CN1166563C - Process for synthesis of ZSM-35 zeolite - Google Patents

Process for synthesis of ZSM-35 zeolite Download PDF

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CN1166563C
CN1166563C CNB011238801A CN01123880A CN1166563C CN 1166563 C CN1166563 C CN 1166563C CN B011238801 A CNB011238801 A CN B011238801A CN 01123880 A CN01123880 A CN 01123880A CN 1166563 C CN1166563 C CN 1166563C
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zeolite
zsm
sio
silicon
synthetic zsm
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CN1401570A (en
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谢素娟
彭建彪
吴治华
王清遐
徐龙伢
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a method for synthesizing ZSM-35 zeolite. Cyclohexylamine is used as templates, and compounds of silicon and/or germanium, salts or oxide of aluminum and/or boron, hydroxide of alkali metal or alkaline earth metal, the cyclohexylamine and deionized water are used as raw materials. The templates and the raw materials are crystallized for a certain time at 90 to 240 DEG C until the reaction is completed, and molecular sieves are formed by hydrothermal synthesis. The proportioning (the molar ratio) range of the raw materials is 10 to 100 of YO2/X2O3, 9 to 120 of H2 O/YO2, 0.1 to 2.0 of R/YO2, 0.05 to 0.7 of OH<->/YO2 and 0.05 to 1.0 of M/YO2, wherein X is aluminum and/or boron, Y is silicon and/or germanium, R is cyclohexylamine, and M is alkali metal or alkaline earth metal. The ZSM-35 zeolite can be widely used for the catalytic reaction of hydrocarbon conversion, such as isomerization, polymerization, aromatization, cracking, etc.

Description

A kind of method of synthetic ZSM-35 zeolite
Technical field
The invention relates to a kind of improved method of synthetic ZSM-35 zeolite.Specifically, providing a kind of is template with the hexahydroaniline, with salt or the oxyhydroxide of oxide compound, basic metal or alkaline-earth metal and the method for the synthetic ZSM-35 zeolite that deionized water is raw material of compound, aluminium and/or the boron of silicon and/or germanium.
Background technology
The ZSM-35 zeolite is the molecular sieve (USP4,016,245) of U.S. Mobil company in a kind of Ferrierite of having of the seventies later development success (FER) topological framework.This zeolite with two-dimentional channel system can be widely used in the catalyzed reaction of the hydrocarbon conversion, as isomerization, polymerization, aromizing and cracking etc.
The same with most of molecular sieves, select suitable material as template, be one of key factor of synthetic ZSM-35 molecular sieve.The template of at present synthetic ZSM-35 zeolite mainly contains quadrol or tetramethyleneimine (USP4,016,245), butanediamine (USP4,107,195), hexamethylene imine (USP4,925,548), 1,4 cyclohexanediamine (USP5,190,736) and the formed organic mixture of hexanolactam shortening (Chinese patent application number be 00110356.3) etc.Relevant in addition document has also been reported the template that some synthetic FER zeolites are adopted, as piperidines (USP4,251,499), 2-aminopyridine (USP4,390,457), diox (USP4,377,502) and pyridine and ethylene glycol (USP4,587259 and USP4,695,440) etc.
Summary of the invention
The objective of the invention is to develop a kind of method of improved synthetic ZSM-35 zeolite, have that the synthetic cost is low, characteristics such as degree of crystallinity height of synthetic good reproducibility and product.
The invention provides a kind of method of synthetic ZSM-35 zeolite, it is characterized in that:
Employed template is a hexahydroaniline.
Oxyhydroxide, template and the deionized water of the salt of employing aluminium and/or boron or oxide compound, basic metal or the alkaline-earth metal of oxide compound, silicon and/or germanium are raw material, under 90～240 ℃, and crystallization 70 hours to 7 days, hydro-thermal synthesizes molecular sieve.The feed molar ratio range of this zeolite synthesis is: YO 2/ X 2O 3=10～100; H 2O/YO 2=9～120; R/YO 2=0.1～2.0; OH -/ YO 2=0.05～0.7; M/YO 2=0.05～1.0, wherein X is aluminium and/or boron, X 2O 3Can be provided by compounds such as aluminium sesquioxide and sodium aluminates, Y is silicon and/or germanium, YO 2Can be provided by compounds such as silicon-dioxide, silicic acid and alkoxyl silicones, R is a hexahydroaniline, and M is basic metal or alkaline-earth metal.
