CN1096295C - Beta-zeolite - Google Patents
Beta-zeolite Download PDFInfo
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- CN1096295C CN1096295C CN98122006A CN98122006A CN1096295C CN 1096295 C CN1096295 C CN 1096295C CN 98122006 A CN98122006 A CN 98122006A CN 98122006 A CN98122006 A CN 98122006A CN 1096295 C CN1096295 C CN 1096295C
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Abstract
The present invention relates to beta-zeolite, the SiO2 to Al2 O3 molar ratio of the beta-zeolite is 10 to 50, the content of Na2O is less than or equal to 0.10 wt%, a specific surface area is 500 to 700 m2/ g, and the pore volume is 0.30 to 0.40 ml / g. The beta-zeolite is used for a transfer reaction of toluene disproportionation and alkyl, the beta-zeolite has the characteristics of high product xylene / benzene molar ratio, and the present invention can be used for industrial production.
Description
The present invention relates to a kind of β zeolite.
The β zeolite is a kind of zeolite of three-dimensional macropore, through suitably making catalyst with a certain amount of binding agent mixing, extrusion, roasting after the modification.The catalyst that elements such as VIII family, VA, group vib in β zeolite and various thulium and the periodic table is mixed or flood various oil refineries such as to make suitable alkane dewaxing, isomerization, catalytic pyrolysis, toluene disproportionation or benzene olefin alkylation and petrochemical industry.
The synthetic of β zeolite synthesized as numerous molecular sieves, and the general reaction mixture of being made up of aluminium source, silicon source, sodium source and organic formwork agent carries out the hydrothermal crystallizing prepared in reaction and forms.Synthetic sodium type β zeolite can remove template agent in the molecular sieve pore passage by suitable high-temperature roasting, improves the specific area of β zeolite.
The β zeolite is synthetic by Wadliger (USP 3308069) at first, its composition (in oxide) be [
(1.01-X) TEA] Al
2O
3YSiO
2WH
2O.Wherein X is less than 1, and M is at least a alkali metal or alkaline-earth metal ions, sodium ion preferably, and n is 1 or 2, and Y is 5～100, and W is 4.The synthetic β zeolite of hydrothermal crystallizing is removed water in the framework of molecular sieve through centrifugation, drying, and roasting at a certain temperature removes the template agent, carries out ion-exchange formation Hydrogen or other metal mold β zeolite with inorganic acid and inorganic ammonium then.The sodium content that is disclosed in the β zeolite after the roasting in 550 ℃ of air in the example 2 of the document is 0.7% (mole); In example 8, with the β zeolite of example 2 with 2% NH
4Cl exchange 48 hours, and wash the removal chlorion with water, dry back the following roasting of 1000F (589 ℃) 3 hours, the sodium content of β zeolite is reduced to 0.07% (mole) as a result.
U.S. Pat P4642226 report is the method for the synthetic β zeolite of template agent with diphenyl dimethyl hydrogen amine-oxides or diphenyl alkyl dimethyl ammonium chloride (dibenzoldimethylamonium hydroxide or chloride).The synthetic β zeolite of this method can be made ion-exchanger with nitric acid and sulfuric acid, and the minimum content of corresponding sodium ion is 0.14% (weight) and 0.11% (weight), its zeolite also can contain hydrogenation component W, V, Mo, Re, Ni, Co, Cr, Mn and precious metals pd, Pt, and can be used as the catalyst of hydrocarbon conversion reaction.
U.S. Pat P5256392 has disclosed the Hydrogen β prepare zeolite method of a kind of low sodium content, high-specific surface area.Its concrete modifying process is as follows:
1. synthetic sodium type β zeolite is carried out the ammonium salt solution exchange, make part sodium ion quilt
Substitute at least 2 hours swap times;
2. roasting 2～10 hours under anhydrous and 400～700 ℃ of conditions is removed the segment template agent and is made the specific area of β zeolite reach 2 times of initial synthetic β zeolite specific surface;
3. to the β zeolite after the roasting, through the ammonium salt solution exchange, make another part sodium ion quilt again
Substitute at least 1 hour swap time;
4. β zeolite after the exchange of the 3rd step and binding agent are mixed, and dry, decompose ammonium ion in 400～700 ℃ of roastings, make the Hydrogen beta-zeolite catalyst.Its surface area is 450m
2/ g, sodium ions content are lower than 0.04% (weight).This catalyst under reaction pressure 400～500psig, carries out benzene and ethene alkylation reaction 200～250 ℃ of reaction temperatures, and catalyst shows high ethylbenzene selectivity, reacts 20 days active nothings and obviously descends.
