CN102464337A - Green synthetic method for rare earth-containing ZSM-35 molecular sieve - Google Patents

Green synthetic method for rare earth-containing ZSM-35 molecular sieve Download PDF

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CN102464337A
CN102464337A CN2010105375015A CN201010537501A CN102464337A CN 102464337 A CN102464337 A CN 102464337A CN 2010105375015 A CN2010105375015 A CN 2010105375015A CN 201010537501 A CN201010537501 A CN 201010537501A CN 102464337 A CN102464337 A CN 102464337A
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molecular sieve
zsm
rare earth
raw material
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徐龙伢
张玲
刘盛林
谢素娟
王清遐
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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 invention provides a green synthetic method for a rare earth-containing ZSM-35 molecular sieve, which is characterized in that silicon source, aluminum source, deionized water, salt of rare earth element, seed and inorganic acid or inorganic base are taken as initial raw materials; wherein the mol ratio of the initial raw materials comprises: SiO2: Al2O3 is 15-40, OH<->:Al2O3 is 2.5-9.2, H2O: Al2O3 is 300-2000, RE2O3: Al2O3 is 0.01-0.56, the addition of the seed accounts for 0.1-10.0% of total mass of raw material silicon aluminum oxide, a reaction initial raw material mixture is crystallized for 20-72 hours under the authigenic pressure and crystallization temperature of 150-200 DEG C, the rare earth-containing ZSM-35 molecular sieve is prepared by hydrothermal synthesis, and the invention has the advantages of simple process, friend environment, low cost and good products crystallization quality, the rare earth element is directly introduced in a molecular sieve frame during the synthesis process, so that the stability of the molecular sieve is enhanced.

Description

A kind of green synthesis method that contains rare earth ZSM-35 molecular sieve
Technical field
The present invention relates to materials chemistry and technical field of catalysis chemistry, a kind of green synthesis method that contains rare earth ZSM-35 molecular sieve is provided especially.
Background technology
The ZSM-35 molecular sieve is the layer molecule sieve material (USP4,016,245) of a kind of Ferrierite of having (FER) topological framework of being developed in 1977 by U.S. Mobil company.ZSM-35 belongs to rhombic system, has the two-dimentional channel system of square crossing, and the ten-ring duct size that wherein is parallel to [001] face is 0.42 * 0.54nm, and the octatomic ring duct size that is parallel to [010] face is 0.35 * 0.48nm.Because its suitable duct, good heat/hydrothermal stability and acidity, the ZSM-35 molecular sieve is widely used in hydrocarbon conversion processes such as isomerizing, polymerization and cracking.
At present, the synthetic used template of ZSM-35 molecular sieve mainly contains: quadrol or tetramethyleneimine (USP4,016,245 and USP4,107,125), tetramethylenediamine (USP4,107; 195), 1,4-lupetazin (USP5,288,475), hexamethylene imine (USP4,925,548), 1,4-cyclohexanediamine (USP5; 190,736), piperidines (USP4,251,499), choline (USP4,046,859), 2; 4-Acetyl Acetone (USP4,323,481), 2-EL-970 (USP4,390,457) 、 diox (USP4,377; 502), hexahydroaniline (CN1,401,570A and CN1,749164A) and the formed organic mixture of hexanolactam shortening etc. (CN1,320,558).Yet for the suitability for industrialized production of ZSM-35, the use of these template has not only increased production cost, also can cause environmental pollution.Simultaneously,, need carry out the calcination process about 500 ℃, make energy consumption increase, also possibly influence its use properties because the incomplete pyrolysis of template causes the hole plug of zeolite to it in order to remove the template in the zeolite sample.Therefore, the no template green synthesis method of exploitation ZSM-35, significant.
REE is introduced the stability that can improve sieve catalyst in the duct of molecular sieve.Because the hydrated rare-earth ionic radius is bigger, it is bigger to adopt traditional ion-exchange techniques to introduce the REE difficulty, and the uniformity coefficient of exchange product is not ideal enough.For fear of above defective, can in the synthesis material of molecular sieve, add the salt that contains REE, make REE in crystallization process, get into the duct of molecular sieve.
To these application backgrounds, the objective of the invention is to develop a kind of green synthesis method that contains rare earth ZSM-35 molecular sieve.
