and gas phase SiCl
4mixed gas in the interior mobile contact of tubular reactor 1, enter afterwards gas-solid separator 2, in gas-solid separator 2, high-silica zeolite d is deposited in the bottom of gas-solid separator 2, directly or regularly discharges.Inert carrier gas and gas phase SiCl
4the outlet by gas-solid separator 2 tops enters in absorption tower 3, contacts with the absorption agent alkali lye in absorption tower 3, and carrier gas (tail gas e) is overflowed from alkali lye, and from absorption tower, the outlet at 3 tops is discharged, SiCl
4, with alkaline reaction, by outlet at bottom, directly or regularly discharge waste water f afterwards.
In the present invention, described molecular sieve can be the various molecular sieves that need aluminium-eliminating and silicon-replenishing, for example, can be the Y zeolite of different content of rare earth, with RE
2o
3meter, described Y zeolite Rare-Earth Content can be 10-20 % by weight.
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1-5 is for illustrating the method for preparing the equipment of molecular sieve and preparing molecular sieve provided by the invention.
Used thickness is the industrial trade mark of the 3 millimeters equipment of preparing molecular sieve shown in stainless steel construction drawing 2 that is NiCr18Ti, wherein the body 13 of tubular reactor 1 is by the first tilting section 131, vertically section the 132 and second tilting section 133 forms, the length of the first tilting section 131 is 20 meters, diameter is 0.8 meter, vertically the length of section 132 is 40 meters, diameter is 0.8 meter, the length of the second tilting section 133 is 15 meters, diameter is 0.8 meter, vertically section 132 is perpendicular to horizontal plane, the axis of the first tilting section 131 and the angle α between horizontal plane are 75 ° (the angle between the first tilting section 131 and vertical section 132 is 15 °), the axis of the second tilting section 133 and the angle β between horizontal plane are 65 ° (the angle between the second tilting section 133 and vertical section 132 is 25 °), the port of the second tilting section 133 is opening for feed, the top of gas-solid separator 2 is that diameter is 6 meters, height is 14 meters cylindrical, bottom is for having opening taper, cone angle is 45 °, and opening part is provided with valve, discharge port is positioned at apart from gas-solid separator top the position of 1 meter, in absorption tower 3, fill the aqueous sodium hydroxide solution that concentration is 10 mol/L, between absorption tower 3 and gas-solid separator 2, by conduit, connect, conduit gos deep in aqueous sodium hydroxide solution, raw material mixed cell 4 comprises that length is 5 meters, diameter is the cylinder mixer of 0.8 meter, one end of cylinder mixer is communicated with opening for feed, the axial position apart from 2.5 meters of opening for feeds along cylinder mixer is provided with molecular sieve entrance, this cylindrical section mixer inner walls from this molecular sieve entrance to opening for feed 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 portions thus, first part is as gas mixer, second section is provided with flase floor, thereby as gas-solid mixer.
Shown in Fig. 2, by temperature, be the SiCl that the dry air of 100 ℃ and temperature are 90 ℃
4after gas is sent into gas mixer in raw material mixed cell 4 and is mixed, enter with molecular sieve entrance from pipeline, the Y zeolite (character is as shown in table 1) containing rare earth that is 600 ℃ from the temperature of stoving oven is by opening for feed, to be sent into continuously in the body 13 of tubular reactor 1 after mixing in gas-solid mixer in being provided with the pipeline of grid, the body of tubular reactor 13 is divided into 15 sections simultaneously, 5 meters of every segment lengths, outer wall on every section of body is wound around a heat tape tubular reactor is heated, make the temperature of tubular reactor 1 interior each several part be 400 ℃, the SiCl of incoming stock mixed cell 4
4controlled and SiCl by mass flowmeter 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 mixed gas makes the residence time of molecular sieve in tubular reactor 1.Reaction was carried out after 1 hour, and the molecular sieve in gas-solid separator 2 is discharged from the opening of conical lower portion, after pulling an oar, wash, filter afterwards and drying in 120 ℃ of baking ovens, obtained high-silica zeolite A with decationized Y sieve water, and its main character is listed in table 2.
