CN1111086C - Rare earth element containing molecular sieve and its preparation - Google Patents
Rare earth element containing molecular sieve and its preparation Download PDFInfo
- Publication number
- CN1111086C CN1111086C CN99105792A CN99105792A CN1111086C CN 1111086 C CN1111086 C CN 1111086C CN 99105792 A CN99105792 A CN 99105792A CN 99105792 A CN99105792 A CN 99105792A CN 1111086 C CN1111086 C CN 1111086C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- rare earth
- zeolite
- rare
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a rare earth containing molecular sieve. At least one part of rare earth elements of the molecular sieve exists in a skeleton rare earth mode. The preparation method comprises the step that a rare earth type molecular sieve calculated by oxide and containing 0.1 to 40 wt% of rare earth is in contact with a solution containing at least one substance in (I) and at least one substance in (II) for at least 0.1 hour at the temperature of 25 to 120 DEG C. The (I) comprises inorganic acid, inorganic alkali, organic acid or a reagent which can form a complex compound with aluminum. The (II) comprises soluble ammonium salt, organic acid salt, amine, ethanol, aldehyde and ketone. The pH value of the solution is from 3 to 12, and the molar ratio of the substance in the (II) to the rare earth element in the rare earth type molecular sieve is from 0.01 to 20.
Description
The invention relates to a kind of molecular sieve and preparation method thereof, more specifically say so about a kind of molecular sieve that contains rare earth and preparation method thereof.
All contain AlO in the overwhelming majority molecular sieve
4Tetrahedron.As natural or artificial synthetic aluminosilicate zeolite by AlO
4And SiO
4Tetrahedron is formed, wherein AlO
4Tetrahedral negative electrical charge is by the cation neutralization of absorption, and this cation can be H
+, NH
4 +, alkali metal ion, alkaline-earth metal ions or other ion, as rare earth ion etc.When the aluminium in the framework of molecular sieve was replaced by other element, these new elements also will form tetrahedral coordination with oxygen, thereby become the part of crystal structure of molecular sieve.
Other element is introduced framework of molecular sieve with the novel molecular sieve that replaces aluminium and preparation method thereof existing report.For example, CN1,037,097A has reported and chromium or tin has been introduced molecular sieve that contains skeleton chromium or tin that molecular sieve obtains and preparation method thereof.
Existing a lot of in the prior art about the report of zeolite of containing rare earth and preparation method thereof.
US4,178,269 is raw material with X, Y zeolite, with rare earth chloride-ammonium chloride solution exchange.US4,152,362 is raw material with X, Y, L type molecular sieve, with rare earth fluoride-ammonium chloride solution exchange.US4,210,522 usefulness molecular sieve raw materials have prepared catalyst, and with the exchange of rare earth compound solution, rare earth compound is the chloride of rare earth, the sulfate of rare earth or the nitrate of rare earth again.US3,894,940 is raw material with NaY, with the re chloride exchange, takes off sodium with the ammonium sulfate exchange more earlier.US4,192,778 is raw material with NaY, with ammonium sulfate-re chloride exchange, the exchange temperature is carried out in autoclave pressure greater than 100 ℃.US4,234,457 is raw material with NaY, with ammonium sulfate-rare earth sulfate solution exchange.US4,339,354 is raw material with NaY, with the ammonium sulfate exchange, with the re chloride exchange, high-temperature roasting is handled then again.US4,900,428 is raw material with the Y zeolite, makes rare earth be deposited on catalyst surface with infusion process, the weight ratio of cerium and lanthanum is greater than 2.0 in the rare earths material.US4,678,765 is raw material with the Y zeolite, with the re chloride exchange, high-temperature roasting then exchanges with ammonium sulfate again.CN8,607,531, CN8,607,598 and CN1,034,680A is a raw material with NaY, super steady Y and high silicon Y molecular sieve respectively, in slurries rare earth is deposited on the molecular sieve.CN1,065,844A is raw material with NaY, with ammonium salt and re chloride exchange, to the super steady processing of molecular sieve, ammonium salt is ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate then.
US4,701,431 have disclosed aluminosilicate zeolite of a kind of scarce aluminium and preparation method thereof, and this zeolite has the crystalline texture of faujasite, and has following anhydrous chemical expression of expressing with terms of oxide moles: (1-z) (aM
2O+bR
2O
3+ 3wRE
2O
3) (1-z) Al
2O
3XSiO
2, wherein, RE represents the mixture of a kind of rare earth ion or multiple rare earth ion; W is 0.054～0.217, is the minimum of described scarce aluminium zeolite middle rare earth, and R is a kind of alkali metal ion; M is selected from H
+, NH4
+Or its mixture; A is 0 to 1-3w; B is 0 to 1-3w; A+b+3w=1, z are 0.92～0.27, are the largest score of the aluminium that can remove in the crystal structure; X is 3.9～54; The lattice constant of described zeolite is the 24.25-24.75 dust, and the lattice constant of this zeolite is a bit larger tham stoichiometric lattice constant.The preparation method that should lack the aluminosilicate zeolite of aluminium comprises (1) with the original Y type of a kind of dealuminzation agent treatment aluminosilicate zeolite, and the condition and the time of processing zeolite are enough to remove at least 5% aluminium from zeolitic frameworks; Described original zeolite has the crystalline texture of faujasite, and has the following anhydrous chemical expression of representing with molal quantity: (aM
2O+bR
2O) Al
2O
3XSiO
2, wherein, R represents a kind of alkaline-earth metal ions; M is the ion that is selected from hydrogen ion, ammonium ion or its mixture; A+b=1; Wherein, a is 0～1; B is 0～1; X gets 3.9～54; The lattice constant of described zeolite is 24.25～24.75 dusts; (2) in step a or afterwards, described zeolite is contacted with a kind of exchange media that contains rare earth ion, rare earth ion is replaced to small part M or R; (3) reclaiming the anhydrous chemical expression of expressing with terms of oxide moles is (1-z) (aM
2O+bR
2O
3+ 3wRE
2O
3) (1-z) Al
2O
3XSiO
2, and through 704 ℃ handle 2 hours after structure cell greater than stoichiometric zeolite.
After rare earth element enters the combination of molecular sieve skeleton, can cause that following variation takes place the combination of molecular sieve rerum natura: (1) since the ionic radius of rare earth element obviously greater than the ionic radius of aluminium, after rare earth element enters skeleton, its structure cell is inevitable obviously to be increased, and contains the zeolite of rare earth described in the prior art, removes US4,701,431 outer do not find this phenomenon, and generally speaking, the lattice constant of zeolite that contains rare earth is all less than original zeolite.And US4, the more original mostly zeolite of lattice constant of 701,431 zeolites that contain rare earth that disclose is little, though the situation of increase is also arranged in individual other example, its increase value is less, and maximum has only 0.04 dust; (2) because the skeleton heavy metal has scattering process to the X-ray, its XRD (X-ray diffraction) diffraction peak intensity will descend significantly, the d spacing increases, and the XRD diffraction peak intensity of the zeolite that contains rare earth that prior art discloses does not descend or fall is less, the d spacing does not only have the tendency of increase, and the tendency that reduces is arranged on the contrary.(3) because rare earth atom radius ratio aluminium is much bigger, after rare earth element enters framework of molecular sieve, its structural stability descends, therefore, its lattice avalanche temperature descends, and the zeolite that contains rare earth that prior art discloses but has higher heat endurance with original zeolite facies ratio, and promptly its lattice avalanche temperature raises; (4) after rare earth element entered framework of molecular sieve, because the rare earth ion electronegativity is big, and the bond distance of RE-O key was longer, and making wave number is 750～830 centimetres
-1The skeleton infrared vibration bands of a spectrum at place move to high wave number direction, and spectral bandwidth reduces, and the zeolite that contains rare earth that prior art discloses is not found this phenomenon.The analysis-by-synthesis The above results shows that in the zeolite that contains rare earth that prior art discloses, rare earth element does not enter framework of molecular sieve yet.
The purpose of this invention is to provide a kind of molecular sieve new, that contain rare earth.Another object of the present invention provides the preparation method of this molecular sieve.
Molecular sieve provided by the invention contains rare element of going up, and wherein, at least a portion of described rare earth element exists with the form of skeleton rare earth.
The preparation method of molecular sieve provided by the invention is included under 25～120 ℃ the temperature, with a kind of in oxide, the solution of at least a material among at least a material in the rare-earth type molecular sieve that contains the heavy % of rare earth 0.1～40 and a kind of containing (I) and (II) contacts at least 0.1 hour, isolate the product that obtains, drying; Wherein, (I) comprise inorganic acid, inorganic base, organic acid or can form the reagent of complex compound with aluminium; (II) comprise solubility ammonium salt, acylate and amine, alcohol, aldehyde, ketone; Wherein, the pH value of solution is 3～12, and (II) mol ratio of contained rare earth element is 0.01～20 in the material in and the rare-earth type molecular sieve; Described rare-earth type molecular sieve refers to the natural or artificial synthetic molecular sieve that partial cation position is at least occupied by rare earth element.
Molecular sieve provided by the invention contains rare earth element, and wherein, at least a portion of described rare earth element exists with the form of skeleton rare earth.