Summary of the invention
The objective of the invention is to develop a kind of green synthesis method that contains rare earth ZSM-35 molecular sieve; Solving problems such as organic formwork synthesis method production cost is high, technological operation is complicated, environmental pollution is serious, and through adding REE to improve the stability of molecular sieve.
The present invention specifically provides a kind of green synthesis method that contains rare earth ZSM-35 molecular sieve; It is characterized in that: this method is an initial feed with salt, crystal seed and mineral acid or the mineral alkali of silicon source, aluminium source, deionized water, REE; Wherein, mineral acid and mineral alkali are used for the potential of hydrogen of modulation system;
The mole proportioning of initial feed is: SiO 2/ Al 2O 3=15～40, OH -/ Al 2O 3=2.5～9.2, H 2O/Al 2O 3=300～2000, RE 2O 3/ Al 2O 3=0.01～0.56, the add-on of crystal seed is the 0.1-10.0% of initial feed sieve and silica-sesquioxide total mass;
Reaction initial feed mixture is under the hydrothermal condition of 150～200 ℃ of autogenous pressure and crystallization temperatures; Crystallization 20～72h; After the reaction kettle cooling; Product mixtures is carried out solid-liquid separation, and solid product wherein obtains the second best in quality rare earth ZSM-35 sieve sample that contains of crystallization through washing, separation and drying.
The green synthesis method that contains rare earth ZSM-35 molecular sieve provided by the invention is characterized in that: said aluminium source is one or more in sodium metaaluminate, the SB powder; The silicon source is one or more in solid silicone, silicon sol, water glass, WHITE CARBON BLACK, tetraethoxy, the silicic acid; Mineral alkali is one or more in sodium hydroxide, the Pottasium Hydroxide; Mineral acid is one or more in sulfuric acid, hydrochloric acid, the nitric acid; Crystal seed is a kind of in ZSM-35 molecular sieve, MCM-22/ZSM-35 cocrystallization molecular sieve or the MCM-49/ZSM-35 cocrystallization molecular sieve; The salt of REE is the hydrochloride of nitrate salt, hydrochloride or the mixed rear earth element of single rare earth element.
The present invention provides a kind of green synthesis method that contains rare earth ZSM-35 molecular sieve.Template synthesis method (USP4,016,245) with the ZSM-35 molecular sieve is compared, compound method provided by the invention, owing to need not to add template in the synthetic system, thereby obviously reduced environmental pollution, and reduced synthetic expense, simplified technological operation; Simultaneously, in building-up process, REE is introduced framework of molecular sieve, improved the stability of molecular sieve.
Sodium type provided by the invention contains rare earth ZSM-35 molecular sieve; Thereby can further give modification through traditional ion exchange technique and be applied to different catalyzed reactions; Containing rare earth ZSM-35 molecular sieve and can be aided with suitable matrix and process the needed catalyzer of various processes after the modification is applied to catalyzed reaction.
The green synthesis method that contains rare earth ZSM-35 molecular sieve provided by the invention, its advantage is: need not to add any organic formwork agent in the synthetic system, this method operating procedure is simple; Environmental friendliness; With low cost, the crystallization quality that obtains product is good, has good application prospects.
Description of drawings
Fig. 1 makes the XRD spectra of product for embodiment 1;
Fig. 2 makes the XRD spectra of product for Comparative Examples 1;
Fig. 3 makes the XRD spectra of product for Comparative Examples 2;
Embodiment
Following embodiment will further explain the present invention, but therefore not limit the present invention.
Embodiment 1
(1) raw material
A. silicon sol (25.7wt%SiO 2, 0.3wt%Na 2O, 0.1wt%Al 2O 3): 59.67g;
B. sodium aluminate solution (NaAlO 2: 16.8wt%Al 2O 3, 31.2wt%NaOH): 7.37g;
C. dilute sulphuric acid (25.6wt%H 2SO 4): 1.40g;
D. deionized water: 156.5g;
E.ZSM-35 crystal seed: 0.03g;
F. Lanthanum trinitrate [La (NO 3) 36H 2O]: 0.11g;
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=20, OH -/ Al 2O 3=4.4, H 2O/Al 2O 3=900, La 2O 3/ Al 2O 3=0.01, the crystal seed add-on is 0.2% of a raw silicon al oxide quality.