Above-mentioned patent has all proposed the method for the low sodium ions content β zeolite of preparation.Because the content of sodium ion directly influences the performance of catalyst in the molecular sieve.USP4185040 has reported the influence to benzene and ethene hydrocarbonylation system ethylbenzene, benzene and propylene hydrocarbonylation preparing isopropylbenzene of X, Y, ZSM-5 molecular sieve sodium content, this patent requires that Na content should be lower than 0.7% (weight) in the molecular sieve of this type of reaction, is preferably lower than 0.5% (weight).U.S. Pat P4851604 has reported the toluene disproportionation process of ZSM-5 molecular sieve, and the content of sodium ion is lower than 0.045% (weight) in its molecular sieve.
Chinese patent (CN1105646A) has been reported a kind of β Zeolite modifying method.With the β zeolite after this method modification, wherein Na
2O content≤0.15% (weight), structural deterioration temperature are 1200 ℃, SiO
2/ Al
2O
3Mol ratio is 55～57, specific surface 600～700m
2/ g, pore volume 0.30～0.40ml/g.The crucial preparation process of this method is as follows: with sodium type β zeolite is raw material, the ammonium salt solution of 0.1～10.0M, and 100 ℃ exchange 0.5～5.0 hour, carry out twice exchange altogether.Exchange back β zeolite is respectively at 150～250 ℃, 250～450 ℃, 450～650 ℃ of branches after the roasting regular hour, carried out dealuminzation in 1.0～3.0 hours with 0.1～5.0ml mineral acid treatment for three sections again in air, at last 500～600 ℃ of following activation processing 2～3 hours.
Though disclosed β zeolite of above-mentioned document or β prepare zeolite method can reach purposes such as sodium content is low, specific area is high, Stability Analysis of Structures, all do not relate to the β zeolite in these documents to toluene disproportionation and C
9Aromatic hydrocarbons transalkylation performance situation.
The objective of the invention is that the β zeolite does not relate to toluene disproportionation and C in order to overcome in the past
9Aromatic hydrocarbons transalkylation reaction performance defect provides a kind of new β zeolite, when this zeolite is used for toluene disproportionation and transalkylation reaction, has the conversion ratio height, the characteristics that product dimethylbenzene/benzene mole ratio is high.
The objective of the invention is to realize by following technical scheme: a kind of β zeolite, its X ray diffracting characteristic peak parameter satisfies following parameter value: 2 θ (°) d value () I/I
o7.65 11.65±0.2 5211.70 7.58±0.1 520.80 4.11±0.1 1522.45 3.93±0.1 10026.85 3.32±0.05 1529.50 3.01±0.05 1443.45 2.07±0.05 8
Wherein 2 θ are the angle of diffraction, and the d value is an interplanar distance, I/I
oBe relative intensity, its largest hole dilatation percentage distributes to average pore diameter and sees Fig. 1.
In the technique scheme, β zeolite SiO
2/ Al
2O
3Mol ratio is 10～50, Na
2O content≤0.10% (weight), specific area are 500～700 meters
2/ gram, pore volume are 0.30～0.40 milliliter/gram.The most probable aperture of β zeolite is 41.1 .
β prepare zeolite method of the present invention is as follows:
Sodium type β zeolite is carried out the exchange of several ammonium salt solution, and purpose is to reduce sodium ions content by different catalytic reaction requirements, generally reduces to Na
2O content≤0.10% (weight).Carry out high-temperature roasting then and take off amine, its specific area is 500～700 meters after the high-temperature roasting
2/ gram, pore volume are 0.30～0.40 milliliter/gram, then directly be selected from bonding agent such as aluminium oxide, silica and nitric acid and be mixed and made into catalyst.
Na type β zeolite used in the present invention its when synthetic the reaction system feed molar form and have following expression formula:
XNa
2O·YAl
2O
3·Z(TEA)
2O：MSiO
2·NH
2O
M/Y=10-50 wherein, X/M=0.04-0.25, Z/M=0.01-0.06, N/M=2-6, TEA are tetraethyl ammonium.
The concrete preparation step of making catalyst with β zeolite of the present invention is poly-as follows:
The exchange of 1 ammonium salt
With the tetraethyl ammonium hydroxide is the template agent, and hydrothermal crystallization method synthesizes SiO
2/ Al
2O
3Mol ratio is the sodium type β zeolite of 10-50.Ammonium salt solution with 1-15% (weight) exchanges, and used ammonium salt can be selected from ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate and composition thereof.In room temperature or be lower than under 100 ℃ the temperature and fully stir.The liquid-solid ratio of selecting for use is 3: 1～6: 1 (weight ratio), is preferably 4: 1～5: 1, and be 1～5 hour swap time, best 2～4 hours, carries out 1～4 exchange altogether.
Amine is taken off in 2 high-temperature roastings
NH after the ammonium salt exchange
4The β zeolite is through the deionized water washing and filtering, and 120 ℃ are dried to butt 〉=85% (weight).In air,, be preferably 2～4 hours in 450 ℃～800 ℃ condition roastings and constant temperature 1～6 hour.
3 Preparation of Catalyst
The NH of the ammonium salt of learning from else's experience exchange
4H β zeolite after β zeolite or the high-temperature roasting and a certain amount of aluminium oxide, silica are or/and clay is mixed, and add the salpeter solution of 10～50% (weight) and an amount of water and mineralizer, after fully kneading, extrusion and moulding, under 400～700 ℃ of air conditionses, carried out roasting 0.5～10 hour, best 2～6 hours.
The petrochemical catalyst that can be used for preparing various hydrocarbon reactions with β zeolite of the present invention by modification, comprise toluene disproportionation, benzene alkeneization, aromatics isomerization, alkane dewaxing or etherification of olefine etc., be specially adapted to toluene disproportionation process, and have conversion ratio height, good stability, characteristics such as dimethylbenzene/benzene (X/B) molar ratio height.Be used for toluene and C
9When aromatic disproportion and transalkylation, during with the pure H β zeolites as catalysts of the present invention, the mol ratio of dimethylbenzene/benzene can be up to 5.32 in the product, add the catalyst that makes behind the aluminium oxide with H β zeolite of the present invention, the molar ratio of dimethylbenzene/benzene also can reach 4.21 in the product, has obtained effect preferably.
Accompanying drawing 1 is the graph of pore diameter distribution of the β zeolite of the inventive method preparation.
The present invention is further illustrated below by embodiment.
[embodiment 1]
Synthesizing of sodium type β zeolite
By the reaction mixture that aluminium source, sodium source, tetraethyl ammonium hydroxide are formed, satisfy following proportioning (mol ratio):
Na
2O/SiO
2＝0.04～0.25，SiO
2/Al2O
3＝10～50，H
2O/SiO
2＝2～6，(TEA)
2O/SiO
2＝0.01～0.06，OH
-/SiO
2＝0.1～0.6。By weight, get 4.95 parts of sodium aluminates, 0.25 part in NaOH after mixing, joins in the solution of 45.3 parts of tetraethyl ammonium hydroxides (2.0M concentration).Stir after the dissolving, join in 49.5 parts of solid silicones, stir, change in the crystallizing kettle, 150 ℃ of crystallization 60 hours are isolated solid product, washing, 120 ℃ of dryings 2 hours Na type β zeolite finished product.
The X ray diffracting spectrum characteristic peak of synthetic sodium type β zeolite is as shown in the table
2 θ (°) d value () I/I
o
7.65 11.55 52
11.70 7.56 5
20.80 4.27 15
22.45 3.96 100
26.85 3.32 15
29.50 3.03 14
43.45 2.08 8
Thermogravimetric analysis (TGA) result of this sodium type β zeolite (air stream heating rate is 20 ℃/minute) as shown in the table
| Temperature range (℃) | ＜200 | 200～450 | 450～800 | Amount to |
| Weightless (weight %) | 3.64 | 12.25 | 1.64 | 17.53 |
The β zeolite that this example explanation the present invention proposes takes off 450～800 ℃ of amine temperature, can satisfy the β zeolite and take off the amine requirement.
[embodiment 2]
The sodium type β zeolite (butt) of getting embodiment 1 preparation adds the ammonium nitrate solution of 10% (weight), Gu liquid /=4: 1, exchange is 4 hours under 90～99 ℃ of stirrings, reduce temperature to 30～40 ℃, centrifugal filtration, filtrate is carried out inductively coupled plasma emission spectrographic analysis (ICP) Na content, and filter cake carries out the exchange second time, and the rest may be inferred carries out the 3rd, the 4th exchange.The filtrate and the filter cake Na content of different exchange number of times are as shown in the table:
| Ion-exchange number of times 1234 | Filtrate Na content, milliliter/liters 800.0 189.0 31.6 14.7 | Filter cake Na content, weight %/0.065 0.035 0.023 |
[embodiment 3]
Get sodium type β zeolite (butt) (reaction system mol ratio SiO by example 1 preparation
2/ Al
2O
3=40), add in the ammonium nitrate solution of 10% weight, Gu liquid /=4: 1 (weight ratio), under the room temperature, stir exchange 3 times, each 4 hours, the 4th exchange, 90～99 ℃ of temperature are carried out in centrifugal filtration, filter cake, stir exchange down 4 hours, be reduced to 30～40 ℃, centrifugal filtration, washing, 120 dryings 2 hours, icp analysis filter cake Na content is 0.07% weight.
[embodiment 4]
Get the NH of embodiment 2
4The β zeolite, through 120 ℃ of dryings 2 hours, 560 ℃ of roastings 4 hours, Hydrogen β zeolite A, it is 712.4 meters that its specific surface is surveyed in nitrogen absorption
2/ gram, the most probable aperture is 41.1 , 0.326 milliliter/gram of pore volume.
[embodiment 5]
Get sodium type β zeolite (reaction system mol ratio SiO by example 1 preparation
2/ Al
2O
3=20), carry out four ammonium exchanges, the NH after the exchange by example 2
4120 ℃ of dryings of β 2 hours, and, get Hydrogen β zeolite B 560 ℃ of following roastings 4 hours.It is 686 meters that its specific surface is surveyed in nitrogen absorption
2/ gram, the most probable aperture is 41.1 , 0.384 milliliter/gram of pore volume.
[embodiment 6]
Get that a certain amount of example 2, example 5 have carried out ammonium exchange and high temperature takes off the NH that amine is handled
4β and H β and a certain amount of aluminium oxide mix, and add nitric acid and water and mineralizer, after fully mixing, and extruded moulding, 120 ℃ of dryings 2 hours, the catalyst A that contains the β zeolite component is made in 550 ℃ of roastings 4 hours
1, B
1Wherein the weight ratio of aluminium oxide and β zeolite is 30: 70%～70: 30%.Nitrogen adsorption method is surveyed A
1, B
1The specific area of catalyst is respectively 562 meters
2/ gram, 524 meters
2/ gram, pore volume be respectively 0.326 milliliter/gram, 0.327 milliliter/gram, the most probable aperture of two kinds of catalyst is 41.1 .
[embodiment 7]
This example is the catalyst made of modified beta zeolite or the toluene disproportionation process performance evaluation of Hydrogen β zeolite.
The mixed toluene and the C that adopt commercial plant to provide
9Aromatic hydrocarbons, this raw material are formed: non-aromatic 0.02%, and benzene 0.69%, toluene 57.22%, ethylbenzene 0.17%, paraxylene 0.26%, meta-xylene 0.13%, ortho-xylene 0.04%, isopropylbenzene 0.20%, n-proplbenzene 1.48%, p-methyl-ethylbenzene 10.97%, 1,3,5-trimethylbenzene 5.05%, o-methylethylbenzene 2.44%, 1,2,4-trimethylbenzene 15.37%, 1,2,3-trimethylbenzene 1.66%, indane 0.50%, C
10Aromatic hydrocarbons 2.57%, wherein toluene: C
9A (weight ratio) is about 6: 4.Reaction condition: 400 ℃ of reaction temperatures, reaction pressure 2.5～3.0MPa, hydrogen/oil (mol ratio) is 6, weight liquid air speed (hr
-1) be that 1.3～2.5,10 milliliters of microreactor catalyst useful loads are 2 milliliters.The gas chromatographic analysis reaction result.Conversion ratio and selectivity computing formula are as follows:
A
1, B
1Catalyst and Hydrogen β zeolite A and the result of B toluene disproportionation process after 5 hours
Annotate: A
1, B
1Air speed be 1.3hr
-1, the air speed of A, B is 2.5hr
-1
| Sample | Toluene conversion, mol% | C 9The A conversion ratio, mol% | Total conversion, mol% | (B+X) overall selectivity, mol% | X/B(mol) |
| A 1 | 39.67 | 55.91 | 45.60 | 97.32 | 4.21 |
| B 1 | 34.80 | 56.67 | 44.11 | 94.35 | 4.06 |
| A | 28.51 | 56.94 | 40.08 | 93.44 | 4.48 |
| B | 36.47 | 54.11 | 43.65 | 86.70 | 5.32 |
" comparative example 1 "
Get commercially available sodium type β zeolite and make H β zeolite C, the SiO of this β zeolite by embodiment 5 described methods
2/ Al
2O
3Mol ratio is 30, Na
2O content is 0.062% (weight), and specific area is 618.7 meters
2/ gram, pore volume are 0.358 milliliter/gram, and with this H β zeolite raw material of embodiment 7 and identical reaction condition, wherein the liquid air speed is 2.5Hr
-1Check and rate, its reaction result is: toluene conversion 36.10%, C
9A conversion ratio 40.51%, total conversion 37.90%, (B+X) overall selectivity 83.39%, and the X/B molar ratio is 3.98.
Claims (2)
1. β zeolite, SiO in the β zeolite
2/ Al
2O
3Mol ratio is 10～50, by weight percentage Na
2O content≤0.10%, specific area are 500～700 meters
2/ gram, pore volume are 0.30～0.40 milliliter/gram, and its X ray diffracting characteristic peak parameter satisfies following parameter value:
2 θ (°) d value () I/I
o
7.65 11.65±0.2 52
11.70 7.58±0.1 5
20.80 4.11±0.1 15
22.45 3.93±0.1 100
26.85 3.32±0.05 15
29.50 3.01±0.05 14
43.45 2.07±0.05 8
Wherein 2 θ are the angle of diffraction, and the d value is an interplanar distance, I/I
oBe relative intensity, its largest hole dilatation percentage distributes to average pore diameter and sees Fig. 1.
2. β zeolite according to claim 1, the most probable aperture that it is characterized in that the β zeolite is 41.1 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122006A CN1096295C (en) | 1998-11-18 | 1998-11-18 | Beta-zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122006A CN1096295C (en) | 1998-11-18 | 1998-11-18 | Beta-zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1253857A CN1253857A (en) | 2000-05-24 |
| CN1096295C true CN1096295C (en) | 2002-12-18 |
Family
ID=5227493
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98122006A Expired - Lifetime CN1096295C (en) | 1998-11-18 | 1998-11-18 | Beta-zeolite |
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| CN (1) | CN1096295C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101852143B1 (en) * | 2010-05-21 | 2018-04-25 | 피큐 코포레이션 | Novel metal - containing zeolite beta for nox reduction |
| CN101857522B (en) * | 2010-05-24 | 2013-07-24 | 江西师范大学 | Method for separating methanol/methyl methacrylate mixed system |
| CN106140248B (en) * | 2015-03-27 | 2018-06-15 | 中国石油化工股份有限公司 | A kind of preparation method of diesel oil hydrogenation modification catalyst carrier |
| CN106140285B (en) * | 2015-03-27 | 2018-10-12 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN106140319B (en) * | 2015-03-27 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of preparation method of middle oil type hydrocracking catalyst carrier |
| CN106145133B (en) * | 2015-03-27 | 2018-06-15 | 中国石油化工股份有限公司 | A kind of H beta molecular sieves and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851604A (en) * | 1987-09-02 | 1989-07-25 | Mobil Oil Corp. | Toluene disproportionation |
| US5256392A (en) * | 1989-06-23 | 1993-10-26 | Fina Technology, Inc. | Modified zeolite beta method of preparation |
| CN1105646A (en) * | 1994-06-29 | 1995-07-26 | 中国石油化工总公司抚顺石油化工研究院 | Beta zeolite and preparing method thereof |
-
1998
- 1998-11-18 CN CN98122006A patent/CN1096295C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851604A (en) * | 1987-09-02 | 1989-07-25 | Mobil Oil Corp. | Toluene disproportionation |
| US5256392A (en) * | 1989-06-23 | 1993-10-26 | Fina Technology, Inc. | Modified zeolite beta method of preparation |
| CN1105646A (en) * | 1994-06-29 | 1995-07-26 | 中国石油化工总公司抚顺石油化工研究院 | Beta zeolite and preparing method thereof |
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