CN104556133B - Montmorillonite-based ZSM-5 molecular sieve composite material and preparation method thereof - Google Patents
Montmorillonite-based ZSM-5 molecular sieve composite material and preparation method thereof Download PDFInfo
- Publication number
- CN104556133B CN104556133B CN201510044730.6A CN201510044730A CN104556133B CN 104556133 B CN104556133 B CN 104556133B CN 201510044730 A CN201510044730 A CN 201510044730A CN 104556133 B CN104556133 B CN 104556133B
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- molecular sieve
- zsm
- composite material
- preparation
- 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.)
- Active
Links
Abstract
The invention relates to a molecular sieve and a preparation method thereof and in particular relates to a montmorillonite-based ZSM-5 molecular sieve composite material and a preparation method thereof. The preparation method comprises the following steps: heating a mixture of inorganic montmorillonite, an organic intercalator and water and collecting obtained organic modified montmorillonite from solution; then providing all of aluminium sources and part of silicoin sources with the organic modified montmorillonite as a raw material, and adding part of silicon sources, strong base and water to obtain the montmorillonite-based ZSM-5 molecular sieve composite material under the condition of hydrothermal crystallization. The preparation method provided by the invention is low in energy consumption, low in environment pollution, simple in preparation process and low in cost. The obtained product is good in hydrothermal stability and high in activity. An in situ crystallization technology is adopted, and the ZSM-5 molecular sieve is formed on montmorillonite so that the ZSM-5 molecular sieve is connected with the montmorillonite in a chemical bond manner; and the ZSM-5 molecular sieve is uniformly distributed on the montmorillonite matrix so that the composite material is high in activity and good in hydrothermal stability.
Description
Technical field
The present invention relates to a kind of molecular sieve and its technology of preparing, specially montmorillonite base ZSM-5 molecular sieve composite material and
Its preparation method.
Background technology
ZSM-5 zeolite molecular sieve is that Mobil company has unique three-dimensional channel design in what 20 century 70s were developed
High silicon five-membered ring (Pentasil type) zeolite.Due to the regular microcellular structure of its uniqueness, high hydrothermal stability, strong acidity and
Anti-carbon deposition ability and excellent selectivity and be widely used as FCC catalyst auxiliary agent, meet oil refining enterprise and reduce gasoline alkene
Hydrocarbon content, the needs of the production low-carbon alkene such as high-knock rating gasoline or producing more propylene.Currently utilize industrial chemicals synthesis ZSM-5 boiling
The technology of stone molecular sieve is quite ripe, and finds more economic, effective synthesis material, especially with cheap natural
Raw mineral materials carrys out synthesis zeolite just becomes focus of concern.
China's natural minerals, such as Kaolin, montmorillonite and kieselguhr etc., aboundresources, but in the process of exploitation
Middle generally existing that deep processed product quality is low, and technological level is low, the outstanding problem such as deficiency in economic performance.Although by Kaolin
Deng natural minerals through high-temperature roasting or acid-alkali treatment activation after as synthesis zeolite part silicon and aluminum source, for synthesize A,
The report of the low silica-alumina ratio molecular sieve such as X and Y type, but because the natural minerals such as Kaolin have crystal structure, silicon-oxy tetrahedron
Aluminum in silicon in subgrade and alumina octahedral subgrade is all relatively stable, occurs chemical reaction relatively difficult with soda acid.Institute
With it is often necessary to it be carried out with high-temperature roasting process activation or acid-alkali treatment activation destroying its intrinsic crystal structure, thus
Obtain required activated silica silicon source.Therefore, it is usually present in natural minerals for the activation process of Material synthesis zeolite molecular sieve
Energy consumption is higher, and acid-alkali treatment environmental pollution is serious, the silicon and aluminum source in mineral fails to be effectively utilized because being dissolved in acid-base solution
The problems such as.