Generally, rare-earth-containing molecular sieve provided by the invention has following unit empirical formula:
(RE
wAl
rR
y) O
2Wherein, RE represents one or more in the rare earth element; R represents silicon, boron or phosphorus atoms; W, x and y represent the molar fraction of the RE, aluminium and the R that exist with the tetrahedronal oxide of skeleton unit respectively, and w gets 0.001～0.5, preferred 0.001～0.06.X gets 0.001～0.5, preferred 0.01～0.3, y gets 0.001～0.998, preferred 0.65～0.95.
" unit empirical formula " described here is meant the simplest molecular formula, it has provided the relative molal quantity of the RE, aluminium and the R that exist with the tetrahedronal oxide of skeleton unit in molecular sieve, do not comprise in this unit empirical formula because other compounds that may exist, cation or the anion that preparation process is brought into.
Rare-earth-containing molecular sieve provided by the invention is to contain that framework aluminum part in the molecular sieve of framework aluminum is replaced by rare earth ion and a kind of novel molecular sieve of forming, and it can have existing aluminosilicate zeolite or other contains the crystalline texture of the hetero-atom molecular-sieve of aluminium.In more detail, the crystalline texture that rare-earth-containing molecular sieve provided by the invention can have existing various aluminosilicate zeolites (at this moment, R in the unit empirical formula represents silicon atom), can have the crystalline texture of zeolites such as A type zeolite, faujasite (comprising X type zeolite and y-type zeolite) L zeolite, modenite, Beta zeolite, omega zeolite, ZSM series zeolite as it.Rare-earth-containing molecular sieve provided by the invention also can have the existing crystalline texture that contains the aluminium hetero-atom molecular-sieve, as has phosphate aluminium molecular sieve (at this moment, R phosphor atom in the unit empirical formula) or the crystalline texture of boron aluminum molecular screen (at this moment, the R in the unit empirical formula represents the boron atom).
As an embodiment preferred of the present invention, the molecular sieve that contains rare earth provided by the invention is the molecular sieve that has as the lower unit empirical formula:
(RE
wAl
xSi
y) O
2Wherein RE represents one or more in the rare earth element; W, x and y represent the molar fraction of the RE, aluminium and the silicon that exist with the tetrahedronal oxide of skeleton unit respectively, and w gets 0.001～0.49, preferred 0.001～0.06; X gets 0.001～0.49, preferred 0.01～0.3; Y gets 0.5～0.998, preferred 0.65～0.95.
According to embodiment preferred of the present invention, rare-earth-containing molecular sieve provided by the invention is the molecular sieve with y-type zeolite structure, its lattice constant is than the lattice constant of original y-type zeolite at least 0.05 dust greatly, under the preferable case, its lattice constant is than big 0.05～0.2 dust of lattice constant of original y-type zeolite.It has following X-ray diffraction types:
| D (nanometer) | Relative intensity (%) |
| 1.408～1.448 | ≤45 |
| 0.858～0.893 | ≤20 |
| 0.553～0.583 | ≤25 |
| 0.461～0.491 | ≤20 |
| 0.422～0.452 | ≤20 |
| 0.367～0.387 | ≤25 |
Under the preferable case, the rare-earth-containing molecular sieve with y-type zeolite structure provided by the invention has following X-ray diffraction types:
| D (nanometer) | Relative intensity (%) |
| 1.425～1.440 | 10～40 |
| 0.873～0.880 | 5～15 |
| 0.560～0.570 | 5～20 |
| 0.475～0.485 | 5～15 |
| 0.437～0.440 | 5～15 |
| 0.377～0.379 | 5～20 |
According to second embodiment preferred of the present invention, rare-earth-containing molecular sieve provided by the invention is the molecular sieve with zeolite L structure, its cell parameter is greater than original L zeolite, under the preferable case, its cell parameter a, b, c are than big 0.04～0.2 dust of original L zeolite difference, and it has following X-ray diffraction types:
| D (nanometer) | Relative intensity (%) |
| 1.574～1.614 | ≤45 |
| 0.737～0.767 | ≤22 |
| 0.587～0.617 | ≤20 |
| 0.445～0.475 | ≤20 |
| 0.382～0.402 | ≤22 |
| 0.356～0.376 | ≤20 |
Under the preferable case, the rare-earth-containing molecular sieve with zeolite L structure provided by the invention has following X-ray diffraction types:
| D (nanometer) | Relative intensity (%) |
| 1.595～1.610 | 5～35 |
| 0.750～0.765 | 5～15 |
| 0.603～0.610 | 5～15 |
| 0.460～0.470 | 5～15 |
| 0.391～0.400 | 5～15 |
| 0.362～0,370 | 5～15 |
According to the 3rd embodiment preferred of the present invention, rare-earth-containing molecular sieve provided by the invention is the molecular sieve with mordenite structure, its cell parameter is greater than original modenite, under the preferable case, its cell parameter a, b, c are than big 0.04～0.2 dust of original modenite difference, and it has following X-ray diffraction types:
| D (nanometer) | Relative intensity (%) |
| 1.338～1.378 | ≤45 |
| 0.889～0.924 | ≤42 |
| 0.643～0.673 | ≤30 |
| 0.625～0.655 | ≤25 |
| 0.390～0.410 | ≤25 |
| 0.338～0.358 | ≤45 |
Under the preferable case, the rare-earth-containing molecular sieve with mordenite structure provided by the invention has following X-ray diffraction types:
| D (nanometer) | Relative intensity (%) |
| 1.355～1.370 | 10～40 |
| 0.903～0.920 | 5～35 |
| 0.660～0.670 | 5～30 |
| 0.640～0.650 | 5～20 |
| 0.400～0.410 | 5～20 |
| 0.345～0.355 | 5～35 |
According to the 4th embodiment preferred of the present invention, the rare earth zeolite that contains provided by the invention is the molecular sieve with omega zeolite structure, its cell parameter is greater than original omega zeolite, under the preferable case, its cell parameter a, b, c are than big 0.04～0.2 dust of original omega zeolite difference, and it has following X-ray diffraction types:
| D (nanometer) | Relative intensity (%) |
| 1.573～1.613 | ≤43 |
| 0.903～0.938 | ≤40 |
| 0.587～0.617 | ≤32 |
| 0.458～0.488 | ≤35 |
| 0.373～0.393 | ≤42 |
| 0.343～0.363 | ≤45 |
Under the preferable case, the rare-earth-containing molecular sieve with omega zeolite structure provided by the invention has following X-ray diffraction types:
| D (nanometer) | Relative intensity (%) |
| 1.590～1.610 | 10～30 |
| 0.920～0.930 | 10～25 |
| 0.600～0.610 | 5～20 |
| 0.472～0.485 | 5～20 |
| 0.382～0.393 | 5～15 |
| 0.355～0.363 | 10～35 |
Wherein, the peak area of the corresponding diffraction maximum of the peak area/original zeolite of the relative intensity of each diffraction maximum=a certain diffraction maximum of rare-earth-containing molecular sieve provided by the invention.
Here, described original zeolite refers to not exchange the raw material zeolite of rare earth element, refers generally to ammonium type zeolite, and original zeolite forms the rare-earth type zeolite after rare earth ion exchanged.With original zeolite facies ratio, the lattice constant of rare-earth type zeolite is generally less than original zeolite, and XRD (X-ray diffraction) diffraction peak intensity is not too big less than decline or fall, the d spacing is less than original zeolite, heat endurance raises, i.e. lattice avalanche temperature raises, and wave number is 750～830 centimetres
-1Absorption band do not have significant change.
Described rare earth element is selected from one or more in the rare earth element.In the preferred lanthanum of described rare earth element, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, ytterbium, the lutetium one or more.The more preferred lanthanum of described rare earth element, cerium or mixed rare-earth elements.
Rare-earth-containing molecular sieve provided by the invention has following feature: compare with the initial molecule sieve, (1) its structure cell obviously increases; (2) its XRD (X-ray diffraction) diffraction peak intensity descends significantly, and the d spacing increases; (3) its lattice avalanche temperature descends; (4) wave number is 750～830 centimetres
-1Absorption band move to high wave number direction, this absorption band width obviously reduces.With the molecular sieve with y-type structure that contains rare earth oxide 8.835 heavy % provided by the invention is example, with original y-type zeolite (NH
4Y) compare, its XRD diffraction peak intensity descends significantly, and the d spacing has increased 0.0001～0.0052 nanometer, and lattice constant has increased 0.05～0.14 dust; Lattice avalanche temperature has descended 20～75 ℃; Wave number is 750～830 centimetres
-1The IR of skeletal vibration (infrared) absorption band width has reduced 18～58%, and has moved 8～48 centimetres to high wave number direction
-1
The analysis-by-synthesis The above results shows, the molecular sieve that contains rare earth provided by the invention has entered framework of molecular sieve to the small part rare earth element.
For molecular sieve provided by the invention is described, be example with the aluminosilicate zeolite, the spy does following explanation:
Original zeolite and the zeolite that contains rare earth provided by the invention can be represented with the tetrahedral molar fraction of skeleton.Wherein, original zeolite can be represented with following formula:
(Al
X 'Si
Y ' Z ') O
2Wherein, the tetrahedral molar fraction of aluminium in x ' the expression skeleton; The tetrahedral molar fraction of silicon in y ' the expression skeleton; Oral thermometer shows the defective locations in the skeleton, the tetrahedral molar fraction of defective locations in z ' the expression skeleton.
x’+y’+z’＝1。(1)
According to US4,678,765 the 11st～12 pages of described methods, zeolitic frameworks defective locations molar fraction=(3710 centimetres
-1Place's zeolitic frameworks vibrates the tetrahedral molar fraction of skeleton defective locations of infrared absolute absorption rate * standard specimen) 3710 centimetres of ÷
-1The infrared absolute absorption rate of place's standard specimen skeletal vibration.