(2) operation steps:
Under condition of stirring, in stainless steel cauldron, add raw material B, 111.5g deionized water (part of raw material D), raw material A, raw material C and raw material F successively, continue stirring it is mixed; Then raw material E is added the 45.0g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it.With the raw mix sealing, 160 ℃ of following crystallization of warp 64 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, the result sees Fig. 1, and product is the ZSM-35 crystal phase structure; Analyze through x-ray fluorescence method (XRF), the weight content that records La in the molecular sieve is 0.2%.
Embodiment 2
(1) raw material:
A. WHITE CARBON BLACK (95wt%SiO 2): 8.89g;
B. sodium aluminate solution (NaAlO 2: 16.8wt%Al 2O 3, 31.2wt%NaOH): 3.91g;
C. sodium hydroxide solution (0.1g NaOH/ml): 2.23ml;
D. deionized water: 135.0g;
E.ZSM-35 crystal seed: 0.10g
F. cerous nitrate [Ce (NO 3) 36H 2O]: 0.84g
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=23, OH -/ Al 2O 3=5.6, H 2O/Al 2O 3=1200, Ce 2O 3/ Al 2O 3=0.15, the crystal seed add-on is 1.0% of a raw silicon al oxide quality.
(2) operation steps:
Under condition of stirring, in stainless steel cauldron, add raw material B, 105.0g deionized water (part of raw material D), raw material C and raw material F successively, continue stirring it is mixed; Then raw material E is added the 30g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it; At last raw material A is added in the said mixture, stirring mixes it.With the raw mix sealing, 162 ℃ of crystallization of warp 52 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, product is the ZSM-35 crystal phase structure; The weight content that records Ce in the molecular sieve through XRF analysis is 2.2%.
Embodiment 3
(1) raw material
A. solid silicone (92wt%SiO 2): 10.08g;
B. sodium aluminate solution (NaAlO 2: 16.8wt%Al 2O 3, 31.2wt%NaOH): 2.34g;
C. sodium hydroxide solution (0.1g NaOH/ml): 6.89g;
D. deionized water: 130.7g;
E.ZSM-35 crystal seed: 0.97g;
F. Lanthanum trichloride (LaCl 36H 2O): 0.27g;
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=40, OH -/ Al 2O 3=9.2, H 2O/Al 2O 3=2000, La 2O 3/ Al 2O 3=0.10, the crystal seed add-on is 10.0% of a raw silicon al oxide quality.
(2) operation steps:
Under condition of stirring, in stainless steel cauldron, add raw material B, 100.7g deionized water (raw material D), raw material C and raw material F successively, continue stirring it is mixed; Then raw material E is added the 30g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it; At last raw material A is added in the said mixture.With the raw mix sealing, 170 ℃ of following crystallization of warp 36 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, product is the ZSM-35 crystal phase structure; The weight content that records La in the molecular sieve through XRF analysis is 0.9%.
Embodiment 4:
(1) raw material
A. silicon sol (25.7wt%SiO 2, 0.3wt%Na 2O, 0.1wt%Al 2O 3): 52.28g;
B.SB powder (77.5wt%Al 2O 3): 1.56g;
C. sodium hydroxide (0.1g NaOH/ml): 7.05ml;
D. Pottasium Hydroxide (0.1g KOH/ml): 12.14ml;
E. deionized water: 77.0g;
F.MCM-49/ZSM-35 crystal seed: 0.29g
G. Lanthanum trinitrate [La (NO 3) 36H 2O]: 3.21g
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=18, OH -/ Al 2O 3=3.6, H 2O/Al 2O 3=600, La 2O 3/ Al 2O 3=0.30, the crystal seed add-on is 2.0% of a raw silicon al oxide quality.
(2) operation steps:
Under condition of stirring, in stainless steel cauldron, add raw material A, 47.0g deionized water (part of raw material E), raw material C, raw material D and raw material G successively, continue stirring it is mixed; Then raw material F is added the 30g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it, adds raw material B at last.With the raw mix sealing, 190 ℃ of following crystallization of warp 24 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, product is the ZSM-35 crystal phase structure; The weight content that records La in the molecular sieve through XRF analysis is 5.8%.