Montmorillonite popular name, bentonite, is the aqueous aluminosilicate mineral containing a small amount of alkali and alkaline-earth metal.With other states
Family compares, the montmorillonite aboundresources of current China, and explored reserves now rank first in the world.The main component of montmorillonite is
Montmorillonite, belongs to 2:The clay of laminar silicate mineral of 1 type three-decker, preferable chemical composition is Al4Si8O2(OH)4.nH2O.Its unit cell presss from both sides one layer of alumina (Al-O) octahedron by two layers of silica (Si-O) tetrahedron and forms.Silicon-oxy tetrahedron with
Alumina octahedral is connected by sharing oxygen atom, structure cell parallel stacked, the Si in silicon-oxy tetrahedron4+Ion and alumina octahedral
The middle Al of body lattice3+Easily isomorphous substitution is occurred to replace by other low price cationes, so that montmorillonite lamella carries
Negative charge, and the negative charge of surplus relies on absorption to be free on the Na of montmorillonite piece interlayer+、K+、Ca2+And Mg2+Reach etc. cation
Charge balance.These calcium between cheating engaging layer, magnesium, potassium, sodium plasma, they are easily replaced by organic cation.So covering de-
Native interlamination region is a special chemical reaction place, is exchanged by interlayer ion, the physico-chemical process such as interlayer is pillared, can make
There is corresponding change in its structure and property.
CN 101239325A discloses a kind of preparation method of montmorillonite/ZSM-5 molecular sieve composite material, discloses profit
Be that raw material provides all or part of silicon source with the refined montmorillonite after natural montmorillonite or flotation, more additional silicon source, silicon source, alkali and
The Material synthesis such as directed agents have gone out the montmorillonite/ZSM-5 molecular sieve composite material of ZSM-5 molecular sieve with small crystal grains type.CN
1803613A discloses a kind of type ZSM 5 molecular sieve and preparation method thereof, with through acid-alkali treatment and high-temperature roasting perlite,
The natural minerals such as montmorillonite are raw material, achieve the growth in situ of ZSM-5 molecular sieve by the method for plus seed.CN
101462740A, CN1798608A and CN 101239327A etc. is all with the Kaolin of high-temperature roasting activation for raw material fabricated in situ
Molecular sieve.CN 101722024A and CN 101723405A is with the tired de- stone of high-temperature roasting activation for raw material fabricated in situ ZSM-
5 molecular sieves.
Above patent is all by the natural minerals of the activity after high-temperature roasting process or acid-alkali treatment for raw material in situ
Synthesis of molecular sieve.High-temperature activation or soda acid activation bring the problems such as high energy consumption, pollution environment, high cost.
Content of the invention
For above-mentioned technical problem, the present invention provides that a kind of low cost, pollution be little, energy consumption is low prepares ZSM-5 molecular sieve
The method of composite, concrete technical scheme is：
The preparation method of montmorillonite base ZSM-5 molecular sieve composite material, comprises the following steps：
(1) organ-mmt is modified
Inorganic montmorillonite is dissolved in water, forms inorganic montmorillonite aqueous solution；
Again organic intercalation agent is dissolved in water, forms aqueous intercalant；
Mix inorganic montmorillonite aqueous solution and organic intercalation agent aqueous solution, heat at 60～90 DEG C with mechanical agitation
0.5～3 hour, form organo montmorillonite aqueous solution；Montmorillonite, organic intercalation agent, water in mass ratio be 1: 0.1～0.8: 40～
80 proportionings；
Described inorganic montmorillonite aqueous solution carries out purification, modification, drying and grinding, obtains organic modification montmonrillonite；
(3) prepare montmorillonite base ZSM-5 molecular sieve composite material
SiO2、Na2O、H2O is 8～11 according to mol ratio：0.8～2.0：350～650 are made into liquid reaction mixture；
Add organic modification montmonrillonite in liquid reaction mixture, according to weight ratio, organic modification montmonrillonite：SiO2With
Na2O total amount is 0.5～5：1, after mix homogeneously, regulation system pH value is 9～14；
Between 110 DEG C～200 DEG C of crystallization temperature, crystallization time carried out crystallization between 24～120 hours；
Reaction carries out cooling down after terminating, sucking filtration, washing, drying, roasting, that is, obtain montmorillonite base ZSM-5 molecular sieve and be combined
Material；Wherein sintering temperature is 550 DEG C, and the time is 6 hours.
Described organic intercalation agent is one of quaternary ammonium salt, specially 4-propyl bromide, TPAOH, four
Ethyl ammonium hydroxide, tetraethylammonium bromide etc..
Inorganic montmorillonite is calcium-base montmorillonite or sodium-based montmorillonite.