Wherein, the preparation method of standard specimen is as follows: use SiCl
4Initial molecule sieve is carried out gas phase mend silicon and handle the sample (its defective locations number is 0) that obtains structural integrity, the sample of the structural integrity that obtains is relaxed dealuminzation in EDTA solution, obtain standard specimen (referring to US3,442,795).The tetrahedral molar fraction of skeleton defective locations of standard specimen equals the molar fraction of its aluminium that removes.
The molecular sieve that contains rare earth provided by the invention can be represented with following formula:
(RE
wAl
xSi
y z) O
2Wherein, w refers to the tetrahedral molar fraction of the rare earth that generates, and x is the tetrahedral molar fraction of aluminium in the framework of molecular sieve, and y is the tetrahedral molar fraction of silicon in the framework of molecular sieve, and z is the tetrahedral molar fraction of defective locations in the framework of molecular sieve.W+x+y+z=1, therefore,
w＝1-x-y-z (2)
In to molecular sieve modified process, framework silicon is difficult to be removed generally speaking, and the influence that rearrangement brought of framework silicon also can be left in the basket, and therefore, can think y=y '.(1-y ')-(x+z) (3) substitution (1) formula so w=:
w＝(x’+z’)-(x+z)
＝(x’-x)+(z’-z)
The molar fraction of the molar fraction of the tetrahedral molar fraction of aluminium in the tetrahedral molar fraction of aluminium-product zeolitic frameworks+original zeolitic frameworks tetrahedral defect position-product zeolitic frameworks tetrahedral defect position in the=original zeolitic frameworks.
The preparation method of molecular sieve provided by the invention is included under 25～120 ℃ the temperature, with a kind of in oxide, the solution of at least a material among at least a material in the rare-earth type molecular sieve that contains the heavy % of rare earth 0.1～40 and a kind of containing (I) and (II) contacts at least 0.1 hour, isolate the product that obtains, drying; Wherein, (I) comprise inorganic acid, inorganic base, organic acid or can form the reagent of complex compound with aluminium; (II) comprise solubility ammonium salt, acylate and amine, alcohol, aldehyde, ketone; Wherein, the pH value of described solution is 3～12, and (II) mol ratio of contained rare earth element is 0.01～20 in the material in and the rare-earth type molecular sieve; Described rare-earth type molecular sieve refers to the natural or artificial synthetic molecular sieve that partial cation position is at least occupied by rare earth element.
According to preparation method provided by the invention, described rare-earth type molecular sieve middle rare earth content is preferably 0.3～20 heavy %
The rare-earth type zeolite that described rare-earth type molecular sieve can be various structure types is as rare-earth type A type zeolite, faujasite (comprising X type zeolite and y-type zeolite), L zeolite, modenite, BETA zeolite, omega zeolite, ZSM series zeolite etc.Described rare-earth type molecular sieve also can be the rare-earth type hetero-atom molecular-sieve of various structure types, as phosphate aluminium molecular sieve, boron aluminum molecular screen.Preferred rare-earth type molecular sieve is rare-earth type y-type zeolite, L zeolite, modenite or omega zeolite.
Described rare-earth type molecular sieve can be purchased and obtain, and also can adopt existing prepared in various methods, as adopts conventional ion-exchange, infusion process etc.For example, the described molecular sieve that contains rare earth can adopt following method preparation: at 25～120 ℃, under preferred 80～100 ℃ temperature, a kind of initial molecule sieve is contacted more than 0.1 hour with a kind of solution that contains rare earth and ammonium salt, filter and washing, obtain the rare-earth type molecular sieve.This rare-earth type molecular sieve can directly use, or uses after drying and/or the roasting.Wherein, in the described solution that contains rare earth and ammonium salt, the consumption of rare earth element is preferably 1～2 times for 1～4 times of the rare-earth-containing molecular sieve middle rare earth content that obtains in advance; The concentration of ammonium salt can be 0.1～5 mol, is preferably 0.5～3 mol.The consumption of the described solution that contains rare earth and ammonium salt at least can wetting described molecular sieve, under the preferable case, describedly contains the solution of rare earth and ammonium salt and the weight ratio of combination of molecular sieve is 1～60, is preferably 10～30.The contact temperature is 25～120 ℃, is preferably 80～100 ℃, and time of contact is for more than at least 0.1 hour, preferred 0.1～8.0 hour, and more preferred 0.5～3.0 hour.Described contact can be carried out being lower than normal pressure, normal pressure or being higher than under the normal pressure.According to the requirement to rare-earth type molecular sieve middle rare earth content, said process can carry out repeatedly.Described ammonium salt can be selected from one or more in ammonium sulfate, ammonium hydrogen sulfate, ammonium fluoride, ammonium chloride, ammonium nitrate, ammonium carbonate, carbonic hydroammonium, ammonium phosphate, ammonium hydrogen phosphate, the ammonium dihydrogen phosphate (ADP).Ammonium salt commonly used is ammonium sulfate, ammonium nitrate, ammonium fluoride or ammonium chloride.Described initial molecule sieve can be the molecular sieve that cation-bit is occupied by alkali metal ion, alkaline-earth metal ions, ammonium ion.
Under the preferable case, described (I) comprises sulfuric acid, hydrofluoric acid, hydrochloric acid, perchloric acid, nitric acid, carbonic acid, alkali-metal hydroxide, ammoniacal liquor, ethylenediamine tetra-acetic acid, formic acid, acetate, oxalic acid, propionic acid, benzoic acid, butyric acid, succinic acid, trichloroacetic acid, trifluoroacetic acid, salicylic acid, N, N-two inferior salicylic acids; Preferably include perchloric acid, alkali-metal hydroxide, ammoniacal liquor, ethylenediamine tetra-acetic acid, formic acid, N, N-two inferior salicylic acids.Described (II) comprises ammonium sulfate, ammonium hydrogen sulfate, ammonium fluoride, ammonium chloride, ammonium nitrate, ammonium carbonate, carbonic hydroammonium, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), organic acid sylvite or ammonium salt, ethylenediamine, N, dinethylformamide, N, N-dimethylacetylamide, urea, have 1～5 carbon atom and 1 or the alcohol of a plurality of hydroxyls, have 1～5 carbon atom and 1 or 2 carbonyl aldehyde, have the ketone of 3～10 carbon atoms and 1 or 2 carbonyl; Preferably include ammonium fluoride, acetaldehyde, ethylenediamine, N, dinethylformamide, ethanol, BA.
The pH value of described solution is preferably 3～6 or 8～11.(II) mol ratio of contained rare earth element is preferably 1～10 in material in and the rare-earth type molecular sieve.
Described rare-earth type molecular sieve with contain (I) at least a material and (II) in the temperature that contacts of the solution of at least a material be 25～120 ℃, preferred 80～100 ℃; The pressure of contact does not limit, and can carry out being lower than normal pressure, normal pressure or being higher than under the normal pressure; At least 0.1 hour time of contact, preferably at least 0.5 hour, more preferred 0.5～8 hour.
The condition of described drying is conventional condition, can be room temperature to 300 ℃ as baking temperature, preferred 120～200 ℃; Drying time is greater than 0.5 hour, preferred 1～24 hour.All right after dry, but be not to carry out roasting, roasting condition is the roasting condition of conventional molecular sieve, as 350～700 ℃ of sintering temperatures, and preferred 450～650 ℃; Roasting time is greater than 0.5 hour, preferred 1～8 hour.
The molecular sieve that contains rare earth through method for preparing provided by the invention can continue to handle one or many with this method, to prepare the higher molecular sieve that contains rare earth of skeleton content of rare earth.
In the molecular sieve that contains rare earth provided by the invention, exist to the form of small part rare earth element with the skeleton rare earth.Still do not find such molecular sieve in the prior art.
Novel molecular sieve provided by the invention can directly be used as the active component of adsorbent or various hydrocarbon conversion catalysts, also can after roasting, be used alone as adsorbent or various hydrocarbon conversion catalyst, can also combine with adsorption activity material or the material with catalytic activity, as active component, the carrier of adsorbent, the active component of various hydrocarbon conversion catalysts or the carrier of various hydrocarbon conversion catalysts of adsorbent.Can also introduce the compound of various metals or metal in the novel molecular sieve provided by the invention, element or compound as IB, IIA, IIB, IIIB, IVA, IVB, VA, VB, VIB, VIIB, VIII in the periodic table of elements, then, be used as active component, the carrier of adsorbent, the active component of various hydrocarbon conversion catalysts or the carrier of various hydrocarbon conversion catalysts of adsorbent.Described hydrocarbon conversion reaction comprises reactions such as catalytic cracking, hydrogenation, HDM, hydrodesulfurization, hydrodenitrogeneration, hydrofinishing, hydrocracking, isomerization, polymerization, disproportionation.
The following examples will the present invention will be further described, but not thereby limiting the invention.
