CN1194941A - Process for preparation of catylist composition containing silicon-rich ultrastable Y zeolite - Google Patents
Process for preparation of catylist composition containing silicon-rich ultrastable Y zeolite Download PDFInfo
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Abstract
A process for preparing catalyst composition containing high-Si superstable Y zeolite features that the SiCl4 gas with water content less than 900 ppm and carried by dry air, NaY zeolite and shaped refractory, dry inorganic oxide material in weight ratio of 0.1-0.8 (SiCl4) : 1 (shaped material) are contacted with each other to react at 150-550 deg.C for 10 min-5 hr. The ratio of shaped dry material particles (32-125 microns) in total particles is over 80%. The weight ratio of NaY zeolite to refractory inorganic oxide is 1 : (0.2-1.0). The Si/Al ratio of NaY zeolite is 3-6. Its advantage is continuous production in large scale as said shaped material has good flowability.
Description
The invention relates to a kind of preparation that contains the catalyst composition of y-type zeolite, the preparation of more specifically saying so and containing the catalyst composition of rich silicon ultra stabilization Y zeolite about a kind of.
Overstable gamma zeolite is meant that structure cell is less, the class y-type zeolite that silica alumina ratio is higher, this type of zeolite has higher hot supporting capacity and to the high stability of water vapor, and have lower hydrogen transfer activity and a higher gasoline selective, be especially suitable for use as the active ingredient of catalyst for cracking heavy oil, it generally prepares by the lower y-type zeolite of silica alumina ratio is carried out dealuminzation.
(the Zeolite Chemistryand Catalysis of C.V.Dvid and P.K.Maher in the preparation method of numerous ultrastable Ys, ACS Monograph171, P285～331, Washington D.C., 1976) the hydrothermal dealumination method of Ti Chuing has become one of method that is most widely used, this method exchanges the NaY zeolite earlier with the aqueous solution that contains ammonium ion, to reduce the sodium ions content in the zeolite, then in 600～825 ℃ of zeolites after roasting ammonium ion exchange under the water vapour atmosphere, make its super stabilizing, this method cost is lower and be easy to large-scale industrialization production, but in this way y-type zeolite is taken out aluminium, when skeleton is removed, in zeolite framework, form a large amount of rooms, and the silicon on the zeolite self-framework can not in time be filled up these rooms, thereby the easy avalanche of the skeleton that causes zeolite product, the structural instability that causes zeolite product, crystallization reservation degree is lower, in addition, when in this way y-type zeolite being taken out aluminium, because of zeolite powder particle too little (being generally 0.1～10 micron), when in fixed bed, carrying out, can cause too high pressure drop, in industrial very difficult application, and when in inclination kiln formula rotary kiln, carrying out, zeolite granular is difficult to carry out uniform contact with water vapor in flowing, some zeolite granulars have contacted too much water vapor and have removed too much framework aluminum, other zeolite granulars then contact water vapor seldom, framework aluminum is not removed basically, this has just caused zeolite granular is carried out product property instability behind the hydrothermal dealumination, catalytic activity and/or selectivity as the resulting zeolite product of experiment of twice similarity condition have very big difference, with the catalytic activity and/or the selectivity of once testing each zeolite granular a great difference are arranged also.
For solving the problem that can not obtain the uniform zeolite product of character when the hydrothermal dealumination method is carried out and can not be used for fixing bed in rotary kiln, at US5,288, disclosed a kind of hydro-thermal treatment method of zeolite process in 396 in the disclosed method for hydrogen cracking, this method for hydrogen cracking is included under the condition of hydrocracking and the existence of outer hydrogenation, hydrocarbon raw material is contacted with a kind of catalyzer, described catalyzer contains the zeolite that unit cell dimension is 24.20～24.40 dusts, this prepare zeolite method comprises: (a) with at least a heat-resistant inorganic oxide and a kind of crystal silicon-aluminate zeolite component extrusion moulding with cracking activity, the unit cell dimension of described crystal silicon-aluminate zeolite is 24.40～24.95 dusts, and it is selected from by y-type zeolite, modified zeolite of Y-type, in one group that X type zeolite and modification X zeolite are formed; And, (b) be higher than roasting forming composition under the 5.0Psia at steam partial pressure, roasting condition should make the unit cell dimension of crystal silicon-aluminate zeolite be contracted to 24.20～24.40 dusts, adopt this method granules of catalyst in rotary kiln, can contact with water vapor equably, the catalyst combination properties that obtains is even, this method also can be carried out in fixed bed, but the lower problem of zeolite product crystallization reservation degree that the unresolved hydrothermal dealumination method of this method obtains, simultaneously, the particle of the catalyst composition of this method preparation is bigger, at least 1/32 inch of diameter (793.75 microns), thereby it only is applicable to and adds. the preparation of hydrogen cracking catalyst, be not suitable for the preparation of fluidized-bed microballoon cracking catalyst, the problem that it solved also is to exist in the hydrothermal dealumination method, meticulous because of zeolite granular, zeolite granular and water vapor can not uniform contact, the uneven problem of zeolite product character that causes.
For there are a large amount of rooms in zeolite after solving dealuminzation, cause the more problem of zeolite product crystallization reservation degree decline, US4 adopts NaY or NH that silica alumina ratio is lower among the preparation method of 503,023 disclosed overstable gamma zeolites
4The reactant aqueous solution of Y zeolite and a kind of silicofluoride is used SiF
6 2-Remove the framework aluminum in the zeolite, and silicon mended behind the dealuminzation in the formed skeleton room, this method has remedied the more defective in hydrothermal method skeleton room, the crystallization reservation degree of product is improved, but this method easily produces some deleterious stray crystals in reaction process, has influenced the use properties of zeolite, because the use of a large amount of silicofluorides, brought again than the serious environmental pollution problem, thereby aluminium extracting and silicon supplementing method that neither a kind of very ideal zeolite.
The dealumination complement silicon method of another kind of zeolite more satisfactory and commonly used is the method for zeolite and silicon halide being carried out gas-phase reaction.
US4,701,313 disclose a kind of control to produce have the method that contains si molecular sieves of certain aluminium content, this method comprises provides a kind of initial aluminium and boron content all greater than zero boracic Beta molecular sieve, handles this zeolite with silicon tetrachloride, and the temperature and time of processing is enough to make silicon to replace boron, and reclaiming boron content reduces, but the siliceous zeolite that keeps initial aluminium content, this method at be boron-containing molecular sieve, obviously be not suitable for Si-Al zeolite.
Te Kaiping 2-20,562 disclose a kind of super stabilizing method of y-type zeolite, this method is included under the condition of exclusion of water, under 150～450 ℃ temperature, with NaY zeolite and the reaction of gaseous state silicon tetrachloride, make the lattice constant of y-type zeolite be contracted to 24.20～24.60 dusts, silica alumina ratio is increased to 6.5～39.9, being equivalent to alumina content is 4.1～18.4 heavy %, and the silica alumina ratio of described raw material zeolite is 3～6, and being equivalent to alumina content is 18.5～29.7 heavy %, when adopting this method, silicon halide can be simultaneously carry out dealuminzation and mend silicon zeolite, products obtained therefrom skeleton room is few, and by product is easy washing and recycling, minor N aCl and AlCl
3Deng material, do not have tangible problem of environmental pollution, but because the reaction of silicon halide and NaY zeolite is more violent, and when comparatively high temps reacted, zeolite structured avalanche was more serious, the crystallization reservation degree of product is wayward in higher level.
For solving the still not high enough problem of overstable gamma zeolite crystallization reservation degree of silicon halide gas phase dealuminzation method preparation, EP0,295,471A
1Proposed a kind of method, be about to dried NaY zeolite and use the zellon multiviscosisty earlier, then with SiCl
4Backflow is boiled and is reacted, reacted product filters the back and uses earlier non-aqueous solvent, wash as methyl alcohol, ethanol etc., and then wash with water, the lattice constant of the overstable gamma zeolite that obtains like this is 24.53～24.60 dusts, crystallization keeps Du Keda 85～95%, but this method is owing to adopted non-aqueous solvent, thereby operate dangerously, production cost also improves greatly, is difficult to carry out large-scale commercial production.
The problem of the attention of another value is, existing silicon halide gas phase dealuminzation method is raw materials used all to be with the raw material of NaY zeolite powder as reaction, because NaY zeolite powder inherent physico-chemical property determines, also because the aluminium that the NaY zeolite removes in reaction process can play the effect of binding agent in the presence of less water, therefore, the NaY zeolite easily is agglomerated into piece in reaction process, and it is mobile very poor, thereby the frequent retentate that is trapped in transport pipe or the rotary kiln that produces, the hardness of these retentates is generally bigger, cause the obstruction of pipeline easily, even not stopping up zeolite also easy and that import later mixes, produce batch mixing, cause that this part zeolite and silicon halide are long duration of contact, cause reaction inhomogeneous, the character of the product that obtains is also inhomogeneous, this part zeolite causes the structural breakdown of zeolite because of long with the silicon halide reaction times even, influences the crystallization reservation degree of zeolite product.Because of the reaction of silicon halide and NaY zeolite is to carry out in closed system, it is infeasible adopting the method for mechanical arm mediation blocking portion, often be prone to owing to equipment stops up the various accidents that produce thermal zone press operation, how to address this problem and become a urgency problem to be solved, moreover, silicon halide is a strong exothermal reaction to the reaction of NaY zeolite dealumination complement silicon, easily cause local superheating, make structure just avalanche before not mending silicon of this overheated partial zeolite, this also is the Another reason that causes zeolite product crystallization reservation degree to descend, thereby based on the problem of above-mentioned existence, in fact strict, this dealumination complement silicon method only is applicable in a small amount at present, as several grams, the dealumination complement silicon of tens gram NaY zeolites, and be difficult for realizing the serialization large-scale commercial production.
The objective of the invention is to overcome the NaY zeolite that has the existence of silicon halide gas phase dealuminzation method now and easily be agglomerated into piece, mobile poor, easily generate retentate, easily result in blockage, thereby be difficult for realizing the industrial shortcoming of serialization, a kind of be difficult for being agglomerated into piece, good fluidity are provided, be difficult for resulting in blockage, easily realize the preparation method of the catalyst composition that contains the rich silicon ultra stabilization Y zeolite that serialization industry produces.
Method provided by the invention comprises water content less than the drying and moulding thing of silicon tetrachloride gas 900ppm, that dry air carries and NaY zeolite and heat-resistant inorganic oxide by the silicon tetrachloride total amount: forming composition=0.1～0.8: 1 weight ratio, 150～550 ℃ of contact reactss 10 minutes to 5 hours, the particle of 35～125 microns of particle diameters accounts for more than 80% of total particle number in the described drying and moulding thing, the weight ratio of NaY zeolite and heat-resistant inorganic oxide is 1: 0.2～1.0, and the silica alumina ratio of NaY zeolite is 3～6.
According to method provided by the invention, used silicon tetrachloride is a kind of strong absorbent material, can generate HCl with the water reaction, it can destroy the structure of zeolite in reaction process, also can etching apparatus, thereby require to carry water-content in the dry air of silicon tetrachloride less than 900ppm, preferably less than 600ppm, water-content should be less than 10 heavy %, preferably less than 4 heavy % in the forming composition of NaY zeolite and heat-resistant inorganic oxide.
Heat-resistant inorganic oxide in the described forming composition can be the inorganic oxide that can be used as catalyst component arbitrarily, heat-resistant inorganic oxide commonly used is silicon oxide, aluminum oxide, silica-alumina, phosphorated aluminum oxide, various clays such as kaolin, modified kaolin, halloysite, diatomite etc., preferred silicon oxide, aluminum oxide, silica-alumina, phosphorated aluminum oxide, more preferred silicon oxide.Described forming composition can by NaY zeolite and silicon sol, aluminium colloidal sol, phosphorus aluminium colloidal sol or silicon-aluminum sol are mixed moulding then, drying prepares; the method of described moulding can adopt spray shaping; the method of spray shaping is preferably adopted in extrusion pelletizing or drip various existent method such as ball forming.
The weight ratio of described NaY zeolite and heat-resistant inorganic oxide can be 1: 0.2～1, preferred 1: 0.2～0.8.
The weight ratio of described silicon tetrachloride and forming composition can be 0.1～0.8: 1, preferred 0.1～0.5: 1.Preferred 250～550 ℃ of the temperature of described reaction, preferred 30 minutes to 3 hours of reaction times.
According to method provided by the invention, the product that obtains after forming composition and the silicon tetrachloride reaction can be handled with existing method, for example, available dry air purged 10 minutes to 2 hours, cooled product with deionized water wash to remove the sodium ion of solubility, chlorion, by products such as aluminum ion, contain lattice constant 24.30～24.50 dusts in the composition that obtains, crystallization reservation degree is greater than 85% rich silicon ultra stabilization Y zeolite, the content of sodium oxide is less than 1 heavy % in the composition, it can directly be used as particularly catalytic cracking catalyst of hydrocarbon conversion catalyst, also can or add other component and be prepared into hydrocarbon conversion catalyst, particularly catalytic cracking catalyst through other modification.For example, it can be pressed the proportioning of each component of catalytic cracking catalyst, it is dispersed in the complete synthesis or semi-synthetic carrier, be prepared into the catalytic cracking catalyst that contains overstable gamma zeolite according to a conventional method, also it can be gone up rare earth with the aqueous solution exchange that contains rare earth ion, it is dispersed in the complete synthesis or semi-synthetic carrier according to a conventional method again, prepares the catalytic cracking catalyst of super-stable Y zeolite containing rare-earth elements.Again for example, can in this catalyst composition, introduce the hydrogenation active metals component,,, or add other carrier adhesive again and be prepared into hydrocracking catalyst directly as hydrocracking catalyst as group VIII and group vib metal.
Method provided by the invention has following advantage:
(1) the present invention adopts and earlier NaY zeolite and heat-resistant inorganic oxide is mixed, the granule number that is prepared into 35～125 microns of particle diameters accounts for the several forming composition more than 80% of total particle, and then with the method for forming composition and silicon tetrachloride reaction, described forming composition good fluidity, be difficult for being agglomerated into piece, thereby avoided the generation of obstruction and retentate, it is a kind of industrial method of serialization that is easy to realize, for example, according to method provided by the invention, the particle that utilizes middle-scale device to prepare 37.79～123.59 microns of particle diameters accounts for the forming composition of total particle several 86.28%, this forming composition is reacted with silicon tetrachloride in rotary kiln, do not find latch up phenomenon and caking phenomenon, also do not find retentate, reaction is carried out serially smoothly.
(2) in method provided by the invention, has interaction between heat-resistant inorganic oxide and the NaY zeolite, a kind of effect is the diluting effect of heat-resistant inorganic oxide to the zeolite body, this reaction heat energy part that silicon tetrachloride and zeolite framework generation dealumination reaction are emitted is absorbed by heat-resistant inorganic oxide, and taken away by air-flow, the zeolite structured destruction of having avoided local superheating to cause, this helps the raising of crystallization of zeolites reservation degree; Another kind of effect is that heat-resistant inorganic oxide is to Na in the zeolite
+Diluting effect, to contain Na ion concentration higher because of the NaY zeolite, and it is lower to contain the sodium amount in the heat-resistant inorganic oxide, and this has just formed the concentration gradient of sodium ion between zeolite and heat-resistant inorganic oxide, when at high temperature handling zeolite, also promoted Na in the zeolite with silicon tetrachloride
+Migration in heat-resistant inorganic oxide helps Na in the product
+The reduction of content.Because the effect of above-mentioned two aspects, in the catalyst composition of preparing according to method provided by the invention, the crystallization of rich silicon ultra stabilization Y zeolite keeps Du Keda more than 85%, sodium oxide content is less than 1 heavy %, be not less than the prior art level, for example, according to method provided by the invention, 250～500 ℃ of temperature, 40～120 minutes reaction times, silicon tetrachloride and forming composition weight ratio 0.10～0.44, under the condition of NaY zeolite and heat-resistant inorganic oxide weight ratio 0.26～0.63, with the forming composition and the silicon tetrachloride reaction of NaY zeolite and silicon oxide, the crystallization of the rich silicon ultra stabilization Y zeolite in the catalyst composition that obtains keeps Du Keda 85～91% in the forming composition, lattice constant is 24.31～24.52 dusts, and sodium oxide content is 0.28～0.90 heavy %.
(3) adopt catalyst composition that contains rich silicon ultra stabilization Y zeolite and heat-resistant inorganic oxide that method provided by the invention prepares and the catalytic cracking catalyst that utilizes said composition further to prepare to have and the equal or higher catalytic performance of preparing by art methods of catalyzer.For example according to method provided by the invention, with NaY zeolite and silica weight than being that 0.63 the NaY zeolite and the forming composition of silicon-dioxide are that initiator is prepared a kind of catalyst composition, with boiling range is that 227～475 ℃ wax oil is a raw material, 482 ℃ of temperature of reaction, and air speed 16 hours
-1, the agent weight of oil is estimated the catalytic performance of crossing 4 hours catalyst composition through 800 ℃ of 100% steam-treated than being under 4 the condition, and the wax oil transformation efficiency can reach 87.4 heavy %, and gasoline yield can reach 59.8 heavy %; With the above-mentioned catalyst composition RECl that is prepared into
3Aqueous solution exchange last 3.1 weighs the rare earth (in oxide compound) of %, and after 4 hours, estimates its activity with 100% steam-treated at 800 ℃ under the situation identical with above-mentioned reaction conditions, and the wax oil transformation efficiency can reach 84.5 heavy %, and gasoline yield can reach 66.6 heavy %.Again for example, above-mentioned catalyst composition is used RECl earlier
3Rare earth is introduced in aqueous solution exchange, it is being dispersed in the containing in the Suzhou kaolin slurry of silicon sol that 20 heavy % solid contents are 25 heavy % of solid content 40%, drying and moulding, the product that obtains is prepared salic 31.7 heavy % at 800 ℃ with 100% steam-treated after 4 hours, rare earth oxide 1.1 heavy %, the catalytic cracking catalyst of sodium oxide 0.19 heavy %, under reaction conditions same as described above, its catalytic performance is estimated, the wax oil transformation efficiency can reach 79.9 heavy %, and gasoline yield can reach 60.6 heavy %.
The following examples will the present invention will be further described.
Example 1
With silica alumina ratio 4.0, lattice constant 24.73 dusts, sodium oxide content 16.0 heavy %, the NaY zeolite of solid content 65.0 heavy % (Qilu Petrochemical company catalyst plant is produced) 73.0 grams grind back and dioxide-containing silica 25.0 heavy %, the silicon sol of PH=4～5 (Changhong chemical plant, Beijing product) 50.0 grams and deionized water mix for 20 milliliters, filter, 110 ℃ of oven dry, sieve is got particle 45.0 grams of 35～125 microns of particle diameters and is put into tube furnace, the dry air that feeds water-content 600ppm under 400 ℃ of temperature purged two hours, to remove the moisture in the forming composition, be warming up to 500 ℃, feed the silicon tetrachloride (SiCl that dry air carries with the speed of 35 ml/min
4Content 95 heavy %, produce in chemical plant, Dagu, Tianjin) reacted 60 minutes, the consumption of silicon tetrachloride is 20.8 grams (silicon tetrachloride and forming composition weight ratio are 0.44), the reaction back fed the dry air purging 1 hour with the speed of 100 ml/min, take out sample and find no coalescent caked phenomenon, use deionized water wash, remove solubility Na
+, Cl
-And Al
3+Deng by product, 110 ℃ of oven dry, must contain the catalyst composition of rich silicon ultra stabilization Y zeolite, be designated as A, its sodium oxide content, the lattice constant of composition mesolite, crystallization reservation degree, and the avalanche temperature is listed in the table 1, sodium oxide content aas determination wherein, lattice constant, crystallization reservation degree is measured with x-ray diffraction method, and the avalanche temperature is measured with differential thermal (DTA) method.
Example 2
With silica alumina ratio 4.5, lattice constant 24.71 dusts, sodium oxide content 15.8 heavy %, the NaY zeolite of solid content 65.0 heavy % (Qilu Petrochemical company catalyst plant is produced) 450 grams grind the back and mix for 150 milliliters with silicon sol (specification is with example 1) 500.0 grams and deionized water, filter, 110 ℃ of oven dry, sieve is got particle 80.0 grams of 35～125 microns of particle diameters and is put into tube furnace, under 300 ℃ of temperature, feed the dry air 3 hours of water-content 800ppm, to remove the moisture in the forming composition, be cooled to 250 ℃, feed the silicon tetrachloride (specification is with example 1) 40 minutes that dry air carries with the speed of 20 ml/min, the consumption of silicon tetrachloride is 18.5 gram (SiCl
4With the forming composition weight ratio be 0.22), the reaction back feeds dry air with the speed of 100 ml/min, purged 2 hours, take out sample, find no coalescent caked phenomenon, press zeolite forming composition: RECl with rare earth chloride (cerium oxide content is greater than 45 heavy %, and produce in the chemical plant, packet header, the technical grade) aqueous solution
3: H
2O=1: 0.13: 10 weight ratio was with product exchange 30 minutes, and 85 ℃ of exchange temperature are filtered, washed to there not being Cl
-110 ℃ of oven dry, get the catalyst composition of rare earth-containing rich silicon ultra stabilization Y zeolite, be designated as B, its sodium oxide content, rare earth oxide content, the lattice constant of composition mesolite, crystallization reservation degree and avalanche temperature are listed in the table 1, and wherein content of rare earth is measured and adopted the X-ray fluorescence analysis.
Example 3 is with silica alumina ratio 5.05, lattice constant 24.66 dusts, sodium oxide content 15.6 heavy %, become in the glue jar with 15.0 kilograms of silicon sol (specification is with example 1) and 13.0 kilograms of 100 liters of packing into of deionized water are medium-sized after 8.0 kilograms of grindings of the NaY zeolite of the heavy % of solid content 75.0 (Qilu Petrochemical company catalyst plant is produced), mix making beating, stir, be delivered to (Denmark APV company introduction in the medium-sized spray tower, throughput is evaporated water 100Kg per hour), spray shaping under 550 ℃ of temperature, the size distribution of forming composition is as shown in table 2, and the MasterSizer E3600 type laser particle analyzer that size distribution adopts Britain Malvem company to produce is measured.7.0 kilograms of dry airs with water content 600ppm of forming composition were purged 2 hours down at 450 ℃, to remove moisture wherein, continuously feed in rotary kiln with 0.16 kilogram/minute speed forming composition, simultaneously, under 450 ℃ of conditions, speed with 875 ml/min feeds the silicon tetrachloride (specification is with example 1) that dry air carries, and be 120 minutes duration of contact that makes forming composition and silicon tetrachloride, and the silicon tetrachloride consumption is 1.1 kilograms of (SiCl
4With the weight ratio of forming composition be 0.15), reacted sample speed is that 8.75 liters/minute dry air purged 1 hour, reaction process can be finished continuously, unit is agglomerated into piece, phenomenon of blocking takes place, and does not have retentate in the rotary kiln substantially.Press zeolite forming composition: RECl with rare earth chloride (specification is with the example 2) aqueous solution
3: H
2O=1: 0.21: 10 weight ratio, under 85 ℃,, filter, wash to there not being Cl with product exchange 0.5 hour
-, 110 ℃ of oven dry, the catalyst composition of super-stable Y zeolite containing rare-earth elements, be designated as C, its sodium oxide content, the lattice constant of content of rare earth and composition mesolite, crystallization reservation degree and avalanche temperature are listed in the table 1.
Example 4
Preceding forming composition 100 grams of silicon tetrachloride dealuminzation that take by weighing preparation in the example 3 place tube furnace, under 400 ℃ of temperature, feed the dry air 3 hours of water-content 600ppm, be cooled to 300 ℃ then, feed silicon tetrachloride (specification is with the example 1) reaction 60 minutes that dry air carries with the speed of 5 ml/min, the consumption of silicon tetrachloride is 10.5 gram (SiCl
4With the forming composition weight ratio be 0.10), reaction back feeds dry air with the speed of 100 ml/min, purges 1 hour, takes out sample, does not see coalescent caked phenomenon, uses rare earth chloride (specification is with the example 2) aqueous solution to press zeolite forming composition: RECl
3: H
2O=1: 0.13: 10 weight ratio, at 85 ℃ reaction product is exchanged 0.5 hour, filter, 110 ℃ of oven dry, get the catalyst composition of super-stable Y zeolite containing rare-earth elements, be designated as D, its sodium oxide content, the lattice constant of rare earth oxide content and composition mesolite, crystallization reservation degree and avalanche temperature are listed in the table 1.
Example 5
Take by weighing by 45.0 grams of the forming composition before the silicon tetrachloride dealuminzation of example 1 preparation and put into tube furnace, under 400 ℃ of temperature, feed the dry air 3 hours of water-content 800ppm, switch speed is the dry air of 5 ml/min silicon tetrachloride (specification is with the example 1) reaction of carrying 60 minutes under same temperature then, and the consumption of silicon tetrachloride is 20.8 gram (SiCl
4With the forming composition weight ratio be 0.44), reaction back feeds dry air with the speed of 100 ml/min, purged 1 hour, with deionized water wash to remove solubility Na
+, Cl
-And Al
3+Deng by product, to filter, 110 ℃ of oven dry must contain the catalyst composition of rich silicon ultra stabilization Y zeolite, are designated as E, its sodium oxide content, the lattice constant of composition mesolite, crystallization reservation degree and avalanche temperature are listed in the table 1.
Example 6
Preceding forming composition 100.0 grams of silicon tetrachloride dealuminzation that take by weighing example 3 preparations place tube furnace, the dry air that feeds water content 900ppm under 450 ℃ of conditions dewatered 2 hours, be cooled to 250 ℃ then, switch speed is that the silicon tetrachloride (specification is with example 1) that the dry air of 5 ml/min carries reacted 45 minutes, and the consumption of silicon tetrachloride is 15.8 gram (SiCl
4With the forming composition weight ratio be 0.15), reaction back feeds dry air with the speed of 100 ml/min, purges 2 hours, takes out product, does not find coalescent caked phenomenon, uses rare earth chloride (specification is with the example 2) aqueous solution to press zeolite forming composition: RECl
3: H
2O=1: 0.24: 10 weight ratio, product is exchanged 0.5 hour under 85 ℃ temperature, filter, wash to there not being Cl
-, the catalyst composition of super-stable Y zeolite containing rare-earth elements, be designated as F, the lattice constant of its sodium oxide, rare earth oxide content and composition mesolite, crystallization reservation degree and avalanche temperature are listed in the table 1.
Table 1
| Example number | The catalyzer numbering | Sodium oxide content, heavy % | Rare earth oxide content, heavy % | Lattice constant, dust | Crystallization reservation degree, % | The avalanche temperature, ℃ |
| ????1 | ????A | ????0.69 | ????0 | ????24.31 | ????85 | ????1000 |
| ????2 | ????B | ????0.28 | ????1.8 | ????24.52 | ????85 | ????1011 |
| ????3 | ????C | ????0.43 | ????3.1 | ????24.39 | ????90 | ????1092 |
| ????4 | ????D | ????0.90 | ????3.1 | ????24.43 | ????86 | ????1034 |
| ????5 | ????E | ????0.30 | ????0 | ????24.39 | ????89 | ????1059 |
| ????6 | ????F | ????0.73 | ????4.5 | ????24.43 | ????91 | ????1070 |
Table 2
| Size range, micron | Account for the percentage ratio of total amount | Size range, micron | Account for the percentage ratio of total amount |
| ????0.50-1.32 | ????0.00 | ????25.46-31.01 | ????0.31 |
| ????1.32-1.60 | ????0.00 | ????31.01-37.79 | ????2.25 |
| ????1.60-1.95 | ????0.00 | ????37.79-46.03 | ????5.64 |
| ????1.95-2.38 | ????0.00 | ????46.03-56.09 | ????10.72 |
| ????2.38-2.90 | ????0.00 | ????56.09-68.33 | ????16.92 |
| ????2.90-3.53 | ????0.00 | ????68.33-83.26 | ????20.71 |
| ????3.53-4.30 | ????0.00 | ????83.26-101.44 | ????19.04 |
| ????4.30-5.24 | ????0.00 | ????101.44-123.59 | ????13.25 |
| ????5.24-6.39 | ????0.00 | ????123.59-150.57 | ????6.96 |
| ????6.39-7.78 | ????0.01 | ????150.57-183.44 | ????2.43 |
| ????7.78-9.48 | ????0.15 | ????183.44-223.51 | ????0.12 |
| ????9.48-11.55 | ????0.26 | ????233.51-272.31 | ????0.00 |
| ????11.55-14.08 | ????0.28 | ????272.31-331.77 | ????0.00 |
| ????14.08-17.15 | ????0.11 | ????331.77-404.21 | ????0.01 |
| ????17.15-20.90 | ????0.00 | ????404.21-492.47 | ????0.47 |
| ????20.90-25.46 | ????0.00 | ????492.47-600.00 | ????0.35 |
Example 7
The catalyst composition D45.0 gram of example 4 preparation is ground to form fine powder, and (the Suzhou machine selects kaolin, and kaolin company in Suzhou produces, and solid content 86% contains SiO with the kaolin of 34 gram solid contents, 40 heavy %
239 heavy %, Al
2O
346 heavy %) slurries mix, and contain silicon sol (specification is with example 1) 20 heavy % in the slurries, drying and moulding, sieve get 20～40 purpose particles 800 ℃ with 100% steam aging 4 hours, catalyzer, be designated as G, salic 31.7 heavy % among the catalyzer G, rare earth oxide 1.1 heavy %, Na
2O 0.19 heavy %, wherein alumina content adopts chemical analysis to measure, and sodium oxide content and rare earth oxide content assaying method are the same.
Example 8～10
The following examples explanation is by the catalytic performance of the catalyzer of method preparation provided by the invention.
With the catalyst composition C of example 3 and 6 preparations and F respectively 800 ℃ with 100% steam aging 4 hours, make catalyzer H and I.With boiling range is that 235～337 ℃ straight distillation light diesel oil is a reaction raw materials, catalyzer loading amount 5 grams, and the catalytic activity of evaluate catalysts G, H, I respectively on the small stationary bed reaction device, reaction conditions is: 360 ℃ of temperature of reaction, weight space velocity 16.0 hours
-1, the agent weight of oil is than 3.2, the reaction product gas chromatographic analysis, and the results are shown in Table 3.
Table 3
| Example number | ????8 | ????9 | ????10 |
| The catalyzer numbering | ????G | ????H | ????I |
| Little index alive, heavy % | ????73.0 | ????86.0 | ????85.0 |
Example 11～13
The following examples explanation is by the catalytic performance of the catalyzer of method preparation provided by the invention.
With boiling range is that 227～475 ℃ wax oil is a reaction raw materials, catalyzer loading amount 5 grams, and the catalytic activity of evaluate catalysts G, H, I respectively on the small stationary bed reaction device, reaction conditions is: 482 ℃ of temperature of reaction, weight space velocity 16.0 hours
-1, the agent weight of oil is than 4.0, the reaction product gas chromatographic analysis, and the results are shown in Table 4.
Table 4
| Example number | ????11 | ????12 | ????13 |
| The catalyzer numbering | ????G | ????H | ????I |
| Transformation efficiency, heavy % | ????79.9 | ????87.4 | ????84.5 |
| Product distributes, heavy % gas coke gasoline, diesel＞330 ℃ of cuts | ????15.8 ????3.5 ????60.6 ????14.6 ????5.5 | ????22.9 ????4.7 ????59.8 ????9.6 ????3.0 | ????14.1 ????3.8 ????66.6 ????12.4 ????3.1 |
Claims (9)
1. preparation method who contains the catalyst composition of rich silicon ultra stabilization Y zeolite, it is characterized in that it comprises water content less than 900ppm's, the silicon tetrachloride gas that dry air carries and the drying and moulding thing of NaY zeolite and heat-resistant inorganic oxide are by the silicon tetrachloride total amount: forming composition=0.1～0.8: 1 weight ratio, 150～550 ℃ of contact reactss 10 minutes to 5 hours, the particle of 35～125 microns of particle diameters accounts for more than 80% of total particle number in the described drying and moulding thing, the weight ratio of NaY zeolite and heat-resistant inorganic oxide is 1: 0.2～1.0, and the silica alumina ratio of NaY zeolite is 3～6.
2. method according to claim 1 is characterized in that described heat-resistant inorganic oxide is selected from one or more in silicon oxide, aluminum oxide, silica-alumina, phosphorated aluminum oxide, kaolin, modified kaolin, halloysite, the diatomite.
3. according to the described method of claim 2, it is characterized in that described heat-resistant inorganic oxide is selected from one or more in silicon oxide, aluminum oxide, silica-alumina, the phosphorated aluminum oxide.
4. according to the described method of claim 3, it is characterized in that described heat-resistant inorganic oxide refers to silicon oxide.
5. according to the described method of claim 1, the weight ratio that it is characterized in that described silicon tetrachloride and forming composition is 0.1～0.5: 1.
6. according to the described method of claim 1, it is characterized in that described temperature of reaction is 250～550 ℃.
7. according to the described method of claim 1, it is characterized in that the described reaction times is 30 minutes to 3 hours.
8. according to the described method of claim 1, it is characterized in that described heat-resistant inorganic oxide refers to silicon oxide, the weight ratio of silicon tetrachloride and forming composition is 0.1～0.5: 1, and temperature of reaction is 250～550 ℃, and the reaction times is 30 minutes to 3 hours.
9. according to any described method of claim 1～8, the weight ratio that it is characterized in that described NaY zeolite and heat-resistant inorganic oxide is 1: 0.2～0.8.
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| US5288396A (en) * | 1979-10-15 | 1994-02-22 | Union Oil Company Of California | Hydrocracking process using a catalyst selective for making middle distillates |
| US4701313A (en) * | 1984-12-19 | 1987-10-20 | Mobil Oil Corporation | Replacing boron with silicon in zeolite beta using SiCl4 |
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