For comparing other natural minerals, montmorillonite has more exchangeable cations because of piece interlayer, therefore can utilize this
Plant characteristic and organically-modified activation is carried out to it, in advance by the organic formwork agent tetrapropyl ammonium ion needed for synthesis ZSM-5 molecular sieve
Be incorporated into the piece interlayer of montmorillonite, then more outside strengthen alkali and silicon source etc. under the conditions of in hydrothermal crystallization process ZSM-5 divide
The lamellar structure of all montmorillonites is gradually all strutted in growth process by son sieve nucleus, but may not be kept completely separate, thus
Reach the effect destroying montmorillonite crystal structure, so not only can avoid the high energy bringing by high-temperature activation or soda acid activation
The problems such as consumption, pollution environment, and due to template TPA+With montmorillonite layer with chemical bonding so that generate ZSM-5
Molecular sieve still can be bonded with chemistry with some undissolved montmorillonite layers, is equivalent to ZSM-5 molecular sieve at these not
Growth in situ on the montmorillonite layer being completely dissolved, and it is limited by the dissolving limit of the raw material such as silicon source and silicon source in lamellar aluminosilicate
System so that generated in-situ ZSM-5 molecular sieve and not have dissolving remaining montmorillonite fragment be mutually gathered in one piece, finally
Obtain ZSM-5/MMT composite.
There is provided whole silicon sources and part silicon source through the modified montmorillonite of organic intercalation agent for raw material, without high-temperature activation
Or soda acid activation, without additionally adding organic formwork agent again, silicon source is supplemented with silicic acid, silicate or Ludox etc. former in hydro-thermal
Can achieve under the crystallization condition of position, this composite is provided simultaneously with montmorillonite and the XRD spectra of ZSM-5 molecular sieve, wherein ZSM-5
The content of molecular sieve is 10wt%～50wt%, the scanning electron microscope (SEM) to this composite and x-ray diffraction
(XRD) analysis shows, montmorillonite and ZSM-5 molecular sieve alternate in this complex, montmorillonite is dispersed in ZSM-5 molecular sieve substrate
In, ZSM-5 molecular sieve is grown in around montmorillonite.
The preparation method of the montmorillonite base ZSM-5 molecular sieve composite material that the present invention provides, energy consumption is low, environmental pollution is little,
Preparation flow is simple, and montmorillonite activation aspect adopts organically-modified method, and the activity that improve montmorillonite also will synthesize ZSM-5 molecule
The required organic intercalation agent of sieve introduces reaction system, simplifies preparation flow, avoid simultaneously high-temperature activation cause high energy consumption and
The shortcomings of soda acid activation causes acid-base waste fluid pollution environment；The montmorillonite using is in China's rich reserves, cheap；Gained produces
Product good hydrothermal stability, activity is high, and using in-situ crystallization technology, in montmorillonite, crystallization forms ZSM-5 molecular sieve so that ZSM-
It is connected in chemical bond mode between 5 molecular sieves and montmorillonite, ZSM-5 molecular sieve is evenly distributed in montmorillonite substrate simultaneously,
Make activity height, the good hydrothermal stability of composite.
Brief description
Fig. 1 is the XRD spectra of the embodiment of the present invention 1 products therefrom；
Fig. 2 is the electromicroscopic photograph of the embodiment of the present invention 1 products therefrom.
Specific embodiment
With reference to embodiment, the present invention is further detailed, but is not limited to the embodiment of the present invention.
Embodiment 1
(1) preparation of organo montmorillonite
The montmorillonite taking 4.5 grams is dissolved in 300ml deionized water, obtains solution A after being uniformly mixed, then in stirring
In the case of be warming up to 80 DEG C.The TPABr 4-propyl bromide simultaneously weighing 1.3g is dissolved in 50ml deionized water, after stirring
Solution B.It is stirred vigorously and middle solution B is added dropwise over solution A.After mix homogeneously, 80 DEG C of constant temperature continue moderate-speed mixer 1.5 hours with
Guarantee that ion exchange reaches balance, sucking filtration after cooling, it is dried, obtains organo montmorillonite, grind sieving for standby.
(2) preparation of montmorillonite base ZSM-5 molecular sieve composite material
Weigh 0.28g sodium hydroxide first to be dissolved in the distilled water of 25ml, then weighing 2.74g silicic acid, to be added to NaOH molten
In liquid, after magnetic agitation mix homogeneously, it is slow added into 2.32g organic modification montmonrillonite, finally use sodium hydroxide regulation system
PH=13.After continuing stirring 30min, mixture gel is poured into in teflon-lined autoclave, seals kettle,
It is placed in 170 DEG C of baking ovens, hydrothermal crystallizing 72 hours, solid product is through filtering, washing, be dried, 550 DEG C in Muffle furnace
Roasting 6h, obtains montmorillonite base ZSM-5 molecular sieve composite material after being cooled to room temperature.
The property of montmorillonite base ZSM-5 molecular sieve composite material is spread out by X ' the Pert PRO MPD of Dutch PANalytical company
Penetrate instrument and Hitachi S4800 type field emission scanning electron microscope is characterized.Experiment condition：Pipe is pressed as 40kV, and tube current is
40mA.
The XRD spectra of this montmorillonite base ZSM-5 molecular sieve composite material and scanning electron microscope as depicted in figs. 1 and 2,
It will be seen from figure 1 that the characteristic peak of montmorillonite and ZSM-5 molecular sieve is suitable in this montmorillonite base ZSM-5 molecular sieve composite material
Substantially.Figure it is seen that ZSM-5 molecular sieve grain growth is around montmorillonite layer.By XRD quantitative analyses,
In this composite, the content of ZSM-5 molecular sieve is about 30%.
Embodiment 2
(1) preparation of organo montmorillonite
The montmorillonite taking 4.5 grams is dissolved in 300ml deionized water, obtains solution A after being uniformly mixed, then in stirring
In the case of be warming up to 80 DEG C.The TPABr simultaneously weighing 0.65g is dissolved in 50ml deionized water, obtains solution B after stirring.Acutely
In stirring, solution B is added dropwise over solution A.After mix homogeneously, 80 DEG C of constant temperature continue moderate-speed mixer and are handed over guaranteeing ion for 1.5 hours
Change and reach balance, sucking filtration after cooling, it is dried, obtains organo montmorillonite, grind sieving for standby.
(2) preparation of montmorillonite base ZSM-5 molecular sieve composite material
Weigh 0.28g sodium hydroxide first to be dissolved in the distilled water of 25ml, then weighing 2.74g silicic acid, to be added to NaOH molten
In liquid, after magnetic agitation mix homogeneously, it is slow added into 2.32g organic modification montmonrillonite, finally use sodium hydroxide regulation system
PH=13.After continuing stirring 30min, mixture gel is poured into in teflon-lined autoclave, seals kettle,
It is placed in 170 DEG C of baking ovens, hydrothermal crystallizing 72 hours, solid product is through filtering, washing, be dried, 550 DEG C in Muffle furnace
Roasting 6h, obtains montmorillonite base ZSM-5 molecular sieve composite material after being cooled to room temperature.
In this composite, the content of ZSM-5 molecular sieve is about 25%.
Embodiment 3
(1) preparation of organo montmorillonite
The montmorillonite taking 4.5 grams is dissolved in 300ml deionized water, obtains solution A after being uniformly mixed, then in stirring
In the case of be warming up to 80 DEG C.The TPABr simultaneously weighing 1.3g is dissolved in 50ml deionized water, obtains solution B after stirring.Acutely stir
Mix and middle solution B is added dropwise over solution A.After mix homogeneously, 80 DEG C of constant temperature continue moderate-speed mixer 1.5 hours to guarantee ion exchange
Reach balance, sucking filtration after cooling, it is dried, obtains organo montmorillonite, grind sieving for standby.
(2) preparation of montmorillonite base ZSM-5 molecular sieve composite material
Weigh 0.28g sodium hydroxide first to be dissolved in the distilled water of 25ml, then weighing 2.74g silicic acid, to be added to NaOH molten
In liquid, after magnetic agitation mix homogeneously, it is slow added into 2.32g organic modification montmonrillonite, finally use sodium hydroxide regulation system
PH=13.After continuing stirring 30min, mixture gel is poured into in teflon-lined autoclave, seals kettle,
It is placed in 170 DEG C of baking ovens, hydrothermal crystallizing 24 hours, solid product is through filtering, washing, be dried, 550 DEG C in Muffle furnace
Roasting 6h, obtains montmorillonite base ZSM-5 molecular sieve composite material after being cooled to room temperature.
In this composite, the content of ZSM-5 molecular sieve is about 18%.