In the example, the unit empirical formula of molecular sieve is got as calculated by the framework silicon that records, framework aluminum and skeleton room molar fraction.Framework silicon, framework aluminum content adopt chemical analysis to measure.In order to get rid of of the influence of zeolite non-framework aluminum to measurement result, at first with 1 equivalent/liter the EDTA aqueous solution at room temperature zeolite is handled, to remove the non-framework aluminum in the zeolite, measure different dealuminzations skeleton room molar fraction in the zeolite during time, when skeleton room molar fraction begins to raise, show that non-framework aluminum has removed fully.With the silicon of chemical analysis mensuration, the content that aluminium content is zeolitic frameworks silicon, aluminium.
Framework aluminum tetrahedron molar fraction=(Al
2O
3Weight content/51) ÷ (SiO
2Weight content/61+Al
2O
3Weight content/51) * (1-skeleton room molar fraction);
Framework silicon tetrahedron molar fraction=1-framework aluminum tetrahedron molar fraction-skeleton room molar fraction.
Skeleton room molar fraction is measured with preceding method.
Wherein, the preparation method of zeolite standard specimen is as follows: at 380 ℃, normal pressure under the condition of weight (hourly) space velocity (WHSV) 1.0, is used SiCl
4Respectively to NH
4(sodium oxide content is 0.8 heavy % to the Y zeolite, lattice constant is 24.73 dusts, the Zhou village catalyst plant is produced), (sodium oxide content is 0.6 heavy % to ammonium type modenite, cell parameter is the a=18.10 dust, b=20.52, the c=7.530 dust, Shanghai chemical reagent work produces), (sodium oxide content is 0.6 heavy % to ammonium type L zeolite, cell parameter is the a=b=18.40 dust, the c=7.50 dust, Shanghai chemical reagent work produces) and ammonium type omega zeolite (sodium oxide content is 0.6 weight %, cell parameter a=b=18.32 dust, the c=7.63 dust, Shanghai chemical reagent work produces) carry out gas phase benefit silicon processing 1 hour, obtain the y-type zeolite of structural integrity respectively, modenite, L zeolite and omega zeolite (its defective locations number is 0), y-type zeolite with the structural integrity that obtains, modenite, L zeolite and omega zeolite respectively concentration be 1 equivalent/liter EDTA solution in, in liquid-solid ratio 20, temperature relaxes dealuminzation 1 hour down for 50 ℃, obtains y-type zeolite respectively, modenite, L zeolite and omega zeolite standard specimen.The skeleton defective locations molar fraction of standard specimen equals the molar fraction of its aluminium that removes.
The lattice constant of molecular sieve or cell parameter adopt X-ray diffraction method, measure on the D5005D X-ray diffractometer that Siemens Company produces.
Lattice avalanche temperature adopts Differential scanning calorimetry to measure.
The weight ratio of lanthanum and cerium adopts x-ray fluorescence spectrometry in molecular sieve middle rare earth oxide content and the rare earth element.
750～830 centimetres
-1The percentage that peak width reduces and 750～830 centimetres
-1The peak is measured on the IFS113V type Fourier infrared spectrograph that German Bruker company produces to high wave number shift value.
Molecular sieve crystallinity is measured with distinct methods.
XRD relative crystallinity C
XRDAdopt x-ray diffraction method on the D5005D X-ray diffractometer that Siemens Company produces, to measure.(, refer to that the d spacing is respectively the peak of 1.408～1.448,0.858～0.893,0.553～0.583,0.461～0.491,0.422～0.452,0.367～0.387 nanometer according to six highest peaks for y-type zeolite.For modenite, refer to that the d spacing is respectively the peak of 1.338～1.378,0.889～0.924,0.643～0.673,0.625～0.655,0.390～0.410,0.338～0.358 nanometer.For the L zeolite, refer to that the d spacing is respectively the peak of 1.574～1.614,0.737～0.767,0.587～0.617,0.445～0.475,0.382～0.402,0.356～0.376 nanometer.For omega zeolite, refer to that the d spacing is respectively the peak of 1.573～1.613,0.903～0.938,0.587～0.617,0.458～0.488,0.373～0.393,0.343～0.363 nanometer.) area and, be calculated as follows out the relative crystallinity (C of product combination of molecular sieve
XRD): C
XRDSix highest peak areas of=rare-earth-containing molecular sieve and/peak area and * 100% of six highest peaks of original zeolite.
BET relative crystallinity C
BETMeasure C with cryogenic nitrogen absorption BET method
BET=contain specific surface * 100% of the specific surface/original zeolite of the molecular sieve of rare earth.
Wherein, original zeolite is respectively ammonium type Y zeolite, ammonium type modenite, ammonium type L zeolite and ammonium type omega zeolite, and their degree of crystallinity is decided to be 100% respectively.
Embodiment 1
The preparation of rare-earth-containing molecular sieve provided by the invention.
With 10 gram (dry basis) NH
4Y zeolite (sodium oxide content is 0.8 heavy %, and lattice constant is 24.73 dusts, and lattice avalanche temperature is 930 ℃, and the Zhou village catalyst plant is produced) adds the NH of 200 milliliter of 0.5 mol
4In the Cl solution, stir into slurries, the rare earth chloride that to add 50 milliliters of rare earth oxide content again be 24 grams per liters is (wherein, with La
2O
3And CeO
2Meter, the weight ratio of lanthanum and cerium is 4.08, Baotou rare earth factory produces) solution, fully stir evenly, regulating its pH with hydrochloric acid is 3.5, is warmed up to 95 ℃ then, stirs 2 hours, filter, earlier with 30 times deionized water washing, be that 4.0 hydrochloric acid solution and pH value are that 10.0 ammonia spirit washs with 30 times pH value respectively again, wash with 20 times of deionized waters at last, drying gets rare-earth type molecular sieve f
1f
1Rare earth oxide content, rare earth oxide in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The peak is to high wave number shift value and unit empirical formula (Al
X 'Si
Y ' Z ') O
2The value of middle x ', y ', z ' is listed in the table 1.D spacing and corresponding peak intensity are listed in the table 2.Also listed NH in the table 2
4Y zeolite d spacing and corresponding peak intensity.
The N of 500 milliliter of 0.09 mol of preparation, N-two inferior salicylic acid solutions, to wherein dripping ethylenediamine and ammoniacal liquor, making the pH value of solution value is 4.0.Above-mentioned rare-earth type molecular sieve added (the ethylenediamine addition makes ethylenediamine and f in this solution
1In the mol ratio of contained rare earth element be 3.0), being warming up to 90 ℃ stirred 2 hours, filter, elder generation washs with 30 times deionized water, be 4.0 hydrochloric acid solution washing again with 30 times pH value, wash with 20 times of deionized waters at last, 120 ℃ of dryings 2 hours, 500 ℃ of roastings 2 hours, rare-earth-containing molecular sieve F provided by the invention
1F
1La in rare earth oxide content, the rare earth oxide
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The peak is to high wave number shift value and unit empirical formula (RE
wAl
xSi
y z) O
2The value of middle w, x, y, z is listed in the table 1.D spacing and corresponding peak intensity are listed in the table 2.
Wherein, in the table 1 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The peak all is fiducial values with original ammonium type zeolite to high wave number shift value.Below example case identical, all are the fiducial values with original ammonium type zeolite, no longer repeat specification.
Table 1
| f 1 | F 1 | |
| Rare earth oxide content, heavy % | 8.835 | 8.835 |
| La 2O 3With CeO 2Weight ratio | 4.08 | 4.08 |
| The value of x ', y ', z ' and w, x, y, z in the unit empirical formula | x’＝0.2791 y’＝0.7003 z’＝0.0206 | w＝0.0027 x＝0.2443 y＝0.7003 z＝0.0527 |
| Lattice constant, dust | 24.68 | 24.81 |
| Skeleton defective molar fraction | 0.0206 | 0.0527 |
| Skeleton rare earth element molar fraction | 0 | 0.0027 |
| C BET | 94 | 90 |
| C XRD | 40 | 21 |
| Lattice avalanche temperature, ℃ | 940 | 880 |
| 750～830 centimetres -1The percentage that peak width reduces, % | 0 | 42 |
| 750～830 centimetres -1The peak is to high wave number shift value, centimetre -1 | 0 | 28 |
Table 2
| Original zeolite | f 1 | F 1 | |||
| D, nanometer | Intensity, % | D, nanometer | Intensity, % | D, nanometer | Intensity, % |
| 1.4278 | 100 | 1.4249 | 37 | 1.4295 | 19 |
| 0.8743 | 100 | 0.8726 | 16 | 0.8754 | 8 |
| 0.5674 | 100 | 0.5662 | 20 | 0.5680 | 11 |
| 0.4759 | 100 | 0.4750 | 17 | 0.4765 | 9 |
| 0.4372 | 100 | 0.4363 | 16 | 0.4377 | 8 |
| 0.3771 | 100 | 0.3764 | 21 | 0.3776 | 11 |
Embodiment 2
The preparation of rare-earth-containing molecular sieve provided by the invention.
With 10 gram (dry basis) NH
4Y zeolite (specification is with example 1) adds the NH of 200 milliliter of 0.5 mol
4In the Cl solution, stir into slurries, the re chloride that to add 50 milliliters of solid contents again be 24 grams per liters, fully stir evenly, regulating its PH with hydrochloric acid is 3.5, is warmed up to 95 ℃ then, stirs 2 hours, filter, earlier with 30 times deionized water washing, be that 4.0 hydrochloric acid solution washs with 30 times pH value again, wash with 20 times of deionized waters at last, drying gets rare-earth type molecular sieve f
2f
2Rare earth oxide content, rare earth oxide in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak x ', y ', z ' in high wave number shift value and unit empirical formula is listed in the table 3.D spacing and corresponding peak intensity are listed in the table 4.
Prepare 200 milliliter of 0.15 equivalent/liter hydrochloric acid solution, add absolute ethyl alcohol and ammoniacal liquor, making the pH value of solution value is 4.5.With above-mentioned rare-earth type molecular sieve f
2Add that (addition of absolute ethyl alcohol makes absolute ethyl alcohol and f in this solution
2In the mol ratio of contained rare earth element be 6.0), being warming up to 85 ℃ stirred 2 hours, filter, elder generation washs with 30 times deionized water, be that 4.0 hydrochloric acid solution and pH value are 10.0 ammonia spirit washing with 30 times pH value respectively again, wash with 20 times of deionized waters at last, 120 ℃ of dryings 2 hours, 500 ℃ of roastings 2 hours, rare-earth-containing molecular sieve F provided by the invention
2F
2Rare earth oxide content, rare earth oxide in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak w, x, y, z in high wave number shift value and unit empirical formula is listed in the table 3.D spacing and corresponding peak intensity are listed in the table 4.
Table 3
| f 2 | F 2 | |
| Rare earth oxide content, heavy % | 8.835 | 8.835 |
| La 2O 3With CeO 2Weight ratio | 4.08 | 4.08 |
| The value of x, y, z or w, x ', y ', z ' in the unit empirical formula | x’＝0.2791 y’＝0.7003 z’＝0.0206 | w＝0.0045 x＝0.2054 y＝0.7003 z＝0.0898 |
| Lattice constant, dust | 24.68 | 24.84 |
| Skeleton defective molar fraction | 0.0206 | 0.0898 |
| Skeleton rare earth element molar fraction | 0 | 0.0045 |
| C BET | 94 | 88 |
| C XRD | 40 | 14 |
| Lattice avalanche temperature, ℃ | 940 | 865 |
| 750～830 centimetres -1The percentage that peak width reduces, % | 0 | 48 |
| 750～830 centimetres -1The peak is to high wave number shift value, centimetre -1 | 0 | 36 |
Table 4
| f 2 | F 2 | ||
| D, nanometer | Intensity, % | D, nanometer | Intensity, % |
| 1.4249 | 37 | 1.4313 | 13 |
| 0.8726 | 16 | 0.8765 | 6 |
| 0.5662 | 20 | 0.5687 | 7 |
| 0.4750 | 17 | 0.4771 | 6 |
| 0.4363 | 16 | 0.4382 | 6 |
| 0.3764 | 21 | 0.3780 | 7 |
Embodiment 3
The preparation of rare-earth-containing molecular sieve provided by the invention.
Method by example 1 prepares rare-earth type zeolite and the molecular sieve that contains rare earth, and different is with NH
4The Y zeolite changes ammonium type modenite (sodium oxide content is 0.6 heavy %, and lattice avalanche temperature is 1030 ℃, and cell parameter is a=18.10, b=20.52, c=7.530, Shanghai chemical reagent work product) into, and the rare-earth type modenite note that makes is made f
3, the addition of ethylenediamine makes ethylenediamine and f
3In the mol ratio of contained rare earth element be 5.5, the rare-earth-containing molecular sieve note provided by the invention that makes is made F
3f
3Rare earth oxide content, rare earth oxide in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak x ', y ', z ' in high wave number shift value and unit empirical formula is listed in the table 5, and d spacing and corresponding peak intensity are listed in the table 6.F
2The mol ratio, rare earth oxide of rare earth oxide content, rare earth element in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak w, x, y, z in high wave number shift value and unit empirical formula is listed in the table 5, and d spacing and corresponding peak intensity are listed in the table 6.The d spacing and the corresponding peak intensity of original ammonium type modenite have also been listed in the table 6.
Table 5
| f 3 | F 3 | |
| Rare earth oxide content, heavy % | 4.833 | 4.833 |
| La 2O 3With CeO 2Weight ratio | 4.08 | 4.08 |
| The value of x, y, z or w, x ', y ', z ' in the unit empirical formula | x’＝0.0872 y’＝0.7228 z’＝0.1900 | w＝0.0021 x＝0.0776 y＝0.7228 z＝0.1975 |
| Lattice constant, dust | a＝18.040 b＝20.480 c＝7.510 | a＝18.180 b＝20.600 c＝7.610 |
| Skeleton defective molar fraction | 0.1900 | 0.1975 |
| Skeleton rare earth element molar fraction | 0 | 0.0021 |
| C BET | 95 | 91 |
| C XRD | 68 | 30 |
| Lattice avalanche temperature, ℃ | 1050 | 960 |
| 750～830 centimetres -1The percentage that peak width reduces, % | 0 | 40 |
| 750～830 centimetres -1The peak is to high wave number shift value, centimetre -1 | 0 | 25 |
Table 6
| Original zeolite | f 3 | F 3 | |||
| D, nanometer | Intensity, % | D, nanometer | Intensity, % | D, nanometer | Intensity, % |
| 1.3574 | 100 | 1.3537 | 65 | 1.3594 | 29 |
| 0.9050 | 100 | 0.9020 | 60 | 0.9060 | 26 |
| 0.6585 | 100 | 0.6567 | 45 | 0.6627 | 20 |
| 0.6398 | 100 | 0.6385 | 40 | 0.6410 | 17 |
| 0.4002 | 100 | 0.3994 | 38 | 0.4010 | 16 |
| 0.3476 | 100 | 0.3467 | 63 | 0.3500 | 28 |
Embodiment 4
The preparation of rare-earth-containing molecular sieve provided by the invention.
Method by example 1 prepares rare-earth type zeolite and the molecular sieve that contains rare earth, and different is with NH
4The Y zeolite changes ammonium type L zeolite (sodium oxide content is 0.6 heavy %, and cell parameter is a=b=18.40, c=7.50, lattice avalanche temperature is 780 ℃, Shanghai chemical reagent work produces) into, and the rare-earth type L zeolite note that makes is made f
4, ethylenediamine and f
4In the mol ratio of contained rare earth element be 5.1, the rare-earth-containing molecular sieve F provided by the invention that makes
4f
4Rare earth oxide content, rare earth oxide in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak x ', y ', z ' in high wave number shift value and unit empirical formula is listed in the table 7, and d spacing and corresponding peak intensity are listed in the table 8.F
4Rare earth oxide content, rare earth oxide in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak w, x, y, z in high wave number shift value and unit empirical formula is listed in the table 7, and d spacing and corresponding peak intensity are listed in the table 8.The d spacing and the corresponding peak intensity of original ammonium type L zeolite have also been listed in the table 8.
Table 7
| f 4 | F 4 | |
| Rare earth oxide content, heavy % | 5.180 | 5.180 |
| La 2O 3With CeO 2Weight ratio | 4.08 | 4.08 |
| The value of x, y, z or w, x ', y ', z ' in the unit empirical formula | x’＝0.2477 y’＝0.7338 z’＝0.0185 | w＝0.0017 x＝0.2313 y＝0.7338 z＝0.0332 |
| Cell parameter, dust | a＝b＝18.360 c＝7.400 | a＝b＝18.490 c＝7.530 |
| Skeleton defective molar fraction | 0.0185 | 0.0332 |
| Skeleton rare earth element molar fraction | 0 | 0.0017 |
| C BET | 93 | 88 |
| C XRD | 62 | 31 |
| Lattice avalanche temperature, ℃ | 800 | 766 |
| 750～830 centimetres -1The percentage that peak width reduces, % | 0 | 33 |
| 750～830 centimetres -1The peak is to high wave number shift value, centimetre -1 | 0 | 19 |
Table 8
| Original zeolite | f 4 | F 4 | |||
| D, nanometer | Intensity, % | D, nanometer | Intensity, % | D, nanometer | Intensity, % |
| 1.5935 | 100 | 1.5900 | 54 | 1.5978 | 28 |
| 0.7500 | 100 | 0.7400 | 25 | 0.7520 | 12 |
| 0.6023 | 100 | 0.6010 | 24 | 0.6039 | 11 |
| 0.4600 | 100 | 0.4590 | 21 | 0.4613 | 10 |
| 0.3921 | 100 | 0.3901 | 26 | 0.3932 | 13 |
| 0.3650 | 100 | 0.3604 | 20 | 0.3660 | 11 |
Embodiment 5
The preparation of rare-earth-containing molecular sieve provided by the invention.
Method by example 1 prepares rare-earth type zeolite and the molecular sieve that contains rare earth, and different is with NH
4The Y zeolite changes ammonium type omega zeolite into, and (sodium oxide content is 0.6 heavy %, lattice avalanche temperature is 670 ℃, cell parameter is the a=b=18.32 dust, the c=7.63 dust, Shanghai chemical reagent work produces), with concentration is the cerous chlorate solution replacement re chloride of 3.0 grams per liters, and the rare-earth type omega zeolite that makes note is made f
5, the addition of ethylenediamine makes ethylenediamine and f
5In the mol ratio of contained Ce elements be 4.3, the rare-earth-containing molecular sieve note provided by the invention that makes is made F
5f
5Cerium oxide content, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak x ', y ', z ' in high wave number shift value and unit empirical formula is listed in the table 9, and d spacing and corresponding peak intensity are listed in the table 10.F
5Cerium oxide content, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature and 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak w, x, y, z in high wave number shift value and unit empirical formula is listed in the table 9, and d spacing and corresponding peak intensity are listed in the table 10.The d spacing and the corresponding peak intensity of original ammonium type omega zeolite have also been listed in the table 10.
Table 9
| f 5 | F 5 | |
| Cerium oxide content, heavy % | 6.141 | 6.141 |
| The value of x, y, z or w, x ', y ', z ' in the unit empirical formula | x’＝0.2605 y’＝0.7102 z’＝0.0293 | w＝0.0029 x＝0.2024 y＝0.7102 z＝0.0845 |
| Cell parameter, dust | a＝b＝18.120， c＝7.610 | a＝b＝18.480， c＝7.79 |
| Skeleton defective molar fraction | 0.029 | 0.0845 |
| Skeleton rare earth element molar fraction | 0 | 0.0029 |
| C BET | 90 | 86 |
| C XRD | 58 | 24 |
| Lattice avalanche temperature, ℃ | 680 | 650 |
| 750～830 centimetres -1The percentage that peak width reduces, % | 0 | 43 |
| 750～830 centimetres -1The peak is to high wave number shift value, centimetre -1 | 0 | 26 |
Table 10
| Original zeolite | F 5 | F 5 | |||
| D, nanometer | Intensity, % | D, nanometer | Intensity, % | D, nanometer | Intensity, % |
| 1.5900 | 100 | 1.5866 | 52 | 1.5970 | 26 |
| 0.9180 | 100 | 0.9160 | 50 | 0.9220 | 21 |
| 0.6010 | 100 | 0.5997 | 39 | 0.6036 | 16 |
| 0.4723 | 100 | 0.4715 | 35 | 0.4758 | 14 |
| 0.3819 | 100 | 0.3812 | 33 | 0.3843 | 12 |
| 0.3525 | 100 | 0.3522 | 51 | 0.3566 | 22 |
Embodiment 6
The preparation of rare-earth-containing molecular sieve provided by the invention.
Method by example 1 prepares rare-earth type zeolite and the molecular sieve that contains rare earth, different is with N, N two inferior salicylic acid solutions and ethylenediamine solution change perchloric acid and the N that concentration is 0.03 mol respectively into, the N dimethyl formamide, the pH of solution is 3, N, the addition of N dimethyl formamide makes N, N dimethyl formamide and f
1The mol ratio of middle rare earth element is 3, the rare-earth-containing molecular sieve F provided by the invention that makes
6F
6Rare earth oxide content, rare earth oxide in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature and 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak w, x, y, z in high wave number shift value and unit empirical formula is listed in the table 11, and d spacing and corresponding peak intensity are listed in the table 12.
Table 11
| F 6 | |
| Rare earth oxide content, heavy % | 8.835 |
| La 2O 3With CeO 2Weight ratio | 4.08 |
| The value of w, x, y, z in the unit empirical formula | w＝0.0049，x＝0.2302 y＝0.7003，z＝0.0646 |
| Lattice constant, dust | 24.87 |
| Skeleton defective molar fraction | 0.00646 |
| Skeleton rare earth element molar fraction | 0.0049 |
| C BET | 91 |
| C XRD | 14 |
| Lattice avalanche temperature, ℃ | 855 |
| 750～830 centimetres -1The percentage that peak width reduces, % | 58 |
| 750～830 centimetres -1The peak is to high wave number shift value, centimetre -1 | 48 |
Table 12
| F 6 | |
| D, nanometer | Intensity, % |
| 1.4330 | 13 |
| 0.8775 | 6 |
| 0.5694 | 6 |
| 0.4777 | 7 |
| 0.4388 | 5 |
| 0.3785 | 7 |
Embodiment 7
The preparation of rare-earth-containing molecular sieve provided by the invention.
Method by example 1 prepares rare-earth type zeolite and the molecular sieve that contains rare earth, and different is also to add acetaldehyde in the solution, and the pH of solution is 5, and the addition of acetaldehyde makes ethylenediamine and acetaldehyde and f
1In the mol ratio of contained rare earth element be 6, the rare-earth-containing molecular sieve note provided by the invention that makes is made F
7F
7Rare earth oxide content, rare earth oxide in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak w, x, y, z in high wave number shift value and unit empirical formula is listed in the table 13, and d spacing and corresponding peak intensity are listed in the table 14.
Table 13
| F 7 | |
| Rare earth oxide content, heavy % | 8.835 |
| La 2O 3With CeO 2Weight ratio | 4.08 |
| The value of w, x, y, z in the unit empirical formula | w＝0.0029，x＝0.2388 y＝0.7003，z＝0.0580 |
| Lattice constant, dust | 24.83 |
| Skeleton defective molar fraction | 0.0580 |
| Skeleton rare earth element molar fraction | 0.0029 |
| C BET | 89 |
| C XRD | 18 |
| Lattice avalanche temperature, ℃ | 875 |
| 750～830 centimetres -1The percentage that peak width reduces, % | 45 |
| 750～830 centimetres -1The peak is to high wave number shift value, centimetre -1 | 35 |
Table 14
| F 7 | |
| D, nanometer | Intensity, % |
| 1.4307 | 15 |
| 0.8761 | 8 |
| 0.5685 | 8 |
| 0.4769 | 9 |
| 0.4381 | 7 |
| 0.3779 | 10 |
Embodiment 8
The preparation of rare-earth-containing molecular sieve provided by the invention.
Method by example 1 prepares rare-earth type zeolite and the molecular sieve that contains rare earth, different is with N, N two inferior salicylic acid solutions and ethylenediamine solution change into respectively concentration be 0.05 equivalent/liter ammoniacal liquor and ammonium fluoride aqueous solution, the pH of solution is 9, the addition of ammonium fluoride makes ammonium fluoride and f
1The mol ratio of middle rare earth element is 6, gets the molecular sieve F that contains rare earth provided by the invention
8F
8Rare earth oxide content, rare earth oxide in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature and 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak w, x, y, z in high wave number shift value and unit empirical formula is listed in the table 15, and d spacing and corresponding peak intensity are listed in the table 16.
Table 15
| F 8 | |
| Rare earth oxide content, heavy % | 8.835 |
| La 2O 3With CeO 2Weight ratio | 4.08 |
| The value of w, x, y, z in the unit empirical formula | w＝0.0016，x＝0.2583 y＝0.7003，z＝0.0398 |
| Lattice constant, dust | 24.79 |
| Skeleton defective molar fraction | 0.0398 |
| Skeleton rare earth element molar fraction | 0.0016 |
| C BET | 92 |
| C XRD | 30 |
| Lattice avalanche temperature, ℃ | 907 |
| 750～830 centimetres -1The percentage that peak width reduces | 21 |
| 750～830 centimetres -1The peak is to high wave number shift value, centimetre -1 | 8 |
Table 16
| F 8 | |
| D, nanometer | Intensity, % |
| 1.4284 | 30 |
| 0.8747 | 12 |
| 0.5676 | 14 |
| 0.4761 | 11 |
| 0.4373 | 12 |
| 0.3773 | 16 |
Embodiment 9
The preparation of rare-earth-containing molecular sieve provided by the invention.
The solution of hydrochloric acid of 500 milliliter of 0.03 mol of preparation, to wherein drip 0.5 equivalent/liter ammoniacal liquor, the pH that makes solution is 3.5, adds BA again, fully stirs evenly, again to wherein adding the rare-earth-containing molecular sieve Fs of 10 grams by the method preparation of embodiment 1
1, the addition of BA makes BA and F
1The mol ratio of middle rare earth element is 2, be warmed up to 95 ℃, stirred 2 hours, filter, earlier with 30 times deionized water washing, be that 4.0 hydrochloric acid solution and pH value are that 10.0 ammonia spirit washs with 30 times pH value respectively again, wash with 20 times of deionized waters at last, 120 ℃ of dryings 2 hours must contain the molecular sieve F that contains provided by the invention
9F
9Rare earth oxide content, rare earth oxide in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak w, x, y, z in high wave number shift value and unit empirical formula is listed in the table 17, and d spacing and corresponding peak intensity are listed in the table 18.
Table 17
| F 9 | |
| Rare earth oxide content, heavy % | 8.835 |
| La 2O 3With CeO 2Weight ratio | 4.08 |
| The value of w, x, y, z in the unit empirical formula | w＝0.0039，x＝0.2223 y＝0.7003，z＝0.0735 |
| Lattice constant, dust | 24.83 |
| Skeleton defective molar fraction | 0.0735 |
| Skeleton rare earth element molar fraction | 0.0039 |
| C BET | 88 |
| C XRD | 18 |
| Lattice avalanche temperature, ℃ | 872 |
| 750～830 centimetres -1The percentage that peak width reduces, % | 45 |
| 750～830 centimetres -1The peak is to high wave number shift value, centimetre -1 | 31 |
Table 18
| F 9 | |
| D, nanometer | Intensity, % |
| 1.4305 | 16 |
| 0.8763 | 8 |
| 0.5683 | 8 |
| 0.4769 | 9 |
| 0.4382 | 6 |
| 0.3779 | 10 |
Embodiment 10
The preparation of rare-earth-containing molecular sieve provided by the invention.