Embodiment 5:
(1) raw material
A. solid silicone (92wt%SiO 2): 5.01g;
B. WHITE CARBON BLACK (95wt%SiO 2): 2.23g;
C.SB powder (77.5wt%Al 2O 3): 0.67g;
D. Pottasium Hydroxide (0.1g KOH/ml): 17.11ml;
E. deionized water: 117.2g;
F.ZSM-35 crystal seed: 0.18g;
G. Lanthanum trinitrate [La (NO 3) 36H 2O]: 0.88g;
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=22, OH -/ Al 2O 3=6.0, H 2O/Al 2O 3=1500, La 2O 3/ Al 2O 3=0.20, the crystal seed add-on is 2.5% of a raw silicon al oxide quality.
(2) operation steps:
Under condition of stirring, in stainless steel cauldron, add raw material D, 87.2g deionized water (part of raw material E) and raw material G, stirring mixes it; Then raw material F is added the 30g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it; Add raw material A, raw material B and raw material C at last.With the raw mix sealing, 180 ℃ of following crystallization of warp 48 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, product is the ZSM-35 crystal phase structure; The weight content that records La in the molecular sieve through XRF analysis is 3.5%.
Embodiment 6:
(1) raw material
A. tetraethoxy (28.0wt%SiO 2): 32.19g;
B. sodium aluminate solution (NaAlO 2: 16.8wt%Al 2O 3, 31.2wt%NaOH): 3.03g;
C. sodium hydroxide solution (0.1g NaOH/ml): 3.33ml;
D. deionized water: 103.4g;
E.ZSM-35 crystal seed: 0.95g;
F. Lanthanum trichloride (LaCl 36H 2O): 0.70g;
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=30, OH -/ Al 2O 3=6.4, H 2O/Al 2O 3=1200, La 2O 3/ Al 2O 3=0.10, the crystal seed add-on is 5.0% of a raw silicon al oxide quality.
(2) operation steps:
Under condition of stirring, in stainless steel cauldron, add raw material C, 73.4g deionized water (part of raw material D), raw material B, raw material A and raw material F successively, continue stirring it is mixed; Then raw material E is added the 30g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it.With the raw mix sealing, 155 ℃ of following crystallization of warp 64 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, product is the ZSM-35 crystal phase structure; The weight content that records La in the molecular sieve through XRF analysis is 1.1%.
Embodiment 7:
(1) raw material
A. silicic acid (calcination loss 24.0wt%SiO 2): 26.49g;
B.SB powder (77.5wt%Al 2O 3): 2.94g;
C. sodium hydroxide solution (0.1g NaOH/ml): 22.34ml;
D. deionized water: 93.5g;
E.ZSM-35 crystal seed: 1.79g;
F. Lanthanum trinitrate [La (NO 3) 36H 2O]: 2.90g;
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=15, OH -/ Al 2O 3=2.50, H 2O/Al 2O 3=300, La 2O 3/ Al 2O 3=0.15, the crystal seed add-on is 8.0% of a raw silicon al oxide quality.
(2) operation steps:
Under condition of stirring, in stainless steel cauldron, add raw material C, 63.5g deionized water (part of raw material D) and raw material F successively, continue stirring it is mixed; Then raw material E is added the 30g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it; At last raw material A and raw material B are added in the said mixture.With the raw mix sealing, 170 ℃ of following crystallization of warp 36 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, product is the ZSM-35 crystal phase structure; The weight content that records La in the molecular sieve through XRF analysis is 3.5%.
Embodiment 8:
(1) raw material
A. water glass (16.97wt%SiO 2, 5.52wt%Na 2O): 69.95g;
B. sodium aluminate solution (NaAlO 2: 16.8wt%Al 2O 3, 31.2wt%NaOH): 5.98g;
C. Hydrogen chloride (30.0wt%HCl): 8.00g;
D. rare nitric acid (30.0wt%HNO 3): 13.82g;
E. deionized water: 54.0g;
F.MCM-22/ZSM-35 crystal seed: 0.26g;
G. Lanthanum trinitrate [La (NO 3) 36H 2O]: 0.68g
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=20, OH -/ Al 2O 3=4.0, H 2O/Al 2O 3=700, La 2O 3/ Al 2O 3=0.08, the crystal seed add-on is 2.0% of a raw silicon al oxide quality.
(2) operation steps:
Under condition of stirring, in stainless steel cauldron, add raw material B, 34.0g deionized water (part of raw material E), raw material A and raw material G successively, continue stirring it is mixed; Then raw material F is added the 20g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it; Under condition of stirring, raw material C and raw material D are added in the said mixture at last, continue stirring it is mixed.With the raw mix sealing, 150 ℃ of following crystallization of warp 72 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, product is the ZSM-35 crystal phase structure; The weight content that records La in the molecular sieve through XRF analysis is 1.4%.
Embodiment 9:
(1) raw material
A. silicon sol (25.7wt%SiO 2, 0.3wt%Na 2O, 0.1wt%Al 2O 3): 30.35g;
B. silicic acid (calcination loss 24.0wt%SiO 2): 4.67g;
C. WHITE CARBON BLACK (95wt%SiO 2): 1.26g;
D.SB powder (77.5wt%Al 2O 3): 0.72g;
E. sodium aluminate solution (NaAlO 2: 16.8wt%Al 2O 3, 31.2wt%NaOH): 2.45g;
F. sodium hydroxide solution (0.1g NaOH/ml): 5.77ml;
G. deionized water: 107.2g;
H.ZSM-35 crystal seed: 0.45g;
I. Lanthanum trichloride (LaCl 36H 2O): 0.34g;
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=17.5, OH -/ Al 2O 3=3.8, H 2O/Al 2O 3=800, La 2O 3/ Al 2O 3=0.05, the crystal seed add-on is 4.0% of a raw silicon al oxide quality.
(2) operation steps:
In stainless steel cauldron, add raw material E, raw material F, 77.2g deionized water (part of raw material G) and raw material I successively, stirring mixes it; Then raw material H is added the 30g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it; Add raw material A, B, C, stirring mixes it; Add raw material D at last.With the raw mix sealing, 195 ℃ of following crystallization of warp 30 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, product is the ZSM-35 crystal phase structure; The weight content that records La in the molecular sieve through XRF analysis is 0.5%.
Embodiment 10:
(1) raw material
A. silicon sol (25.7wt%SiO 2, 0.3wt%Na 2O, 0.1wt%Al 2O 3): 22.82g;
B. solid silicone (92wt%SiO 2): 4.84g;
C. sodium aluminate solution (NaAlO 2: 16.8wt%Al 2O 3, 31.2wt%NaOH): 2.89g;
D. sodium hydroxide solution (0.1g NaOH/ml): 7.82ml;
E. deionized water: 116.5g;
F.MCM-49/ZSM-35 crystal seed: 0.65g;
G. Lanthanum trinitrate [La (NO 3) 36H 2O]: 2.16g
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=35, OH -/ Al 2O 3=9.0, H 2O/Al 2O 3=1600, La 2O 3/ Al 2O 3=0.50, the crystal seed add-on is 6.0% of a raw silicon al oxide quality.
(2) operation steps:
In stainless steel cauldron, add raw material C, raw material D, 86.5g deionized water (part of raw material E) and raw material G successively, stirring mixes it; Then raw material F is added the 30g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it; Add raw material A, stirring mixes it; Add raw material B at last.With the raw mix sealing, 200 ℃ of following crystallization of warp 20 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, product is the ZSM-35 crystal phase structure; The weight content that records La in the molecular sieve through XRF analysis is 4.3%.
Embodiment 11:
(1) raw material:
A. solid silicone (92wt%SiO 2): 6.88g;
B.SB powder (77.5wt%Al 2O 3): 0.70g;
C. sodium hydroxide solution (0.1g NaOH/ml): 10.56ml;
D. deionized water: 132.1g;
E.ZSM-35 crystal seed: 0.21g;
F. Lanthanum trinitrate [La (NO 3) 36H 2O]: 2.16g
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=20, OH -/ Al 2O 3=5.0, H 2O/Al 2O 3=1500, Re 2O 3/ Al 2O 3=0.56, the crystal seed add-on is 3.0% of a raw silicon al oxide quality.
(2) operation steps:
Raw material C, 102.1g deionized water (part of raw material D), raw material B and raw material F are added stainless steel cauldron, and stirring mixes it; Then raw material E is added the 30g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it; Add raw material A at last.With the raw mix sealing, 175 ℃ of crystallization of warp 42 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, product is the ZSM-35 crystal phase structure; Mass content through its La of XRF test, Ce is respectively 3.7% and 4.0%.