Claims (3)
1. the preparation method of montmorillonite base ZSM-5 molecular sieve composite material is it is characterised in that comprise the following steps：
(1) organ-mmt is modified
Inorganic montmorillonite is dissolved in deionized water, after stirring, obtains inorganic montmorillonite aqueous solution, under agitation will be no
Machine montmorillonite aqueous solution is warming up to 80 DEG C；
Organic intercalation agent is dissolved in deionized water, after stirring, obtains aqueous intercalant；
With stirring, described aqueous intercalant is added dropwise in described inorganic montmorillonite aqueous solution, then continues at 80 DEG C
Continuous stirring 0.5～3 hour, obtains organo montmorillonite aqueous solution；When preparing described organo montmorillonite aqueous solution, each raw material dosage
Mass ratio is, montmorillonite：Organic intercalation agent：Water=1: 0.1～0.8: 40～80；
After described organo montmorillonite aqueous solution is cooled down, then sieve through sucking filtration, drying, grinding, obtain organic modification montmonrillonite；
Described organic intercalation agent is the quaternary ammonium salt organic formwork agent for synthesizing ZSM-5 molecular sieve；
(2) prepare montmorillonite base ZSM-5 molecular sieve composite material
SiO2、Na2O、H2O is made into liquid reaction mixture according to mol ratio for 8～11: 0.8～2.0: 350～650；
Add organic modification montmonrillonite in liquid reaction mixture, according to weight ratio, organic modification montmonrillonite：SiO2And Na2O
Total amount is 0.5～5: 1, and after mix homogeneously, regulation system pH value is 9～14；
Between 110 DEG C～200 DEG C of crystallization temperature, crystallization time carried out crystallization between 24～120 hours；
Reaction carries out cooling down after terminating, sucking filtration, washing, drying, roasting, that is, obtain montmorillonite base ZSM-5 molecular sieve composite material；
Wherein sintering temperature is 550 DEG C, and the time is 6 hours.
2. the preparation method of montmorillonite base ZSM-5 molecular sieve composite material according to claim 1 is it is characterised in that institute
The organic intercalation agent stated is 4-propyl bromide, TPAOH, tetraethyl ammonium hydroxide, in tetraethylammonium bromide one
Kind.
3. montmorillonite base ZSM-5 molecular sieve composite material according to claim 1 and 2 preparation method it is characterised in that
Described inorganic montmorillonite is calcium-base montmorillonite or sodium-based montmorillonite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510044730.6A CN104556133B (en) | 2015-01-29 | 2015-01-29 | Montmorillonite-based ZSM-5 molecular sieve composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510044730.6A CN104556133B (en) | 2015-01-29 | 2015-01-29 | Montmorillonite-based ZSM-5 molecular sieve composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104556133A CN104556133A (en) | 2015-04-29 |
| CN104556133B true CN104556133B (en) | 2017-02-22 |
Family
ID=53073340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510044730.6A Active CN104556133B (en) | 2015-01-29 | 2015-01-29 | Montmorillonite-based ZSM-5 molecular sieve composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104556133B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776246A (en) * | 2016-01-28 | 2016-07-20 | 中国石油大学(华东) | Method for low-cost synthesis of ZSM-5 molecular sieve |
| CN106006663B (en) * | 2016-05-13 | 2018-06-29 | 北京化工大学 | A kind of metal atom doped molecular sieve column montmorillonite composite material and preparation method |
| CN106495175A (en) * | 2016-12-23 | 2017-03-15 | 仲恺农业工程学院 | A kind of preparation method of organic modification montmonrillonite |
| CN113751058B (en) * | 2021-09-28 | 2023-12-01 | 无锡威孚环保催化剂有限公司 | Preparation method of Pd/ZSM-5 catalyst |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803613A (en) * | 2005-12-30 | 2006-07-19 | 中国石油大学(北京) | ZSM-5 type molecular sieve and method for preparing the same |
| DE102006018679A1 (en) * | 2005-04-19 | 2006-10-26 | Tricat Zeolites Gmbh | Preparation of zeolite beta from a layer silicate comprises intercalating a template in the layer silicate, and converting the solid powder to the zeolite beta |
| CN101797516A (en) * | 2009-02-06 | 2010-08-11 | 中国石油天然气股份有限公司 | Method for preparing ZSM-5 zeolite/clay composite catalytic material |