The edta solution of 500 milliliters of 0.09M of preparation, to wherein adding 5 milliliters of formic acid, add 0.5 equivalent/liter the pH of ammonia spirit regulator solution be 4.0, add ammonium fluoride, stir, be warmed up to 90 ℃, to the rare-earth-containing molecular sieve F that wherein adds 10 gram embodiment, 4 preparations
4, the addition of ammonium fluoride makes ammonium fluoride and F
4The mol ratio of middle rare earth element is 1.3, continuous stirring 2 hours, filter, elder generation washs with 30 times deionized water, be that 4.0 hydrochloric acid solution and pH value are 10.0 ammonia spirit washing with 30 times pH value respectively again, at last with the washing of 20 times of deionized waters, 120 ℃ of dryings 2 hours, rare-earth-containing molecular sieve F provided by the invention
10F
10Rare earth oxide content, rare earth oxide in La
2O
3With CeO
2Weight ratio, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak w, x, y, z in high wave number shift value and unit empirical formula is listed in the table 19, and d spacing and corresponding peak intensity are listed in the table 20.
Table 19
| F 10 | |
| Rare earth oxide content, heavy % | 5.180 |
| La 2O 3With CeO 2Weight ratio | 4.08 |
| The value of w, x, y, z in the unit empirical formula | w＝0.0028，x＝0.2089 y＝0.7338，z＝0.0545 |
| Cell parameter, dust | a＝b＝18.55，c＝7.610 |
| Skeleton defective molar fraction | 0.0545 |
| Skeleton rare earth element molar fraction | 0.0028 |
| C BET | 85 |
| C XRD | 20 |
| Lattice avalanche temperature, ℃ | 732 |
| 750～830 centimetres -1The percentage that peak width reduces, % | 38 |
| 750～830 centimetres -1The peak is to high wave number shift value, centimetre -1 | 24 |
Table 20
| F 10 | |
| D, nanometer | Intensity, % |
| 1.6030 | 17 |
| 0.7600 | 8 |
| 0.6059 | 7 |
| 0.4628 | 7 |
| 0.3952 | 9 |
| 0.3698 | 7 |
Embodiment 11
The preparation of rare-earth-containing molecular sieve provided by the invention.
Take by weighing 0.7 gram NH
4F puts into 400 milliliters of decationized Y sieve water, fully stirs, and is warmed up to 95 ℃, to wherein adding 0.1 gram ethylenediamine tetra-acetic acid, fully stirs evenly, add 0.5 equivalent/liter ammonia spirit to make the pH of solution be 4.0.The rare-earth-containing molecular sieve F that adds 10 gram embodiment, 5 preparations again
5, NH
4The addition of F makes NH
4F and F
5The mol ratio of middle Ce elements is 5.6, stirred 2 hours, filter, elder generation washs with 30 times deionized water, be that 4.0 hydrochloric acid solution and pH value are 10.0 ammonia spirit washing with 30 times pH value respectively again, at last with the washing of 20 times of deionized waters, 120 ℃ of dryings 2 hours, rare-earth-containing molecular sieve F provided by the invention
11F
11Cerium oxide content, relative crystallinity, lattice constant, skeleton defective molar fraction, lattice avalanche temperature, 750～830 centimetres
-1The percentage that peak width reduces, 750～830 centimetres
-1The value of peak w, x, y, z in high wave number shift value (all with example 5 described original zeolite contrasts) and unit empirical formula is listed in the table 21, and d spacing and corresponding peak intensity are listed in the table 22.
Table 21
| F 11 | |
| Cerium oxide content, heavy % | 6.14 |
| The value of w, x, y, z in the unit empirical formula | w＝0.0035 x＝0.1933 y＝0.7102 z＝0.0930 |
| Lattice constant, dust | a＝b＝18.57，c＝7.824 |
| Skeleton defective molar fraction | 0.0930 |
| Skeleton rare earth element molar fraction | 0.0035 |
| C BET | 83 |
| C XRD | 15 |
| Lattice avalanche temperature, ℃ | 635 |
| 750～830 centimetres -1The percentage that peak width reduces, % | 49 |
| 750～830 centimetres -1The peak is to high wave number shift value, centimetre -1 | 31 |
Table 22
| F 11 | |
| D, nanometer | Intensity, % |
| 1.6047 | 15 |
| 0.9265 | 13 |
| 0.6065 | 10 |
| 0.4792 | 8 |
| 0.3868 | 7 |
| 0.3602 | 14 |
Claims (25)
1. molecular sieve that contains rare earth, this molecular sieve contains rare earth element, and at least a portion that it is characterized in that described rare earth element exists with the form of skeleton rare earth, and it has following unit empirical formula:
(RE
wAl
xR
y) O
2Wherein RE represents one or more in the rare earth element; R represents silicon, boron or phosphorus atoms; W, x and y represent the molar fraction of the RE, aluminium and the R that exist with the tetrahedronal oxide of skeleton unit respectively, and w gets 0.001～0.5, and x gets 0.001～0.5, and y gets 0.001～0.998.
2. molecular sieve according to claim 1 is characterized in that described w gets 0.001～0.06, and x gets 0.01～0.3, y gets 0.65～0.95.
3. molecular sieve according to claim 1 is characterized in that it has as the lower unit empirical formula:
(RE
wAl
xSi
y) O
2Wherein RE represents one or more in the rare earth element; W, x and y represent the molar fraction of the RE, aluminium and the silicon that exist with the tetrahedronal oxide of skeleton unit respectively, and w gets 0.001～0.49, and x gets 0.001～0.49, and y gets 0.5～0.998.
4. molecular sieve according to claim 3 is characterized in that described w gets 0.001～0.06, and x gets 0.01～0.3, y gets 0.65～0.95.
5. molecular sieve according to claim 3 is characterized in that described molecular sieve has the structure of y-type zeolite, and its lattice constant is than the lattice constant of original y-type zeolite at least 0.05 dust greatly, and it has following X-ray diffraction types:
d(nm) Relative intensity (%)
1.408～1.448 ≤45
0.858～0.893 ≤20
0.553～0.583 ≤25
0.461～0.491 ≤20
0.422～0.452 ≤20
0.367～0.387 ≤25
6. molecular sieve according to claim 5 is characterized in that, described molecular sieve has following X-ray diffraction types:
d(nm) Relative intensity (%)
1.425～1.440 10～40
0.873～0.880 5～15
0.560～0.570 5～20
0.475～0.485 5～15
0.437～0.440 5～15
0.377～0.379 5～20
7. molecular sieve according to claim 5 is characterized in that lattice constant big 0.05～0.2 dust of the lattice constant of described molecular sieve than original y-type zeolite.
8. molecular sieve according to claim 3 is characterized in that described molecular sieve has the structure of L zeolite, and its cell parameter is greater than original zeolite L, and it has following X-ray diffraction types:
d(nm) Relative intensity (%)
1.574～1.614 ≤45
0.737～0.767 ≤22
0.587～0.61 7 ≤20
0.445～0.475 ≤20
0.382～0.402 ≤22
0.356～0.376 ≤20
9. molecular sieve according to claim 8 is characterized in that, described molecular sieve has following X-ray diffraction types:
d(nm) Relative intensity (%)
1.595～1.610 5～35
0.750～0.765 5～15
0.603～0.610 5～15
0.460～0.470 5～15
0.391～0.400 5～15
0.362～0.370 5～15
10. molecular sieve according to claim 8 is characterized in that cell parameter a, the b of described molecular sieve, c distinguish big 0.04～0.2 dust than original zeolite L.
11. molecular sieve according to claim 3 is characterized in that, described molecular sieve has the structure of modenite, and its cell parameter is greater than original modenite, and it has following X-ray diffraction types:
d(nm) Relative intensity (%)
1.338～1.378 ≤45
0.889～0.924 ≤42
0.643～0.673 ≤30
0.625～0.655 ≤25
0.390～0.410 ≤25
0.338～0.358 ≤45
12. molecular sieve according to claim 11 is characterized in that, described molecular sieve has following X-ray diffraction types:
d(nm) Relative intensity (%)
1.355～1.370 10～40
0.903～0.920 5～35
0.660～0.670 5～30
0.640～0.650 5～20
0.400～0.410 5～20
0.345～0.355 5～35
13. molecular sieve according to claim 11 is characterized in that cell parameter a, the b of described molecular sieve, c distinguish big 0.04～0.2 dust than original modenite.
14. molecular sieve according to claim 3 is characterized in that, described molecular sieve has the structure of omega zeolite, and its cell parameter is greater than original omega zeolite, and it has following X-ray diffraction types:
d(nm) Relative intensity (%)
1.573～1.613 ≤43
0.903～0.938 ≤40
0.587～0.617 ≤32
0.458～0.488 ≤35
0.373～0.393 ≤42
0.343～0.363 ≤45
15. molecular sieve according to claim 14 is characterized in that, described molecular sieve has following X-ray diffraction types:
d(nm) Relative intensity (%)
1.590～1.610 10～30
0.920～0.930 10～25
0.600～0.610 5～20
0.472～0.485 5～20
0.382～0.393 5～15
0.355～0.363 10～35
16. molecular sieve according to claim 14 is characterized in that cell parameter a, the b of described molecular sieve, c distinguish big 0.04～0.2 dust than original omega zeolite.
17., it is characterized in that described rare earth element is selected from one or more in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, ytterbium, the lutetium according to claim 1 or 3 described molecular sieves.
18. the preparation method of claim 1 molecular sieve, it is characterized in that this method is included under 25～120 ℃ the temperature, with a kind of in oxide, the solution of at least a material at least a material in the rare-earth type molecular sieve that contains the heavy % of rare earth 0.1～40 and a kind of containing (I) and (11) contacts at least 0.1 hour, isolate the product that obtains, drying; Wherein, (I) comprise inorganic acid, inorganic base, organic acid or can form the reagent of complex compound, (II) comprise solubility ammonium salt, acylate and amine, alcohol, aldehyde, ketone with aluminium; The pH value of described solution is 3～12, and (II) mol ratio of contained rare earth element is 0.01～20 in the material in and the rare-earth type molecular sieve; Described rare-earth type molecular sieve refers to the natural or artificial synthetic molecular sieve that partial cation position is at least occupied by rare earth element.
19. method according to claim 18 is characterized in that, in oxide, described rare-earth type molecular sieve middle rare earth content is 0.3～20 heavy %
20. method according to claim 18 is characterized in that described rare-earth type aluminosilicate zeolite refers to rare-earth type faujasite, L zeolite, modenite, BETA zeolite, omega zeolite, A type zeolite or ZSM series zeolite.
21. method according to claim 20 is characterized in that described rare-earth type aluminosilicate zeolite refers to rare-earth type y-type zeolite, L zeolite, modenite or omega zeolite.
22. method according to claim 20, it is characterized in that (I) comprises sulfuric acid, hydrofluoric acid, hydrochloric acid, perchloric acid, nitric acid, carbonic acid, alkali-metal hydroxide, ammoniacal liquor, ethylenediamine tetra-acetic acid, formic acid, acetate, oxalic acid, propionic acid, benzoic acid, butyric acid, succinic acid, trichloroacetic acid, trifluoroacetic acid, salicylic acid, N, N-two inferior salicylic acids; (II) comprise ammonium sulfate, ammonium hydrogen sulfate, ammonium fluoride, ammonium chloride, ammonium nitrate, ammonium carbonate, carbonic hydroammonium, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), organic acid sylvite or ammonium salt, ethylenediamine, N, dinethylformamide, N, N-dimethylacetylamide, urea, have 1～5 carbon atom and 1 or the alcohol of a plurality of hydroxyls, have 1～5 carbon atom and 1 or 2 carbonyl aldehyde, have the ketone of 3～10 carbon atoms and 1 or 2 carbonyl.
23. method according to claim 22 is characterized in that (I) comprises perchloric acid, alkali-metal hydroxide, ammoniacal liquor, ethylenediamine tetra-acetic acid, formic acid, N, N-two inferior salicylic acids; (II) comprise ammonium fluoride, acetaldehyde, ethylenediamine, N, dinethylformamide, ethanol, BA.
24. method according to claim 18, the pH value that it is characterized in that described solution is 3～6 or 8～11, and (II) mol ratio of contained rare earth element is 1～10 in the material in and the rare-earth type molecular sieve.
25. method according to claim 18, the temperature that it is characterized in that described contact is 80～100 ℃; The time of contact is 0.5～8 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99105792A CN1111086C (en) | 1999-04-16 | 1999-04-16 | Rare earth element containing molecular sieve and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99105792A CN1111086C (en) | 1999-04-16 | 1999-04-16 | Rare earth element containing molecular sieve and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1270852A CN1270852A (en) | 2000-10-25 |
| CN1111086C true CN1111086C (en) | 2003-06-11 |
Family
ID=5272131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99105792A Expired - Lifetime CN1111086C (en) | 1999-04-16 | 1999-04-16 | Rare earth element containing molecular sieve and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1111086C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332760C (en) * | 2004-04-06 | 2007-08-22 | 中国石油化工股份有限公司 | Rare earth silicon aluminium phosphate molecular sieve and synthesis thereof |
| US8476477B2 (en) | 2009-02-27 | 2013-07-02 | China Petroleum & Chemical Corp. | Process of oxidative conversion of methanol |
| US11111152B2 (en) | 2015-08-05 | 2021-09-07 | Petrochina Company Limited | Preparation method for modified molecular sieve and modified molecular sieve-containing catalytic cracking catalyst |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104355319A (en) * | 2014-10-17 | 2015-02-18 | 上海应用技术学院 | Rear earth gadolinium atom aluminophosphate molecular sieve and preparation method thereof |
| WO2017020848A1 (en) | 2015-08-05 | 2017-02-09 | 中国石油天然气股份有限公司 | Molecular sieve modification method and catalytic cracking catalyst containing molecular sieve |
| WO2017210812A1 (en) * | 2016-06-06 | 2017-12-14 | Rhodia Operations | Rare earth zeolite and the method of preparation thereof |
| CN108285151B (en) * | 2018-01-10 | 2020-02-14 | 中科合成油技术有限公司 | Ce isomorphous substituted LTL molecular sieve and preparation method thereof |
| US11219886B2 (en) * | 2018-05-25 | 2022-01-11 | Basf Se | Rare earth element containing aluminum-rich zeolitic material |
| CN113457618A (en) * | 2021-07-27 | 2021-10-01 | 北京师范大学珠海校区 | Lanthanum-doped ordered mesoporous molecular sieve for environmental remediation and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4701431A (en) * | 1984-12-24 | 1987-10-20 | Exxon Research And Engineering Company | Rare earth stabilized aluminum deficient zeolite |
| CN1034680A (en) * | 1988-02-05 | 1989-08-16 | 中国石油化工总公司石油化工科学研究院 | The rich silicon molecular sieve by crystal Cracking catalyst that contains rare earth |
-
1999
- 1999-04-16 CN CN99105792A patent/CN1111086C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4701431A (en) * | 1984-12-24 | 1987-10-20 | Exxon Research And Engineering Company | Rare earth stabilized aluminum deficient zeolite |
| CN1034680A (en) * | 1988-02-05 | 1989-08-16 | 中国石油化工总公司石油化工科学研究院 | The rich silicon molecular sieve by crystal Cracking catalyst that contains rare earth |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332760C (en) * | 2004-04-06 | 2007-08-22 | 中国石油化工股份有限公司 | Rare earth silicon aluminium phosphate molecular sieve and synthesis thereof |
| US8476477B2 (en) | 2009-02-27 | 2013-07-02 | China Petroleum & Chemical Corp. | Process of oxidative conversion of methanol |
| US11111152B2 (en) | 2015-08-05 | 2021-09-07 | Petrochina Company Limited | Preparation method for modified molecular sieve and modified molecular sieve-containing catalytic cracking catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1270852A (en) | 2000-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1313372C (en) | Crystalline aluminosilicate zeolitic composition: UZM-4M | |
| CN1017797B (en) | Production of aromatic hydrocarbons | |
| CN1164491C (en) | Synthesis of ZSM-5 and ZSM-11 | |
| CN1111086C (en) | Rare earth element containing molecular sieve and its preparation | |
| CN1049406C (en) | Phosphorus and RE containing molecular sieve with MFI structure | |
| CN1027632C (en) | Process for preparing high-Si zeolite containing rare-earth five-membered ring structure | |
| CN1096496A (en) | With the diethylamine is the template synthesized silicon-aluminum phosphate molecular sieve | |
| CN1020269C (en) | Penta-ring structure high silicon zeolite containing rave earth and synthesis | |
| CN1072031C (en) | Preparation method for penta-basic cyclic molecular sieve composite | |
| CN1296276C (en) | Synthetic method for ZSM-5/mordenite mixed crystal material | |
| CN1098214C (en) | Molecular sieve of silicon aluminium phosphate with AEL structure and its synthesis process | |
| CN1296275C (en) | Process for preparing mordenite/ZSM-5 mixed crystal material | |
| CN1608992A (en) | Modified molecular sieve and its prepn process | |
| CN1197771C (en) | Preparation method of aluminium silicone phosphate molecular sieve | |
| CN1242918C (en) | Mole cular sieve with composite structure and preparing method thereof | |
| CN1353087A (en) | Process for preparing ZSM-5 molecular sieve | |
| CN1714045A (en) | Porous crystalline material (ITQ-21) and the method of obtaining the same in the absence of fluoride ions | |
| CN1180059C (en) | Hydrocarbon cracking catalyst containing phosphorus and its prepn | |
| CN1676577A (en) | Petroleum hydrocarbon cracking catalys containing rare earth superstable Y-type zeolite | |
| CN1242917C (en) | Small moleoule rare-earth atom containing composite molecular sieve and preparing method thereof | |
| CN1112246C (en) | Catalyst for cracking hydrocarbon containing phosphorus and rareearth and preparation process thereof | |
| CN1060304A (en) | The phosphorated hydrocarbon cracking catalyzer | |
| CN1272247C (en) | Synthesis method of AEL structured aluminium silicon phosphate molecular sieve | |
| CN1088407C (en) | Zeolite containing phosphorus and its preparing process | |
| CN1915817A (en) | Method for synthesizing beta zeolite in small crystal grain |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20030611 |