The synthetic ZSM-35 zeolite of the present invention feed molar ratio range preferably is: YO 2/ X 2O 3=12～65; H 2O/YO 2=14～55; R/YO 2=0.2～1.0; OH -/ YO 2=0.1～0.5; M/YO 2=0.1～0.6.
Synthetic ZSM-35 zeolite of the present invention through 540 ℃ of roasting certain hours after, have the X-ray diffract spectral line of table 1.
The synthetic ZSM-35 of institute zeolite of the present invention, its primary positively charged ion (as basic metal or alkaline earth metal cation) can be by ion exchange technique by other cationic moiety or replacement fully.These replace precursor such as ammonium ion and their mixture that positively charged ion comprises metal ion, hydrogen ion, hydrogen, and wherein metal ion can be the metal ion among IIA, IIIA, IVA, IB, IIB, IIIB, IVB and the VIII in the rare earth metal and the periodic table of elements.Typical ion-exchange techniques, be with the cationic salt of replacement such as halogenide, nitrate and vitriol, contact with synthesis type ZSM-35 zeolite, through washing, 1～48 hour, 220～550 ℃ roastings of 60～220 ℃ of dryings 1～48 hour, can obtain containing required cationic ZSM-35 zeolite again.
Table 1, the X-ray diffract spectral line that the synthetic ZSM-35 of the present invention is had *
Spacing d () Diffraction peak relative intensity I/I 0(×100) Spacing d () Diffraction peak relative intensity I/I 0(×100)
9.6±0.2 VS 3.78±0.08 S
7.10±0.15 M 3.74±0.08 W
6.98±0.14 M 3.66±0.07 M
6.64±0.14 W-M 3.54±0.07 VS
5.78±0.12 W-M 3.48±0.07 VS
5.68±0.12 W 3.39±0.07 W
4.97±0.10 W 3.32±0.07 W-M
4.58±0.09 W 3.14±0.06 W-M
3.99±0.08 S 2.90±0.06 W
3.94±0.08 M-S 2.85±0.06 W
3.85±0.08 M
*W, M, S and VS represent the weak, medium, strong and very strong of diffraction peak respectively, and its numerical range is W=0～20, M=20～40, S=40～60, VS=60～100.
Embodiment
The present invention will be further described below by example, but do not limit application of the present invention.
Synthesizing of example 1:ZSM-35 zeolite
(1) raw material:
A. sodium aluminate solution [contains 13.4% (w) Al 2O 3, 19.3% (w) Na 2O, as follows]: 5.7 grams;
B. sodium hydroxide solution [containing 10.0% (w) NaOH, as follows]: 3.8 grams;
C. hexahydroaniline: 6.5 grams;
D. deionized water: 113.5 grams;
E. solid silicone [contains 90.5% (w) SiO 2, as follows]: 7.5 grams;
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=15; H 2O/SiO 2=60; R/SiO 2=0.58 (R finger ring hexylamine, as follows); OH -/ SiO 2=0.40; Na/SiO 2=0.40.
(2) operation steps:
At room temperature earlier with raw material (A) with (B) in 200 milliliters of stainless steel cauldrons, mix, then under agitation with raw material (C) with (D) add in the still successively, stirred 10 minutes, add raw material (E) again, continue to stir after 20 minutes, reactor is sealed, 172 ℃ of following crystallization 70 hours, sudden cold after, with the rotating speed centrifugation of solid and mother liquor with 5000 rev/mins, solid through deionized water wash to PH8～9,120 ℃ of following dry airs 8 hours, make the ZSM-35 zeolite, the X-ray diffraction spectral line behind 540 ℃ of roasting 4h is shown in table 2, records its SiO 2/ Al 2O 3Be 13.8 (mol ratios, as follows).