| CN102240572A (en) * | 2010-05-10 | 2011-11-16 | 北京化工大学 | Preparation method of composite material of montmorillonite-aluminium phosphate molecular sieve |
| CN103253684A (en) * | 2012-02-16 | 2013-08-21 | 中国石油天然气股份有限公司 | Method for in-situ crystallized synthesis of small-grain ZSM-5 molecular sieve by using direct method |
| CN103359759A (en) * | 2012-03-26 | 2013-10-23 | 中国石油天然气集团公司 | Preparation method of ZSM-5 molecular sieve with multi-level pore channel structure |
-
2015
- 2015-01-29 CN CN201510044730.6A patent/CN104556133B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006018679A1 (en) * | 2005-04-19 | 2006-10-26 | Tricat Zeolites Gmbh | Preparation of zeolite beta from a layer silicate comprises intercalating a template in the layer silicate, and converting the solid powder to the zeolite beta |
| CN1803613A (en) * | 2005-12-30 | 2006-07-19 | 中国石油大学(北京) | ZSM-5 type molecular sieve and method for preparing the same |
| CN101797516A (en) * | 2009-02-06 | 2010-08-11 | 中国石油天然气股份有限公司 | Method for preparing ZSM-5 zeolite/clay composite catalytic material |
| CN102240572A (en) * | 2010-05-10 | 2011-11-16 | 北京化工大学 | Preparation method of composite material of montmorillonite-aluminium phosphate molecular sieve |
| CN103253684A (en) * | 2012-02-16 | 2013-08-21 | 中国石油天然气股份有限公司 | Method for in-situ crystallized synthesis of small-grain ZSM-5 molecular sieve by using direct method |
| CN103359759A (en) * | 2012-03-26 | 2013-10-23 | 中国石油天然气集团公司 | Preparation method of ZSM-5 molecular sieve with multi-level pore channel structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104556133A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105016355B (en) | A kind of molecular sieves of FeZSM 5 and its synthetic method | |
| CN103848439B (en) | Synthetic method of ZSM-5 type molecular sieve | |
| CN106622359B (en) | A kind of SSZ-39/ZSM-5 composite molecular screen and its synthetic method and application | |
| CN102502696B (en) | Synthetic method of ZSM-5 zeolites | |
| CN107555446A (en) | A kind of preparation method of multi-stage porous Y type molecular sieve | |
| CN104556133B (en) | Montmorillonite-based ZSM-5 molecular sieve composite material and preparation method thereof | |
| CN106185977A (en) | A kind of method of green syt ZSM 5 molecular sieve | |
| CN1733605A (en) | Method of synthesizing crystalline metalloalunimo-silicate salt by direct synthesis | |
| CN1930083A (en) | Synthesis of ZSM-48 crystals with heterostructural, non ZSM-48, seeding | |
| CN101717095A (en) | Synthesizing method of small-crystal particle rare earth-ZSM5/ZSM11 co-crystallizing zeolite | |
| CN1041508C (en) | Improved zeolite | |
| CN106830003B (en) | SSZ-13/SCM-9 composite molecular screen and its synthetic method | |
| CN103787355B (en) | Beta molecular sieve synthesizing method | |
| CN101618884B (en) | Method for preparing Magadiite/ZSM-35 eutectic molecular sieve | |
| US10287172B2 (en) | Preparation method for beta zeolite | |
| CN105712371B (en) | A kind of USY Y compound molecular sieves and preparation method thereof | |
| CN102198950B (en) | Method for preparing NaY molecular sieve with high aluminum-silicon ratio | |
| Feng et al. | Recent progress in synthesis of zeolite from natural clay | |
| CN1847147A (en) | Novel method for the synthesis of zeolite ZBM-30 from a mixture of amine compounds | |
| CN104556122B (en) | Molecular sieve supported nanocrystal Y-type molecular sieve and synthesis method thereof | |
| CN112174164B (en) | ZSM-5 molecular sieve and preparation method thereof | |
| CN101239325B (en) | Montmorillonite/ZSM-5 molecular sieve composite material and preparation thereof | |
| CN104936898B (en) | EUO NES NON zeolite UZM 43 | |
| CN106673001A (en) | Synthesis method of ZSM-11 molecular sieve and ZSM-11 molecular sieve synthesized through same | |
| CN101722024A (en) | ZSM-5/rectorite composite catalytic material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160407 Address after: 100007 Beijing, Dongzhimen, North Street, No. 9, No. Applicant after: China National Petroleum Corporation Applicant after: China Petroleum University (East China) Address before: 266580 Qingdao economic and Technological Development Zone, Changjiang Road, No. 66, Shandong Applicant before: China Petroleum University (East China) |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |