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CN108689416A - A kind of preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves - Google Patents

A kind of preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves Download PDF

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Publication number
CN108689416A
CN108689416A CN201810507380.6A CN201810507380A CN108689416A CN 108689416 A CN108689416 A CN 108689416A CN 201810507380 A CN201810507380 A CN 201810507380A CN 108689416 A CN108689416 A CN 108689416A
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zsm
doping
rare earth
earth metal
molecular sieves
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徐霆
岑诗雨
杜立方
刘会康
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Henan Normal University
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Henan Normal University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
    • B01J29/505—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses the preparation method that a kind of rare earth metal Ce adulterates H-ZSM-34 molecular sieves, the preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves is:Silicon source is added in water, continuously adds alkali source, silicon source, is aged after stirring and obtains clear seed-solution.Aluminum sulfate crystal is sequentially added after sequentially adding sodium hydroxide, the stirring of water-soluble silica gel in the aqueous solution of certain volume and the seed-solution of certain volume obtains precursor liquid.Ce (the NO into precursor liquid3)3·6H2O solids.It stirs at room temperature, enters kettle, crystallization goes out kettle, and filtering and washing is dry, and air roasting obtains the Na-ZSM-34 of Ce doping.The Ce Na-ZSM-34 adulterated are added in ammonium nitrate solution, are stirred, filtering and washing, it is dry.It is repeated four times after ammonium exchanges and obtains NH4-ZSM-34.Through air roasting, rare earth metal Ce doping H-ZSM-34 molecular sieves are obtained.Ce adulterates H-ZSM-34 molecular sieves, and conversion ratio is up to 78.9% in chloromethane, and Propylene Selectivity is up to 40.6%, and propene yield is up to 32%, and without deactivation phenomenom in 7h.Have the advantages that simple process, production efficiency are high.

