CN100343167C - Synthesis method of mesoporous molecular sieve - Google Patents
Synthesis method of mesoporous molecular sieve Download PDFInfo
- Publication number
- CN100343167C CN100343167C CNB2004100198860A CN200410019886A CN100343167C CN 100343167 C CN100343167 C CN 100343167C CN B2004100198860 A CNB2004100198860 A CN B2004100198860A CN 200410019886 A CN200410019886 A CN 200410019886A CN 100343167 C CN100343167 C CN 100343167C
- Authority
- CN
- China
- Prior art keywords
- acid
- molecular sieve
- zsm
- zeolite
- sio
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a synthetic method for mesoporous molecular sieve materials, particularly to method for synthesizing mesoporous molecular sieves containing ZSM-5 zeolite primary structural units with cheap silicon and aluminum sources, such as water glass, aluminum sulfate, etc. A 'direct method' is adopted in the preparation of colloid ZSM-5, nanometer zeolite particles containing zeolite primary structural units are obtained by carrying out pretreatment to the colloid ZSM-5, and the nanometer zeolite particles and cationic surface active agents (hexadecyl trimethyl ammonium bromide) are assembled into mesoporous MCM-41 molecular sieves with ZSM-5 zeolite primary structural units by itself. Mesoporous molecular sieves prepared by the present invention exist in the center of B acid, and the main type is L acid. The mesoporous molecular sieves prepared by the present invention have strong acidity and high hydrothermal stability simultaneously, and have favorable etherification performance.
Description
Technical field:
The present invention relates to a kind of synthetic method of mesopore molecular sieve, it be a kind of be the synthetic method that contains the mesopore molecular sieve of ZSM-5 zeolite primary structure units of presoma with direct method colloidal state ZSM-5.
Background technology:
Scientist (J.Am.Chem.Soc. from Mobil company in 1992,114,10834,1992) since Cheng Gong the synthesising mesoporous molecular sieve, because this material has regular adjustable aperture, high BET surface-area and characteristics such as pore volume and high thermal stability, become the focus of catalytic material research.Especially in the organic chemical reactions of mink cell focus processing and macromole participation, should have broad application prospects.But, because the hole wall of mesopore molecular sieve is in metamict, to compare with the micro-pore zeolite crystal, mesopore molecular sieve hydrothermal stability and acidity are all lower, have limited its scope of using in practice greatly.Therefore, the mesopore molecular sieve that synthetic and micro-pore zeolite has similar acidity and hydrothermal stability becomes the focus that people study, and worldwide for this reason scientist has carried out a large amount of research work.
People (J.Am.Chem.Soc.2000 such as Liu Yu, 122,8791) reported that the crystal seed and CTAB (cetyl trimethylammonium bromide) interaction that will have the y-type zeolite basic structural unit are self-assembled into the meso-porous molecular sieve material Al-MSU-S with high hydrothermal stability with six sides arrangement, people (Angew.Chem.Int.Ed.2001 such as Liu Yu subsequently, 40,1255) adopt the crystal seed of Beta and ZSM-5 zeolite and CTAB to be assembled into meso-porous molecular sieve material MSU-S-Beta and MSU-S-ZSM5 again with high hydrothermal stability.
People such as Xiao Fengshou (J.Am.Chem.Soc.2001,123,5014) reported the Beta guiding agent for zeolite has been prepared in TEAOH (tetraethyl ammonium hydroxide) and silica-alumina gel effect, then this directed agents and CTAB interaction are self-assembled into the molecular screen material MAS-5 with six sides arrangement, this meso-porous molecular sieve material MAS-5 not only has the strength of acid of high hydrothermal stability but also its strength of acid and Beta zeolite suitable.
People such as Xiao Fengshou (Microporous and Mesoporous Materials 2003,62,221) have reported the mesopore molecular sieve MAS-3 that utilizes the assembling of zeolite L crystal seed again, have hydrothermal stability and acidity preferably equally.
More than the conclusion of these reports to get up mainly be at first to prepare the nano zeolite particle with zeolite basic structural unit, and then these nano zeolite particles and tensio-active agent are self-assembled into the mesopore molecular sieve that has than strongly-acid and good hydrothermal stability.But the chemical reagent cost of material that is adopted in the preparation of molecular screen material in the above-mentioned report is higher, especially uses organic amine such as TEAOH to increase synthetic cost especially greatly, has limited it and has produced and use widely in industrial feeding intake on a large scale.Adopt cheap raw material such as water glass and Tai-Ace S 150, up to the present the work of " direct method " synthetic zeolite structured unit of colloidal state ZSM-5 mesopore molecular sieve, still do not have report in this respect.