Table 2, the X-ray diffraction spectral line of sample in the example 1
Spacing d () Diffraction peak relative intensity I/I 0(×100) Spacing d () Diffraction peak relative intensity I/I 0(×100)
9.55 71 3.79 45
7.14 26 3.67 23
6.99 23 3.56 100
6.67 20 3.49 80
5.81 14 3.40 11
4.00 55 3.33 23
3.95 33 3.14 27
3.85 25 3.05 18
Synthesizing of example 2:ZSM-35 zeolite
In example 1, change the add-on of sodium aluminate solution into 4.6 grams, the add-on of hexahydroaniline changes 3.9 grams into, the add-on of deionized water changes 136.2 grams into, the add-on of solid silicone changes 11.9 grams into, hydro-oxidation sodium solution not, and the mole of reaction mixture consists of: SiO 2/ Al 2O 3=30; H 2O/SiO 2=43.33; R/SiO 2=0.22; OH -/ SiO 2=0.16; Na/SiO 2=0.16.150 ℃ of following crystallization 7 days, product was the ZSM-35 molecular sieve.The X-ray diffraction spectral line of sample behind 540 ℃ of roasting 4h is shown in table 3, records its SiO 2/ Al 2O 3Be 28.7.
Table 3, the X-ray diffraction spectral line of sample in the example 2
Spacing d () Diffraction peak relative intensity I/I 0(×100) Spacing d () Diffraction peak relative intensity I/I 0(×100)
9.45 100 3.77 42
7.10 22 3.65 25
6.94 30 3.54 81
6.59 24 3.47 67
5.75 19 3.36 15
3.98 54 3.31 20
3.92 30 3.13 24
3.83 27 3.04 17
Synthesizing of example 3:ZSM-35 zeolite
In example 1, change the add-on of sodium hydroxide solution into 3.2 grams, the add-on of hexahydroaniline changes 9.1 grams into, and the add-on of deionized water changes 126.1 grams into, and the add-on of solid silicone changes 22.4 grams into, and the add-on of all the other components is constant.The mole of reaction mixture consists of: SiO 2/ Al 2O 3=45; H 2O/SiO 2=22.22; R/SiO 2=0.27, OH -/ SiO 2=0.13; Na/SiO 2=0.13.168 ℃ of following crystallization 4 days, product was the ZSM-35 molecular sieve.The X-ray diffraction spectral line of sample behind 540 ℃ of roasting 4h is shown in table 4, records its SiO 2/ Al 2O 3Be 40.6.
Synthesizing of example 4:ZSM-35 zeolite
In example 1, use 10 liter synthesis reactors instead, change the add-on of sodium aluminate solution into 285.5 grams, the add-on of sodium hydroxide solution changes 129.0 grams into, the add-on of hexahydroaniline changes 389.8 grams into, the add-on of deionized water changes 6033.5 grams into, and the add-on of solid silicone changes 745.8 grams into, and the mole of reaction mixture consists of: SiO 2/ Al 2O 3=30; H 2O/SiO 2=31.7; R/SiO 2=0.35, OH -/ SiO 2=0.19; Na/SiO 2=0.19.Under 172 ℃ and 20 rev/mins of conditions of synthesis reactor velocity of rotation, crystallization 3.5 days, product is the ZSM-35 molecular sieve.The X-ray diffraction spectral line of sample behind 540 ℃ of roasting 4h is shown in table 5, records its SiO 2/ Al 2O 3Be 29.3.
Table 4, the X-ray diffraction spectral line of sample in the example 3
Spacing d () Diffraction peak relative intensity I/I 0(×100) Spacing d () Diffraction peak relative intensity I/I 0(×100)
9.47 100 3.78 50
7.10 29 3.65 32
6.97 24 3.55 92
6.63 21 3.47 73
5.76 27 3.38 14
4.97 15 3.32 27
3.99 62 3.13 27
3.93 40 3.04 22
3.84 34
Table 5, the X-ray diffraction spectral line of sample in the example 4
Spacing d () Diffraction peak relative intensity I/I 0(×100) Spacing d () Diffraction peak relative intensity I/I 0(×100)
9.51 89 3.78 48
7.11 26 3.65 24
6.97 20 3.55 100
6.64 17 3.47 75
5.77 18 3.35 22
3.99 64 3.32 26
3.94 37 3.13 27
3.84 26 3.04 18
Synthesizing of example 5:ZSM-35 zeolite
In example 1, change the add-on of sodium hydroxide solution into 9.2 grams, the add-on of hexahydroaniline changes 5.6 grams into, the add-on of deionized water changes 101.3 grams into, the add-on of solid silicone changes 14.9 grams into, other adds mother liquor 4.1 grams with MCM-22 molecular sieve structure and makes crystal seed, and the add-on of all the other components is constant.The mole of reaction mixture consists of: SiO 2/ Al 2O 3=30; H 2O/SiO 2=28.33; R/SiO 2=0.25, OH -/ SiO 2=0.26; Na/SiO 2=0.26, the add-on of crystal seed is 3% of a raw material weight.164 ℃ of following crystallization 4 days, product was the ZSM-35 molecular sieve.X-ray diffraction spectral line and the example 2 of sample behind 540 ℃ of roasting 4h is similar, therefore repeats no more, and records the SiO of this sample 2/ Al 2O 3Be 29.5.
Synthesizing of example 6:ZSM-35 zeolite
In example 1, with boric acid (H 3BO 3) be the boron source, H 3BO 3Add-on be 0.1 the gram, change the add-on of sodium aluminate solution into 5.1 grams, the add-on of sodium hydroxide solution changes 1.7 grams into, the add-on of hexahydroaniline changes 6.7 grams into, the add-on of deionized water changes 121.9 grams into, the add-on of solid silicone changes 14.9 grams into, and the mole of reaction mixture consists of: SiO 2/ (Al 2O 3+ B 2O 3)=29.70; SiO 2/ Al 2O 3=33.33; H 2O/SiO 2=31.67; R/SiO 2=0.30; OH -/ SiO 2=0.16; Na/SiO 2=0.16.160 ℃ of following crystallization 5 days, product was the ZSM-35 molecular sieve.X-ray diffraction spectral line and the example 2 of sample behind 540 ℃ of roasting 4h is similar, records its SiO 2/ Al 2O 3Be 27.6.
Example 7:ZSM-35 molecular sieve catalyst is used for the catalytic performance of catalytically cracked gasoline modification
At present external gasoline mainly is catalytic reforming gasoline, and its aromatic hydrocarbon content is higher, and olefin(e) centent is low, and the stability of therefore external gasoline is better.Therefore and China's gasoline mainly is catalytically cracked gasoline, and aromatic hydrocarbon content is lower, and olefin(e) centent is higher, and the stability of gasoline is poor, more serious to the damage ratio of environment, reduces that olefin(e) centent is the important channel of China's gasoline development in the gasoline.Its effective means can be by the new catalysis technique of the isomerization of exploitation catalytic gasoline hydrogenation, aromizing, unsaturated acyclic hydrocarbon in the gasoline is converted into isoparaffin and aromizing product, guaranteeing under the prerequisite that gasoline octane rating does not descend, improving the quality and the stability of catalytically cracked gasoline.This example utilizes the ZSM-35 molecular sieve as the catalytic gasoline hydrogenation isomerization catalyst, is isoparaffin and aromatic hydrocarbons with conversion of olefines in the gasoline, obtains result preferably.
Get a certain amount of example 4 synthetic ZSM-35 molecular sieves and an amount of γ-Al 2O 3Powder (ZSM35/Al 2O 3=7/3, weight ratio), add an amount of rare nitric acid, pinch through mixing, extruded moulding, room temperature dry, behind 110 ℃ of dry 4h and the 540 ℃ of roasting 3h, with the NH of 0.8mol/l 4NO 3Solution exchange three times through washing, 110 ℃ of dry 2h and 500 ℃ of roasting 2h, obtains Hydrogen ZSM-35 molecular sieve catalyst (H-ZSM35) again.With having certain density Ni (NO 3) 2Solution carries out vacuum impregnation to H-ZSM35, obtains containing the ZSM-35 molecular sieve catalyst (1.0%Ni/ZSM35) of 1.0%Ni.
In the fixed-bed reactor of continuous flow, add 7 gram 1%Ni/ZSM35 catalyzer, keep the weight space velocity 1.0h of reaction pressure 0.4MPa, 250 ℃ of temperature of reaction, hydrogen/gasoline=400 and gasoline -1, investigate the composition of catalytically cracked gasoline before and after reaction and change, the results are shown in table 6.
