CN102452660A - Method for preparing molecular sieve - Google Patents
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- CN102452660A CN102452660A CN2010105152197A CN201010515219A CN102452660A CN 102452660 A CN102452660 A CN 102452660A CN 2010105152197 A CN2010105152197 A CN 2010105152197A CN 201010515219 A CN201010515219 A CN 201010515219A CN 102452660 A CN102452660 A CN 102452660A
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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, also is very important a kind of component simultaneously, and the performance of molecular sieve has directly had influence on the reactivity worth of catalytic cracking catalyst.According to different needs, can carry out different modifications to reach the requirement of use to molecular sieve.It is required generally to be considered to catalytic cracking catalyst such as the molecular sieve of high silica alumina ratio.
Aspect the molecular sieve of preparation high silica alumina ratio, mainly contain following several method: ammonium 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 (being also referred to as the chemical method aluminium-eliminating and silicon-replenishing) mainly is to use the ammonium silicofluoride dealumination complement silicon, and the percent crystallinity of the molecular sieve of acquisition is high, and Si/Al when thermostability is high, but the indissoluble thing AlF that forms in the dealumination process
3Influence hydrothermal stability with residual silicofluoride, also pollute the environment.
Hydrothermal method is still the method that generally adopts in the present industry; But benefit silicon is untimely after in water-heat process, having dealuminzation, is prone to cause lattice to subside, and non-framework aluminum clogged with fragments duct; This has not only influenced the accessibility in active site, also influences the further raising of its thermostability.
The characteristics of gas chemistry method aluminium-eliminating and silicon-replenishing are that dealuminzation is even, and it is timely to mend silicon, and product crystallization reservation degree is high, Heat stability is good, and the duct is unimpeded.For example; CN1057977C discloses a kind of preparation method who contains the catalyst composition of rich silicon ultra stabilization Y zeolite; The drying and moulding thing that it comprises silicon tetrachloride gas that water cut is carried less than the dry air of 900ppm 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; Particle diameter is that the particle of 35-125 micron accounts for more than 80% of total particle number in the said drying and moulding thing, and the weight ratio of NaY zeolite and heat-resistant inorganic oxide is 1: 0.2-1.0, the silica alumina ratio of NaY zeolite are 3-6.The used forming composition good fluidity of this method has avoided being agglomerated into piece and phenomenon of blocking, is easy to realize serialization scale operation.
CN1121903C discloses a kind of preparation method of rare-earth type high-silicon gamma-zeolite, and this method comprises carries out drying treatment with the y-type zeolite that contains rare earth, make its water-content be lower than 10 weight % after; According to silicon tetrachloride: Y zeolite=0.1-0.9: 1 weight ratio feeds the silicon tetrachloride gas that dry air carries, under temperature 150-600 ℃; Reacted 10 minutes to 6 hours; After the reaction, purged 5 minutes to 2 hours, remove Na remaining in the zeolite with the decationized Y sieve water washing with dry air
+, Cl
-, Al
3+Etc. the solubility by product.This method is simpler than prior art, the saving energy and pollution-free.
CN1281493C discloses Y type zeolites containing rare-earth and high content of silicon and preparation method thereof, and this zeolite contains rare earth, and the silica alumina ratio of this zeolite is 5-30, and initial lattice constant is 2.430-2.465nm, and the balance lattice constant is at least 0.985 with the ratio of initial lattice constant.This prepare zeolite method comprises and contacting with silicon tetrachloride containing rare earth Y type zeolite that said contact is carried out in a conversion unit, this equipment is as shown in Figure 1; Comprise a reaction kettle (1), an opening for feed (2) and an air outlet (3) also comprise a whisking appliance (4) in the inside of reaction kettle (1); A gas-solid separator (5) is installed on the air outlet (3); The bore dia of gas-solid separator (5) contained hole and porosity guarantee gas can through and the zeolitic solid particle can not pass through, the agitator arm of whisking appliance (4) stretches out outside the reaction kettle (1), under the stirring of whisking appliance (4); The said y-type zeolite that contains rare earth contacts with carbon tetrachloride gas; The temperature of contact is 100-500 ℃, and the time of contact is 5 minutes to 10 hours, and containing the y-type zeolite of rare earth and the weight ratio of tetracol phenixin is 1: 0.05-0.5; The said silica alumina ratio that contains the y-type zeolite of rare earth is 3-8, and lattice constant is 2.45-2.48nm.This method makes silicon tetrachloride gas and molecular sieve solid particle contact reacts more even; Avoid the phenomenon that is agglomerated into the compact mass thing between the molecular sieve solid particle, can reduce labour intensity, can reduce environmental pollution; Reduce production cost significantly, be easy to carry out large-scale industrial application.
Obviously, above said method generally all long required duration of contact, need several hours; Add the discharging after charging and reaction before the reaction finishes, can only carry out once above-mentioned dealumination complement silicon reaction a general day shift at the most, even if adopt the mode of operation of break tour also can only carry out twice above-mentioned dealumination complement silicon reaction; And owing to need in the reaction kettle to stir, so reaction kettle also can not be infinitely great, based on present level; The production capacity of reaction kettle that can be used for the maximum of above-mentioned dealumination complement silicon reaction is 600kg; Continue the augmenting response still, then be difficult in the reaction kettle guarantee fully to stir, therefore; Adopt the mode of aforesaid reaction vessel, can obtain the high-silica zeolite of 1200kg in one day at the most.And in the method for above-mentioned prior art, the high silicon content for the molecular sieve that guarantees to obtain generally all makes SiCl
4Excessive far away, excessive SiCl
4Use increased production cost and expenses of environmental protection undoubtedly.On the other hand; Aforesaid method all needs very numerous and diverse manual operation; Such as: hand charging, manual cleaning reach needs long scavenging line etc. after reaction is accomplished, these not only bring hand labor intensity big, the problem that production efficiency is very low; And, molecular sieve dust when charging and discharging and excessive SiCl
4Also cause serious environmental pollution and serious harm operator's health.Therefore, the ultra steady technology of the gas phase of above-mentioned still formula is difficult to carry out suitability for industrialized production.
Summary of the invention
To the critical defect that the ultra steady technology of the gas phase of still formula exists, the objective of the invention is to develop and a kind ofly can reduce SiCl
4Consumption, 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, this method comprises molecular sieve and contains gas phase SiCl
4Gas mix to form mixture flow, the said 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 the mixture flow is with gas flow, and with gas gas phase SiCl
4Under flow state, contact molecular sieve and gas phase SiCl
4Duration of contact be 10 seconds to 100 minutes.
The method for preparing molecular sieve provided by the invention with molecular sieve with contain SiCl
4Send in the tubular reactor from the opening for feed of tubular reactor with the mixed gas of inert carrier gas; Fully the laggard promoting the circulation of qi of reaction separates admittedly in tubular reactor; Solid then is required high-silica zeolite, and gaseous component then gets into the absorption tower, sponges a small amount of excessive SiCl
4After air can directly discharge.This shows that 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, through flow velocity and the length of tubular reactor of control mixed gas, 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 through making molecular sieve and containing gas phase SiCl
4The gas uniform mixing after reaction again, thereby guaranteed that the benefit pasc reaction can evenly and fully carry out, therefore the percent crystallinity of the molecular sieve of preparation is higher, quality is more stable, performance is better.
Compare with the ultra steady technology of existing still formula gas phase; The method for preparing molecular sieve provided by the invention can realize the ultra steady reaction of serialization gas phase; And operation can carry out in all robotization serializations, and hand labor intensity is little, and production efficiency is high; Product performance are stable, make the suitability for industrialized production of the ultra steady technology of molecular sieve serialization gas phase become a reality.Experiment showed, the disclosed still reaction method of CN1281493C that adopts, even if adopt the mode of operation of break tour; Also can produce the high-silica zeolite of 1200kg every day at the most; And adopt aforesaid device provided by the invention, and per hour can produce the high-silica zeolite of 1000kg, can produce the high-silica zeolite of 24000kg every day; Its production efficiency is 20 times of the disclosed still reaction method of CN1281493C; And workman's labor operation intensity also greatly reduces, and this shows that the economic benefit for preparing the method for molecular sieve provided by the invention is very significant.
Description of drawings
Fig. 1 is the structural representation of equipment of method that is used to prepare high-silica zeolite of prior art;
Fig. 2 is the synoptic diagram for preparing being used to of the present invention relates to the method equipment used of molecular sieve;
Fig. 3 is axis and the synoptic diagram of the angle between the horizontal plane of first tilting section 131 of the tubular reactor 1 of equipment shown in Figure 2;
Fig. 4 is axis and the synoptic diagram of the angle β between the horizontal plane of second tilting section 133 of the tubular reactor 1 of equipment shown in Figure 2.
Embodiment
Based on the method for preparing molecular sieve provided by the invention, send in the reactor after can be directly gas phase silicon tetrachloride and molecular sieve being mixed and react; Also can be earlier that carrier gas mixes with the gas phase silicon tetrachloride with inert gas, form mist, send into after again this mist and molecular sieve being mixed and carry out haptoreaction in the reactor; Also can earlier inert gas be mixed with molecular sieve, molecular sieve is mixed with the gas phase silicon tetrachloride with flow regime under the drive of inert gas; Send in the reactor together after can also simultaneously inert gas, molecular sieve and gas phase silicon tetrachloride being mixed and react.Under the preferable case, is that carrier gas mixes with the gas phase silicon tetrachloride with rare gas element earlier, the formation mixed gas is sent into after this mixed gas and molecular sieve being mixed again and is carried out contact reacts in the reactor drum.
Said 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 the neutral element gas in air, nitrogen and the periodic table of elements.Because SiCl
4To water sensitive, therefore, under the preferable case, above-mentioned inert carrier gas is the exsiccant inert carrier gas, and further the water cut of preferred said inert carrier gas is no more than 100ppm.
The condition of said contact comprises that the solid content of molecular sieve is preferably greater than 98 weight %, and the solid content of said molecular sieve is that molecular sieve is through the weight after the high-temperature roasting and the weight ratio before the roasting, the i.e. water cut of the solid content of molecular sieve=100%-molecular sieve; SiCl
4Be preferably 0.01-1 with the weight ratio of molecular sieve: 1, further be preferably 0.05-0.60: 1, the flow velocity of mixed gas makes SiCl
4With the residence time of molecular sieve in reactor drum is to be duration of contact 10 seconds to 100 minutes, is preferably 1 minute to 20 minutes.The flow velocity of molecular sieve is preferably 0.015-3m/s in the mixture flow, and more preferably 0.03-3m/s further is preferably 0.1-2.5m/s.With respect to diameter is that 0.01-1.5 rice, length are the tubular reactor of 50-95 rice, and the flow of molecular sieve is preferably 50-2000kg/ hour, further is preferably 100-1500kg/ hour, further is preferably 200-1200kg/ hour.Under these conditions, molecular sieve and gas phase SiCl both can have been guaranteed
4Through reactor drum, can guarantee molecular sieve and gas phase SiCl with the successive airflow pattern again
4Contact can fully carry out.From above-mentioned gas phase SiCl
4Can find out with the numerical value of the weight ratio of molecular sieve, adopt method provided by the invention can reduce gas phase SiCl greatly
4Consumption.