Comparative Examples 1
(1) raw material:
A. sodium aluminate solution (NaAlO 2: 16.8wt%Al 2O 3, 31.2wt%NaOH): 4.55g;
B. sodium hydroxide solution (0.1g NaOH/ml): 3.8ml;
C. hexahydroaniline (C 6H 13N): 6.5g;
C. deionized water: 114.8g;
D. solid silicone (92wt%SiO 2): 7.38g;
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=15, OH -/ Al 2O 3=6.0, H 2O/Al 2O 3=900, C 6H 13N/Al 2O 3=8.7.
(2) operation steps:
Raw material A, raw material B are added stainless steel cauldron, and stirring mixes it; Add raw material C and raw material D then successively, stirring mixes it, adds raw material E at last.With the raw mix sealing, 170 ℃ of crystallization of warp 70 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, the result sees Fig. 2, and product is the ZSM-35 crystal phase structure.
Comparative Examples 2
(1) raw material
A. solid silicone (92wt%SiO 2): 25.29g;
B. sodium aluminate solution (NaAlO 2: 16.8wt%Al 2O 3, 31.2wt%NaOH): 19.59g;
C. dilute sulphuric acid (25.6wt%H 2SO 4): 4.53g;
D. deionized water: 100.6g;
E.ZSM-35 crystal seed: 0.53g;
F. Lanthanum trinitrate [La (NO 3) 36H 2O]: 0.84g;
The mole of reaction mixture consists of: SiO 2/ Al 2O 3=12, OH -/ Al 2O 3=4.0, H 2O/Al 2O 3=200, La 2O 3/ Al 2O 3=0.03, the crystal seed add-on is 2.0% of a raw silicon al oxide quality.
(2) operation steps:
Under condition of stirring, in stainless steel cauldron, add raw material B, 70.6g deionized water (part of raw material D), raw material C and raw material F successively, continue stirring it is mixed; Then raw material E is added the 30.0g deionized water, add behind the ultra-sonic dispersion in the said mixture, stirring mixes it, adds raw material A at last.With the raw mix sealing, 160 ℃ of following crystallization of warp 72 hours.Cooling, separation, washing, drying get zeolite sample.Through XRD analysis, the result sees Fig. 3, contains the crystal phase structure of mordenite and ZSM-35 molecular sieve in the product simultaneously.

Claims (6)

1. green synthesis method that contains rare earth ZSM-35 molecular sieve, it is characterized in that: salt, crystal seed and mineral acid or mineral alkali with silicon source, aluminium source, deionized water, REE are initial feed;
Wherein, the mole proportioning of said initial feed is: SiO 2/ Al 2O 3=15～40, OH -/ Al 2O 3=2.5～9.2, H 2O/Al 2O 3=300～2000, RE 2O 3/ Al 2O 3=0.01～0.56, the add-on of crystal seed is the 0.1-10.0% of raw silicon al oxide total mass;
Reaction initial feed mixture crystallization 20～72 hours under the condition of 150～200 ℃ of autogenous pressure and crystallization temperatures, hydro-thermal synthesizes and contains rare earth ZSM-35 molecular sieve.
2. according to the said green synthesis method that contains rare earth ZSM-35 molecular sieve of claim 1, it is characterized in that: said aluminium source is one or more in sodium metaaluminate, the SB powder.
3. according to the said green synthesis method that contains rare earth ZSM-35 molecular sieve of claim 1, it is characterized in that: said silicon source is one or more in solid silicone, silicon sol, water glass, WHITE CARBON BLACK, tetraethoxy, the silicic acid.
4. according to the said green synthesis method that contains rare earth ZSM-35 molecular sieve of claim 1; It is characterized in that: with the potential of hydrogen of mineral acid or mineral alkali regulation system; Said mineral alkali is one or more in sodium hydroxide, the Pottasium Hydroxide, and said mineral acid is one or more in sulfuric acid, hydrochloric acid, the nitric acid.
5. according to the said green synthesis method that contains rare earth ZSM-35 molecular sieve of claim 1, it is characterized in that: said crystal seed is a kind of in ZSM-35 molecular sieve, MCM-22/ZSM-35 cocrystallization molecular sieve or the MCM-49/ZSM-35 cocrystallization molecular sieve.
6. according to the said green synthesis method that contains rare earth ZSM-35 molecular sieve of claim 1, it is characterized in that: the salt of said REE is the hydrochloride of nitrate salt, hydrochloride or the mixed rear earth element of single rare earth element.
CN2010105375015A 2010-11-10 2010-11-10 Green synthetic method for rare earth-containing ZSM-35 molecular sieve Pending CN102464337A (en)

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CN104338554A (en) * 2013-08-01 2015-02-11 中国科学院大连化学物理研究所 Green synthesis method of ZSM-35/MOR eutectic molecular sieve
WO2015021611A1 (en) * 2013-08-14 2015-02-19 中国科学院大连化学物理研究所 Zsm-22 molecular sieve and synthesis method for me-zsm-22
WO2015021610A1 (en) * 2013-08-14 2015-02-19 中国科学院大连化学物理研究所 Zsm-35 molecular sieve and synthesis method for me-zsm-35
CN104370295A (en) * 2013-08-14 2015-02-25 中国科学院大连化学物理研究所 ZSM-35 molecular sieve and Me-ZSM-35 synthesis methods
CN105460949A (en) * 2014-09-09 2016-04-06 中国石油化工股份有限公司 Method for synthesizing rare-earth containing MFI zeolite
EP3240632A4 (en) * 2015-01-04 2018-07-25 Dalian Institute Of Chemical Physics Chinese Academy of Sciences A method for the synthesis of a type of fer/mor composite molecular sieve
CZ307536B6 (en) * 2017-11-02 2018-11-14 Unipetrol výzkumně vzdělávací centrum, a.s. A method of producing zeolite ferrierite
CN110877912A (en) * 2018-09-06 2020-03-13 中国科学院大连化学物理研究所 Rapid synthesis method of FER molecular sieve with controllable size
CN111762794A (en) * 2020-07-13 2020-10-13 包头稀土研究院 Molecular sieve and preparation method thereof
CN112371079A (en) * 2020-11-02 2021-02-19 江苏方天电力技术有限公司 Deteriorated oil regeneration treatment adsorbent and preparation method thereof

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CN104338554A (en) * 2013-08-01 2015-02-11 中国科学院大连化学物理研究所 Green synthesis method of ZSM-35/MOR eutectic molecular sieve
CN104338554B (en) * 2013-08-01 2016-09-07 中国科学院大连化学物理研究所 A kind of green synthesis method of ZSM-35/MOR eutectic molecular sieve
CN104370295A (en) * 2013-08-14 2015-02-25 中国科学院大连化学物理研究所 ZSM-35 molecular sieve and Me-ZSM-35 synthesis methods
WO2015021610A1 (en) * 2013-08-14 2015-02-19 中国科学院大连化学物理研究所 Zsm-35 molecular sieve and synthesis method for me-zsm-35
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
WO2015021611A1 (en) * 2013-08-14 2015-02-19 中国科学院大连化学物理研究所 Zsm-22 molecular sieve and synthesis method for me-zsm-22
CN105460949A (en) * 2014-09-09 2016-04-06 中国石油化工股份有限公司 Method for synthesizing rare-earth containing MFI zeolite
EP3240632A4 (en) * 2015-01-04 2018-07-25 Dalian Institute Of Chemical Physics Chinese Academy of Sciences A method for the synthesis of a type of fer/mor composite molecular sieve
TWI745283B (en) * 2015-01-04 2021-11-11 中國科學院大連化學物理研究所 A method for the synthesis of a type of fer/mor composite molecular sieve
US11260377B2 (en) 2015-01-04 2022-03-01 Bp (China) Holdings Limited Method for synthesizing a FER/MOR composite molecular sieve
CZ307536B6 (en) * 2017-11-02 2018-11-14 Unipetrol výzkumně vzdělávací centrum, a.s. A method of producing zeolite ferrierite
CN110877912A (en) * 2018-09-06 2020-03-13 中国科学院大连化学物理研究所 Rapid synthesis method of FER molecular sieve with controllable size
CN110877912B (en) * 2018-09-06 2023-01-13 中国科学院大连化学物理研究所 Rapid synthesis method of FER molecular sieve with controllable size
CN111762794A (en) * 2020-07-13 2020-10-13 包头稀土研究院 Molecular sieve and preparation method thereof
CN112371079A (en) * 2020-11-02 2021-02-19 江苏方天电力技术有限公司 Deteriorated oil regeneration treatment adsorbent and preparation method thereof

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