Summary of the invention:
The synthetic method that the purpose of this invention is to provide a kind of meso-porous molecular sieve material can overcome the deficiency of prior art.The present invention is to be the method that silicon and aluminum source prepares mesoporous molecular sieve with high hydrothermal stability with cheap water glass and Tai-Ace S 150, it is with water glass and the synthetic colloidal state ZSM-5 that contains the zeolite primary structure units of Tai-Ace S 150 " direct method ", is assembled into the method for mesopore molecular sieve then under the effect of tensio-active agent.Raw water glass and Tai-Ace S 150 are cheap and easy to get, adopt " direct method " to reduce synthetic cost when synthesizing presoma, are particularly suitable for industrial scale operation.The mesopore molecular sieve hole wall of the present invention's preparation contains ZSM-5 zeolite primary structure units, probe reaction shows that the catalyzer of preparation has high etherificate (Ethyl Tertisry Butyl Ether, tert amyl methyl ether(TAME)) activity, hydrothermal stability and acidity obviously are better than traditional mesopore molecular sieve, can satisfy the demand of scale operation and industrial practical application.
The present invention is to provide meso-porous molecular sieve material, is basal component with silicon, aluminium, oxygen, has hexagonal mesoporous structure, is characterized in containing on the hole wall primary structure units of zeolite; Its infrared spectrum is presented at 500～600cm
-1Between absorption peak is arranged and at 960cm
-1Near absorption peak is arranged; NH
3Temperature programmed desorption experiment shows that its desorption temperature is 350～420 ℃; The infrared hydrogen type molecular sieve that shows of pyridine adsorption exists B acid site, NH
3Temperature programmed desorption experiment and pyridine adsorption are infrared to be shown, the acid site type mainly exists with L acid form; Etherification reaction performance evaluation shows that it has good etherificate performance.
Preparation method of the present invention is through following step:
1) silicon source and aluminium source are mixed by proportioning, add inorganic acid for adjusting pH between 9.5～11, after mixing, generate white gels,, obtain containing the colloidal state ZSM-5 of zeolite primary structure units then 25～150 ℃ of hydrothermal treatment consists 0～96 hour.
2) the colloidal state ZSM-5 gel that obtains joins in the solution of tensio-active agent cetyl trimethylammonium bromide, and inorganic acid for adjusting pH value is 10～11, changes over to after the stirring in the stainless steel cauldron, continues crystallization 24～96 hours at 90～140 ℃; Crystallization finish the back solid product after filtration, washing is to neutral.
3) 80 ℃ of oven dry, again with dried sample 540 ℃ of roastings 6 hours.
Described silicon source is a water glass, and the aluminium source is Tai-Ace S 150 or sodium metaaluminate; Described mineral acid is sulfuric acid, hydrochloric acid or nitric acid.
The mole proportioning of reaction system: SiO in the step 1)
2/ Al
2O
3/ H
2O=20～150/1.0/20～100.
Step 2) the used molar ratio of material of crystallization system described in: SiO
2: Al
2O
3=20～150: 1, cetyl trimethylammonium bromide: SiO
2=0.05～0.5: 1, H
2O: SiO
2=30～150: 1.
The present invention compared with prior art needn't use reagent such as organic amine as additional materials, is the directly synthetic colloidal state ZSM-5 aqueous precursor gel that contains the zeolite primary structure units of raw material and only use water glass, aluminium salt (or aluminate) and mineral acid.The mesopore molecular sieve hole wall of the present invention's preparation contains ZSM-5 zeolite primary structure units, and hydrothermal stability, acidity and etherificate (Ethyl Tertisry Butyl Ether, tert amyl methyl ether(TAME)) reactivity worth is apparently higher than traditional mesopore molecular sieve.The present invention has following characteristics: raw material adopts silicon and aluminum source cheap and easy to get, adopts " direct method " synthetic presoma, has reduced synthetic cost, is particularly suitable for industrial scale operation.
Description of drawings:
Fig. 1 is embodiment 1 x-ray diffractogram of powder (XPD).
Fig. 2 is embodiment 2 x-ray diffractogram of powder (XRD).
Fig. 3 is embodiment 3 x-ray diffractogram of powder (XRD).