Although as long as guarantee molecular sieve and gas phase SiCl
4Catalytic temperature is common molecular sieve and gas phase SiCl
4Catalytic temperature gets final product, but under the preferable case, can be in order to make reaction at molecular sieve and gas phase SiCl
4Carry out fast after the contact, the temperature of the preferred said molecular sieve of the present invention is 200-600 ℃, gas phase SiCl
4Temperature be 60-150 ℃, the temperature of carrier gas such as air is 60-200 ℃.Under these conditions, need not reactor drum is provided with well heater separately, can guarantee that the temperature in the reactor drum satisfies molecular sieve and gas phase SiCl
4Catalytic needs.Because the temperature of the molecular sieve after the roasting is generally more than 300 ℃; Therefore the temperature of above-mentioned molecular sieve can obtain through reactor drum is combined with stoving oven, that is to say, under the preferable case; Said molecular sieve is the molecular sieve of just discharging from stoving oven; Can utilize the thermal source of the high temperature of molecular sieve after the roasting so on the one hand, start the dealumination complement silicon reaction as the dealumination complement silicon reaction, thus save energy; Can also practice thrift the time of heating molecular sieve on the other hand, be reflected in the short time and can fully carry out thereby make.In addition, although through making air and SiCl
4The temperature of gas raises also can reach the required temperature of reaction, and still, obviously extraneous heating can only make molecular sieve heating gradually from outside to inside, thereby more cannot say for sure to demonstrate,prove fully carrying out of dealumination complement silicon reaction comparatively speaking.
The reaction of dealumination complement silicon described in the present invention can carried out in the reactor drum arbitrarily, as long as satisfy molecular sieve and gas phase SiCl among the present invention
4Contact conditions get final product, for example can in reactor drums such as fluidized-bed, fixed bed, tubular reactor, carry out, but under the preferable case, dealumination complement silicon according to the invention is reflected in the tubular reactor and carries out.
According to a kind of preferred implementation, the method for preparing molecular sieve described in the present invention is carried out in equipment shown in Figure 2, and this equipment comprises tubular reactor 1, gas-solid separator 2, absorption tower 3 and raw materials mix unit 4.
Said tubular reactor 1 comprises at least one opening for feed, discharge port and body 13, and opening for feed in the said opening for feed and discharge port lay respectively at two ends of said body 13;
Said gas-solid separator 2 is communicated with said tubular reactor 1 through said discharge port; The top of said gas-solid separator 2 is communicated with said absorption tower 3, and the position that said gas-solid separator 2 is connected with discharge port is lower than the position that said gas-solid separator 2 is connected with said absorption tower 3;
Said raw materials mix unit 4 is used for different gas is mixed and/or gas is mixed with solid, and said raw materials mix unit 4 is communicated with said tubular reactor 1 through one in the said opening for feed.
The length of said tubular reactor 1 is to guarantee said 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 helps duration of contact of providing longer; But pipeline is long more; The required power of raw materials such as required delivery of molecules sieve and gas is big more, and is also just high more to the requirement of device that power is provided accordingly, and; Reaction times is oversize, causes the percent crystallinity of molecular sieve to reduce easily.Therefore; That takes all factors into consideration reaction fully carries out, reacts required power and production efficiency, and contriver of the present invention finds that the length of said tubular reactor 1 is preferable for 5-100 rice; Therefore; The length of the preferred said tubular reactor 1 of the present invention is 5-100 rice, further is preferably 7-95 rice, further is preferably 50-95 rice.The diameter of said tubular reactor 1 is preferably 0.01-1.5 rice, further is preferably 0.02-1.4 rice, further is preferably 0.1-1.4 rice.
According to the present invention, although the collinear pipeline also can be realized molecular sieve and SiCl
4The sufficient reacting purpose of carrying out; But, under the preferable case, for the flow backwards generation of the situation in the tubular reactor 1 of the molecular sieve in the gas-solid separator 2 that prevents in tubular reactor 1, to cause under the unsettled situation of air-flow; And further fully guarantee in short pipeline, to realize contacting more fully; As shown in Figure 2, said body 13 comprises first tilting section 131 and vertical section 132, and an end of said first tilting section 131 and said vertical section 132 end join; Said discharge port is positioned at the other end of said first tilting section 131, and said first tilting section 131 is higher than the position that said discharge port belongs to said vertical section 132 position that is connected.Under this preferable case, the setting of said first tilting section 131 can effectively prevent the generation of above-mentioned suck-back phenomenon, and said vertical section 132 make said tubular reactor be similar to riser reactor.Among the present invention, said vertical section is not that absolute vertical is in horizontal plane, as long as look like vertically up promptly by in this scope.
Angle between said first tilting section 131 and the vertical section 132 can be 10-90 °; Be preferably 30-80 °; Promptly when said vertical section 132 during perpendicular to horizontal plane, as shown in Figure 3, the axis of said first tilting section 131 and the angle between the horizontal plane can be for greater than 0 ° to 80 °; Under the preferable case, the axis of said first tilting section 131 and the angle between the horizontal plane are 10 ° to 60 °.Under this preferable case, can make molecular sieve and SiCl
4Also can fully react at first tilting section 131, and unlikelyly get into fast in the gas-solid separator 2 because of action of gravity.
According to the present invention, under the preferable case, the length of said first tilting section 131 and vertical section 132 is than being 0.1-10: 1, further be preferably 0.2-9: and 1, further preferred 0.4-0.6: 1.
A preferred embodiment of the invention, said body 13 also comprises second tilting section 133, and an end and said vertical section 132 the other end of said second tilting section 133 join, and said first opening for feed is positioned at the other end of said second tilting section 133.Be provided with 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 the preferable case, the position at said opening for feed place is higher than said second tilting section 133 and said vertical section 132 position that is connected, so that material can fast, directly get in second tilting section 133, further carries then.
Angle between said second tilting section 133 and the vertical section 132 can be 10-90 °; Be preferably 30-80 °; Promptly, as shown in Figure 4 when said vertical section 132 during perpendicular to horizontal plane, according to equipment provided by the invention; The axis of said second tilting section 133 and the angle β between the horizontal plane can be preferably 10 ° to 60 ° for greater than 0 ° to 80 °.Under this preferable case, can make molecular sieve and SiCl
4Also can fully react at first tilting section 131, and the unlikely end that gets into vertical section 132 because of action of gravity fast.
Further under the preferable case, the length of said second tilting section 133 and vertical section 132 is than being 0.1-10: 1, and 0.2-9 more preferably: 1, further be preferably 0.3-0.9: 1.
According to the present invention, said raw materials mix unit 4 comprises gas-solid mixing tank and/or gas mixer, and said gas-solid mixing tank and/or gas mixer are communicated with said tubular reactor 1 through one in the said opening for feed.
When said raw materials mix unit only comprises gas mixer and does not comprise the gas-solid mixing tank; During for the ease of the industriallization continuous production with the cooperating of other devices; Said tubular reactor 1 preferably includes two opening for feeds; One of them opening for feed i.e. first opening for feed is the port of tubular reactor 1, and another opening for feed is positioned at and the said first opening for feed position adjacent.Wherein any in two opening for feeds is communicated with this gas-solid mixing tank, and another opening for feed then is communicated with molecular sieve feeding unit (not shown).During use, said carrier gas air and gas phase SiCl
4After in gas mixer, mixing; Get into the body 13 of said tubular reactor 1 through the opening for feed that is communicated with said gas mixer; Molecular sieve then gets into the body 13 of said tubular reactor 1 from another opening for feed, thereby in the body 13 of tubular reactor 1, reacts.Said molecular sieve feeding unit is preferably stoving oven, that is to say, another opening for feed of the equipment of preparation molecular sieve of the present invention is communicated with stoving oven usually.In order effectively to utilize the length of tubular reactor; Preferred first opening for feed and second opening for feed as far as possible near; But it is simultaneously also as far as possible little for the interference between the charging that guarantees two opening for feeds; Distance between preferred said first opening for feed and said second opening for feed is the 0.5-15% of the length of said tubular reactor 1, further is preferably 1-10%.
Further under the preferable case; Said opening for feed is one; Said raw materials mix unit 4 comprises gas-solid mixing tank and gas mixer, and gas mixer is communicated with the gas-solid mixing tank, and the gas-solid mixing tank is communicated with said tubular reactor 1 through one in the said opening for feed.Said carrier gas air and gas phase SiCl
4After in the gas mixer of raw materials mix unit 4, mixing, entering gas-solid mixing tank carries out gas-solid with molecular sieve to be mixed, and mixes the back and gets in the tubular reactor 1 through opening for feed.
Said gas mixer can be to well known to a person skilled in the art variously can realize gas phase silicon tetrachloride and carrier gas blended device, for example, can be pipeline, is about to the gas phase silicon tetrachloride and sends in the pipeline simultaneously with carrier gas and mix.Said gas-solid mixing tank can be to well known to a person skilled in the art the various devices that gas phase silicon tetrachloride and/or carrier gas and molecular sieve are mixed that can be used in; For example said gas-solid mixing tank can be cylinder mixer, and this cylinder mixer comprises cylindrical body and the grid that is positioned at cylindrical body.Said grid is preferably along the axial of cylindrical body and is fixed on the stainless steel plate on the cylindrical body inwall with spiralling mode; It is that gas phase silicon tetrachloride and molecular sieve are uniformly dispersed and increase duration of contact of stock yard that grid is used to make 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 said gas mixer and gas-solid mixing tank are round tube type, and the cylinder of the two is structure as a whole.
Among the present invention, said gas-solid separator 2 is used for collecting and SiCl
4Molecular sieve after the gas contact.In this gas-solid separator, solid molecular sieves is separated with gas, thereby obtain the high-silica zeolite product.The various containers of above-mentioned purpose of can realizing all can be used as gas-solid separator 2 of the present invention, and the present invention can not have special qualification to its shape, for example can be for cylindric.Further under the preferable case, the bottom of said gas-solid separator 2 has the taper of opening for the end.Thereby the high-silica zeolite that obtains can be discharged from said opening.
In order to make gaseous fraction in the post reaction mixture get into the absorption tower as far as possible and not discharge from above-mentioned opening, under the preferable case, the position that said gas-solid separator 2 is connected with tubular reactor 1 discharge port is higher than the zero position of said taper.Further under the preferable case, the position that said gas-solid separator 2 is connected with tubular reactor 1 discharge port is positioned at the middle and upper part of said gas-solid separator 2, and gas-solid separator 2 is communicated with said absorption tower 3 through its top gas outlet.
Said absorption tower 3 is used to absorb excessive unreacted SiCl
4Thereby the gas that gas-solid separator is come out reaches emission standard.Said absorption tower 3 can be conventional various absorption towers of using, this area, as long as can absorb SiCl
4Get final product.General alkali lye such as the aqueous sodium hydroxide solution of using absorbs SiCl
4Therefore, among the present invention, said absorption tower 3 preferably includes two inlets and two outlets; One of them said inlet is communicated with gas-solid separator 2; Be preferably placed at the middle and upper part on said absorption tower, another inlet is used to add alkali lye, and this inlet preferably also is positioned at the middle and upper part on said absorption tower.Said two outlets lay respectively at the top and the bottom on said absorption tower, are respectively applied for emission gases (air) and absorb waste liquid.For SiCl in the air that guarantees to discharge
4Content is enough low, and under the preferable case, said absorption tower is placed in-line a plurality of.Placed in-line a plurality of absorption tower is to SiCl
4Form multistage absorption.
Among the present invention, said carrier gas can be various at gas phase SiCl
4Be inert gasses under the condition of molecular sieve reaction, promptly said carrier gas can be the various gas phase SiCl that do not disturb
4With the gas of molecular sieve, for example can be in air, nitrogen, helium, neon, argon gas and the xenon one or more at the tubular reactor internal reaction.
According to method provided by the invention, under the preferable case, this method also comprises carries out gas solid separation with contact back products therefrom, obtains solid high-silica zeolite product and gaseous fraction.
As shown in Figure 2, said gas solid separation is preferably carried out in gas-solid separator 2, and said gas-solid separator generally comprises opening for feed and top gas outlet.The other end of said first tilting section is communicated with said gas-solid separator, and the sectional area of said gas-solid separator is greater than the cross-sectional area of said tubular reactor body.Sectional area through making said gas-solid separator is greater than the cross-sectional area of said tubular reactor body, can realize making being suspended in SiCl originally
4Air-flow or SiCl
4The sedimentation of molecular sieve 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 said gas-solid separator is 2-10 with the ratio of the cross-sectional area of said tubular reactor body: 1, can fully realize the rapid subsidence of molecular sieve like this.In order to guarantee that further molecular sieve fully is deposited in the gas-solid separator, the present invention also height of preferred said gas-solid separator is not less than 5 meters, for example 5-10 rice.Further under the preferable case, the opening for feed of said gas-solid separator is positioned at the middle part of said gas-solid separator, can guarantee so on the one hand the molecular sieve that is deposited in the gas-solid separator bottom not to be produced to stir, and can also guarantee the settling time fully on the other hand.
Further under the preferable case, said gas-solid separator also comprises the bottom solid outlet, is used to discharge the molecular sieve solid that separation obtains.Further under the preferable case, said gas-solid separator also comprises and is used to control the valve that said bottom solid outlet is opened and closed, thus can be in good time the molecular sieve solid of collecting in the gas-solid separator is discharged.
The various containers of above-mentioned purpose of can realizing all can be used as gas-solid separator 2 of the present invention, and the present invention can not have special qualification to its shape, for example can be for cylindric.Further under the preferable case, the bottom of said gas-solid separator 2 has the taper of opening for the end.Thereby the high-silica zeolite that obtains can be discharged from said opening.
In order to make gaseous fraction in the post reaction mixture get into the absorption tower as far as possible and not discharge from above-mentioned opening, under the preferable case, the position that said gas-solid separator 2 is connected with discharge port is higher than the zero position of said taper.Further under the preferable case, the position that said gas-solid separator 2 is connected with discharge port is positioned at the middle and upper part of said gas-solid separator 2, and the absorption tower 3 that gas-solid separator 2 will be described through its open top and hereinafter is communicated with.
Because molecular sieve and SiCl
4Contact reacts in, common SiCl
4It is excessive to have part, therefore, and in order to prevent SiCl
4Environmental pollution, under the preferable case, this method also comprises said gaseous fraction is contacted with absorption agent, to remove the SiCl in the gaseous fraction
4
As shown in Figure 2, said absorption is preferably carried out in the absorption tower, and absorption agent is contained in the said absorption tower, is used to absorb excessive unreacted SiCl
4Thereby, make air reach emission standard.Said absorption tower 3 can be conventional various absorption towers of using, this area, as long as can absorb SiCl
4Get final product.General alkali lye such as the aqueous sodium hydroxide solution of using absorbs SiCl
4Therefore, among the present invention, said absorption tower 3 preferably includes two inlets and two outlets; One of them said inlet is communicated with gas-solid separator 2; Be preferably placed at the middle and upper part on said absorption tower, another inlet is used to add alkali lye, and this inlet preferably also is positioned at the middle and upper part on said absorption tower.Said two outlets lay respectively at the top and the bottom on said absorption tower, are respectively applied for discharged air and absorb waste liquid.For SiCl in the air that guarantees to discharge
4Content is enough low, and under the preferable case, said absorption tower is placed in-line a plurality of.Placed in-line a plurality of absorption tower is to SiCl
4Form multistage absorption.
According to preferred implementation of the present invention, it is as shown in Figure 2 that bonding apparatus is described the process flow sheet of the method for preparing high-silica zeolite provided by the invention.Temperature is 200-600 ℃ molecular sieve a, carrier gas c and gas phase SiCl
4After raw material b mixes in raw materials mix unit 4, send in the tubular reactor 1 from opening for feed, molecular sieve is with carrier gas and gas phase SiCl
4The mixed gas contact of in tubular reactor 1, flowing, get into gas-solid separator 2 afterwards, in gas-solid separator 2, high-silica zeolite d is deposited in the bottom of gas-solid separator 2, directly or regularly discharges carrier gas and gas phase SiCl
4Then the outlet through gas-solid separator 2 tops gets in the absorption tower 3, contact with absorption agent alkali lye in the absorption tower 3, and carrier gas (tail gas e) is overflowed from alkali lye, the outlet at the 3 tops discharge from the absorption tower, SiCl
4Then, directly or regularly discharge waste water f through outlet at bottom afterwards with alkaline reaction.
Molecular sieve gas phase dealumination complement silicon method provided by the invention can be used for various molecular sieves are carried out the gas phase dealumination complement silicon, and for example said molecular sieve can be the Y zeolite of different content of rare earth, with RE
2O
3Meter, said Y zeolite middle-weight rare earths content is preferably 10-20 weight %.
Following embodiment will further explain the present invention, but therefore not limit the present invention.
Embodiment 1-5 is used to explain the method for the used molecular sieve of catalytic cracking catalyst of the present invention.
Used thickness is that 3 millimeters the industrial trade mark is that the stainless steel of NiCr18Ti is made molecular sieve gas phase shown in Figure 2 and mended silicon equipment, and wherein the body 13 of tubular reactor 1 is by first tilting section 131, vertically section 132 and second tilting section 133 constitutes, and the length of first tilting section 131 is 20 meters; Diameter is 0.8 meter, and vertically the length of section 132 is 40 meters, and diameter is 0.8 meter; The length of second tilting section 133 is 15 meters; Diameter is 0.8 meter, and vertically section 132 is perpendicular to horizontal plane, and the axis of first tilting section 131 and the angle between the horizontal plane are 75 ° (promptly the angle between first tilting section 131 and the vertical section 132 is 15 °); The axis of second tilting section 133 and the angle β between the horizontal plane are 65 ° (promptly the angle between second tilting section 133 and the vertical section 132 is 25 °); The port of second tilting section 133 is an opening for feed, and raw materials mix unit 4 comprises that length is that 5 meters, diameter are 0.8 meter cylinder mixer, and an end of cylinder mixer is communicated with opening for feed; Axial position apart from 2.5 meters of opening for feeds along cylinder mixer is provided with the molecular sieve inlet; Entering the mouth to this cylindrical section mixer inner walls of opening for feed from this molecular sieve is distributed with one group of spiralling stainless steel flase floor, and the pitch of flase floor is 0.3 meter, and the width of flase floor is 0.4 meter; This cylinder mixer is divided into two portions thus; First part is as gas mixer, and second section is provided with flase floor, thereby as the gas-solid mixing tank; The top of gas-solid separator 2 is that diameter is that 6 meters, height are 14 meters cylindrical; The bottom is for having the opening taper, and cone angle is 45 °, and opening part is provided with valve; Discharge port is positioned at apart from the gas-solid separator top 1 meter position; Fill the aqueous sodium hydroxide solution that concentration is 10 mol in the absorption tower 3, connect through conduit between absorption tower 3 and the gas-solid separator 2, conduit gos deep in the aqueous sodium hydroxide solution.
According to shown in Figure 2, be the SiCl that 100 ℃ dry air and temperature is 90 ℃ with temperature
4After gas mixer in the gas charging feed mixed cell 4 mixes; With get into from the molecular sieve of pipeline inlet, be that 350 ℃ the Y zeolite that contains rare earth (character is as shown in table 1) is to mix the back the gas-solid mixing tank to be sent in the body 13 of tubular reactor 1 SiCl of incoming stock mixed cell 4 continuously by opening for feed in being provided with the pipeline of grid from the temperature of stoving oven
4Flow by mass flowmeter control and SiCl
4With the weight ratio of molecular sieve be 0.30, the inlet amount of molecular sieve is 800kg/ hour, it is 10 minutes that the flow of mixed gas makes the residence time of molecular sieve in tubular reactor 1.After reaction is carried out 1 hour, gas-solid separator 2 interior molecular sieves are discharged from the opening of conical lower portion, after pulling an oar, wash, filter with decationized Y sieve water afterwards and in 120 ℃ of baking ovens, drying, obtain high-silica zeolite A, its main character is listed in the table 2.
Used thickness is that 3 millimeters the industrial trade mark is that the stainless steel of NiCr18Ti is made molecular sieve gas phase shown in Figure 2 and mended silicon equipment, and wherein the body 13 of tubular reactor 1 is by first tilting section 131, vertically section 132 and second tilting section 133 constitutes, and the length of first tilting section 131 is 25 meters; Diameter is 0.4 meter, and vertically the length of section 132 is 45 meters, and diameter is 0.4 meter; The length of second tilting section 133 is 25 meters; Diameter is 0.4 meter, and vertically section 132 is perpendicular to horizontal plane, and the axis of first tilting section 131 and the angle between the horizontal plane are 55 ° (promptly the angle between first tilting section 131 and the vertical section 132 is 35 °); The axis of second tilting section 133 and the angle β between the horizontal plane are 55 ° (promptly the angle between second tilting section 133 and the vertical section 132 is 35 °); The port of second tilting section 133 is an opening for feed, and raw materials mix unit 4 comprises that length is that 5 meters, diameter are 0.8 meter cylinder mixer, and an end of cylinder mixer is communicated with opening for feed; Axial position apart from 2.5 meters of opening for feeds along cylinder mixer is provided with the molecular sieve inlet; Entering the mouth to this cylindrical section mixer inner walls of opening for feed from this molecular sieve is distributed with one group of spiralling stainless steel flase floor, and the pitch of flase floor is 0.3 meter, and the width of flase floor is 0.4 meter; This cylinder mixer is divided into two portions thus; First part is as gas mixer, and second section is provided with flase floor, thereby as the gas-solid mixing tank; The top of gas-solid separator 2 is that diameter is that 5 meters, height are 10 meters cylindrical; The bottom is for having the opening taper, and cone angle is 35 °, and opening part is provided with valve; Discharge port is positioned at apart from the gas-solid separator top 2 meters position; Fill the aqueous sodium hydroxide solution that concentration is 1 mol in the absorption tower 3, connect through conduit between absorption tower 3 and the gas-solid separator 2, conduit gos deep in the aqueous sodium hydroxide solution.
According to shown in Figure 2, be the SiCl that 200 ℃ dry air and temperature is 130 ℃ with temperature
4After mixing in the gas mixer in the gas charging feed mixed cell 4; With get into from the molecular sieve of pipeline inlet, be that 350 ℃ the Y zeolite that contains rare earth (character is as shown in table 1) is to mix the back the gas-solid mixing tank to be sent in the body 13 of tubular reactor 1 SiCl continuously by opening for feed in being provided with the pipeline of grid from the temperature of stoving oven
4Flow control and SiCl by mass flowmeter
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, gas-solid separator 2 interior molecular sieves are discharged from the opening of conical lower portion, after pulling an oar, wash, filter with decationized Y sieve water afterwards and in 120 ℃ of baking ovens, drying, obtain high-silica zeolite B, its main character is listed in the table 2.
Used thickness is that 3 millimeters the industrial trade mark is that the stainless steel of NiCr18Ti is made molecular sieve gas phase shown in Figure 2 and mended silicon equipment, and wherein the body 13 of tubular reactor 1 is by first tilting section 131, vertically section 132 and second tilting section 133 constitutes, and the length of first tilting section 131 is 15 meters; Diameter is 1.2 meters, and vertically the length of section 132 is 35 meters, and diameter is 1.2 meters; The length of second tilting section 133 is 30 meters; Diameter is 1.2 meters, and vertically section 132 is perpendicular to horizontal plane, and the axis of first tilting section 131 and the angle between the horizontal plane are 45 ° (promptly the angle between first tilting section 131 and the vertical section 132 is 45 °); The axis of second tilting section 133 and the angle β between the horizontal plane are 45 ° (promptly the angle between second tilting section 133 and the vertical section 132 is 45 °); The port of second tilting section 133 is an opening for feed, and raw materials mix unit 4 comprises that length is that 5 meters, diameter are 0.8 meter cylinder mixer, and an end of cylinder mixer is communicated with opening for feed; Axial position apart from 2.5 meters of opening for feeds along cylinder mixer is provided with the molecular sieve inlet; Entering the mouth to this cylindrical section mixer inner walls of opening for feed from this molecular sieve is distributed with one group of spiralling stainless steel flase floor, and the pitch of flase floor is 0.3 meter, and the width of flase floor is 0.4 meter; This cylinder mixer is divided into two portions thus; First part is as gas mixer, and second section is provided with flase floor, thereby as the gas-solid mixing tank; The top of gas-solid separator 2 is that diameter is that 9 meters, height are 12 meters cylindrical; The bottom is for having the opening taper, and cone angle is 30 °, and opening part is provided with valve; Discharge port is positioned at apart from the gas-solid separator top 4 meters position; Fill the aqueous sodium hydroxide solution that concentration is 1 mol in the absorption tower 3, connect through conduit between absorption tower 3 and the gas-solid separator 2, conduit gos deep in the aqueous sodium hydroxide solution.
According to shown in Figure 2, be the SiCl that 140 ℃ dry air and temperature is 80 ℃ with temperature
4After mixing in the gas mixer in the gas charging feed mixed cell 4; With get into from the molecular sieve of pipeline inlet, be that 350 ℃ the Y zeolite that contains rare earth (character is as shown in table 1) is to mix the back the gas-solid mixing tank to be sent in the body 13 of tubular reactor 1 SiCl continuously by opening for feed in being provided with the pipeline of grid from the temperature of stoving oven
4Flow by mass rate agent control, and SiCl
4With the weight ratio of molecular sieve be 0.05, the inlet amount of molecular sieve is 1000kg/ hour, it is 1 minute that the flow of dry air makes the residence time of molecular sieve in tubular reactor.After reaction is carried out 1 hour, gas-solid separator 2 interior molecular sieves are discharged from the opening of conical lower portion, after pulling an oar, wash, filter with decationized Y sieve water afterwards and in 120 ℃ of baking ovens, drying, obtain high-silica zeolite C, its main character is listed in the table 2.
Method according to embodiment 3 prepares high-silica zeolite, and different is that the length of tubular reactor 1 is 25 meters; Wherein the length of first tilting section 131 is 4.7 meters, and diameter is 1.2 meters, and vertically the length of section 132 is 10.9 meters; Diameter is 1.2 meters, and the length of second tilting section 133 is 9.4 meters, and diameter is 1.2 meters; 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, obtained high-silica zeolite D, and its main character is listed in the table 2.
Method according to embodiment 3 prepares high-silica zeolite, and different is, it is 40 minutes that the flow of mixed gas makes the residence time of molecular sieve in tubular reactor, obtains high-silica zeolite E, and its main character is listed in the table 2.
Table 1
| The Y zeolite that contains | Embodiment | 1 | |
|
| Lattice constant, nm | 2.466 | 2.466 | 2.466 | |
| Relative crystallinity, % | 54 | 52 | 49 | |
| Framework si-al ratio (SiO 2/Al 2O 3Mol ratio) | 5.11 | 5.11 | 5.11 | |
| Lattice avalanche temperature, ℃ | 975 | 972 | 970 | |
| Specific surface area, m 2/g | 673 | 665 | 648 | |
| Na 2O content, weight % | 4.5 | 4.4 | 4.1 | |
| RE 2O 3Content, weight % | 11.9 | 13.2 | 16.3 |
Table 2
Can find out from the result of table 2, compare that adopting the framework si-al ratio of the molecular sieve that method provided by the invention makes is SiO with industrial REY
2/ Al
2O
3Mol ratio improves greatly, shows that dealumination complement silicon is effective.In addition; Can find out that from the result of table 2 compare with industrial REY, the molecular sieve that adopts method provided by the invention to make has better relative crystallinity; Higher lattice avalanche temperature; And specific surface area obviously improves, and sodium oxide content reduces greatly, shows the excellent performance of the molecular sieve that method provided by the invention makes.
Embodiment 6-10 is used to explain that the molecular sieve that adopts embodiment 1-5 to make prepares catalyzer.
According to (material butt) molecular sieve: kaolin: pseudo-boehmite: aluminium colloidal sol=38: 30: 22: 10 part by weight 450 ℃ of following spraying dryings, obtains spherical catalytic cracking catalyst then with above-mentioned mixing of materials, making beating.High-silica zeolite A, B, C, D and E that molecular sieve selects for use embodiment 1-5 to make respectively obtain catalyzer C-1, C-2, C-3, C-4 and C-5 respectively, and its main character is listed in the table 3.
Comparative Examples 1
Adopt industrial REY type molecular sieve (main character is listed in the table 2) preparation catalyzer according to the method described above, the gained catalyzer is counted reference catalyst CC-1, and its main character is listed in the table 3.
The catalytic cracking performance test of catalyzer
Light oil microactivity is estimated: the light oil microactivity that adopts standard method (seeing volumes such as " petrochemical complex analytical procedure " (RIPP TP) Yang Cuiding, Science Press, the nineteen ninety publication) assess sample of RIPP92-90; The catalyzer loading amount is 5.0g; Temperature of reaction is 460 ℃, and raw oil is boiling range 235-337 ℃ huge port solar oil, and product is made up of gas chromatographic analysis; Calculate light oil microactivity according to the product composition, the result is in table 3.
Light oil microactivity (MA)=(being lower than gasoline output+gas yield+coke output of 216 ℃ in the product)/charging total amount * 100%
Heavy oil cracking performance evaluation condition: catalyzer is earlier at 800 ℃, and 100% steam aging 12 hours is estimated on ACE (fixed fluidized bed) device then, and raw oil is military three heavy oil (character is seen table 4) that mix, 500 ℃ of temperature of reaction, and 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
Estimate the catalytic cracking performance of the catalyzer of embodiment 6-10 and Comparative Examples 1 preparation according to the method described above respectively, the result lists 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/weight % | 48.3 | 48.6 | 49.5 | 50.9 | 51.7 | 52.1 |
| Na 2O content/weight % | 0.07 | 0.07 | 0.08 | 0.13 | 0.12 | 0.19 |
| Sulfate radical content/weight % | 1.1 | 1.2 | 1.1 | 1.2 | 1.2 | 1.3 |
| Burning decrement/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/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 |
Can find out that from the result of table 3 when adopting the molecular sieve that is made by method provided by the invention to prepare catalyzer, the sodium oxide content of gained catalyzer significantly reduces, 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, 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, weight % | 74.17 | 76.3 | 74.48 | 72.67 | 71.96 | 67.16 |
| Coke selectivity, weight % | 6.93 | 7.04 | 6.95 | 7.44 | 7.38 | 8.56 |
| Yield of light oil, weight % | 72.6 | 73.33 | 72.9 | 69.71 | 69.11 | 67.08 |
| Liquid yield, weight % | 85.71 | 87.02 | 85.98 | 84 | 83.73 | 80.09 |
Can find out from the result of table 5; CC-1 compares with reference catalyst, and adopting the molecular sieve that is made by method provided by the invention is that the catalyzer of active ingredient preparation has higher transformation efficiency, higher liquid yield, higher yield of light oil and lower coke selectivity.
Claims (22)
1. a method for preparing high-silica zeolite is characterized in that, this method comprises molecular sieve and contains gas phase SiCl
4Gas mix to form mixture flow, the said 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 the 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.
2. method according to claim 1, wherein, the molecular sieve in the said mixture flow is 0.015-3m/s with the flow velocity of gas flow.
3. method according to claim 1 and 2, wherein, said gas is gas phase SiCl
4Mixed gas with inert carrier gas.
4. method according to claim 1 and 2, wherein, said gas phase SiCl
4With the weight ratio of molecular sieve be 0.01-1: 1, the inlet amount of said molecular sieve be the 50-2000 kilogram/hour.
5. method according to claim 4, wherein, said gas phase SiCl
4With the weight ratio of molecular sieve be 0.05-0.6: 1, the inlet amount of said molecular sieve be the 100-1500 kilogram/hour.
6. according to any described method in the claim 1,2 and 5, wherein, the temperature of said molecular sieve is 200-600 ℃, the said SiCl that contains
4The temperature of gas be 60-200 ℃.
7. method according to claim 6, wherein, said contact is carried out in tubular reactor, and the method that forms said mixture flow is at molecular sieve and contains SiCl
4Gas mix through a raw materials mix unit earlier before getting into the contact of said tubular reactor.
8. method according to claim 7, wherein, said raw materials mix unit comprises gas-solid mixing tank and/or gas mixer.
9. method according to claim 8; Wherein, said opening for feed is one, and said raw materials mix unit (4) comprises gas-solid mixing tank and gas mixer; Gas mixer is communicated with the gas-solid mixing tank, and the gas-solid mixing tank is communicated with said tubular reactor (1) through one in the said opening for feed.
10. method according to claim 7, wherein, the length of tubular reactor is 5-100 rice, diameter is a 0.01-1.5 rice.
11. according to any described method among the claim 7-10; Wherein, Said tubular reactor comprises body and at least one opening for feed and the discharge port that are positioned at the body two ends; Carry out contact reacts in the said body of entering of said mixture flow from said opening for feed, the product after the contact reacts is outside discharge port is discharged said body, and said tubular reactor is connected with the raw materials mix unit through one in the said opening for feed.
12. method according to claim 11; Wherein, Said body comprises first tilting section and vertical section; One end of said first tilting section and a said vertical section end join, and said discharge port is positioned at the other end of said first tilting section, and said first tilting section is higher than the position that said discharge port belongs to said vertical section position that is connected.
13. method according to claim 12, wherein, the angle between said first tilting section and the vertical section is greater than 10 ° to 90 °.
14. method according to claim 13, wherein, the angle between said first tilting section and the vertical section is greater than 30 ° to 80 °.
15. method according to claim 12, wherein, the length of said first tilting section and vertical section is than being 0.1-10: 1.
16. method according to claim 12, wherein, said body also comprises second tilting section, and an end and the said vertical section the other end of said second tilting section join, and said opening for feed is positioned at the other end of said second tilting section.
17. method according to claim 16, wherein, the position at said opening for feed place is higher than said second tilting section and said vertical section position that is connected.
18. method according to claim 16, wherein, the angle between said second tilting section and the vertical section is greater than 10 ° to 90 °.
19. method according to claim 18, wherein, the angle between said second tilting section and the vertical section is 30 ° to 80 °.
20. according to any described method among the claim 16-19, wherein, the length of said second tilting section and vertical section is than being 0.1-10: 1.
21. method according to claim 1, wherein, this method also comprises carries out gas solid separation with contact back products therefrom, obtains solid high-silica zeolite product and gaseous fraction.
22. method according to claim 21, wherein, this method also comprises said gaseous fraction is contacted with absorption agent, to remove the SiCl in the gaseous fraction
4
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9895681B2 (en) | 2012-10-26 | 2018-02-20 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst preparation method |
| US9993811B2 (en) | 2012-10-26 | 2018-06-12 | China Petroleum & Chemical Corporation | Process and apparatus for preparing a molecular sieve and a catalytic cracking catalyst |
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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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