CN102050460B - Equipment for preparing molecular sieve - Google Patents
Equipment for preparing molecular sieve Download PDFInfo
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- CN102050460B CN102050460B CN200910236633A CN200910236633A CN102050460B CN 102050460 B CN102050460 B CN 102050460B CN 200910236633 A CN200910236633 A CN 200910236633A CN 200910236633 A CN200910236633 A CN 200910236633A CN 102050460 B CN102050460 B CN 102050460B
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Abstract
The invention relates to equipment for preparing a molecular sieve, which comprises a tubular reactor, a gas-solid separator and an absorption column, wherein the tubular reactor comprises a first feeding hole, a discharging hole and a tube body, the first feeding hole and the discharging hole are respectively positioned at two end parts of the tube body, the tubular reactor is communicated with the gas-solid separator through the discharging hole, the upper part of the gas-solid separator is communicated with the absorption column, and the position where the gas-solid separator is connected with the discharging hole is lower than that where the gas-solid separator is connected with the absorption column. The equipment for preparing the molecular sieve, provided by the invention, can realize the continuous operation of the contact reaction of the molecular sieve and SiCl4, and can control the contact time of the molecular sieve and the SiCl4 through controlling the length of the tubular reactor and the flow speed of the carrier gas, thereby being capable of enabling the contact reaction of the molecular sieve with the SiCl4 to be fully carried out in the tubular reactor.
Description
Technical field
The invention relates to a kind of equipment 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, reduce labour intensity and the equipment of the preparation molecular sieve that is applicable to the serialization suitability for industrialized production of greatly enhancing productivity.
The invention provides a kind of equipment for preparing molecular sieve; Wherein, This equipment comprises tubular reactor, gas-solid separator and absorption tower; Said tubular reactor comprises first opening for feed, discharge port and body, and said first opening for feed and discharge port lay respectively at two ends of said body, and said tubular reactor is communicated with said gas-solid separator through said discharge port; The top of said gas-solid separator is communicated with said absorption tower, and the position that said gas-solid separator is connected with discharge port is lower than the position that said gas-solid separator is connected with said absorption tower.
The equipment of preparation molecular sieve provided by the invention passes through molecular sieve and SiCl
4And the carrier gas air is sent in the tubular reactor from the opening for feed of tubular reactor; In tubular reactor, fully be expelled to the gas-solid separator from discharge port again after the reaction; Solid is stayed in the gas-solid separator, and gaseous component then gets into the absorption tower, sponges a small amount of excessive SiCl
4After air can directly discharge.This shows that vapor phase process provided by the invention prepares the equipment of high-silica zeolite owing to make molecular sieve and SiCl
4Contact in tubular reactor, carry out, thereby can realize molecular sieve and SiCl
4Contact reacts carry out continuously, through flow velocity and the length of tubular reactor of control carrier gas, can control molecular sieve and SiCl
4The time of contact, thus can make molecular sieve and SiCl
4Contact reacts in tubular reactor, carry out fully.
Compare with the ultra steady technology of existing still formula gas phase; Vapor phase process provided by the invention prepares the equipment of high-silica zeolite 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 of equipment provided by the invention is very significant.
Description of drawings
Fig. 1 is the structural representation that vapor phase process prepares the equipment of high-silica zeolite that is used for of prior art;
Fig. 2 is the structural representation that is used to prepare the equipment of molecular sieve provided by the invention.
Embodiment
Below in conjunction with accompanying drawing further explain equipment provided by the invention.
According to the equipment that is used to prepare molecular sieve provided by the invention, wherein, 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 maybe be 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 is preferable for 5-100 rice; Therefore; The length of the preferred said tubular reactor 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 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 equipment provided by the 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 of the molecular sieve in the gas-solid separator that prevents in tubular reactor, to cause under the unsettled situation of air-flow; And further fully guarantee in short pipeline, to realize contacting more fully; As shown in Figure 2, said body 13 comprises first tilting section 131 and vertical section 132, and an end of said first tilting section 131 and said vertical section 132 end join; Said 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.
The axis of said first tilting section 131 and the angle between the horizontal plane can be for greater than 0 ° to 80 °, and 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 equipment provided by the invention, under the preferable case, the length of said first tilting section 131 and vertical section 132 is than being 0.1-10: 1, further be preferably 0.2-9: and 1, further preferred 0.4-0.6: 1.
A preferred embodiment of the invention, said body 13 also comprises second tilting section 133, and an end and said vertical section 132 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 first opening for feed place is higher than said second tilting section 133 and said vertical section 132 position that is connected; So that the molecular sieve solid material can dependence itself action of gravity directly get in second tilting section 133, can under the carrying of carrier gas, further carry then.
According to equipment provided by the invention, the axis of said second tilting section 133 and the angle 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.
Have only at equipment provided by the invention under the situation of an opening for feed, can make molecular sieve, carrier gas and SiCl
4Send into by this opening for feed in the body of tubular reactor 1, but under the preferable case, during for the ease of the industriallization continuous production with the cooperating of other devices; Said molecular sieve is generally the thermo-molecular sieve from stoving oven, that is to say that this opening for feed is communicated with stoving oven usually; Therefore; Preferable case, said tubular reactor 1 also comprises second opening for feed, said second opening for feed be positioned at body 13 the end and with the said first opening for feed position adjacent; Said second opening for feed is the gas feed mouth, and said first opening for feed is the feeding-in solid body mouth.In this case, carrier gas and gas phase SiCl
4Sent into by second opening for feed, molecular sieve is then sent into by said first opening for feed.
Further under the preferable case, said tubular reactor 1 also comprises the 3rd opening for feed, said the 3rd opening for feed be positioned at body 13 the end and with the said first opening for feed position adjacent, said the 3rd opening for feed is the gas feed mouth.In this case, carrier gas and SiCl
4Can send into by different opening for feeds respectively.Can independently control carrier gas and SiCl like this
4The amount of gas.
Further under the preferable case, the position at said the 3rd opening for feed place compared to said second opening for feed further from said first opening for feed, and in this case, carrier gas and SiCl
4Send into by second opening for feed and the 3rd opening for feed respectively, thus make carrier gas in advance to the molecular sieve solid material disperse after again with SiCl
4Contact reacts is to avoid a large amount of SiCl
4The local reaction intensity that directly contacts with a large amount of molecular sieve materials simultaneously and cause is excessive, and then causes the loss of the percent crystallinity of zeolite product.
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 in said absorption tower 3 through its open top.
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 an inlet and two outlets, and said inlet is communicated with gas-solid separator 2, is preferably placed at the middle and upper part on said absorption tower.Said two outlets lay respectively at the top and the bottom on said absorption tower, are respectively applied for 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.
According to preferred implementation of the present invention, it is as shown in Figure 2 to adopt equipment provided by the invention to prepare the workflow of high-silica zeolite.Temperature is 200-600 ℃ molecular sieve a, air c and gas phase SiCl
4Raw material b sends in the tubular reactor 1 from first opening for feed, second opening for feed and the 3rd opening for feed respectively, and molecular sieve is with air and gas phase SiCl
4In tubular reactor 1, flowing contacts, and gets into gas-solid separator 2 afterwards, and in gas-solid separator 2, pressure reduces, and high-silica zeolite d is deposited in the bottom of gas-solid separator 2, directly or regularly discharges air 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 air (tail gas e) overflows 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.
When adopting molecular sieve gas phase dealumination complement silicon equipment provided by the invention that molecular sieve is carried out the gas phase dealumination complement silicon; The condition of said gas phase dealumination complement silicon comprises that the solid content of molecular sieve is preferably greater than 98 weight %; The solid content of said molecular sieve is that molecular sieve is through the weight after the high-temperature roasting and the weight ratio before the roasting, the i.e. water cut of the solid content of molecular sieve=100%-molecular sieve; The temperature of molecular sieve is 200-600 ℃, SiCl
4Temperature be 60-150 ℃, SiCl
4Be preferably 0.01-1 with the weight ratio of molecular sieve, further be preferably 0.05-0.60, the flow velocity of carrier gas makes SiCl
4With the residence time of molecular sieve in tubular reactor be 10 seconds to 100 minutes, be preferably 1 minute to 20 minutes, the residence time of molecular sieve in tubular reactor is the value of the length of tubular reactor divided by the flow velocity gained of molecular sieve.Because molecular sieve is by carrier gas and SiCl in tubular reactor
4Gas carries jointly and in tubular reactor, is fluidized, so the flow velocity of molecular sieve equals carrier gas and SiCl
4The flow velocity of gas gas mixture.The flow velocity of inert carrier gas flow is preferably 0.015-3m/s, 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.The temperature of air is preferably 50-350 ℃, further is preferably 100-250 ℃.Because the temperature of the molecular sieve after the roasting is generally more than 300 ℃, therefore the temperature of above-mentioned molecular sieve can obtain through tubular reactor is combined with stoving oven, that is to say; Under the preferable case; The evaluation method selecting optimal equipment of preparation molecular sieve provided by the invention is communicated with stoving oven, and as the upstream device of stoving oven, can utilize the thermal source of the high temperature of molecular sieve after the roasting as the dealumination complement silicon reaction so on the one hand; Start the dealumination complement silicon reaction, thus 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.
Molecular sieve gas phase provided by the invention is mended silicon equipment and 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.
Following embodiment will further explain the present invention, but therefore not limit the present invention.
Embodiment 1-5 is used to explain the equipment of preparation molecular sieve provided by the 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, and diameter is 0.8 meter, and vertically section 132 is perpendicular to horizontal plane; The axis of first tilting section 131 and the angle between the horizontal plane are 75 °, and the axis of second tilting section 133 and the angle between the horizontal plane are 65 °, and the port of second tilting section 132 is first opening for feed; Be respectively arranged with second opening for feed and the 3rd opening for feed with first opening for feed at a distance of the position of 3 meters and 8 meters, the top of gas-solid separator 2 is that diameter is that 6 meters, height are 14 meters cylindrical, and the bottom is for having the opening taper; Cone angle is 45 °; And opening part is provided with valve, and discharge port is positioned at apart from the gas-solid separator top 1 meter position, fills 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, will be the SiCl that 350 ℃ REY molecular sieve, dry air that temperature is 100 ℃ and temperature are 90 ℃ from the temperature of stoving oven
4Gas is sent in the body 13 of tubular reactor 1 by first opening for feed, second opening for feed and the 3rd opening for feed respectively continuously, SiCl
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 dry air 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 1.
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, and diameter is 0.4 meter, and vertically section 132 is perpendicular to horizontal plane; The axis of first tilting section 131 and the angle between the horizontal plane are 55 °, and the axis of second tilting section 133 and the angle between the horizontal plane are 55 °, and the port of second tilting section 132 is first opening for feed; Be respectively arranged with second opening for feed and the 3rd opening for feed with first opening for feed at a distance of the position of 6 meters and 10 meters, the top of gas-solid separator 2 is that diameter is that 5 meters, height are 10 meters cylindrical, and the bottom is for having the opening taper; Cone angle is 35 °; And opening part is provided with valve, and discharge port is positioned at apart from the gas-solid separator top 2 meters position, fills 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 500 ℃ REY molecular sieve, dry air that temperature is 200 ℃ and temperature are 130 ℃ with temperature
4Gas is sent in the body 13 of tubular reactor 1 by first opening for feed, second opening for feed and the 3rd opening for feed respectively continuously, SiCl
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 dry air 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 1.
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, and diameter is 1.2 meters, and vertically section 132 is perpendicular to horizontal plane; The axis of first tilting section 131 and the angle between the horizontal plane are 45 °, and the axis of second tilting section 133 and the angle between the horizontal plane are 45 °, and the port of second tilting section 132 is first opening for feed; Be respectively arranged with second opening for feed and the 3rd opening for feed with first opening for feed at a distance of the position of 2 meters and 6 meters, the top of gas-solid separator 2 is that diameter is that 9 meters, height are 12 meters cylindrical, and the bottom is for having the opening taper; Cone angle is 30 °; And opening part is provided with valve, and discharge port is positioned at apart from the gas-solid separator top 4 meters position, fills 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 300 ℃ REY molecular sieve, dry air that temperature is 140 ℃ and temperature are 80 ℃ with temperature
4Gas is sent in the body 13 of tubular reactor 1 by first opening for feed, second opening for feed and the 3rd opening for feed respectively continuously, SiCl
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 1.
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 1.
Embodiment 5
Method according to embodiment 3 prepares high-silica zeolite, and different is, it is 40 minutes that the flow of dry air makes the residence time of molecular sieve in tubular reactor, obtains high-silica zeolite E, and its main character is listed in the table 1.
Table 1
| The molecular sieve numbering | A | B | C | D | E | Industry REY |
| Lattice constant, nm | 2.453 | 2.451 | 2.455 | 2.460 | 2.450 | 2.465 |
| Relative crystallinity, % | 54 | 55 | 58 | 60 | 51 | 46 |
| Framework si-al ratio (SiO 2/Al 2O 3Mol ratio) | 7.84 | 8.45 | 7.29 | 6.15 | 8.79 | 5.26 |
| Lattice avalanche temperature, ℃ | 1029 | 1022 | 1025 | 1019 | 1017 | 972 |
| Specific surface area, m 2/g | 647 | 632 | 651 | 623 | 595 | 588 |
| Na 2O content, weight % | 0.28 | 0.31 | 0.35 | 1.05 | 0.41 | 2.21 |
| RE 2O 3Content, weight % | 10.9 | 13.7 | 16.4 | 14.2 | 10.7 | 16.6 |
Can find out that from the result of table 1 (industrial REY) compares with raw material, adopting the framework si-al ratio of the molecular sieve that equipment provided by the invention makes is SiO
2/ Al
2O
3Mol ratio improves greatly, shows that dealumination complement silicon is effective.In addition; Can find out from the result of table 1; (industrial REY) compares with raw material; Adopt relative crystallinity, lattice avalanche temperature and the specific surface area of the molecular sieve that equipment provided by the invention makes obviously to improve, sodium oxide content obviously reduces, and shows the excellent performance of the molecular sieve that equipment provided by the invention makes.
Embodiment 6-10 is used to explain that the high-silica zeolite 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 catalyst A-1, A-2, A-3, A-4 and A-5 respectively, and its main character is listed in the table 2.
Comparative Examples 1
Adopt industrial REY type molecular sieve (main character is listed in the table 1) preparation 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 2.
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 2.
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 3) 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
Coke selectivity=coke 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 4.
Table 2
| The catalyzer numbering | A-1 | A-2 | A-3 | A-4 | A-5 | CC-1 |
| The molecular sieve numbering | A | B | C | D | E | Industry REY |
| Al 2O 3Content/weight % | 48.2 | 48.8 | 49.1 | 51.6 | 51.2 | 52.1 |
| Na 2O content/weight % | 0.08 | 0.07 | 0.09 | 0.15 | 0.17 | 0.19 |
| Sulfate radical content/weight % | 1.2 | 1.3 | 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) | 0.40 | 0.41 | 0.42 | 0.39 | 0.37 | 0.35 |
| Specific surface area/(m 2·g) | 268 | 269 | 271 | 265 | 255 | 245 |
| Abrasion index/(%h -1) | 1.5 | 1.6 | 1.3 | 1.4 | 1.3 | 1.9 |
| Apparent bulk density/(gmL -1) | 0.75 | 0.76 | 0.75 | 0.75 | 0.76 | 0.75 |
| Micro-activity (800,4h)/% | 82 | 81 | 83 | 79 | 78 | 74 |
| Screening distribution/weight % | ||||||
| 0～20μm | 3.7 | 2.9 | 3.1 | 4.2 | 3.2 | 3.8 |
| 0～40μm | 19.7 | 18.2 | 17.8 | 19 | 17 | 18.9 |
| 0～149μm | 93.3 | 93.6 | 92.1 | 92.5 | 91.8 | 93.4 |
| Average particulate diameter (micron) | 67.7 | 66.4 | 70.6 | 70.3 | 72.8 | 69.4 |
Can find out that from the result of table 2 when adopting the molecular sieve that is made by equipment provided by the invention to prepare catalyzer, the pore volume and the specific surface area of gained catalyzer obviously increase, micro-activity obviously improves.
Table 3
| Raw oil | ACE estimates |
| Density (20 ℃), g/cm 3 | 0.9044 |
| Refractive power (70 ℃) | 1.5217(20℃) |
| Viscosity (100 ℃), mm 2/s | 9.96 |
| Zero pour, ℃ | 40 |
| Aniline point, ℃ | 95.8 |
| C weight % H weight % S weight % N weight % | 85.98 12.86 0.55 0.18 |
| Carbon residue, m% | 3.0 |
| Boiling range, ℃ over point 5% 10% 30% 50% 70% 90% | ?243 294 316 395 429 473 ?- |
Table 4
| Catalyzer | A-1 | A-2 | A-3 | A-4 | A-5 | CC-1 |
| Product distributes, weight % | ||||||
| Dry gas | 1.24 | 1.25 | 1.17 | 1.28 | 1.27 | 1.23 |
| Liquefied gas | 12.31 | 13.39 | 12.71 | 14.41 | 14.58 | 13.01 |
| Coke | 5.54 | 5.72 | 5.35 | 5.71 | 5.42 | 5.75 |
| Gasoline | 54.29 | 55.66 | 54.57 | 50.68 | 49.7 | 47.17 |
| Diesel oil | 18.09 | 17.11 | 18.25 | 18.03 | 18.55 | 19.91 |
| Heavy oil | 8.53 | 6.87 | 7.95 | 9.89 | 10.48 | 12.93 |
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 |
| Transformation efficiency, weight % | 73.38 | 76.02 | 73.8 | 72.08 | 70.97 | 67.16 |
| Coke selectivity, weight % | 7.55 | 7.52 | 7.25 | 7.92 | 7.64 | 8.56 |
| Yield of light oil, weight % | 72.38 | 72.77 | 72.82 | 68.71 | 68.25 | 67.08 |
| Liquefied gas+gasoline+diesel oil, weight % | 84.69 | 86.16 | 85.53 | 83.12 | 82.83 | 80.09 |
Can find out from the result of table 4; CC-1 compares with reference catalyst; The molecular sieve that employing is made by equipment provided by the invention is that the catalyzer of active ingredient preparation has higher heavy oil conversion rate, higher liquid yield and yield of light oil, coke selectivity preferably.
Claims (14)
1. equipment for preparing molecular sieve; It is characterized in that; This equipment comprises tubular reactor (1), gas-solid separator (2) and absorption tower (3); Said tubular reactor (1) comprises first opening for feed, discharge port and body (13); Said first opening for feed and discharge port lay respectively at two ends of said body (13); Said tubular reactor (1) is communicated with said gas-solid separator (2) through said discharge port, and 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 body (13) comprises first tilting section (131) and vertical section (132); One end of said first tilting section (131) and an end of said vertical section (132) join, and said discharge port is positioned at the other end of said first tilting section (131), and the position that said first tilting section (131) is connected with said vertical section (132) is higher than the position that said discharge port belongs to.
2. equipment according to claim 1, wherein, the length of said tubular reactor (1) is 5-100 rice, diameter is a 0.01-1.5 rice.
3. equipment according to claim 1, wherein, the axis of said first tilting section (131) and the angle of horizontal plane are greater than 0 ° to 80 °.
4. equipment according to claim 3, wherein, the axis of said first tilting section (131) and the angle between the horizontal plane are 10 ° to 60 °.
5. equipment according to claim 1, wherein, the length of said first tilting section (131) and vertical section (132) is than being 0.1-10:1.
6. equipment according to claim 1; Wherein, Said body (13) also comprises second tilting section (133), and an end of said second tilting section (133) and the other end of said vertical section (132) join, and said first opening for feed is positioned at the other end of said second tilting section (133).
7. equipment according to claim 6, wherein, the position at said first opening for feed place is higher than said second tilting section (133) and the said vertical section position that (132) are connected.
8. equipment according to claim 7, wherein, the axis of said second tilting section (133) and the angle between the horizontal plane are greater than 0 ° to 80 °.
9. equipment according to claim 8, wherein, the axis of said second tilting section (133) and the angle between the horizontal plane are 10 ° to 60 °.
10. according to claim 6 or 7 described equipment, wherein, the length of said second tilting section (133) and vertical section (132) is than being 0.1-10:1.
11. according to claim 1 or 6 described equipment, wherein, said tubular reactor (1) also comprises second opening for feed, said second opening for feed be positioned at body (13) the end and with the said first opening for feed position adjacent.
12. equipment according to claim 11; Wherein, Said tubular reactor (1) also comprises the 3rd opening for feed; Said the 3rd opening for feed be positioned at body (13) the end and with the said first opening for feed position adjacent, and the position at said the 3rd opening for feed place compared to said second opening for feed further from said first opening for feed.
13. equipment according to claim 1, wherein, the bottom of said gas-solid separator (2) has the taper of opening for the end.
14. equipment according to claim 13, wherein, the position that said gas-solid separator (2) is connected with discharge port is higher than the zero position of said taper.
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| CN103785436B (en) * | 2012-10-26 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of equipment preparing catalytic cracking catalyst |
| CN103785437B (en) * | 2012-10-26 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of method preparing catalytic cracking catalyst |
| CN103787353B (en) * | 2012-10-26 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of equipment preparing molecular sieve |
| TWI614214B (en) | 2012-10-26 | 2018-02-11 | China Petrochemical Technology Co Ltd | Method and apparatus for preparing molecular sieves and catalysts for catalytic cracking |
| WO2014063445A1 (en) * | 2012-10-26 | 2014-05-01 | 中国石油化工股份有限公司 | Catalytic cracking catalyst preparation method |
| CN103785438B (en) * | 2012-10-26 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of equipment preparing catalytic cracking catalyst |
| CN111111568A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Gas-solid reactor for preparing molecular sieve and equipment for preparing molecular sieve |
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| EP1180521A1 (en) * | 2000-08-18 | 2002-02-20 | Degussa AG | Method of producing allyltrichlorosilane |
| CN1683245A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | High silicon Y-type zeolite containing rare-earth and its preparing method |
| CN101544545A (en) * | 2008-03-27 | 2009-09-30 | 中国石油化工股份有限公司 | Method for producing dimethyl ether from methanol |
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| EP1180521A1 (en) * | 2000-08-18 | 2002-02-20 | Degussa AG | Method of producing allyltrichlorosilane |
| CN1683245A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | High silicon Y-type zeolite containing rare-earth and its preparing method |
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