Fig. 4 is embodiment 4 x-ray diffractogram of powder (XRD).
Fig. 5 is the NH of embodiment 1 sample after the acid exchange
3-TPD spectrogram.
Fig. 6 is the infrared spectrum (IR) after the embodiment 1 sample roasting.
Fig. 7 is the pyridine adsorption infrared spectrum (Py-IR) of embodiment 1 sample after the acid exchange.
Fig. 8 is embodiment 1 sample is handled back and other industrial molecular sieve with Hydrogen sample poach after the acid exchange an etherification reaction ETBE productive rate comparison diagram.
Fig. 9 is embodiment 1 sample through the etherification reaction TAME productive rate comparison diagram of acid exchange back and industrial H-MCM-41.
Embodiment:
Further describe feature of the present invention below by example, but the present invention is not limited to following example.
Embodiment 1
According to proportioning: 4Na
2O: 80SiO
2: Al
2O
3: 1500H
2O adds water glass (SiO successively
2: 3.782 mol, Na
2The O:1.142 mol) 158.8 milliliters, 71.4 ml deionized water, 12.4 milliliters of H
2SO
4(6.12 mol) and concentration are the Al of (0.8847 mol)
2(SO
4)
38.48 milliliters of solution, stir and mixed in 60 minutes, generate white gels, join in the cetyl trimethylammonium bromide that concentration is 0.06 grams per milliliter (CTAB) solution without crossing the pretreated mixture of high-temperature water heat above-mentioned then, regulate about pH value to 11 with dilute sulphuric acid, the mole of final crystallization system consists of: 80SiO
2: Al
2O
3: 4CTAB: 2400H
2O.Stirring at room changed stainless steel cauldron over to after 30 minutes, 100 ℃ of crystallization 72 hours, was cooled to room temperature, product is filtered, and washing was 80 ℃ of oven dry 12 hours, sample after the oven dry is removed template in 6 hours in 540 ℃ of roastings, obtain the said mesopore molecular sieve of the present invention.Its XRD figure such as Fig. 1.Fig. 5 is the NH of embodiment 1 sample after the acid exchange
3-TPD spectrogram, sample has very strong acid site after the acid exchange as seen from the figure.Fig. 6 is the IR figure after the embodiment 1 sample roasting, can see at 960cm
-1Place and 556cm
-1There is absorption peak at the place, belongs to silicon hydroxyl and two pentacyclic vibration peak respectively, shows the primary structure units that contains ZSM-5 on the synthetic mesopore molecular sieve hole wall.Fig. 7 is the Py-IR figure after the embodiment 1 sample acid exchange, can see that there is the B acid site in catalyzer, in conjunction with NH
3-TPD proof acid site type mainly exists with L acid form.The Hydrogen product of embodiment 1 is through poach after 24 hours, its etherification activity not reduction increases on the contrary, sees relatively that with other molecular sieve (catalyzed reaction is the fixed bed flowing reactive to Fig. 8,1.2～1.8 normal atmosphere of pressure, 6.4 milliliters/hour of air speeds, catalyst levels 1g.), can see that the sample of embodiment 1 has good ETBE etherificate performance.Fig. 9 is the TAME productive rate comparison diagram of embodiment 1 Hydrogen sample and industrial Hydrogen MCM-41, compare with industrial MCM-41, embodiment 1 Hydrogen sample has good TAME etherificate performance, and (catalyzed reaction is the fixed bed flowing reactive, 1.0～1.5 normal atmosphere of pressure, 6.4 milliliters/hour of air speeds, catalyst levels 1g.)。
According to proportioning: 4Na
2O: 40SiO
2: Al
2O
3: 1000H
2O adds water glass (SiO successively
2: 3.782 mol, Na
2The O:1.142 mol) 79.4 milliliters, 47.6 ml deionized water, 6.24 milliliters of H
2SO
4(6.12 mol) and concentration are the Al of (0.8847 mol)
2(SO
4)
38.48 milliliters of solution stir and mixed in 60 minutes, generate white gels, 140 ℃ of reactions 32 hours down.Then the pretreated mixture of above-mentioned process is joined in the cetyl trimethylammonium bromide that concentration is 0.06 grams per milliliter (CTAB) solution, regulate about pH value to 10.5 with dilute sulphuric acid, the mole of final crystallization system consists of: 40SiO
2: Al
2O
3: 4CTAB: 2400H
2O.Stirring at room changed stainless steel cauldron over to after 30 minutes, 100 ℃ of crystallization 72 hours, was cooled to room temperature, product is filtered, and washing was 80 ℃ of oven dry 12 hours, sample after the oven dry is removed template in 6 hours in 540 ℃ of roastings, obtain the said mesoporous MCM-41 molecular sieve of the present invention.Its XRD figure such as Fig. 2.
