CN85104995A - Synthetic and the purposes of premolding zeolite - Google Patents

Synthetic and the purposes of premolding zeolite Download PDF

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CN85104995A
CN85104995A CN198585104995A CN85104995A CN85104995A CN 85104995 A CN85104995 A CN 85104995A CN 198585104995 A CN198585104995 A CN 198585104995A CN 85104995 A CN85104995 A CN 85104995A CN 85104995 A CN85104995 A CN 85104995A
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zeolite
group
described method
oxide
gram
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鲁埃特
迪弗雷纳
古思
雷蒙·韦
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IFP Energies Nouvelles IFPEN
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    • B01J20/16—Alumino-silicates
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    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
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    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
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    • C01B39/30—Erionite or offretite type, e.g. zeolite T
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    • C01B39/32—Type L
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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract

The invention relates to a kind of premolding synthetic zeolite, this zeolite is selected from by y, omega zeolite, and Si-Al-K boils, erionite, the L zeolite, the group that ferrierite is formed, their Si/Al atomic ratio rf is 1.5 to 100.The premolding synthetic zeolite makes from a kind of premolding aluminium silicon materials, and its Si/Al atomic ratio ri is lower than rf, from 0.5 to 90.Its preparation method is to handle the aluminium silicon materials with a kind of silica product that contains in the presence of at least a organic or inorganic alkali.
This zeolite is in absorption, and ion mixing or heterogeneous catalyst aspect are particularly useful.

Description

Synthetic and the purposes of premolding zeolite
Zeolite is crystalline silico-aluminate, has general formula { 1/ (n) M n+ AlO 2(SiO 2) r* H 2O }, M is a kind of basic metal or alkaline-earth metal of n valency in the formula, r is the Si/Al atomic ratio.Its structure is by the AlO by the interconnection of oxygen ridge 4And SiO 4Tetrahedron constitutes.This tetrahedral spatial array constitutes the tetrahedron of a kind of lattice that limits passage, grid or depression.Positively charged ion M is distributed in their energy balances by AlO 4Tetrahedron is taken on the next anionic locations of structures.AlO 4And SiO 4Therefore tetrahedron can have multiple arrangement, exists many different zeolite structured.
This gang's product obtains a large amount of industrial application, is used in especially in a large number in absorption and these two general field of catalysis.
Figure 85104995_IMG1
In their high microporosity, zeolite is used as sorbent material: drying, separating gas mixture etc..
Owing to can easily exchange positively charged ion, make like this to prepare the acid solids, be used as the zeolite of the common shape of catalyzer or catalyzer basic component.
Zeolite makes in the inorganic or organic bases to one or more by mixing one or more silicon and aluminum feedstock usually.
Mainly obtain the powdery zeolite, their particulate mean size is usually less than 100 μ.
Obviously, for being used for absorption or catalysis on a large scale, it is useful using the product of moulding, because fine powder has caused pressure-losses problem.The method of zeolite powder caking is well known in the prior art, and they require to add a kind of binding agent usually, and this binding agent is used for moulding and gives product with enough physical strengths.But, the purity drop that to add this consequence that does not have the binding agent of zeolite characteristic be product, thus the usefulness of moulding product reduces.
United States Patent (USP) 3119660 discloses and has prepared zeolite from the kaolin of moulding and give moulded zeolite to obtain.
The object of the invention, on the one hand, preparation contains the extrusion moulding thing of 100% zeolite, improves the physical strength of these products on the other hand.In fact, the usual production that the method for zeolite moulding is made with the adding binding agent must contain minimum binding agent, to avoid reducing significantly their activity.But this is unfavorable in physical strength.Between purity and physical strength, must seek a kind of taking into account., physical strength is for being used as or sorbent material, and perhaps catalyzer perhaps loads fixed bed, and perhaps let alone the Industrial products of moving-bed are a kind of basic parameters.The method of movable bed catalyst more and more is usually used in petroleum refining industry and requires catalyzer that special wear resistance is arranged.Even in technique for fixing, also enough physical strengths must be arranged, fall to avoid pressure too big in device.In addition, catalyst regeneration more and more manyly is finished in the device outside now, requires many catalyzer to rotate like this, requires catalyzer that the favorable mechanical performance is arranged for this reason.
The invention summary
These purposes that propose have been realized with zeolite of the present invention, though zeolite of the present invention does not contain binding agent, but it has good mechanical property, particularly shows by shatter strength value and attrition value (using method described below), and above-mentioned value is difficult to obtain by general forming method.
Another aspect of the present invention is about preparing little microcrystalline zeolite.In fact, using a kind of zeolite that is made of very tiny crystal may be advantageous for catalytic applications, from 0.1 to 0.3 micron of the mean size of this fine crystals.A kind of like this product can not cause serious crystallization problem, can be very difficult but separate this crystal from synthesis mother liquid.Filtration consuming time or centrifugation meeting are a kind of obstacles to the such product of industrial production.
Method of the present invention does not have these problems and directly provides and Powdered synthetic very little microcrystalline zeolite inequality.
Like this, the present invention provides the high mechanical strength moulded zeolite simultaneously, is made up of 100% pure zeolite, and its crystallite is usually less than 1 micron.
This zeolite can identify that these methods comprise chemical analysis, X-ray diffraction by different characteristic methods, the absorption of multiple molecule such as n-hexane and hexanaphthene, in addition, crystallite size can be measured with scanning electronic microscope, and physical strength is judged by measuring wearing and tearing and shatter strength.
The content and the cation ratio of silicon-dioxide and aluminum oxide are measured by chemical analysis.
X-ray diffraction is measured the spacing " d " between the lattice plane, and corresponding to the relative intensity of each spacing, said relative intensity is to represent with the stronger line with respect to spectrogram.Distance-intensity line is to being the feature of each zeolite, though along with slight variation may appear in the positively charged ion that is present in the structure.
Adsorptive power is measured in general Mac Bain type instrument.Zeolite activates under 5 backing pressure power, about 400 ℃ of temperature.Then, sample contacts with the product that will adsorb under the pressure pressure at known minute at temperature required (common 20 ℃) down.
The size of crystallite can be measured with scanning electronic microscope according to following step.After the crushing particle, powder deposition is on specimen slides, and is then that sample is gold-plated, sends into the Came bax type microscope of CAMECA company.
Carried out the test of two physical strengths: one comprises measurement crushing individual particle, and another is to measure wearing and tearing.
Shatter strength is measured with increasing gradually particulate loaded.The instrument that uses is a kind of atom grinding mill that has moveable piston of ERWEKA trade mark.Measurement is carried out on 30 particles, calculates arithmetical av.To the extrusion molding thing, the value of consideration is to be the ratio of the required crushing strength of fragmentation (representing with kilogram or newton) to the length (representing with millimeter) of extrusion molding thing.
Second test measuring the product mechanical property comprises measures grain bed and is doing the wearing and tearing of time spent with the pressure that puts on said bed.Operating method is as follows: the 20c.c. particle is placed high 50mm.In the garden tube of internal diameter 27.6mm.Particle is covered with the thick steel ball of 5c.c.4.5mm.The use piston increases the pressure segmentation that puts on the steel ball.The fine powder that screening and separating obtains under different pressures is also weighed.Particle by mesh is considered to fine powder, and the hole of mesh equals 2/3 of feed particles lower limit characteristic dimension.Represent with MPa with the corresponding resistance to abrasion of force value, obtain 0.5 fine powder under this pressure, above-mentioned value is measured with interpolation being given on the figure that closes the ratio of gained fine powder under kind of the pressure.
The invention relates to the synthetic moulded zeolite that gives, these zeolites are selected from following group: Y zeolite, omega zeolite, offretite, erionite, L zeolite, ferrierite.These zeolites are from the raw material of at least a product of aluminium and silicon makes based on containing at least.This raw produce can be a crystal or amorphous.It can be made of a kind of crystalline zeolite or a kind of non-crystalline state zeolite that is made by previous processing.Above-mentioned zeolite or natural or synthetic, and can constitute by any crystallite.
The example of natural zeolite is an euthalite, chabazite, and clinoptilolite, erionite, faujusite, ferrierite and mordenite, these zeolites are little high-purity, and that usually finds is mixture and is attended by the non-crystalline state product.It may be significant directly using the particle that obtains by the ore crushing.
The example of synthetic zeolite is the A zeolite, X and Y zeolite, and mordenite, these zeolites can be buied on market.In addition, other zeolite also can use, as long as their Si/Al atomic ratio is lower than the atomic ratio of the product that will obtain.The x-ray diffraction pattern of X and Y faujusite is reported in French Patent 1117756 and 1231239 respectively.
The diffraction spectra of mordenite is reported in SAND and the COLL paper: Adv.Chem.Ser.Acs WASHINGTON DC(1971), 101 P.120 A zeolite diffraction spectra in United States Patent (USP) 2882243, provide.
All these zeolites can be at least in part and other cationic exchange except that their the original cation, for example K +, Li +, NH + 4, H +, exchange rate from 0 to 100% does not wait.
According to the general method of prior art, these zeolites also can be removed aluminium and improvement to some extent by processing.
Use synthetic silicon one aluminium of extrusion molding thing or particle or bead or other non-crystalline state also to be fine, can synthesize these products for this purpose, also can in the city, buy as raw material.
Also can use the clay of kaolin or metakaolin type.
Also can use the mixture of top mentioned product.Particularly by means of the easy moulding of binding agent zeolite, this binding agent can for example be made up of aluminum oxide or clay.
According to the present invention, give the moulding synthetic zeolite for making, giving moulding product contacts with at least a organic or inorganic alkali lye, these alkali are selected from following one group of compound: Lithium Oxide 98min, potassium hydroxide, sodium hydroxide, ammonium hydroxide and tetraalkylphosphoniuhydroxide hydroxide one ammonium, for example tetramethylphosphonihydroxide hydroxide base or tetraethyl-or tetrapropyl or TBuA.
At least a silica product (it can be made up of for example a kind of amorphous silicon di-oxide or a kind of colloidal silica) that contains is joined this containing in the reaction medium that gives formed material and at least a alkali lye and (gives formed material Si/Al atomic ratio and equal ri), give moulded zeolite with preparation.This Si/Al of moulded zeolite that gives is than being rf, greater than ri.The zeolite that makes like this has good physical strength.
Or rather, these synthesis conditions that give moulded zeolite are as follows: the Si/Al atomic ratio ri that gives shaping raw material must be in 0.5 to 90 scope; (OH) of alkali -Anion concentration must be in every liter of solution 0.01 to 10 molar range; Tetraalkylammonium cation with (OH) -Anionic mol ratio is 0 to 0.5.Used silica volume must be the used anhydrous silica-alumina material of from 0.1 to 30 gram/gram.Liquid phase must be from 2 to 30 to the weight ratio that raw material gives the moulding silico-aluminate; From 50 to 200 ℃ of temperature ranges; Treatment time must be from 2 hours to about 200 days.
The Si/Al atomic ratio rf of the zeolite that makes must be higher than atomic ratio ri, from 1.5 to 100.
In the product that can make according to the present invention, special case is y and omega zeolite, offretite, erionite, L zeolite and ferrierite.
The y zeolite is characterized as the three-dimensional channel lattice, and its hole approximately is 8 (8.10-10m).Usually make to contain na form, its Si/Al atomic ratio from 1.5 to 3 according to the present invention, and from 2.0 to 2.7 is more excellent.Its x-ray diffraction pattern is listed in table 1(and is selected from USP3130007); D is the spacing between the lattice plane, represents with rice, and I/I 0(or I/I max) than with the intensity of arbitrary given line I to the strongest line I 0Or the percentage of Imax is represented.Only consider to accord with I/Imax or I/I 0Than these lines that are higher than 10.Certainly, spacing d, and I/I 0Beguine can have little variation according to the product of being studied.This variation does not show structural modification, but because some positively charged ion is replaced by other positively charged ion or because the difference of Si/Al ratio.
Figure 85104995_IMG3
According to the present invention, omega zeolite has a kind ofly has an appointment 8
Figure 85104995_IMG4
The one dimension passage lattice in aperture; It contains less Na +Ion, its Si/Al atomic ratio generally from 2 to 6.Its diffractogram that provides corresponding the strongest distance between centers of tracks is listed in table 2(and is selected from USP 3578723).
Figure 85104995_IMG5
Offretite has a kind ofly has an appointment 6.5
Figure 85104995_IMG6
The one dimension passage lattice in aperture, a narrower patterned perpendicular is in the former simultaneously.Generally have potassium cationic and Si/Al atomic ratio from 2 to 8 at least for synthetic offretite of the present invention.Its expression correspondence diffractogram of strong distance between centers of tracks is listed in table 3.
Figure 85104995_IMG7
Erionite is a kind of structure relevant with offretite, but different stacked arrangement faces is arranged.Laminated layer sequence is regular to the pure wool zeolite; Irregular laminated layer sequence with a kind of contain corresponding to the defective in the offretite structure of T erionite relevant.It has and a kind ofly has 4 to 5
Figure 85104995_IMG8
The micropore lattice in aperture; Can from 2 to 6 variations for Si/Al atomic ratio of the present invention.Its x-ray diffraction pattern (the strongest line) is listed in table 4(and is selected from USP 2950952).
Figure 85104995_IMG9
The L zeolite is the about 6.5-7 in a kind of micropore aperture Zeolite, Si/Al atomic ratio generally from 2 to 4.Its x-ray diffraction pattern (the strongest line) is listed in table 5(and is selected from USP 3216789).
Figure 85104995_IMG11
Ferrierite is that a kind of micropore aperture is from about 5 to 5.5
Figure 85104995_IMG12
Zeolite, to Si/Al of the present invention than generally from 3 to 100(atomic ratios).Its x-ray diffraction pattern (the strongest line) is listed in table 6(and is selected from USP 4017590).
Figure 85104995_IMG13
Table 8 provides principal character of giving the required operating characteristics of moulding synthetic zeolite and these synthetic zeolites (wide region and preferred range) produced according to the present invention to 13.Table 8 is about the preparation of y faujusite, and table 9 is about the preparation of omega zeolite, and table 10 is about the preparation of offretite, and table 11 is about the preparation of erionite, and table 12 is about the L prepare zeolite, and table 13 is about the preparation of ferrierite.
Table 7
Synthetic parameters
r iRaw material gives the Si/Al atomic ratio of moulding silico-aluminate.
The alkali that B chooses.
S 1Liquid phase/raw material gives the weight ratio of moulding silico-aluminate.
S 2(OH) -Ionic concn (mol).
S 3Tetraalkylammonium cation/OH -Anionic mol ratio.
The every gram raw material of Q gives the contained silica volume of dried silicon-dioxide of the dried silico-aluminate of moulding, in gram.
The T temperature (℃).
T gives the silico-aluminate treatment time (in the sky) of moulding with alkali lye and silicon-dioxide.
D makes the elemental crystal size of zeolite, in micron.
r fMake the Si/Al atomic ratio of zeolite.
Figure 85104995_IMG15
Figure 85104995_IMG16
Figure 85104995_IMG17
Figure 85104995_IMG19
The synthetic zeolite of Huo Deing can be used for relevant for example absorption, heterogeneous catalyst and cationic exchange like this.
They can use like this, but will make it carry out handling for example at least a pre-treatment for needed certain modification of desired use usually.May need these preformed synthetic zeolites are carried out pretreated example be: cationic exchange, heat-treat with for example different calcination atmosphere.The zeolite that after synthetic and washing, obtains, especially in order to remove organic cation synthetic selected use and that in for example tetrapropyl ammonium or TBuA type structure, still exist, can be by roasting.For absorption, catalysis or cationic exchange purposes, these preformed synthetic zeolites can with any other possible cationic exchange, especially to catalysis use, mainly be acid catalysis, it is favourable removing the alkali metal cation that exists in the structure and replacing them with proton, this normally by with ionized ammonium salt, as nitrate, vitriol, muriate, acetate or equivalent one or many cationic exchange are finished; Then will by with or different steam, with or without gas clean-up in 300～900 ℃ of temperature ranges roasting to remove deammoniation.This processing can cause Zeolite modifying commonly known in the art and be called as stable and overstable processing.Handle the zeolite that also can obtain the proton attitude with organic or inorganic acid, and can from crystal lattice, partially or completely remove aluminium.Also can under gas phase treatment, remove aluminium with sequestrant or by using silicon tetrachloride, hydrochlorate or other to be equal to compound.
Introduce other positively charged ions, particularly alkaline earth metal cation, rare-earth cation or VI B, VII B, I B, II B, III A, IV A, V A, VI A family metallic cation also may be significant.
To requiring two function catalyzer, promptly a kind of acid function, the catalysis use of the catalyzer that combines with a kind of metal function (so-called mutually active), can add one or more metals or metal compound with method well known in the prior art, this method can be by cationic exchange, dry method is injected, formations such as vapor deposition.Metal or metalloid parent compound can add during synthetic premolding zeolite selectively.
The moulded zeolite of this type is in absorption, and ion-exchange and catalysis aspect have many purposes.
Particularly, zeolite of the present invention is suitable for catalysis use satisfactorily: for example, the performance when improving the cooling of gas-oil distillate, making this cut may be favourable by handling under hydrogen pressure on the prepared catalyzer of the present invention.This catalyzer can contain a kind of precious metal of VIII family or a kind of metal of base metal and/or other families of the periodic table of elements at least, support of the catalyst for example contains, offretite, ferrierite or erionite, zeolite is offretite and ferrierite preferably.Catalytic cracking reaction when usually, the catalyzer of these types is suitable for being with or without matrix or other solid chemical compounds and exists.
Another purposes relates to the normal paraffin that contains by cracking to improve gasoline octane rating in mixture.The quality of reformate can be improved by the catalyst treatment with the present invention's preparation.This catalyzer will be by offretite, and ferrierite or erionite are formed, and zeolite is ferrierite and erionite preferably, contains the precious metal or the base metal of a small amount of at least a VIII family selectively.
The zeolite of the application of the invention also can advantageously carry out the aromatic series conversion reaction, and Fan Ying example is like this: toluene disproportionation effect, xylene isomerization effect, toluene-methyl alcohol alkyl metalepsy, benzene-vinyl alkyl metalepsy.
When existing, the zeolite that has the present invention to make advantageously to make the middle runnings hydrocracking to last running.This catalyzer must contain a kind of metal of VIII family, this metal selectively with a kind of melts combine of VI B family.At hydrogen pressure 20-200 crust, under 220-450 ℃ of temperature, carry out this technological process.
Use the catalyzer that a kind of its carrier contains a kind of zeolite of the present invention's preparation at least also can carry out methanol conversion.This reaction is to carry out under pressure 10 crust and in 300-550 ℃ of temperature the time, to make the methyl alcohol condensation compound.This method or contain the light olefin of 2-4 carbon atom for synthetic per molecule basically, or for synthetic to be used as the automobile fuel mixture may be best.
The dehydrocyclization of paraffins also is a purposes of the present invention.This is at institute of the present invention synthetic and contain mainly that to carry out on a kind of L zeolite of potassium ion may be favourable.Add at least a VIII family metal, platinum preferably, this metal selectively combines with the another kind of metallographic phase of for example VIII B family and meets the requirements.This catalyzer is used for the condition of approximate catalytic reforming and has the charging that contains high cut paraffins, so that obtain the effluent of high aromatic content.
Embodiment:
Following examples explanation the present invention.
The preparation of example 1:y zeolite (y faujusite)
Method 1
Dioxide-containing silica be 40%(by weight) colloidal silica 230 gram and concentration sodium hydroxide 670 millis that are 2.1 moles open and be added into 40 and restrain A zeolite extrusion molding thing (r i=0.95) in.Synthetic parameters (see Table 7 and table 8) is as follows: S 2=21.35; S 2=1.65 moles/open; S 3=0; Q=2.3.After 7 days, filter washing and dry this extrusion molding thing 100 ℃ of heating.Shown in X-ray diffraction, they are by having Si/Al atomic ratio, r fBe that 2.65 y faujusite is formed.Respectively with 3.3 Newton/millimeter of A zeolite and 0.9 MPa relatively, its one by one the particulate shatter strength be 18.3 Newton/millimeter, the shatter strength in bed is 1.3 MPas.The sample of desorb under vacuum in the time of 300 ℃, 30 ℃ and the adsorptive poweies of benzene with 35 holder pressure components be 20.4%(by weight).The BET specific surface is 880 meters 2/ gram.Crystallite size by micro-mensuration is about 0.3 micron.
Method 2
With 819 gram water, 75 gram particle shape sodium hydroxide and contain 227 gram silicon-dioxide 40%(by weight) colloidal silica add and contain 70% silicon-dioxide and 30% aluminum oxide (r i=1.98) in the 63 gram non-crystalline state extrusion molding things.Synthetic parameters following (seeing Table 7 and 8): S 1=15.16; S 2=1.96; S 3=0 and Q=1.44.At 5 days post-heating to 100 of 40 ℃ of slakings ℃ through 24 hours.Filter washing and dry this extrusion molding thing then.Its diffraction spectra and y faujusite (r f=2.30) conform to.
Method 3
With 50 gram kaolinite extrusion molding thing (r i=1) with 280 gram dioxide-containing silicas be 40%(by weight) colloidal silica, 70 gram sodium hydroxide and 840 ml waters mix synthetic parameters following (seeing Table 7 and 8): S 1=20.16; S 2=1.74; S 3=0 and Q=2.24.After 5 days, filter washing and dry this product 40 ℃ of slakings one day with 100 ℃ of heating.Its diffraction spectra and y zeolite (r f=1.245) conform to.
Example 2: ω (Omega) prepare zeolite
Method 1
5 gram A zeolite extrusion molding things are added 105 millis open and contain 6.1%, 1.68% respectively, 31.8%(is by weight) sodium hydroxide, in the solution of tetramethyl ammonium hydroxide and silicon-dioxide.As follows according to table 9 synthetic parameters: S 1=21.0; S 2=2.38 moles/open; S 3=0.106; Q=9.32 gram/gram.
, after 24 hours this extrusion molding thing is filtered 170 ℃ of heating, washing, dry and in 600 ℃ of roastings.Like this, obtain 9.4 grams and have Si/Al atomic ratio (r f) be 3.54 omega zeolite.The X-diffraction shows that it has high purity.
Particulate shatter strength and the shatter strength in bed relatively are 21.2 Newton/millimeter and 1.4 MPas with 3.3 Newton/millimeter and 0.9 MPa of 4A zeolite respectively one by one.
The size of zeolite elemental crystal is determined as the 0.08-0.8 micron according to scanning electronic microscope.
Method 2
With 3.76 gram amorphous silicon di-oxides, 1.76 gram particle shape sodium hydroxide and 32 milliliters of 0.13 milliliter of mole tetramethyl ammonium hydroxide solutions join in the 2.5 gram sodium y zeolite extrusion molding things r of this forming composition iThan equaling 2.6.Its synthetic parameters is as follows: S 2=12.8; S 2=1.51 moles/open; S 3=0.086; Q=1.50 gram/gram.
With the mixture that makes like this in autocrave in 170 ℃ of heating 36 hours, filter, washing and dry after obtain 3.7 gram omega zeolite (r f=3.7).
Method 3
With 5 gram kaolinite extrusion molding thing (r i=1) join 95 milliliters and contain 6%, 1.5%, 30% sodium hydroxide respectively, in the solution of tetramethyl ammonium hydroxide and silicon-dioxide, its synthetic parameters is as follows: S 2=19.0; S 2=1.67; S 3=0.099; Q=7.83., after 24 hours this extrusion molding thing is filtered 170 ℃ of heating, washing, dry and in 600 ℃ of roastings, particulate shatter strength and the shatter strength in bed one by one are with initial kaolinite (r f=3.8) 9.9 Newton/millimeter and 0.9 MPa relatively are respectively 21.9 Newton/millimeter and 1.4 MPas.
Example 3: the preparation of offretite
Method 1
It is that 2.5 sodium y zeolite is suspended in 200 milliliters of ammonium nitrate molar solutions through 14 hours at 80 ℃ that 50 grams are had the Si/Al atomic ratio.After filtering and washing, repeat this operation secondary.Then solid phase is separated from liquid, wash with water and in 100 ℃ of dryings 4 hours.After 3 hours, obtain 41 gram hydrogen y zeolite extrusion molding things 550 ℃ of roasting combustions.
With 25 grams, 2 moles of hydrogen potassium oxide solutions, 5 milliliters of 20%(are by weight) tetramethyl ammonium hydroxide solution and 7.5 grams contain 40%(by weight) colloidal silica of silicon-dioxide joins in the 2.5 gram hydrogen y zeolites.
According to table 10, synthetic parameters is as follows: S 1=14.4; S 2=1.69 moles/open; S 3=0.179; Q=1.2 gram/gram.
Whole mixtures were heated 24 hours in 170 ℃ in autocrave.After the cooling, the extrusion molding thing is filtered, wash with water, 100 ℃ of dryings 3 hours, at last 550 ℃ of roastings 3 hours.The extrusion molding thing that makes like this has the offretite of being similar to and Si/Al atomic ratio (r f) be 4.5 diffractogram.The mean value of particle shatter strength is 10.4 Newton/millimeter one by one; To initial sodium y zeolite is 5.3.Shatter strength and initial product 1.05 in the bed relatively are 1.58 MPas.The hexanaphthene adsorptive power during in 20 ℃ under pressure 65 holder be 6.5%(by weight).In ammonium nitrate solution after four successive cationic exchange, then in 500 ℃ of roastings, adsorptive power be 3.9%(by weight), thereby proved the high purity of this product.The content of potassium is 2.1%.
Scanning electronic microscope shows that the mean size of the elemental crystal of zeolite is about 0.3 micron.
Method 2
100 gram Si/Al atomic ratio (r i) equal 1 4A zeolite extrusion molding thing and 500 milliliter of 1 molar acetate ammonium in No. three meters of 60 ℃ of exchanges 24 hours.Washing with water and 100 ℃ of dryings after 3 hours, with the extrusion molding thing 500 ℃ of roastings 4 hours.Obtain 87 gram extrusion molding things like this.Synthetic parameters is as follows: S 1=21.5; S 2=3.02; S 3=0.19; Q=9.75.
40 these extrusion molding things of gram are contained 9.1%, 3.46%, 31.5% sodium hydroxide respectively as going into to 860 milliliters, in the solution of tetramethyl ammonium hydroxide and silicon-dioxide.In autocrave, after 24 hours, this extrusion molding thing is filtered in 170 ℃ of heating, washing, dry and 550 ℃ of roastings 4 hours.Obtain 84 gram offretites like this, this zeolite adsorbs 6.8(by weight in 20 ℃ under 65 mmhg) hexanaphthene.
The mean value of particle shatter strength one by one is in a ratio of 29 Newton/millimeter with 8.3 Newton/millimeter of 4A zeolite.Shatter strength and 4A zeolite (r in the bed f=3.85) 0.9 MPa is in a ratio of 1.6 MPas.
Method 3
With 24 gram potassium hydroxide, 1.95 gram chlorinations, four potassium ammoniums, 29 gram amorphous silicon di-oxides and 40 ml waters join 5 gram kaolin (r i=1) (synthetic parameters: S in 1=8; S 2=4.89; S 3=0.091; Q=5.8).This mixture is placed 170 ℃ through 24 hours and with the extrusion molding thing filtration that obtains, and washing is also dry.Obtain 9.1 gram offretite (r like this f=3.8), this zeolite adsorbs 8.2% normal hexanes in 20 ℃ under 95 mmhg.Particulate shatter strength and the shatter strength in bed are in a ratio of 23 Newton/millimeter and 1.4 MPas with initial kaolinic 9.9 Newton/millimeter and 0.9 MPa respectively.
Method 4
Restrain water, 6.21 gram amorphous silicon di-oxides, 5.23 gram potassium hydroxide, 1.6 gram Tetramethylammonium chlorides adding Si/Al ratios, r with 44 iEqual in 1.1 the sodium X zeolite extrusion molding thing, then with this mixture 170 ℃ of heating 24 hours.Filter, after washing and the drying, the offretite that obtains has Si/Al than (r f) equal 3.9.Synthetic parameters is as follows: S 1=17.6; S 2=2.45; S 3=0.135; Q=2.48.
Method 5
With 3.7 gram sodium hydroxide, 2.15 gram potassium hydroxide, 6 milliliters of 10%(are by weight) tetramethyl ammonium hydroxide solution and 16.4 gram dioxide-containing silica 40%(by weight) colloidal silica add 5 grams and contain in the non-crystalline state extrusion molding thing of 75% silicon-dioxide and 25% aluminum oxide.The mixture that makes was like this heated 24 hours at 140 ℃.Then this extrusion molding thing is filtered, washing, dry and 530 ℃ of roastings 4 hours.Obtain 8.64 gram offretite extruding like this, this zeolite adsorbs 8.2% hexanaphthenes in 20 ℃ under 65 mmhg.Synthetic parameters is as follows: r i=2.55; S 1=3.8; S 2=7.18; S 3=0.0048; Q=1.31; r f=4.7.
Example 4: the preparation of erionite
Method 1
10 grams are contained non-crystalline state extrusion molding thing and 91 ml waters, 4.75 sodium hydroxide, 2.57 potassium hydroxide and the 6.84 gram amorphous silicon di-oxides mixing of 80% silicon-dioxide and 20% aluminum oxide.According to table 11, synthetic parameters is as follows: S 1=9.1; S 2=1.81 moles/open; S 3=0; Q=0.68 gram/gram (r i=3.4).After 24 hours, obtain 7.6 gram erionite extrusion molding things 140 ℃ of heating, the Si/Al atomic ratio of this zeolite is 3.95.Shown in X-ray diffraction and electron microscope, they do not have the L zeolite.After 300 ℃ of desorbs, this product adsorbs 8.2% normal hexane and 1.3% hexanaphthene under vacuum.
10.1 Newton/millimeter of particulate shatter strength and initial product are in a ratio of 12.4 Newton/millimeter one by one, and 8.9 MPas of shatter strength in bed and initial product are in a ratio of 12.5 MPas.
Method 2
With 5 grammeatom ratio, r iEqual 2.45 sodium y zeolite extrusion molding thing and 3.45 gram particle shape sodium hydroxide, 2.87 gram potassium hydroxide, 6.56 gram amorphous silicon di-oxides and 50 ml waters mix, and synthetic parameters is: S 1=10; S 2=2.75 moles/open; S 3=0; Q=1.31 gram/gram.After 36 hours, obtain a kind of erionite type zeolite (r 170 ℃ of heating as showing by X-ray diffraction f=3.5).
Method 3
With 46 gram water, 12.10 gram amorphous silicon di-oxides, 5.42 gram sodium hydroxide and 4.40 gram particle shape potassium hydroxide are added to 2.5 gram Si/Al ratios, r iEqual in 1.1 the sodium X zeolite., after 43 hours this extrusion molding thing is filtered 170 ℃ of heating, washing was 120 ℃ of heating 3 hours.Obtain the no L zeolite of 4.15 grams like this, have atomic ratio r fIt is 3.2 erionite.Synthetic parameters is as follows: S 1=16; S 2=4.65; S 3=0; Q=4.84.
Method 4
5 grams are pre-granulated into the kaolin (r of type i=1) with 80 gram water, 22 gram amorphous silicon di-oxides, 10 gram sodium hydroxide and 8 gram potassium hydroxide mix., after 48 hours this pellet is filtered 170 ℃ of heating, washing is also dry; Its diffraction spectra conforms to erionite, has atomic ratio, r fBe 3.2.Synthetic parameters is as follows: S 1=16; S 2=4.91; S 3=0; Q=4.4.
Example 5L prepare zeolite
Method 1
With 50 gram 3A zeolite extrusion molding thing (r i=1) adds 1020 milliliters and contain 23% potassium hydroxide; In the solution of 0.2% sodium hydroxide and 32% silicon-dioxide.According to table 12, preparation parameter is: S 1=20.4; S 2=2.48 mol; S 3=9.27 gram/grams.
This mixture was kept 18 hours in 160 ℃ in autocrave.Filter then, washing conforms to the L zeolite with dry this its diffraction spectra of extrusion molding thing.Depressing the benzene adsorptive power at the branch of 70 holders is 16.5%.Si/Al ratio, r fBe 3.05, potassium content is 13.0%.
The particulate shatter strength is 20.9 Newton/millimeter one by one, and the shatter strength in bed is 1.2 MPas, is not respectively 8.1 Newton/millimeter and 0.9 MPa of initial 3A zeolite.Electron microscope observation to the mean size of granularity be 0.4 micron.
Method 2
With 20 gram kaolin beads and 52.5 gram potassium hydroxide, 2 gram sodium hydroxide, 110 gram amorphous silicon di-oxides and 150 ml waters mix, with mixture place 170 ℃ through 24 hours then with glomerular filtration and wash.Diffraction spectra and the L zeolite (r that do not conform to f=3).Synthetic parameters is as follows: r i=1; S 1=7.5; S 2=6.25; S 2=0; Q=5.5.
Method 3
With the non-crystalline state extrusion molding thing and 71 gram potassium hydroxide that 50 grams contain 75% silicon-dioxide and 25% aluminum oxide, 2 gram sodium hydroxide and 230 gram dioxide-containing silicas be 30%(by weight) the colloidal silica mixing.This mixture was heated 2 hours at 150 ℃.Filter washing and dry this extrusion molding thing.Diffraction spectra (the r that conforms to the L zeolite f=3.2).Synthetic parameters is as follows: r i=2.55; S 1=3.68; S 2=7.15; S 3=0; Q=1.38.
Example 6: the preparation of ferrierite
Method 1
10 grams had Si/Al than (r i) equal 5 Na-Type Mordenit add contain 23 milliliters of 1.08 moles of tetramethyl ammonium hydroxides) 4 gram particle shape sodium hydroxide and 44 gram dioxide-containing silicas be 30%(by weight) colloidal-silica solution in., after 16 hours solid phase is filtered 250 ℃ of heating, washing is also dry.It is 7.5 that the solid extrusion molding thing that obtains has Si/Al, and its diffraction spectra is pure ferrierite.Synthetic parameters is as follows: S 1=5.82; S 2=2.21; S 3=0.221; Q=1.32; r f=10.2.
Method 2
Restrain Si/Al than (r with 10 i) be 2.4 sodium y zeolite extrusion molding thing and 9 gram amorphous silicon di-oxides, 1.7 gram particle shape sodium hydroxide, 1.91 gram 5 hydronium(ion) oxidation tetramethyl-ammoniums and 45 ml waters mix.After 16 hours, this extrusion molding thing is filtered washing and 120 ℃ of dryings 3 hours 250 ℃ of heating.The Si/Al of the ferrierite extrusion molding thing that obtains is than (r f) be 5.Synthetic parameters is as follows: S 2=4.5; S 2=1.17; S 3=0.198; Q=0.90.
Method 3
With 4 gram dioxide-containing silicas be 40%(by weight) colloidal silica, 23 milliliters of sodium hydroxide molar solutions and 1.01 gram Tetramethylammonium chlorides add 5 grams and contain in the non-crystalline state extrusion molding thing of 75% silicon-dioxide and 25% aluminum oxide.According to table 13, synthetic parameters is as follows: S 1=5.24; B 2=10 mol; S 2=0.286; Q=1.0 gram/gram; r i=2.55.
After 22 hours, obtain 10.1 gram Si/Al 235 ℃ of heating than (r f) be 7.9 ferrierite extrusion molding thing.Particulate shatter strength and initial preformed silico-aluminate 12.3 are in a ratio of 24.3 Newton/millimeter one by one, and 1.14 MPas of shatter strength in bed and initial product are in a ratio of 1.6 MPas.
Example 7: the performance when improving gas-oil cooling with offretite.
The zeolite that is used for this purpose is according to example 3, make with method 1, with the ammonium nitrate exchange after, said zeolite contains 2.1%(by weight) potassium.Then by with 5.10 -3The positively charged ion parent Pd(NH of volumetric molar concentration 3) 4(NO 3) 2Or the exchange of nitric acid four ammonia palladiums adds 0.4%(by weight) palladium.Thereafter with this product 500 ℃ of roastings in air, under hydrogen, reduce in a catalytic unit in 450 ℃ then.
For the usefulness of once feeding, its feature is given in table 14 then.
Table 14
Distillation proportion (20 °): 0.876
Starting point: 220 ℃ of sulphur (%): 1.6(by weight)
10% 305 ℃ of nitrogen (PPm): 260
50% 328 ℃ of pour points (℃): 21
90% 362 ℃ (AENOR standard NO7.042)
Terminal point: 375 ℃ of cloud points (℃): 21
Test is at pressure 40 crust, carries out under 410 ℃ of the temperature, and feed air speed (VVH is with hour expression of stocking volume/catalyst volume) is 1, H 2/ gas-oil volume ratio is 500 liters/liter.20 days or the longer time after, 200 +The cloud point and the pour point of cut be respectively+and 3 and 0 ℃.(cloud point is consistent with the temperature that wax crystal first occurs; Pour point is consistent with the solid matter temperature of solidification).Example 8: improve the performance of gas-oil when cooling off with ferrierite.
Ferrierite extrusion molding thing that example 6 is obtained according to method 3 and ammonium sulfate molar solution carry out secondary and exchange continuously, so that sodium content is reduced to 0.2%(by weight), once exchange with 0.1 molar acetate nickel solution subsequently, make nickel content be 2.1%(by weight), roasting and the reduction after, this catalyzer is carried out as example 7 said identical test, operational condition is identical, different temperature be 380 ℃, after 200 hours, 200 +The turbidity of cut and pour point respectively+6 and+3 ℃.
Example 9: the hydrocracking on the y zeolite.
The y zeolite extrusion molding thing that obtains by method 1 in the example 1 is carried out 4 times cationic exchange in 1.5 moles of ammonium chloride solutions so that sodium content to 0.15%, at last in static atmosphere in 700 ℃ of roastings, make by dipping Palladous chloride parent later on to add 0.5% palladium.With this catalyzer in dry air in 500 ℃ of roastings and prereduction in hydrocracking pilot plant reactor.
The charging feature is listed in table 15
Table 15
Distillation
Starting point (℃): (by weight) 1.2% 20.1 S(%)
50% point (℃): 332
Terminal point (℃): 435 N(PPm) 840
In advance with this charging hydrotreatment to remove most of the nitrogen and sulphur compound (in the effluent less than 5PPm nitrogen); In hydrotreatment in advance, form, comprise H 2S and NH 3Effluent above following condition is on zeolite catalyst, pass through:
-pressure (crust): 120
-volumetric rate (rise/liter/hour) per hour: 1.5
-H 2/ charging (gas liter/liquid liter): 1000
355 ℃ of temperature down test reach 69% after 200 hours and be transformed into boiling point and be lower than 200 ℃ product, have selectivity (by weight) to C5-130 ℃ of cut 75%.
Example 10: the hydrocracking on omega zeolite.
The zeolite of the example 2 that will be obtained by method 1 carries out cationic exchange, and this exchange makes sodium content be reduced to 0.5%(by weight).Then by adding 0.3% platinum with the exchange of nitric acid four ammonia platinum.This catalyzer 500 ℃ of following roastings and at testing apparatus in 500 ℃ of prereduction in hydrogen.
With this catalyzer in the charging that the hydrogen treatment identical with example 8 crossed except that temperature, under identical condition, to carry out the hydrocracking test.
In the test of 380 ℃ of temperature after 200 hours, change into the product that boiling point is lower than 220 ℃ and add up 60%, to the selectivity of C5-180 ℃ of cut be 78%(by weight).
Example 11: the methanol conversion on offretite.
The zeolite of the example 1 that will be obtained by method 1 carries out four times the successive cationic exchange in 2 molar nitric acid ammonium solutions, dry then and in 500 ℃ of roastings.The content of potassium is 2.1%.
Test with 15co effluent adding reactor and with the methyl alcohol charging.Under atmospheric pressure, feed air speed (VVH, methyl alcohol volume/catalyst volume hour) is 2,400 ℃ of temperature, and it the results are shown in table 16 after 10 minutes.
Table 16
Transform: methyl alcohol 100%
Yield (by weight): ethene 29%
Propylene 25%
Butylene 11%
Methane 6%
Ethane 1%
Propane 16%
Butane 7%
C + 55%
Example 12: the aromizing on the L zeolite.
The zeolite of the example 5 that will be obtained by method 1 is invaded and is contained 0.3 grams per liter P t(NH 3) ++ 4In the ionic potassium nitrate solution.At 450 ℃ of these products of roasting and by using rhenium carbonyl solution (Re 2(CO) 10) dipping adding rhenium.After packing in the catalytic unit, place it in the hydrogen in 450 ℃ activate after, use the mixture passivation of hydrogen and 1% hydrogen sulfide then, in hydrogen, purify 8 hours pressing under institute's 10 crust subsequently in 500 ℃.
Under following condition, add the normal hexane charging then: 470 ℃ of temperature, pressure: 3 crust, molecular ratio: hydrogen/normal hexane=3, tested after 25 hours hour volumetric rate=3, hexane conversion is 93%, to the selectivity of benzene be 78%(by weight), to C 1-C 5Product selectivity 3.1%.
Figure 85104995_IMG20

Claims (15)

1, a kind of premolding synthetic zeolite, this zeolite is selected from by y, ω, offretite, erionite, the group that L and ferrierite are formed, its Si/Al atomic ratio, r fScope from 1.5 to 100, and be selected from by natural or synthetic zeolite from least a, the premolding silica-alumina material of the group that amorphous silicon di-oxide one aluminum oxide and clay are formed obtains, described material has Si/Al atomic ratio r iLess than r fIts scope from 0.5 to 90, described premolding synthetic zeolite is by with a kind of silica product that contains, at least a being selected from by Lithium Oxide 98min arranged, sodium hydroxide, handle described material when the organic or inorganic tool of the group that potassium hydroxide and tetraalkylammonium hydroxides are formed exists and make (the OH of described alkali -) anion concentration scope from 0.01 to 10 mol solution, tetramethylammonium cation is to (OH -) anionic mol ratio from 0 to 0.5, the silica volume from 0.1 to 30 that joins described material restrains/restrains anhydrous silica-alumina material, liquid phase/anhydrous silica-alumina material is from 2 to 30 than (by weight), and described processing is carried out when from 50 to 200 ℃ of temperature, and the time was from 2 hours to about 200 days.
2, the described a kind of method of claim 1, wherein natural zeolite is for being selected from by euthalite chabazite, clinoptilolite, erionite, faujusite, the group that ferrierite and mordenite are formed.
3, the described method of claim 2, its mesolite uses with broken particle.
4, the described method of claim 1, wherein synthetic zeolite is for being selected from the zeolite by A, the group that X and y zeolite and mordenite are formed.
5, the described method of one of claim 1-4, wherein said preforming material is a kind of crystalline zeolite, this zeolite its a kind of positively charged ion at least is different from unborn cationic exchange in described material with at least a at least in part, and described positively charged ion is selected from by K +, Li +, NH + 4, H +The group of forming, this cationic exchange can randomly be carried out a thermal treatment subsequently.
6, the described method of one of claim 1-5, wherein said material are a kind of crystalline zeolites, and this zeolite to small part had been carried out removing aluminium and handled.
7, the described method of one of claim 1-6, for from being selected from zeolite by A, X faujusite, preparation " y faujasite-type " zeolite in the material of the group that amorphous silicon di-oxide one aluminum oxide and kaolin are formed.By being selected from by sodium hydroxide with at least a, potassium hydroxide, Lithium Oxide 98min, the mineral alkali of the group that tetraalkylammonium hydroxides and described oxyhydroxide parent are formed is handled described material, and described method feature is: the T shown in the table 7 2, S 1, S 2, S 3, Q, T, t, d, T fValue is in the pointed wide region of table 8.
8, the described method of one of claim 1-6, for from being selected from zeolite by A, X and y faujusite, prepare omega zeolite in the material of the group that amorphous silicon di-oxide-aluminum oxide and kaolin are formed, by be selected from by sodium hydroxide potassium hydroxide, Lithium Oxide 98min with at least a, the mineral alkali of the group that the parent of tetraalkylammonium hydroxides and described oxide compound is formed is handled described material, and described method feature is: the T shown in the table 7 i, S 1, S 2, B 3, Q, T, t, d, T fValue is in the pointed wide region of table 9.
9, the described method of one of claim 1-6, for from being selected from zeolite by A, X and y faujusite, preparation " offretite type " zeolite in the material of the group that amorphous silicon di-oxide one aluminum oxide and kaolin are formed, by be selected from by sodium hydroxide potassium hydroxide, Lithium Oxide 98min with at least a, the mineral alkali of the group that tetraalkylammonium hydroxides and described oxyhydroxide parent are formed is handled described material, and described method is characterised in that: the T shown in the table 7 i, S 1, S 2, S 2, Q, T, t, d, T fValue is in the pointed wide region of table 11.
10, the described method of one of claim 1-6, for from being selected from zeolite by A, X and y faujusite, preparation a kind of " erionite type " zeolite in the material of the group that amorphous silicon di-oxide one aluminum oxide and kaolin are formed, by be selected from by sodium hydroxide potassium hydroxide, Lithium Oxide 98min with at least a, the mineral alkali of the group that the parent of tetraalkylammonium hydroxides and described oxyhydroxide is formed is handled described material, and described method is characterised in that: the T shown in the table 7 i, S 1, S 2, S 3, Q, T, t, d, T fValue is in the pointed wide region of table 11.
11, the described method of one of claim 1-6, for from being selected from zeolite by A, X and y faujusite, a kind of L zeolite of preparation in the material of the group that amorphous silicon di-oxide one aluminum oxide and kaolin are formed, by be selected from by sodium hydroxide potassium hydroxide, Lithium Oxide 98min with at least a, the mineral alkali of the group that the parent of tetraalkylammonium hydroxides and described oxyhydroxide is formed is handled described material, and described method feature is: the T shown in the table 7 i, S 1, S 2, S 3, Q, T, t, d, T f, be in the pointed wide region of table 12.
12, the described method of one of claim 1-6, for from being selected from zeolite by A, X and y faujusite, amorphous silicon di-oxide one aluminum oxide, preparation " ferrierite type " zeolite in the material of the group that mordenite and kaolin are formed is by being selected from by sodium hydroxide with at least a, potassium hydroxide, Lithium Oxide 98min, the mineral alkali of the group that tetraalkylammonium hydroxides and described oxyhydroxide parent are formed is handled described material, and described method feature is: the T shown in the table 7 i, S 1, S 2, S 3, Q, T, t, d, T fValue is in the pointed wide region of table 13.
13, a kind of premolding zeolite that makes according to one of claim 1 to 12 is in absorption or ion-exchange or as catalyzer or support of the catalyst, use in heterogeneous catalyst, described zeolite are used separately or to use with at least a form of mixtures that is selected from other components of carrier or matrix and metal or metalloid group.
14, the described use of claim 13, wherein preformed zeolite is carried out a pre-treatment before use at least, and described pre-treatment is to be selected from cationic exchange, with at least a organic or inorganic acid treatment and heat treated a kind of operation.
15, according to the effect of the prepared premolding zeolite of one of claim 1 to 12 in catalytic cracking or hydrocracking, said zeolite uses separately or conduct and at least a carrier that is selected from, and the mixture of the component of matrix and metal or metalloid group uses.
CN198585104995A 1984-06-18 1985-07-01 Synthetic and the purposes of premolding zeolite Pending CN85104995A (en)

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GB8515366D0 (en) 1985-07-17
JPS6114117A (en) 1986-01-22
NL8501731A (en) 1986-01-16
GB2160517A (en) 1985-12-24
DE3521675A1 (en) 1985-12-19
FR2565847B1 (en) 1986-08-29
FR2565847A1 (en) 1985-12-20

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