Used thickness is the industrial trade mark of the 3 millimeters equipment of preparing molecular sieve shown in stainless steel construction drawing 2 that is NiCr18Ti, wherein the body 13 of tubular reactor 1 is by the first tilting section 131, vertically section the 132 and second tilting section 133 forms, the length of the first tilting section 131 is 20 meters, diameter is 0.4 meter, vertically the length of section 132 is 50 meters, diameter is 0.4 meter, the length of the second tilting section 133 is 20 meters, diameter is 0.4 meter, vertically section 132 is perpendicular to horizontal plane, the axis of the first tilting section 131 and the angle α between horizontal plane are 55 ° (the angle between the first tilting section 131 and vertical section 132 is 35 °), the axis of the second tilting section 133 and the angle β between horizontal plane are 55 ° (the angle between the second tilting section 133 and vertical section 132 is 35 °), the port of the second tilting section 133 is opening for feed, the top of gas-solid separator 2 is that diameter is 5 meters, height is 10 meters cylindrical, bottom is for having opening taper, cone angle is 35 °, and opening part is provided with valve, discharge port is positioned at apart from gas-solid separator top the position of 2 meters, in absorption tower 3, fill the aqueous sodium hydroxide solution that concentration is 1 mol/L, between absorption tower 3 and gas-solid separator 2, by conduit, connect, conduit gos deep in aqueous sodium hydroxide solution, raw material mixed cell 4 comprises that length is 5 meters, diameter is the cylinder mixer of 0.8 meter, one end of cylinder mixer is communicated with opening for feed, the axial position apart from 2.5 meters of opening for feeds along cylinder mixer is provided with molecular sieve entrance, this cylindrical section mixer inner walls from this molecular sieve entrance to opening for feed 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 portions thus, first part is as gas mixer, second section is provided with flase floor, thereby as gas-solid mixer.
Shown in Fig. 2, by temperature, be the SiCl that the dry air of 200 ℃ and temperature are 130 ℃
4after gas is sent into gas mixer in raw material mixed cell 4 and is mixed, enter with molecular sieve entrance from pipeline, the Y zeolite (character is as shown in table 1) containing rare earth that is 500 ℃ from the temperature of stoving oven is by opening for feed, to be sent into continuously in the body 13 of tubular reactor 1 after mixing in gas-solid mixer in being provided with the pipeline of grid, the body of tubular reactor 13 is divided into 9 sections simultaneously, 10 meters of every segment lengths, outer wall on every section of body is wound around a heat tape tubular reactor is heated, make the temperature of tubular reactor 1 interior each several part be 500 ℃, the SiCl of incoming stock mixed cell 4
4controlled and SiCl by mass flowmeter 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 mixed gas makes the residence time of molecular sieve in tubular reactor.Reaction was carried out after 2 hours, and the molecular sieve in gas-solid separator 2 is discharged from the opening of conical lower portion, after pulling an oar, wash, filter afterwards and drying in 120 ℃ of baking ovens, obtained high-silica zeolite B with decationized Y sieve water, and its main character is listed in table 2.
Used thickness is that the industrial trade mark of 3 millimeters is NiCr18Ti the molecular sieve gas phase shown in stainless steel construction drawing 2 is mended silicon equipment, wherein the body 13 of tubular reactor 1 is by the first tilting section 131, vertically section the 132 and second tilting section 133 forms, the length of the first tilting section 131 is 15 meters, diameter is 1.2 meters, vertically the length of section 132 is 35 meters, diameter is 1.2 meters, the length of the second tilting section 133 is 30 meters, diameter is 1.2 meters, vertically section 132 is perpendicular to horizontal plane, the axis of the first tilting section 131 and the angle α between horizontal plane are 45 ° (the angle between the first tilting section 131 and vertical section 132 is 45 °), the axis of the second tilting section 133 and the angle β between horizontal plane are 45 ° (the angle between the second tilting section 133 and vertical section 132 is 45 °), the port of the second tilting section 133 is opening for feed, the top of gas-solid separator 2 is that diameter is 9 meters, height is 12 meters cylindrical, bottom is for having opening taper, cone angle is 30 °, and opening part is provided with valve, discharge port is positioned at apart from gas-solid separator top the position of 4 meters, in absorption tower 3, fill the aqueous sodium hydroxide solution that concentration is 1 mol/L, between absorption tower 3 and gas-solid separator 2, by conduit, connect, conduit gos deep in aqueous sodium hydroxide solution, raw material mixed cell 4 comprises that length is 5 meters, diameter is the cylinder mixer of 0.8 meter, one end of cylinder mixer is communicated with opening for feed, the axial position apart from 2.5 meters of opening for feeds along cylinder mixer is provided with molecular sieve entrance, this cylindrical section mixer inner walls from this molecular sieve entrance to opening for feed 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 portions thus, first part is as gas mixer, second section is provided with flase floor, thereby as gas-solid mixer.
Shown in Fig. 2, by temperature, be the SiCl that the dry air of 140 ℃ and temperature are 80 ℃
4after gas is sent into gas mixer in raw material mixed cell 4 and is mixed, enter with molecular sieve entrance from pipeline, the Y zeolite (character is as shown in table 1) containing rare earth that is 300 ℃ from the temperature of stoving oven is by opening for feed, to be sent into continuously in the body 13 of tubular reactor 1 after mixing in gas-solid mixer in being provided with the pipeline of grid, the body of tubular reactor 13 is divided into 16 sections simultaneously, 5 meters of every segment lengths, outer wall on every section of body is wound around a heat tape tubular reactor is heated, make the temperature of tubular reactor 1 interior each several part be 300 ℃, the SiCl of incoming stock mixed cell 4
4controlled and SiCl by mass flowmeter 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 residence time of molecular sieve in tubular reactor.Reaction was carried out after 1 hour, and the molecular sieve in gas-solid separator 2 is discharged from the opening of conical lower portion, after pulling an oar, wash, filter afterwards and drying in 120 ℃ of baking ovens, obtained high-silica zeolite C with decationized Y sieve water, and its main character is listed in table 2.
Method according to embodiment 3 is prepared high-silica zeolite, different is, the length of tubular reactor 1 is 25 meters, wherein the length of the first tilting section 131 is 5 meters, diameter is 1.2 meters, vertically the length of section 132 is 10 meters, diameter is 1.2 meters, the length of the second tilting section 133 is 10 meters, diameter is 1.2 meters, the body of tubular reactor 13 is divided into 5 sections simultaneously, 5 meters of every segment lengths, outer wall on every section of body is wound around a heat tape tubular reactor is heated, make the temperature of tubular reactor 1 interior each several part be 300 ℃, the inlet amount of molecular sieve is 1000kg/ hour, it was 30 seconds that the flow of dry air makes the residence time of molecular sieve in tubular reactor, obtain high-silica zeolite D, its main character is listed in table 2.
Method according to embodiment 3 is prepared high-silica zeolite, different, and it is 40 minutes that the flow of mixed gas makes the residence time of molecular sieve in tubular reactor, obtains high-silica zeolite E, and its main character is listed in table 2.
Table 1
| Y zeolite containing | Embodiment | 1 | |
|
| Lattice constant, nm | 2.466 | 2.466 | 2.466 | |
| Relative crystallinity, % | 54 | 52 | 49 | |
| Framework si-al ratio (SiO 2/Al 2O 3Mol ratio) | 5.11 | 5.11 | 5.11 | |
| Lattice avalanche temperature, ℃ | 975 | 972 | 970 | |
| Specific surface area, m 2/g | 673 | 665 | 648 | |
| Na 2O content, % by weight | 4.5 | 4.4 | 4.1 | |
| RE 2O 3Content, % by weight | 11.9 | 13.2 | 16.3 |
Table 2
From the results shown in Table 2, compare with industrial REY, adopting the framework si-al ratio of the molecular sieve that method of the present invention makes is SiO
2/ Al
2o
3mol ratio improves greatly, shows that dealumination complement silicon is effective.In addition, from the results shown in Table 2, compare with industrial REY, adopt relative crystallinity, lattice avalanche temperature and the specific surface area of the molecular sieve that method of the present invention makes obviously to improve, sodium oxide content obviously reduces, and shows the excellent performance of the molecular sieve that method of the present invention makes.
Embodiment 6-10 is for illustrating the high-silica zeolite Kaolinite Preparation of Catalyst that adopts embodiment 1-5 to make.
According to (material butt) molecular sieve: kaolin: pseudo-boehmite: aluminium colloidal sol=38: the part by weight of 30: 22: 10 is by above-mentioned mixing of materials, making beating, and then at 450 ℃, spraying is dry, obtains spherical catalytic cracking catalyst.High-silica zeolite A, B, C, D and E that molecular sieve selects respectively embodiment 1-5 to make, obtain respectively catalyst A-1, A-2, A-3, A-4, A-5, and its main character is listed in table 3.
Comparative example 1
Adopt according to the method described above industrial REY type molecular sieve (main character is listed in table 2) Kaolinite Preparation of Catalyst, gained catalyzer is counted reference catalyst CC-1, and its main character is listed in table 3.
The Catalytic Cracking Performance test of catalyzer
Light oil microactivity is evaluated: adopt the standard method of RIPP92-90 (to see the volumes such as < < Petrochemical Engineering Analysis method > > (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publication) light oil microactivity of assess sample, catalyzer loading amount is 5.0g, temperature of reaction is 460 ℃, stock oil is the huge port solar oil of boiling range 235-337 ℃, product composition is by gas chromatographic analysis, according to product composition, calculate light oil microactivity, result is in table 3.
Light oil microactivity (the MA)=gasoline output+gas yield+coke output of 216 ℃ (in the product lower than)/charging total amount * 100%
Heavy oil cracking performance evaluation condition: catalyzer is first at 800 ℃, 100% steam aging 12 hours is then evaluated on ACE (fixed fluidized bed) device, and stock oil is military mixed three heavy oil (character is in Table 4), 500 ℃ of temperature of reaction, agent weight of oil ratio is 4.
Wherein, transformation efficiency=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/transformation efficiency
The Catalytic Cracking Performance of the catalyzer that respectively prepared by Evaluation operation example 6-10 and comparative example 1 according to the method described above, the results are shown in table 5.
Table 3
From the results shown in Table 3, adopt pore volume and the specific surface area of the catalyzer of being prepared by method of the present invention obviously to increase, micro-activity obviously improves.
Table 4
Table 5
| Catalyzer | A-1 | A-2 | A-3 | A-4 | A-5 | CC-1 |
| Product distributes, % by 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 |
| Transformation efficiency, % by weight | 74.91 | 76.96 | 75 | 73.74 | 73.04 | 67.16 |
| Coke selectivity, % by weight | 6.55 | 6.30 | 6.68 | 6.93 | 7.05 | 8.56 |
| Yield of light oil, % by weight | 73.38 | 74.34 | 73.57 | 71.14 | 70.44 | 67.08 |
| Liquid yield, % by weight | 86.57 | 88.03 | 86.65 | 85.43 | 84.89 | 80.09 |
From the results shown in Table 5, CC-1 compares with reference catalyst, and adopting the molecular sieve being made by method of the present invention is that catalyzer prepared by active ingredient has higher transformation efficiency, higher liquid yield and yield of light oil, lower coke selectivity.
Claims (15)
1. a preparation method for molecular sieve, is characterized in that, the method comprises molecular sieve and contains gas phase SiCl
4gas be mixed to form mixture flow, described in contain gas phase SiCl
4gas be gas phase SiCl
4or gas phase SiCl
4with the mixed gas of inert carrier gas, the molecular sieve in mixture flow is with gas flow, and with gas in gas phase SiCl
4under flow state, contact molecular sieve and gas phase SiCl
4duration of contact be 10 seconds to 100 minutes, and in contact process to molecular sieve and gas phase SiCl
4heating, so that molecular sieve and gas phase SiCl
4the temperature of contact is 250-700 ℃, and wherein, the molecular sieve in described mixture flow is 0.015-3m/s with the flow velocity of gas flow, and the inlet amount of described molecular sieve is 50-2000 kg/hr;
Described contact is carried out in tubular reactor, the method for described formation mixture flow by molecular sieve with contain SiCl
4gas first by a raw material mixed cell, mix before entering the contact of described tubular reactor; Described tubular reactor comprises well heater, body and is positioned at opening for feed and the discharge port at body two ends, described well heater can be to described body heating, described mixture flow enters in described body and carries out contact reacts from opening for feed, and the product after contact reacts is from discharge port is discharged described body; Described body comprises the first tilting section and vertical section, one end of one end of described the first tilting section and described vertical section joins, described discharge port is positioned at the other end of described the first tilting section, and described the first tilting section and the position of the described vertical section of position being connected higher than described discharge port place; Described body also comprises the second tilting section, and the other end of one end of described the second tilting section and described vertical section joins, and described opening for feed is positioned at the other end of described the second tilting section; The position at described opening for feed place is higher than described the second tilting section and the described vertical section of position being connected; Wherein, the length of tubular reactor is 5-100 rice, and diameter is 0.01-1.5 rice; Described the first tilting section and the vertically angle between section are for being greater than 10 ° to being less than or equal to 90 °, and described the first tilting section and the vertically Length Ratio of section are 0.1-10:1; Described the second tilting section and the vertically angle between section are for being greater than 10 ° to being less than or equal to 90 °, and described the second tilting section and the vertically Length Ratio of section are 0.1-10:1.
2. method according to claim 1, wherein, described molecular sieve and gas phase SiCl
4contact Temperature be 300-650 ℃.
3. method according to claim 1, wherein, described in contain gas phase SiCl
4gas be gas phase SiCl
4mixed gas with inert carrier gas.
4. method according to claim 1, wherein, described gas phase SiCl
4with the weight ratio of molecular sieve be 0.01-1:1.
5. method according to claim 4, wherein, described gas phase SiCl
4with the weight ratio of molecular sieve be 0.05-0.60:1, the inlet amount of described molecular sieve is 100-1500 kg/hr.
6. according to the method described in any one in claim 1,4 and 5, wherein, the temperature of described molecular sieve is 200-600 ℃, described gas phase SiCl
4temperature be 60-150 ℃, the temperature of described inert carrier gas is 50-350 ℃.
7. method according to claim 1, wherein, described raw material mixed cell comprises gas-solid mixer and/or gas mixer.
8. method according to claim 7, wherein, described opening for feed is one, and described raw material mixed cell comprises gas-solid mixer and gas mixer, gas mixer is communicated with gas-solid mixer, and gas-solid mixer is communicated with described tubular reactor by one in described opening for feed.
9. method according to claim 1, wherein, described well heater is to be arranged on one or more in described tube wall and/or inner heat tape, steam jacket, spiral heater.
10. method according to claim 9, wherein, described well heater is heat tape, and described heat tape is many, and body is divided into multistage, at the outer wall of every section of body, is wound around respectively a heat tape.
11. methods according to claim 10, wherein, the length of every section of body is 2-20 rice.
12. methods according to claim 1, wherein, described the first tilting section and the vertically angle between section are 30 ° to 80 °.
13. methods according to claim 1, wherein, described the second tilting section and the vertically angle between section are 30 ° to 80 °.
14. methods according to claim 1, wherein, the method also comprises carries out gas solid separation by products therefrom after contact, obtains solid high-silica zeolite product and gaseous fraction.
15. methods according to claim 14, wherein, the method also comprises described gaseous fraction is contacted with absorption agent, to remove the SiCl in gaseous fraction
4.
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| CN1683244A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | Gas phase aluminium extracting and silicon supplementing method of molecular sieve |
| CN101081369A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Y type zeolites containing rare-earth and high content of silicon and method of making the same |
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| CN1683244A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | Gas phase aluminium extracting and silicon supplementing method of molecular sieve |
| CN101081369A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Y type zeolites containing rare-earth and high content of silicon and method of making the same |
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