Description

A kind of preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves
Technical field
The present invention relates to energy catalytic fields, and in particular to a kind of preparation of rare earth metal Ce doping H-ZSM-34 molecular sieves Method.
Background technology
Propylene can be used for producing polypropylene, propylene oxide, acetone, isopropanol, phenol, and the important chemical products such as glycerine are The indispensable Chemical Manufacture raw material of development of modern society economy, however the less efficient of propylene is prepared at present, cause for not answering It asks, it is therefore desirable to the method for the efficient production propylene of exploitation.
The production path of halide propylene is ripe at present, and halide propylene needs molecular sieve catalyst, Although this method improves the yield of propylene, but due to the pore passage structure of molecular sieve catalyst, acidity etc., it is made to be easy Inactivation, therefore it is particularly important to prepare long catalytic life, stability is good, catalytic performance is high molecular sieve catalyst.
Invention content
The present invention adulterates H-ZSM-34 to overcome the shortcomings of that existing molecular sieve catalyst provides a kind of rare earth metal Ce The preparation method of molecular sieve.
Realize that technical solution of the invention is:Include the following steps:
1. the preparation of precursor liquid:Silicon source, alkali source, silicon source and water are uniformly mixed, ageing obtains mixture A;By water, sodium hydroxide Mixture B is obtained after being stirred with water-soluble silica gel, aluminum sulfate crystal and mixture A are added into mixture B, obtains precursor liquid;
2. after precursor liquid is stirred 0.5 h, Ce (NO are added into precursor liquid3)3·6H2O stirs 13 h, enters at room temperature Kettle, 120 DEG C of 7 d of crystallization go out kettle, filtering and washing, 100 DEG C of dryings, and 550 DEG C of 6 h of air roasting obtain the Na- of Ce doping ZSM-34;
3. the Ce Na-ZSM-34 adulterated are added in ammonium nitrate solution, 80 DEG C of 3 h of stirring, filtering and washing, by what is obtained Solid is in 100 DEG C of dryings;
4. repetitive operation step 3. four times(It is repeated four times ammonium exchange)The NH of Ce doping is obtained afterwards4-ZSM-34;
5. the NH of Ce doping4- ZSM-34 obtains rare earth metal Ce doping H-ZSM-34 molecular sieves through 6 h of air roasting.
Preferably, 1. middle silicon source is sodium metaaluminate to the step, and silicon source is water-soluble silica gel, and alkali source is sodium hydroxide and hydrogen-oxygen Change potassium.
Preferably, the step 2. in press Ce/Al(Molar ratio)=0.06~0.08:Ce is added into precursor liquid for 1 ratio (NO3)3·6H2O solids.
Preferably, the step 3. in be added ammonium nitrate solution a concentration of 1mol/L.
Preferably, 5. air roasting temperature is 550 DEG C to the step.
Preferably, mole group of mixture A becomes n (Al2O): n(Na2O): n(K2O):n(SiO2):n(H2O) =1: 5.1:9.13:10.54: 129.98。
The advantageous effect that the present invention generates compared with the existing technology is:Rare earth metal Ce doping H-ZSM-34 molecular sieves have Unique pore passage structure, suitable acidity, good stability and larger specific surface area are the reactions of chloromethane propylene In potential excellent catalysts.In addition to this catalysis that can be also used for hydro carbons, has wide range of applications.In addition rare earth metal On the basis of so that the molecular sieve stability improves, and catalytic performance improves, and the service life is elongated.H-ZSM-34 points of rare earth metal Ce doping Conversion ratio is up to 78.9% in chloromethane for son sieve, and Propylene Selectivity is up to 40.6%, and propene yield is up to 32%, and in 7h There is no deactivation phenomenom.And this method has the advantages that simple process, production efficiency are high.
Specific implementation mode
The specific implementation mode of form by the following examples is described in further details the above of the present invention, But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to embodiment below, all to be based on the above of the present invention The technology of realization all belongs to the scope of the present invention.Water-soluble silica gel used in following embodiment is purchased from the limited public affairs of Qingdao Haiyang chemical industry Department, trade name:JN-40, alkaline 40% purity Ludox.
Embodiment 1
A kind of preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves, includes the following steps:
1. by 3.5 g NaAlO2, 7 g NaOH, the 22 water-soluble silica gel of g KOH, 67.5 g are added sequentially to 100 m L water In, 0.5 h is stirred, mixture is aged 3 days, clear seed-solution is obtained(Mixture A);By 5.54 g NaOH, The water-soluble silica gel of 28.85 g is added sequentially in 83 m L water, is stirred 5 h, is sequentially added 2.71 g Al2(SO4)3· 18H2O and 10m L mixtures A obtains precursor liquid;
2. after precursor liquid is stirred 0.5 h, in the ratio of Ce/Al=0.06, Ce (NO are added into precursor liquid3)3·6H2O is solid Body stirs 13 h at room temperature, enters kettle, and 120 DEG C of 7 d of crystallization go out kettle, filtering and washing, 100 DEG C of dryings, 550 DEG C of air roastings 6 h obtain the Na-ZSM-34 of Ce doping;
3. the 2g Ce Na-ZSM-34 adulterated are added in 40 mL 1mol/L ammonium nitrate solutions, 80 DEG C of 3 h of stirring take out Filter washing, obtained solid is 5 hours dry at 100 DEG C;
4. 3. repetitive operation step obtains the NH of Ce doping after four times4-ZSM-34;
5. through 6 h of air roasting, rare earth metal Ce doping H-ZSM-34 molecular sieves are obtained.
Rare earth metal Ce doped molecular sieve H-ZSM-34 catalyst prepared by embodiment 1 is for chloromethane propylene It reacts, conversion ratio is up to 64.4% in chloromethane, and up to 35.7%, propene yield does not have up to 23% in 6h Propylene Selectivity There is deactivation phenomenom.
Embodiment 2
A kind of preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves, includes the following steps:
1. by 3.5 g Na Al O2, 7 g NaOH, the 22 water-soluble silica gel of g KOH, 67.5 g are added sequentially to 100 m L water In, stir 0.5 h.Mixture is aged 3 days, clear seed-solution is obtained(Mixture A);By 5.54 g NaOH, The water-soluble silica gel of 28.85 g is added sequentially in 83 m L water, is stirred 5 h, is sequentially added 2.71 g Al2(SO4)3· 18H2O and 10m L mixtures A obtains precursor liquid;
2. after precursor liquid is stirred 0.5 h, in the ratio of Ce/Al=0.07, Ce (NO are added into precursor liquid3)3·6H2O is solid Body stirs 13 h at room temperature, enters kettle, and 120 DEG C of 7 d of crystallization go out kettle, filtering and washing, 100 DEG C of dryings, 550 DEG C of air roastings 6 h obtain the Na-ZSM-34 of Ce doping;
3. the 2g Ce Na-ZSM-34 adulterated are added in 40 mL 1mol/L ammonium nitrate solutions, 80 DEG C of 3 h of stirring take out Filter washing, obtained solid is 5 hours dry at 100 DEG C;
4. 3. repetitive operation step obtains the NH of Ce doping after four times4-ZSM-34;
5. through 6 h of air roasting, rare earth metal Ce doping H-ZSM-34 molecular sieves are obtained.
Rare earth metal Ce doped molecular sieve H-ZSM-34 catalyst prepared by embodiment 2 is for chloromethane propylene Reaction, conversion ratio is up to 66.4% in chloromethane, and Propylene Selectivity is up to 35.9%, and propene yield is up to 23.8%, and in 7h There is no deactivation phenomenom.
Embodiment 3
A kind of preparation method of rare earth metal Ce doped molecular sieves H-ZSM-35, includes the following steps:
1. by 3.5 g Na Al O2, 7 g NaOH, the 22 water-soluble silica gel of g KOH, 67.5 g are added sequentially to 100 m L water In, 0.5 h is stirred, mixture is aged 3 days, clear seed-solution is obtained(Mixture A);By 5.54 g NaOH, The water-soluble silica gel of 28.85 g is added sequentially in 83 m L water, is stirred 5 h, is sequentially added 2.71 g Al2(SO4)3· 18H2O and 10m L mixtures A obtains precursor liquid;
2. after precursor liquid is stirred 0.5 h, in the ratio of Ce/Al=0.08, Ce (NO are added into precursor liquid3)3·6H2O is solid Body stirs 13 h at room temperature, enters kettle, and 120 DEG C of 7 d of crystallization go out kettle, filtering and washing, 100 DEG C of dryings, 550 DEG C of air roastings 6 h obtain the Na-ZSM-34 of Ce doping;
3. the 2g Ce Na-ZSM-34 adulterated are added in 40 mL 1mol/L ammonium nitrate solutions, 80 DEG C of 3 h of stirring take out Filter washing, obtained solid is 5 hours dry at 100 DEG C;
4. 3. repetitive operation step obtains the NH of Ce doping after four times4-ZSM-34;
5. through 6 h of air roasting, rare earth metal Ce doping H-ZSM-34 molecular sieves are obtained.
Rare earth metal Ce doped molecular sieve H-ZSM-34 catalyst prepared by embodiment 3 is for chloromethane propylene Reaction, chloromethane conversion ratio is up to 78.9%, and up to 40.6%, propene yield does not have up to 32% in 7h Propylene Selectivity Deactivation phenomenom.
Above example is explained and is described to the synthetic ratio and method of modifying of the present invention, and of the present invention one The preparation method of kind rare earth metal Ce doped molecular sieves H-ZSM-34 provides the rare earth gold that catalytic performance is preferable, lasts a long time Belong to Ce doped molecular sieves, when Ce/Al=0.08 constantly, prepared rare earth metal Ce doped molecular sieve H-ZSM-34 performances are best, Longest-lived, in the reaction of chloromethane propylene, for chloromethane conversion ratio up to 78.9%, Propylene Selectivity is reachable 40.6%, propene yield is up to 32%, and without deactivation phenomenom in 7h.This method is simple for process, method is convenient, has good Application prospect.

Claims (7)

1. a kind of preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves, which is characterized in that include the following steps:
1. the preparation of precursor liquid:Silicon source, alkali source, silicon source and water are uniformly mixed, ageing obtains mixture A;By water, sodium hydroxide Mixture B is obtained after being stirred with water-soluble silica gel, aluminum sulfate crystal and mixture A are added into mixture B, obtains precursor liquid;
2. after precursor liquid is stirred 0.5 h, Ce (NO are added into precursor liquid3)3·6H2O stirs 13 h, enters at room temperature Kettle, 120 DEG C of 7 d of crystallization go out kettle, filtering and washing, 100 DEG C of dryings, and 550 DEG C of 6 h of air roasting obtain the Na- of Ce doping ZSM-34;
3. the Ce Na-ZSM-34 adulterated are added in ammonium nitrate solution, 80 DEG C of 3 h of stirring, filtering and washing, by what is obtained Solid is in 100 DEG C of dryings;
4. 3. repetitive operation step obtains the NH of Ce doping after four times4-ZSM-34;
5. through 6 h of air roasting, rare earth metal Ce doping H-ZSM-34 molecular sieves are obtained.
2. the preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves as described in claim 1, it is characterised in that:The step Suddenly 1. middle silicon source is sodium metaaluminate, and silicon source is water-soluble silica gel, and alkali source is sodium hydroxide and potassium hydroxide.
3. the preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves as described in claim 1, it is characterised in that:The step Suddenly 2. in the ratio of Ce/Al=0.06 ~ 0.08 Ce (NO are added into precursor liquid3)3·6H2O solids.
4. the preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves as described in claim 1, it is characterised in that:The step The rapid 3. middle a concentration of 1mol/L that ammonium nitrate solution is added.
5. the preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves as described in claim 1, it is characterised in that:The step Suddenly 5. air roasting temperature is 550 DEG C.
6. the preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves as described in claim 1, it is characterised in that:Mixture Mole group of A becomes n (Al2O): n(Na2O): n(K2O):n(SiO2):n(H2O) =1:5.1:9.13:10.54: 129.98。
7. adulterating H-ZSM-34 molecular sieves using rare earth metal Ce prepared by claim 1-6 either method.
CN201810507380.6A 2018-05-24 2018-05-24 A kind of preparation method of rare earth metal Ce doping H-ZSM-34 molecular sieves Pending CN108689416A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0198437A2 (en) * 1985-04-16 1986-10-22 BASF Aktiengesellschaft Crystalline zeolite borosilicate catalysts, process for their preparation and their use
CN106673000A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 Synthesis method of ZSM-11 molecular sieve comprising rare earth metals and synthesized molecular sieve
CN107500312A (en) * 2017-08-10 2017-12-22 河南师范大学 A kind of fluorine richness molecular sieve H ZSM 35 and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0198437A2 (en) * 1985-04-16 1986-10-22 BASF Aktiengesellschaft Crystalline zeolite borosilicate catalysts, process for their preparation and their use
CN106673000A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 Synthesis method of ZSM-11 molecular sieve comprising rare earth metals and synthesized molecular sieve
CN107500312A (en) * 2017-08-10 2017-12-22 河南师范大学 A kind of fluorine richness molecular sieve H ZSM 35 and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
徐霆: ""改性分子筛催化剂上卤代甲烷制备丙烯和乙烯的研究"", 《万方数据知识服务平台》 *

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