CN102452660B - Method for preparing molecular sieve - Google Patents
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- CN102452660B CN102452660B CN 201010515219 CN201010515219A CN102452660B CN 102452660 B CN102452660 B CN 102452660B CN 201010515219 CN201010515219 CN 201010515219 CN 201010515219 A CN201010515219 A CN 201010515219A CN 102452660 B CN102452660 B CN 102452660B
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Abstract
The invention discloses a method for preparing a molecular sieve. The method for preparing a molecular sieve comprises the following steps that a molecular sieve and SiCl4 gas phase-containing gas are mixed into a mixture flow; wherein the SiCl4 gas phase-containing gas is SiCl4 gas or a mixed gas of SiCl4 gas and inert carrier gas; and the molecular sieve of the mixture flow flows with the SiCl4 gas phase-containing gas and contacts with the SiCl4 gas in the SiCl4 gas phase-containing gas in a flowing state, wherein the contact time is in a range of 10 seconds to 100 minutes. The method for preparing a molecular sieve realizes a continuous contact reaction of a molecular sieve and SiCl4. The method for preparing a molecular sieve also realizes that through control of a mixed gas flow rate and tubular reactor length, the time of the contact between a molecular sieve and SiCl4 is controlled so that the molecular sieve and SiCl4 undergo a full reaction in a tubular reactor.
Description
Technical field
The invention relates to a kind of method for preparing 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, generally to be 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 the chemical method aluminium-eliminating and silicon-replenishing) is mainly to use the 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 formed in dealumination process
3affect hydrothermal stability with residual silicofluoride, also pollute the environment.
Hydrothermal method is still the at present industrial method generally adopted, but mend silicon not in time have 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 characteristics of gas chemistry method aluminium-eliminating and silicon-replenishing are that dealuminzation is even, mend 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 the 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, the particle that in described drying and moulding thing, particle diameter is the 35-125 micron accounts for 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, 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, under temperature 150-600 ℃, react 10 minutes to 6 hours, after reaction, with dry air, purge 5 minutes to 2 hours, with the decationized Y sieve water washing, remove Na remaining in zeolite
+, Cl
-, Al
3+etc. the solubility by product.The 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.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), also comprise an agitator (4) in the inside of reactor (1), 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 the 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, avoided the phenomenon that is agglomerated into the compact mass thing between the molecular sieve solid particle, can reduce labour intensity, the energy environmental contamination reduction, 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 the reaction before charging 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 reactor of the maximum that can react for above-mentioned dealumination complement silicon is 600kg, continue the 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, the high silicon content for the molecular sieve that guarantees to obtain, 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 need long scavenging line etc. after reaction completes, 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 existed for the super steady technique of the gas phase of autoclave, the objective of the invention is to develop and a kind ofly can reduce SiCl
4consumption, the method for preparing molecular sieve that is applicable to the serialization suitability for industrialized production that reduces labour intensity and greatly enhance productivity.
The invention provides a kind of method for preparing molecular sieve, wherein, the method comprises molecular sieve and contains gas phase SiCl
4gas be mixed to form mixture flow, the described gas phase SiCl that contains
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 gas phase SiCl
4contact molecular sieve and gas phase SiCl under flow state
4duration of contact be 10 seconds to 100 minutes.
The method for preparing molecular sieve provided by the invention by molecular sieve with contain SiCl
4with the mixed gas of inert carrier gas, from the opening for feed of tubular reactor, send in tubular reactor, in tubular reactor, fully the laggard promoting the circulation of qi of reaction separates admittedly, solid is required high-silica zeolite, and gaseous component enters absorption tower, sponges a small amount of excessive SiCl
4after air can directly discharge.As can be seen here, the method for preparing the method for high-silica zeolite provided by the invention can realize molecular sieve and SiCl
4contact reacts carry out continuously, the flow velocity by controlling mixed 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 in tubular reactor, carry out fully.The present invention is by making molecular sieve and containing gas phase SiCl
4gas uniform react again after mixing, 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.
With the super steady technique of existing autoclave gas phase, compare, the method for preparing molecular sieve provided by the invention can realize the super steady reaction of serialization gas phase, and operation can all automatization serializations carries out, hand labor intensity is little, and production efficiency is high, product performance are stable, make the suitability for industrialized production of the super steady technique 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 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, 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, as can be seen here, the economic benefit for preparing the method for molecular sieve provided by the invention is very significant.
The accompanying drawing explanation
The structural representation of the equipment of the method for the preparation of high-silica zeolite that Fig. 1 is prior art;
The schematic diagram that Fig. 2 is the equipment used of the method for the preparation of molecular sieve that the present invention relates to;
The axis of the first tilting section 131 of the tubular reactor 1 that Fig. 3 is Fig. 2 apparatus shown and the schematic diagram of the angle α between horizontal plane;
The axis of the second tilting section 133 of the tubular reactor 1 that Fig. 4 is Fig. 2 apparatus shown and the schematic diagram of the angle β between horizontal plane.
Embodiment
According to the method for preparing molecular sieve provided by the invention, can be directly the gas phase silicon tetrachloride be reacted with sending in reactor after molecular sieve mixes; Can by rare gas element, be first also that carrier gas mixes with the gas phase silicon tetrachloride, form mixed gas, then this mixed gas is carried out to contact reacts with sending in reactor after molecular sieve mixes; Also can first rare gas element be mixed with molecular sieve, molecular sieve is mixed with the gas phase silicon tetrachloride with flow state under the drive of rare gas element; Can also be simultaneously by rare gas element, molecular sieve with after the gas phase silicon tetrachloride mixes together with send in reactor and reacted.Under preferable case, by rare gas element, be first that carrier gas mixes with the gas phase silicon tetrachloride, form mixed gas, then this mixed gas is carried out to contact reacts with sending in reactor after molecular sieve mixes.
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, 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 of molecular sieve=100%-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, the flow velocity of mixed gas makes SiCl
4the residence time with molecular sieve in reactor is to be duration of contact 10 seconds to 100 minutes, is preferably 1 minute to 20 minutes.In mixture flow, the flow velocity of molecular sieve is preferably 0.015-3m/s, more preferably 0.03-3m/s, more preferably 0.1-2.5m/s.With respect to diameter, be the tubular reactor that 0.01-1.5 rice, length are 50-95 rice, the flow of molecular sieve is preferably 50-2000kg/ hour, and more preferably 100-1500kg/ hour, further be preferably 200-1200kg/ hour.Under these conditions, molecular sieve and gas phase SiCl both can have been guaranteed
4by reactor, can guarantee again molecular sieve and gas phase SiCl with continuous airflow pattern
4contact can fully carry out.From above-mentioned gas phase SiCl
4can find out with the numerical value of the weight ratio of molecular sieve, adopt method provided by the invention can greatly reduce gas phase SiCl
4consumption.
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 preferable case, can be at molecular sieve and gas phase SiCl in order to make reaction
4after contact, carry out fast, the temperature of the preferred described molecular sieve of the present invention is 200-600 ℃, gas phase SiCl
4temperature be 60-150 ℃, carrier gas is 60-200 ℃ as the temperature of air.Under these conditions, without reactor is arranged separately to well heater, can guarantee that the temperature in reactor meets molecular sieve and gas phase SiCl
4catalytic needs.Because the temperature of the molecular sieve after roasting is generally more than 300 ℃, therefore the temperature of above-mentioned molecular sieve can be by combining reactor to obtain with 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 thermal source of the high temperature of molecular sieve after roasting as the dealumination complement silicon reaction, start the 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.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 is difficult to ensure comparatively speaking fully carrying out of card dealumination complement silicon reaction.
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 get final product, 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, the method for preparing molecular sieve described in the present invention is carried out in the equipment shown in Fig. 2, and 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 and body 13, and opening for feed in described opening for feed and discharge port lay respectively at two ends of described body 13;
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 mixes for the gas by different 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.
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 the duration of contact that provides longer, but pipeline is longer, the required power of the raw materials such as required delivery of molecules sieve and gas is larger, requirement to device that power is provided accordingly is also just higher, and, reaction times is oversize, easily causes the degree of crystallinity of molecular sieve to reduce.Therefore, what consider reaction fully carries out, reacts required power and production efficiency, the present inventor finds, the length of described tubular reactor 1 is that 5-100 rice is preferably, 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 be 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 be 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 preferable case, for the molecular sieve in the gas-solid separator 2 that prevents from causing in the unsettled situation of the interior air-flow of tubular reactor 1 flows back to the generation of the situation in tubular reactor 1, and further fully guarantee in shorter pipeline, to realize contacting more fully, as shown in Figure 2, described body 13 comprises the first tilting section 131 and vertical section 132, one end of described the first tilting section 131 and an end of described vertical section 132 join, 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 be 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 this scope.
Angle between described the first tilting section 131 and vertical 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
4also can fully be reacted at the first tilting section 131, and unlikelyly be entered fast in gas-solid separator 2 because of action of gravity.
According to the present invention, under preferable case, described the first tilting section 131 and vertically the Length Ratio of section 132 be 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 an end of described the second tilting section 133 and the other end of described vertical section 132 join, and described the first opening for feed is positioned at the other end of described the second tilting section 133.Arrange like this and can avoid the 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,, higher than described the second tilting section 133 and described vertical section 132 position be connected, so that material can fast, directly enter in the second tilting section 133, then further carry the position at described opening for feed place.
Angle between described the second tilting section 133 and vertical 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 equipment provided by the 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
4also can fully be reacted at the first tilting section 131, and unlikelyly be entered fast the end of vertical section 132 because of action of gravity.
Further under preferable case, described the second tilting section 133 and vertically the Length Ratio of section 132 be 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 mixer and/or gas mixer, and described gas-solid mixer and/or gas mixer are communicated with described tubular reactor 1 by one in described opening for feed.
When described raw material mixed cell only comprises gas mixer and does not comprise gas-solid mixer, while producing continuously for the ease of industrialization with the coordinating of other devices, described tubular reactor 1 preferably includes two opening for feeds, one of them opening for feed port that the first opening for feed is tubular reactor 1, another opening for feed is positioned at the position adjacent with described the first opening for feed.Wherein any one in two opening for feeds is communicated with this gas-solid mixer, and another opening for feed is communicated with molecular sieve feeding unit (not shown).During use, described carrier gas air and gas phase SiCl
4after mixing in gas mixer, enter the body 13 of described tubular reactor 1 by the opening for feed be communicated with described gas mixer, molecular sieve enters the body 13 of described tubular reactor 1 from another opening for feed, thereby is reacted in the body 13 of tubular reactor 1.Described molecular sieve feeding unit is preferably stoving oven, that is to say, another opening for feed for preparing the equipment of molecular sieve of the present invention is communicated with stoving oven usually.In order effectively to utilize the length of tubular reactor, preferably the first opening for feed and the second opening for feed are as far as possible close, but simultaneously also as far as possible little for the interference between the charging that guarantees two opening for feeds, preferably the distance between described the first opening for feed and described the second opening for feed is the 0.5-15% of the length of described tubular reactor 1, more preferably 1-10%.
Further under preferable case, described opening for feed 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 one in described opening for feed.Described carrier gas air and gas phase SiCl
4after mixing in the gas mixer of raw material mixed cell 4, enter gas-solid mixer and molecular sieve and carry out gas-solid mixing, enter in tubular reactor 1 by opening for feed after mixing.
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, is about to the gas phase silicon tetrachloride and sends in pipeline and mixed 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 the 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 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 mixer are round tube type, and the cylinder of the two is structure as a whole.
In the present invention, described gas-solid separator 2 is for collecting and SiCl
4molecular sieve after the gas contact.In this gas-solid separator, solid molecular sieves is separated with gas, thereby obtained the high-silica zeolite product.Variously can realize that the container of above-mentioned purpose all can be used as gas-solid separator 2 of the present invention, 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 obtained 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 tubular reactor 1 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 tubular reactor 1 discharge port 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 for absorbing excessive unreacted SiCl
4thereby, make gas-solid separator gas out reach emission standard.Described absorption tower 3 can be conventional various absorption towers of using, this area, as long as can absorb SiCl
4get final product.The general alkali lye that uses absorbs SiCl as aqueous sodium hydroxide solution
4.Therefore, in 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 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 used to emission gases (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.
In the present invention, described carrier gas can be various at gas phase SiCl
4the gas that is inertia under the condition of reacting with molecular sieve, i.e. described carrier gas can be the various gas phase SiCl that do not disturb
4the gas reacted in tubular reactor with molecular sieve can be for example one or more in air, nitrogen, helium, neon, argon gas and xenon.
According to method provided by the invention, under preferable case, the method also comprises carries out gas solid separation by products therefrom after contact, obtains solid 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.Be greater than the cross-sectional area of described tubular reactor body by the sectional area that makes described gas-solid separator, can realize making originally being 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 fully is 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 the molecular sieve that is deposited in the gas-solid separator bottom not to be produced and stirs, and can also guarantee the more sufficient settling time on the other hand.
Further, under preferable case, described gas-solid separator also comprises the bottom solid outlet, for discharging, separates the molecular sieve solid obtained.Further, under preferable case, described gas-solid separator also comprises the valve of opening and closing for controlling described bottom solid outlet, thereby the molecular sieve solid by collecting in gas-solid separator that can be in good time is discharged.
Variously can realize that the container of above-mentioned purpose all can be used as gas-solid separator 2 of the present invention, 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 obtained 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 hereinafter 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
4get final product.The general alkali lye that uses absorbs SiCl as aqueous sodium hydroxide solution
4.Therefore, in 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 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 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, the process flow sheet that bonding apparatus is described the method for preparing high-silica zeolite provided by the invention as shown in Figure 2.The molecular sieve a that temperature is 200-600 ℃, carrier gas c and gas phase SiCl
4after raw material b mixes in raw material mixed cell 4, from opening for feed, send in tubular reactor 1, molecular sieve is with 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 carrier gas and gas phase SiCl
4the outlet by gas-solid separator 2 tops enters in absorption tower 3, with the absorption agent alkali lye in absorption tower 3, contacts, 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, directly or regularly discharge waste water f by outlet at bottom afterwards.
Molecular sieve gas phase dealumination complement silicon method provided by the invention can be for carrying out the gas phase dealumination complement silicon to various molecular sieves, and for example described molecular sieve can be the Y zeolite of different content of rare earth, with RE
2o
3meter, described Y zeolite Rare-Earth Content is preferably the 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 catalytic cracking catalyst of the present invention molecular sieve used.
Molecular sieve gas phase shown in the stainless steel construction drawing 2 that the industrial trade mark that used thickness is 3 millimeters is NiCr18Ti 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 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, raw material mixed cell 4 comprises that length is 5 meters, the cylinder mixer that diameter is 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 the 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, the top of gas-solid separator 2 is that diameter is that 6 meters, height are 14 meters cylindrical, bottom is for having the opening taper, cone angle is 45 °, and opening part is provided with valve, discharge port is positioned at apart from the gas-solid separator top position of 1 meter, fill the aqueous sodium hydroxide solution that concentration is 10 mol/L in absorption tower 3, connect by conduit between absorption tower 3 and gas-solid separator 2, conduit gos deep in aqueous sodium hydroxide solution.
Shown in Fig. 2, the SiCl that the dry air that is 100 ℃ by temperature and temperature are 90 ℃
4after gas is sent into gas mixer in raw material mixed cell 4 and is mixed, the Y zeolite (character is as shown in table 1) containing rare earth entered with molecular sieve entrance from pipeline, be 350 ℃ 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 gas-solid mixer in being provided with the pipeline of grid, the SiCl of incoming stock mixed cell 4
4flow by mass flowmeter, controlled 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 mixed gas makes the residence time of molecular sieve in tubular reactor 1.After reaction is carried out 1 hour, the molecular sieve in gas-solid separator 2 is 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 table 2.
Molecular sieve gas phase shown in the stainless steel construction drawing 2 that the industrial trade mark that used thickness is 3 millimeters is NiCr18Ti 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 25 meters, diameter is 0.4 meter, vertically the length of section 132 is 45 meters, diameter is 0.4 meter, the length of the second tilting section 133 is 25 meters, diameter is 0.4 meter, vertically section 132 is perpendicular to horizontal plane, 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, raw material mixed cell 4 comprises that length is 5 meters, the cylinder mixer that diameter is 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 the 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, the top of gas-solid separator 2 is that diameter is that 5 meters, height are 10 meters cylindrical, bottom is for having the opening taper, cone angle is 35 °, and opening part is provided with valve, discharge port is positioned at apart from the gas-solid separator top position of 2 meters, fill the aqueous sodium hydroxide solution that concentration is 1 mol/L in absorption tower 3, connect by conduit between absorption tower 3 and gas-solid separator 2, conduit gos deep in aqueous sodium hydroxide solution.
Shown in Fig. 2, the SiCl that the dry air that is 200 ℃ by temperature and temperature are 130 ℃
4after gas is sent in the gas mixer in raw material mixed cell 4 and is mixed, the Y zeolite (character is as shown in table 1) containing rare earth entered with molecular sieve entrance from pipeline, be 350 ℃ 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 gas-solid mixer in being provided with the pipeline of grid, SiCl
4flow by mass flowmeter, controlled, and SiCl
4with the weight ratio of molecular sieve be 0.55, the inlet amount of molecular sieve is 700kg/ hour, it is 15 minutes that the flow of mixed gas makes the residence time of molecular sieve in tubular reactor.After reaction is carried out 2 hours, the molecular sieve in gas-solid separator 2 is 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 table 2.
Molecular sieve gas phase shown in the stainless steel construction drawing 2 that the industrial trade mark that used thickness is 3 millimeters is NiCr18Ti 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, raw material mixed cell 4 comprises that length is 5 meters, the cylinder mixer that diameter is 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 the 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, the top of gas-solid separator 2 is that diameter is that 9 meters, height are 12 meters cylindrical, bottom is for having the opening taper, cone angle is 30 °, and opening part is provided with valve, discharge port is positioned at apart from the gas-solid separator top position of 4 meters, fill the aqueous sodium hydroxide solution that concentration is 1 mol/L in absorption tower 3, connect by conduit between absorption tower 3 and gas-solid separator 2, conduit gos deep in aqueous sodium hydroxide solution.
Shown in Fig. 2, the SiCl that the dry air that is 140 ℃ by temperature and temperature are 80 ℃
4after gas is sent in the gas mixer in raw material mixed cell 4 and is mixed, the Y zeolite (character is as shown in table 1) containing rare earth entered with molecular sieve entrance from pipeline, be 350 ℃ 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 gas-solid mixer in being provided with the pipeline of grid, SiCl
4flow by the mass rate agent, controlled, 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 residence time of molecular sieve in tubular reactor.After reaction is carried out 1 hour, the molecular sieve in gas-solid separator 2 is 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 table 2.
Method according to embodiment 3 prepares high-silica zeolite, different is, the length of tubular reactor 1 is 25 meters, wherein the length of the 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 the 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 residence time of molecular sieve in tubular reactor, obtain high-silica zeolite D, its main character is listed in table 2.
Embodiment 5
Method according to embodiment 3 prepares 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, with industrial REY, compare, the framework si-al ratio of the molecular sieve that adopts method provided by the invention to make 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, with industrial REY, compare, the molecular sieve that adopts method provided by the invention to make has better relative crystallinity, higher lattice avalanche temperature, and specific surface area obviously improves, sodium oxide content reduces greatly, shows the excellent performance of the molecular sieve that method provided by the invention makes.
Embodiment 6-10 is for illustrating the molecular sieve catalyzer that adopts embodiment 1-5 to make.
According to (material butt) molecular sieve: kaolin: pseudo-boehmite: aluminium colloidal sol=38: 30: 22: 10 part by weight, by above-mentioned mixing of materials, making beating, then, 450 ℃ of lower spraying dryings, 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 catalyzer C-1, C-2, C-3, C-4 and C-5, and its main character is listed in table 3.
Comparative Examples 1
Adopt according to the method described above industrial REY type molecular sieve (main character is listed in table 2) Kaolinite Preparation of Catalyst, the 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 estimated: adopt the standard method of RIPP92-90 (to see the volumes such as " Petrochemical Engineering Analysis method " (RIPP test method) Yang Cuiding, Science Press, the nineteen ninety publication) light oil microactivity of assess sample, the catalyzer loading amount is 5.0g, temperature of reaction is 460 ℃, the huge port solar oil that stock oil is boiling range 235-337 ℃, and product composition is by gas chromatographic analysis, calculate light oil microactivity according to product composition, result is in table 3.
Light oil microactivity (MA)=(in product lower than the gasoline output+gas yield of 216 ℃+coke output)/charging total amount * 100%
Heavy oil cracking performance evaluation condition: catalyzer is first at 800 ℃, 100% steam aging 12 hours is then estimated 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=yield of liquefied gas+yield of gasoline+diesel yield
Coke selectivity=coking yield/transformation efficiency
The Catalytic Cracking Performance of the catalyzer that respectively prepared by Evaluation operation example 6-10 and Comparative Examples 1 according to the method described above, the results are shown in table 5.
Table 3
| The catalyzer numbering | C-1 | C-2 | C-3 | C-4 | C-5 | CC-1 |
| The molecular sieve numbering | A | B | C | D | E | Industry REY |
| Al 2O 3Content/% by weight | 48.3 | 48.6 | 49.5 | 50.9 | 51.7 | 52.1 |
| Na 2O content/% by weight | 0.07 | 0.07 | 0.08 | 0.13 | 0.12 | 0.19 |
| Sulfate radical content/% by weight | 1.1 | 1.2 | 1.1 | 1.2 | 1.2 | 1.3 |
| Burning decrement/% by weight | 11.8 | 12.2 | 12.1 | 12.2 | 11.9 | 12.1 |
| Pore volume/(mLg -1) | 0.41 | 0.42 | 0.43 | 0.41 | 0.39 | 0.35 |
| Specific surface area/( m2·g -1) | 279 | 286 | 295 | 284 | 276 | 245 |
| Abrasion index/(%h -1) | 1.7 | 1.5 | 1.1 | 1.6 | 1.8 | 1.9 |
| Apparent bulk density/(gmL -1) | 0.74 | 0.73 | 0.74 | 0.72 | 0.73 | 0.75 |
| Micro-activity (800,4h)/% | 83 | 83 | 84 | 81 | 82 | 74 |
| Screening distribution/% by weight | ||||||
| 0～ |
3 | 3.5 | 3.5 | 2.8 | 3.7 | 3.8 |
| 0～40μm | 18.4 | 18.2 | 17.4 | 16.3 | 18.8 | 18.9 |
| 0～149μm | 92.2 | 92.3 | 91.6 | 91.9 | 92.9 | 93.4 |
| Average particulate diameter (micron) | 69.8 | 71.1 | 72.5 | 73.5 | 69.7 | 69.4 |
From the results shown in Table 3, while adopting the molecular sieve catalyzer made by method provided by the invention, the sodium oxide content of gained catalyzer significantly reduces, and pore volume and specific surface area obviously increase, and micro-activity obviously improves.
Table 4
Table 5
| Catalyzer | C-1 | C-2 | C-3 | C-4 | C-5 | CC-1 |
| Product distributes, % by 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 |
| Transformation efficiency, % by weight | 74.17 | 76.3 | 74.48 | 72.67 | 71.96 | 67.16 |
| Coke selectivity, % by weight | 6.93 | 7.04 | 6.95 | 7.44 | 7.38 | 8.56 |
| Yield of light oil, % by weight | 72.6 | 73.33 | 72.9 | 69.71 | 69.11 | 67.08 |
| Liquid yield, % by weight | 85.71 | 87.02 | 85.98 | 84 | 83.73 | 80.09 |
From the results shown in Table 5, with reference catalyst, CC-1 compares, and adopting the molecular sieve made by method provided by the invention is that catalyzer prepared by active ingredient has higher transformation efficiency, higher liquid yield, higher yield of light oil and lower coke selectivity.
Claims (17)
1. a method for preparing high-silica zeolite, is characterized in that, the method comprises molecular sieve and contains gas phase SiCl
4gas be mixed to form mixture flow, the described gas phase SiCl that contains
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
4contact molecular sieve and gas phase SiCl under flow state
4duration of contact be 10 seconds to 100 minutes;
Described contact is carried out in tubular reactor, and the method that forms described mixture flow is at molecular sieve and contains SiCl
4gas first by a raw material mixed cell, mixed before entering the contact of described tubular reactor;
Described tubular reactor comprises body and is positioned at least one opening for feed and the discharge port at body two ends, from described opening for feed one of described mixture flow enters in described body and carries out contact reacts, product after contact reacts is from discharge port is discharged described body, and described tubular reactor is connected with the raw material mixed cell by one in described opening for feed;
Described body comprises the first tilting section and vertical section, one end of described the first tilting section and an end of described vertical section join, 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 position be connected higher than described discharge port place;
Described body also comprises the second tilting section, and an end of described the second tilting section and the other end of described vertical section join, 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 position be connected.
2. method according to claim 1, wherein, the molecular sieve in described mixture flow 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
4mixed gas 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 is 50-2000 kg/hr.
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 is 100-1500 kg/hr.
6. according to the described method of any one in 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 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, described raw material mixed cell (4) 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 (1) by one in described opening for feed.
9. method according to claim 1, wherein, the length of tubular reactor is 5-100 rice, diameter is 0.01-1.5 rice.
10. method according to claim 1, wherein, described the first tilting section and vertically the angle between section for being greater than 10 ° to being less than or equal to 90 °.
11. method according to claim 10, wherein, the angle between described the first tilting section and vertical section is for being greater than 30 ° to being less than or equal to 80 °.
12. method according to claim 1, wherein, the Length Ratio of described the first tilting section and vertical section is 0.1-10:1.
13. method according to claim 1, wherein, the angle between described the second tilting section and vertical section is for being greater than 10 ° to being less than or equal to 90 °.
14. method according to claim 13, wherein, described the second tilting section and vertically the angle between section be 30 ° to being less than or equal to 80 °.
15., according to claim 1,13 or 14 described methods, wherein, the Length Ratio of described the second tilting section and vertical section is 0.1-10:1.
16. method 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.
17. method according to claim 16, 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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| CN1382525A (en) * | 2001-04-28 | 2002-12-04 | 中国石油化工股份有限公司 | Process for preparing rare-earth type high-silicon gamma-zeolite |
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| CN1382525A (en) * | 2001-04-28 | 2002-12-04 | 中国石油化工股份有限公司 | Process for preparing rare-earth type high-silicon gamma-zeolite |
| CN2797341Y (en) * | 2002-04-30 | 2006-07-19 | 中国科学院过程工程研究所 | Device for preparing titanium tatrachloride by chlorization of titanium containing mineral |
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