Table 6, the 1%Ni/ZSM35 catalyzer is used for the reactivity worth of catalytically cracked gasoline modification
The positive positive structure isomery of structure isomery
Cyclic hydrocarbon aromatic hydrocarbons
Alkane alkane alkene alkene
Raw material 4.39 22.13 18.33 24.52 13.27 16.45
Product 5.40 29.89 3.86 26.17 13.67 20.04
Investigation 1%Ni/ZSM35 catalyzer shows the reactivity worth (table 6) of catalytically cracked gasoline modification, guaranteeing under the prerequisite that gasoline octane rating does not descend, the Ni/ZSM-35 catalyzer can reduce the olefin(e) centent (being dropped to the 30.03.% of product by 42.85% of raw material) in the catalytically cracked gasoline, increase the content (increasing by 3.59%) of isoparaffin (increasing by 7.76%) and aromatic hydrocarbons, thereby obviously improved the quality of catalytically cracked gasoline than raw material than raw material.

Claims (7)

1. the method for a synthetic ZSM-35 zeolite, it is characterized in that employed template is a hexahydroaniline, the salt of compound, aluminium and/or the boron of employing silicon and/or germanium or oxyhydroxide, hexahydroaniline and the deionized water of oxide compound, basic metal or alkaline-earth metal are raw material, under 90～240 ℃, crystallization 70 hours to 7 days, until reacting completely, hydro-thermal synthesizes molecular sieve; Proportioning raw materials (mol ratio) scope is: YO 2/ X 2O 3=10～100; H 2O/YO 2=9～120; R/YO 2=0.1～2.0; OH -/ YO 2=0.05～0.7; M/YO 2=0.05～1.0, wherein X is aluminium and/or boron, and Y is silicon and/or germanium, and R is a hexahydroaniline, and M is basic metal or alkaline-earth metal.
2. by the method for the described synthetic ZSM-35 zeolite of claim 1, it is characterized in that the mole ratio range of raw material is: YO 2/ X 2O 3=12～65; H 2O/YO 2=14～55; R/YO 2=0.2～1.0; OH -/ YO 2=0.1～0.5; M/YO 2=0.1～0.6.
3. by the method for claim 1 or 2 described synthetic ZSM-35 zeolites, it is characterized in that X is an aluminium.
4. by the method for claim 1 or 2 described synthetic ZSM-35 zeolites, it is characterized in that Y is a silicon.
5. by the method for claim 1 or 2 described synthetic ZSM-35 zeolites, it is characterized in that X 2O 3Provide by aluminium sesquioxide or sodium aluminate.
6. by the method for claim 1 or 2 described synthetic ZSM-35 zeolites, it is characterized in that YO 2Provide by silicon-dioxide, silicic acid or alkoxyl silicone.
7. by the method for the described synthetic ZSM-35 zeolite of claim 1, it is characterized in that: add crystal seed in synthesis material, the crystal seed that is added has the crystalline structure of ZSM-35 zeolite or MCM-22 zeolite.
CNB011238801A 2001-08-09 2001-08-09 Process for synthesis of ZSM-35 zeolite Expired - Fee Related CN1166563C (en)

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Publication number Priority date Publication date Assignee Title
CN1299989C (en) * 2004-09-17 2007-02-14 中国科学院大连化学物理研究所 Process for preparing 2SM-35 molecular sieve
CN101928011B (en) * 2009-06-18 2012-12-12 中国石油化工股份有限公司 Method for preparing ZSM-35 molecular sieve
CN101973563B (en) * 2010-09-07 2012-08-22 浙江大学 Method for synthetizing ZSM-35 molecular sieve by seed crystal process
CN104370295B (en) * 2013-08-14 2016-06-08 中国科学院大连化学物理研究所 A kind of synthetic method of ZSM-35 molecular sieve and Me-ZSM-35
CN106698466B (en) * 2015-11-12 2018-10-12 中国石油化工股份有限公司 A method of preparing a nanometer ZSM-35 molecular sieve
CN106809850A (en) * 2015-11-30 2017-06-09 中国科学院大连化学物理研究所 A kind of synthetic method of little crystal grain FER molecular sieve
CN107265478B (en) * 2017-06-06 2019-05-28 中国石油大学(北京) A kind of boron modification ferrierite molecular sieve catalyst and the preparation method and application thereof

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