The preparation of colloidal state ZSM-5 gel is reacted the gel that generates 46 hours down at 140 ℃ with embodiment 2.Then the pretreated mixture of above-mentioned process is joined in the cetyl trimethylammonium bromide that concentration is 0.06 grams per milliliter (CTAB) solution, regulate about pH value to 10 with dilute sulphuric acid, the mole of final crystallization system consists of: 40SiO
2: Al
2O
3: 4CTAB: 2400H
2O.Stirring at room changed stainless steel cauldron over to after 30 minutes, 100 ℃ of crystallization 72 hours, was cooled to room temperature, product is filtered, and washing was 80 ℃ of oven dry 12 hours, sample after the oven dry is removed template in 6 hours in 540 ℃ of roastings, obtain the said mesopore molecular sieve of the present invention.Its XRD figure such as Fig. 3.
The preparation of colloidal state ZSM-5 gel is reacted the gel that generates 96 hours down at 140 ℃ with embodiment 2.Then the pretreated mixture of above-mentioned process is joined in the cetyl trimethylammonium bromide that concentration is 0.06 grams per milliliter (CTAB) solution, regulate about pH value to 10.5 with dilute sulphuric acid, the mole of final crystallization system consists of: 40SiO
2: Al
2O
3: 4CTAB: 2400H
2O.Stirring at room changed stainless steel cauldron over to after 30 minutes, 100 ℃ of crystallization 72 hours, was cooled to room temperature, product is filtered, and washing was 80 ℃ of oven dry 12 hours, sample after the oven dry is removed template in 6 hours in 540 ℃ of roastings, obtain the said mesopore molecular sieve of the present invention.Its XRD figure such as Fig. 4.
Claims (2)
1, a kind of synthetic method of meso-porous molecular sieve material is characterized in that it is through following step:
1) silicon source and aluminium source are mixed by proportioning, add inorganic acid for adjusting pH between 9.5～11, after mixing, generate white gels,, obtain containing the colloidal state ZSM-5 of zeolite primary structure units then 25～150 ℃ of hydrothermal treatment consists 0～96 hour;
2) the colloidal state ZSM-5 gel that obtains joins in the solution of tensio-active agent cetyl trimethylammonium bromide, and inorganic acid for adjusting pH value is 10～11, changes over to after the stirring in the stainless steel cauldron, continues crystallization 24～96 hours at 90～140 ℃; Crystallization finish the back solid product after filtration, washing is to neutral;
3) 80 ℃ of oven dry, again with dried sample 540 ℃ of roastings 6 hours;
Described silicon source is a water glass, and the aluminium source is Tai-Ace S 150 or sodium metaaluminate;
The mole proportioning of reaction system: SiO in the step 1)
2/ Al
2O
3/ H
2O=20～150/1.0/20～100;
Step 2) the used molar ratio of material of crystallization system described in: SiO
2: Al
2O
3=20～150: 1, cetyl trimethylammonium bromide: SiO
2=0.05～0.5: 1, H
2O: SiO
2=30～150: 1.
2,, it is characterized in that described mineral acid is sulfuric acid, hydrochloric acid or nitric acid according to the synthetic method of the described meso-porous molecular sieve material of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100198860A CN100343167C (en) | 2004-07-07 | 2004-07-07 | Synthesis method of mesoporous molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100198860A CN100343167C (en) | 2004-07-07 | 2004-07-07 | Synthesis method of mesoporous molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1594088A CN1594088A (en) | 2005-03-16 |
| CN100343167C true CN100343167C (en) | 2007-10-17 |
Family
ID=34663109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100198860A Expired - Fee Related CN100343167C (en) | 2004-07-07 | 2004-07-07 | Synthesis method of mesoporous molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100343167C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060310B (en) * | 2009-11-11 | 2012-12-12 | 中国石油天然气股份有限公司 | Method for preparing ZSM-5 zeolite secondary structural unit-containing molecular sieve |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103771450B (en) * | 2012-10-24 | 2015-07-22 | 中国石油化工股份有限公司 | Preparation method of micropore hollow ball molecular sieve |
| CN106006666B (en) * | 2016-04-22 | 2019-02-05 | 宁夏大学 | Nano-lamellar structure multi-stage porous ZSM-5 molecular sieve and its synthetic method |
| CN110775984B (en) * | 2019-12-05 | 2021-10-08 | 神华准能资源综合开发有限公司 | Method for preparing ZSM-5 molecular sieve by taking white mud as raw material without template agent and ZSM-5 molecular sieve |
| CN112939017B (en) * | 2019-12-11 | 2022-11-08 | 中国科学院大连化学物理研究所 | Synthesis method of MTW type molecular sieve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5098684A (en) * | 1990-01-25 | 1992-03-24 | Mobil Oil Corp. | Synthetic mesoporous crystaline material |
| CN1349929A (en) * | 2001-04-02 | 2002-05-22 | 吉林大学 | Mesoporous molecular sieve material with strong acidity and high hydrothermal stability and its prepn |
| CN1488578A (en) * | 2003-08-07 | 2004-04-14 | 复旦大学 | Mesoporous molecular sieve cortaining beta zeolite secondary constitutional unit and preparing method thereof |
-
2004
- 2004-07-07 CN CNB2004100198860A patent/CN100343167C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5098684A (en) * | 1990-01-25 | 1992-03-24 | Mobil Oil Corp. | Synthetic mesoporous crystaline material |
| CN1349929A (en) * | 2001-04-02 | 2002-05-22 | 吉林大学 | Mesoporous molecular sieve material with strong acidity and high hydrothermal stability and its prepn |
| CN1488578A (en) * | 2003-08-07 | 2004-04-14 | 复旦大学 | Mesoporous molecular sieve cortaining beta zeolite secondary constitutional unit and preparing method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060310B (en) * | 2009-11-11 | 2012-12-12 | 中国石油天然气股份有限公司 | Method for preparing ZSM-5 zeolite secondary structural unit-containing molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1594088A (en) | 2005-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101172243B (en) | Mesoporous material/micropore molecular sieve composite material and preparation method thereof | |
| CN1304290C (en) | Method for preparing MSU-S-Y mesoporous molecular screen using ion liquid as mould | |
| CN1915819A (en) | Method for preparing ZSM-5 zeolite in small crystal grain | |
| CN102039200A (en) | Y-beta/MCM-41 double microporous-mesoporous composite molecular sieve and preparation method thereof | |
| CN103172081B (en) | High-molecular organic polymer template synthesized compound pore structure molecular sieve and preparation method thereof | |
| CN105000573B (en) | Large block porous zeolite composed of nano-crystal grains and preparation method thereof | |
| CN105692644A (en) | Hierarchical-porous zeolite preparation method | |
| CN111886202B (en) | Process for the synthesis of zeolite SSZ-13 | |
| CN1654330A (en) | Method for preparing aluminium-containing MCM-41 inter-aperture molecular screen using metakaolin as raw material | |
| CN1749161A (en) | Hard template synthetic composite hole zeolite molecular sieve and its preparing method | |
| CN101205073B (en) | Method for preparing aluminium-containing MCM-41 molecular sieve | |
| CN100343167C (en) | Synthesis method of mesoporous molecular sieve | |
| CN1749162A (en) | High molecule polymer template synthetic composite hole zeolite molecular sieve and its preparing method | |
| CN1762806A (en) | Method for mesoporous molecular sieve overgrowth on microporous molecular sieve surface | |
| CN106946268B (en) | A kind of MOR/ZSM-35 composite molecular screen and its synthetic method | |
| CN1267345C (en) | Preparation method of NaY molecular sieve | |
| CN1160249C (en) | Mesoporous molecular sieve material with strong acidity and high hydrothermal stability and its prepn | |
| CN100360405C (en) | LTA and FAU molecular screen nanocrystalline preparation method | |
| CN103011191B (en) | Mordenite and beta zeolite core-shell molecular sieve and preparation method thereof | |
| CN1220631C (en) | Process of preparing velence pore molecular siever by natural kaolinite | |
| CN1160250C (en) | Double Si-Al mesopore molecular sieve and its synthesis | |
| CN113135578B (en) | Preparation method of silicon-germanium ISV zeolite molecular sieve | |
| CN1151067C (en) | process for preparing cubic mesoporous Si-Al molecular sieve with strong acidic site | |
| CN105084388A (en) | Method for preparing and modifying Y-type molecular sieve | |
| CN1272246C (en) | Synthesis method of NaY molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |