CN101555022A - Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve - Google Patents
Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve Download PDFInfo
- Publication number
- CN101555022A CN101555022A CNA200910082917XA CN200910082917A CN101555022A CN 101555022 A CN101555022 A CN 101555022A CN A200910082917X A CNA200910082917X A CN A200910082917XA CN 200910082917 A CN200910082917 A CN 200910082917A CN 101555022 A CN101555022 A CN 101555022A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- metal
- modified sapo
- sapo
- source
- 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.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a metal-modified SAPO-34 molecular sieve. The method includes: first mixing a template agent with metal salt solution to form a metal complex in the preparation process of raw powder of the molecular sieve; then adding materials such as aluminum source, phosphorus source, silicon source to prepare gel mixture; and finally obtaining the metal-modified SAPO-34 molecular sieve through ageing, hydrothermal crystallization, washing, drying, roasting and the like. The metal-modified SAPO-34 molecular sieve prepared by the method has comparatively high degree of crystallinity and can effectively improve the selectivity of ethene and propylene as reaction catalyst for preparing olefins by methanol. The invention discloses a preparation method of the metal-modified SAPO-34 molecular sieve and a catalyst containing the molecular sieve.
Description
Technical field
The present invention is specifically related to a kind of novel metal modified SAPO-34 molecular sieve and contains metal-modified SAPO-34 molecular sieve Preparation of catalysts method.
Background technology
Novel silicon aluminium phosphate series molecular sieve (US 4440871, US4499327)-SAPO-n molecular sieve that U.S. combinating carbide company (UCC) researched and developed out in 1984, be be template with the organic amine, be aluminium source, phosphorus source and silicon source with hydrated aluminum oxide, phosphoric acid, silicon sol respectively, at first obtain having the organic amine/aluminum phosphate/silicon complex body of micropore phase, remove by roasting then that template (organic amine) obtains by hydrothermal crystallization method.SAPO-34 is wherein a kind of, and its similar chabazite has the three dimensional intersection duct, and the aperture is about 0.38nm, belongs to isometric system.Because it has suitable proton acidity, suitable pore passage structure, bigger specific surface area, absorption property and thermostability and hydrothermal stability etc. preferably preferably, makes it present catalytic activity and selectivity preferably in as the methanol to olefins reaction catalyzer.
Catalytic efficiency was relatively low when yet simple SAPO-34 was used as the methanol-to-olefins catalyzer, need carry out suitable modification to SAPO-34 usually.At present, improvement to the SAPO-34 molecular sieve mainly is that various metallic elements are introduced on the SAPO-34 framework of molecular sieve, change acidic zeolite and aperture size, obtain the acid site of aperture bore and medium tenacity, and the aperture diminishes and has limited macromolecular diffusion, help small-numerator olefin and optionally improve, thus the selectivity of low-carbon alkenes such as raising ethene, propylene.Usually, the synthesis mode of metal-modified SAPO-34 molecular sieve has two kinds, a kind of is two-step approach or post-treatment method, promptly at the synthetic laggard row metal ion modification of SAPO-34 molecular sieve, in the former powder of SAPO-34, introduce metal ion as (CN1067603C) such as Cai Guangyu by ion-exchange techniques, catalytic activity and ethene, propylene selectivity have had certain improvement, but it is more to generate the byproduct methane amount.Another kind of (single stage method) promptly in building-up process the change by starting raw material metal ion is introduced framework of molecular sieve or cation-bit, ditto to compare this method simple and convenient for the kind method.Prepare the SAPO molecular sieve of different metal modification in proper order by the interpolation of phosphorus source, aluminium source, silicon source, metal-salt, template as (US 4752651) such as Kaiser.Magnify and control etc. that (Microporous andMesoporous Materials 2008,116 684-692) mixes pseudo-boehmite earlier with phosphoric acid, silicon sol, stir afterwards adding template triethylamine and magnesium acetate have made magnesium-modified SAPO-34 molecular sieve.Aforesaid method all is to adopt to make phosphorus source and aluminium source form the aluminum phosphate skeleton earlier, then silicon source, template and metal-salt etc. are introduced in the skeleton, may make some template and metal-salt can not enter among the skeleton like this, finally influence the rerum natura and the catalytic performance of molecular sieve.Therefore, the preparation method of the better metal-modified SAPO-34 molecular sieve of development research is necessary.
Summary of the invention
At above-mentioned technical problem, the object of the invention is by at first forming metal-template complex compound, make materials such as aluminium source, phosphorus source, silicon source can wrap the outside surface that is attached to metal-template complex compound then, thereby form complex body, just can obtain the metal-modified SAPO-34 molecular sieve of metal adhesion on porous skeleton by roasting with micropore phase.
Therefore, the invention provides a kind of preparation method of metal-modified SAPO-34 molecular sieve, described method comprises the steps:
1) earlier template is mixed the formation metal complex with metal-salt, add materials such as aluminium source, phosphorus source, silicon source again, stirring mixed in 1-10 hour under 25-80 ℃, and the final blending GOLD FROM PLATING SOLUTION belongs to element: template: SiO
2: Al
2O
3: P
2O
5: H
2The mol ratio of O is 0.01-1.0: 1.0-5.0: 1.0: 2-1.5: 0.2-2.0: 20-200; Wherein, SiO
2, Al
2O
3, P
2O
5Mol ratio be respectively that corresponding silicon source, aluminium source, the conversion of phosphorus source are SiO
2, Al
2O
3, P
2O
5Mol ratio.
2) mixing solutions was worn out under 25-80 ℃ 1-24 hour.
3) crystallizing kettle of packing into of the mixing solutions after will wearing out airtightly is heated to crystallization temperature 150-250 ℃, carries out under constant crystallization temperature then crystallization 10-120 hour.
4) mixture after the crystallization is carried out centrifugation, filtration, washing after, solid sample obtains the former powder of metal-modified SAPO-34 molecular sieve by heat drying.
5) with the former powder of metal-modified SAPO-34 molecular sieve at 450-650 ℃ of following roasting 4-8 hour, metal-modified SAPO-34 molecular sieve.
In preparation method of the present invention, described template can be the template of this area routine, and as the organic amine template, the present invention is preferably tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine or their any mixture.
In preparation method of the present invention, described metallic element is Ag, Cu, Mg, Co, Ni, Ca, Ba, Sr, Fe, Zn or their any mixture, and the content of described metallic element is 0.01~1.0% of molecular sieve weight.Metallic element described in the present invention is the form of their this areas hydrochlorate commonly used, for example, and metal nitrate, metal acetate salt, or the form of other hydrochlorate.
In preparation method of the present invention, described silicon source can be the silicon source of this area routine, and the present invention is preferably silicon sol, silicic acid, silicon-dioxide, white carbon black, water glass or the tetraethoxy of silica comprises 40 weight %, and they are mixture arbitrarily.
In preparation method of the present invention, described phosphorus source can be the phosphorus source of this area routine, includes but not limited to phosphoric acid, phosphoric acid salt or phosphite or they mixture arbitrarily, and further preferred phosphorus source is a phosphoric acid, and described phosphoric acid contains the ortho-phosphoric acid of 85 weight %.
In preparation method of the present invention, described aluminium source can be the aluminium source of this area routine, and the present invention is preferably pseudo-boehmite, aluminum isopropylate, aluminum oxide, aluminium hydroxide or they mixture arbitrarily.
The present invention also provides a kind of metal-modified SAPO-34 molecular sieve Preparation of catalysts method, and described method comprises the steps: with A) and quality summation meter B),
A) quality is the former powder of metal-modified SAPO-34 molecular sieve of the present invention of 10~100% preparation; And B) 0~90% binding agent mixes, 50~150 ℃ of dryings, and 350~650 ℃ of roastings moulding in 1~8 hour then promptly makes the metal-modified SAPO-34 molecular sieve catalyzer.
The present invention further preferred described method comprises the steps: with A) and quality summation meter B), A) quality is the former powder of metal-modified SAPO-34 molecular sieve of the present invention's preparation of 30~800%; And B) 20~70% binding agent mixes, 50~150 ℃ of dryings, and 350~650 ℃ of roastings moulding in 1~8 hour then promptly makes the metal-modified SAPO-34 molecular sieve catalyzer.
In the metal-modified SAPO-34 molecular sieve Preparation of catalysts method of the present invention, described binding agent is in aluminum oxide, aluminium hydroxide, aluminum phosphate, pure aluminium silicate, silicon oxide or the magnesium oxide or they make up arbitrarily.
In the metal-modified SAPO-34 molecular sieve Preparation of catalysts method of the present invention, described method also comprises the adding pore-forming material, described pore-forming material can be the pore-forming material of this area routine, the present invention is preferably sesbania powder, carboxymethyl cellulose or starch, and the consumption of described pore-forming material is 1~15% of a metal-modified SAPO-34 molecular sieve catalyst quality.
In the metal-modified SAPO-34 molecular sieve Preparation of catalysts method of the present invention, the content of metallic element is 0.01~1.0% of molecular sieve weight.
Compare with the molecular screen primary powder that prior art makes, the degree of crystallinity of the former powder of metal-modified SAPO-34 molecular sieve that the inventive method makes has had tangible improvement; And because various metallic elements are introduced on the SAPO-34 framework of molecular sieve, not only make metal-modified SAPO-34 molecular sieve have certain acidity, also can give oxidation-reduction quality, as methanol-to-olefins (MTO) catalysts the time, improve the selectivity of low-carbon alkene ethene and propylene.
When metal-modified SAPO-34 molecular sieve catalyzer of the present invention is used for methanol to olefins reaction, when temperature of reaction is 300~500 ℃, reaction pressure is 0~0.5MPa, and preferable reaction temperature is 400~500 ℃, the mass space velocity of methyl alcohol is 1.0~5.0 o'clock, and feed stock conversion can reach 100%.
The metal-modified SAPO-34 molecular sieve of the inventive method preparation has higher degree of crystallinity, can improve the selectivity of ethene and propylene effectively as the methanol to olefins reaction catalyzer.
Description of drawings
Fig. 1 is comparative example 1 a process flow sheet;
Fig. 2 is comparative example 2 a process flow sheet;
Fig. 3 is comparative example 3 a process flow sheet;
Fig. 4 is comparative example 4 a process flow sheet;
Fig. 5 is the process flow sheet of embodiment 1, embodiment 4;
Fig. 6 is the process flow sheet of embodiment 2, embodiment 3, embodiment 5;
Fig. 7 is comparative example 1-4, X-ray diffraction (XRD) figure of embodiment 1-5 products obtained therefrom.
Embodiment
Now further specify the present invention, but the present invention is not limited to this by following comparative example, embodiment and test example.
Comparative example's 1 ion exchange method is synthesized the AgAPSO-34 molecular sieve.
85% phosphoric acid of 12.3g, the pseudo-boehmite of 8.768g, the triethylamine of 16.16g, the deionized water of 49.568g, 40% silicon sol of 4.8g and the 1M silver nitrate solution of 30ml are prepared according to operation shown in Figure 1, wherein aging condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Roasting condition: temperature: 550 ℃, the time: 7 hours; Get product (a) at last.
The comparative example 2
85% phosphoric acid of 12.3g, the pseudo-boehmite of 8.768g, 40% silicon sol of 4.8g, the triethylamine of 16.16g, the deionized water of 49.568g and the Silver Nitrate of 0.544g are prepared according to operation shown in Figure 2, wherein aging condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Roasting condition: temperature: 550 ℃, the time: 7 hours; Get product (b) at last.
The comparative example 3
85% phosphoric acid of 12.3g, the pseudo-boehmite of 8.768g, 40% silicon sol of 4.8g, the triethylamine of 16.16g, the deionized water of 49.568g and the Silver Nitrate of 0.544g are prepared according to operation shown in Figure 3, wherein aging condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Roasting condition: temperature: 550 ℃, the time: 7 hours; Get product (c) at last.
The comparative example 4
85% phosphoric acid of 12.3g, the pseudo-boehmite of 8.768g, 40% silicon sol of 4.8g, the triethylamine of 16.16g, the deionized water of 49.568g and the Silver Nitrate of 0.544g are prepared according to operation shown in Figure 4, wherein aging condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Roasting condition: temperature: 550 ℃, the time: 7 hours; Get product (d) at last.
Embodiment 1
85% phosphoric acid of 12.3g, the pseudo-boehmite of 8.768g, 40% silicon sol of 4.8g, the triethylamine of 16.16g, the deionized water of 49.568g and the Silver Nitrate of 0.544g are prepared according to operation shown in Figure 5, wherein aging condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Roasting condition: temperature: 550 ℃, the time: 7 hours; Get product (i) at last.
Embodiment 2
85% phosphoric acid of 12.3g, the pseudo-boehmite of 8.768g, 40% silicon sol of 4.8g, the triethylamine of 16.16g, the deionized water of 49.568g and the Silver Nitrate of 0.544g are prepared according to operation shown in Figure 6, wherein aging condition is: temperature: 25 ℃, and the time: 4 hours; Crystallization condition is: temperature: 200 ℃, and the time: 48 hours; Roasting condition: temperature: 550 ℃, the time: 7 hours; Get product (h) at last.
Embodiment 3
85% phosphoric acid of 12.3g, the pseudo-boehmite of 8.768g, 40% silicon sol of 4.8g, the triethylamine of 16.16g, the deionized water of 49.568g and the zinc nitrate of 0.58g are prepared according to operation shown in Figure 6, wherein aging condition is: temperature: 50 ℃, and the time: 8 hours; Crystallization condition is: temperature: 210 ℃, and the time: 68 hours; Roasting condition: temperature: 540 ℃, the time: 7.5 hours; Get product (g) at last.
Embodiment 4
85% phosphoric acid of 14.98g, the pseudo-boehmite of 10.69g, 40% silicon sol of 5.86g, the triethylamine of 19.55g, the deionized water of 60.29g and the magnesium nitrate of 0.5g are prepared according to operation shown in Figure 5, wherein aging condition is: temperature: 35 ℃, and the time: 15 hours; Crystallization condition is: temperature: 220 ℃, and the time: 36 hours; Roasting condition: temperature: 600 ℃, the time: 6 hours; Get product (f) at last.
85% phosphoric acid of 14.98g, the pseudo-boehmite of 10.69g, 40% silicon sol of 5.86g, the triethylamine of 19.55g, the deionized water of 60.29g and the nickelous nitrate of 0.57g are prepared according to operation shown in Figure 6, wherein aging condition is: temperature: 60 ℃, and the time: 2 hours; Crystallization condition is: temperature: 180 ℃, and the time: 72 hours; Roasting condition: temperature: 500 ℃, the time: 8 hours; Get product (e) at last.
The preparation of embodiment 6 molecular sieve catalysts
Get Comparative Examples 1,2,3,4 respectively, former powder 6 grams that make among the embodiment 1,2 are with rAl
2O
3H
2O6 gram, sesbania powder 2 grams mix, and add 9 milliliters in the rare nitric acid of 3wt%, mediate, extruded moulding, 120 ℃ of dry down 8 hours, 600 ℃ following roastings 3 hours, and broken back sieve is got 20~40 purpose granularity parts, waits to check and rate.
The detection of test example 1 degree of crystallinity
Method: detect according to the degree of crystallinity of X-ray diffraction method to embodiment 1-5, comparative example 1-4 products obtained therefrom, and the degree of crystallinity of embodiment 2 products obtained therefroms is set at 100%, degree of crystallinity with other embodiment and comparative example's product compares with it then, the results are shown in Table 1.
The former powder degree of crystallinity of each embodiment of table 1, embodiment gained molecular sieve
Sample | Relative crystallinity/% |
Comparative Examples 1 | 82.87 |
Comparative Examples 2 | 89.38 |
Comparative Examples 3 | 84.23 |
Comparative Examples 4 | 85.72 |
Embodiment 1 | 91.22 |
Embodiment 2 | 100 |
Embodiment 3 | 92.88 |
Embodiment 4 | 92.79 |
|
91.53 |
As can be found from Table 1, under the constant situation of other condition, significantly improved the degree of crystallinity of metal-modified SAPO-34 molecular sieve according to preparation metal-modified SAPO-34 technology shown in the present.
The examination of test example 2 molecular sieve catalysts
Adopt fixed-bed catalytic reactor, embodiment 1, the embodiment 2, Comparative Examples 1, Comparative Examples 2, Comparative Examples 3, the Comparative Examples 4 that obtain are carried out catalyzer examination experiment, experiment condition: loaded catalyst 2.0 grams, 450 ℃ of temperature of reaction, air speed are 3h
-1, the results are shown in following table 2.
Table 2 methanol conversion system alkene appraisal result
Embodiment 1 | Embodiment 2 | The comparative example 1 | The comparative example 2 | The comparative example 3 | The comparative example 4 | |
Methanol conversion (%) | 100 | 100 | 100 | 100 | 100 | 100 |
CH 4 | 2.32 | 2.42 | 3.52 | 3.31 | 3.07 | 3.14 |
C 2H 4 | 44.98 | 45.7 | 42.08 | 44.33 | 41.37 | 41.14 |
C 2H 6 | 0.08 | 0.07 | 1.90 | 0.66 | 1.57 | 1.56 |
C 3H 6 | 44.15 | 43.41 | 39.11 | 38.60 | 40.13 | 39.66 |
C 3H 8 | 2.22 | 2.17 | 2.56 | 5.02 | 3.45 | 3.67 |
C 4H 8 | 0.67 | 0.59 | 1.41 | 0.62 | 2.13 | 2.15 |
C 4H 10 | 0.89 | 0.99 | 1.58 | 0.02 | 1.32 | 1.45 |
C 5 + | 0.65 | 0.60 | 0.89 | 0.70 | 0.78 | 0.76 |
CO 2 | 0.42 | 0.37 | 0.67 | 0.84 | 0.45 | 0.53 |
CO | 0.30 | 0.25 | 0.56 | 0.58 | 0.40 | 0.43 |
Carbon deposit | 3.32 | 3.43 | 5.72 | 5.32 | 5.33 | 5.51 |
C 2 =+C 3 = | 89.13 | 89.11 | 81.19 | 82.93 | 81.50 | 80.80 |
Conclusion: show the former powder preparation process of metal modified molecular screen from table 1, table 2, adopt earlier template to be mixed with metal salt solution and form metal complex, and then add materials such as aluminium source, phosphorus source, silicon source and be prepared into gel mixture, metal-modified SAPO-34 molecular sieve through the preparation of operations such as overaging, hydrothermal crystallizing, washing, drying and roasting has relative higher degree of crystallinity, can improve the selectivity of low-carbon alkene (ethene and propylene) effectively as the methanol to olefins reaction catalyzer.
Claims (10)
1, a kind of method of metal-modified SAPO-34 molecular sieve preparation is characterized in that described method comprises the steps:
1) earlier template is mixed the formation metal complex with metal-salt, and then add aluminium source, phosphorus source and silicon source, stirring mixed in 1-10 hour under 25-80 ℃; The final blending GOLD FROM PLATING SOLUTION belongs to element: template: SiO
2: Al
2O
3: P
2O
5: H
2The mol ratio of O is 0.01-1.0: 1.0-5.0: 2-1.5: 1.0: 0.2-2.0: 20-200;
2) mixing solutions was worn out under 25-80 ℃ 1-24 hour;
3) crystallizing kettle of packing into of the mixing solutions after will wearing out airtightly is heated to crystallization temperature 150-250 ℃, carries out under constant crystallization temperature then crystallization 10-120 hour;
4) mixture after the crystallization is carried out centrifugation, filtration, washing after, solid sample obtains the former powder of metal-modified SAPO-34 molecular sieve by heat drying;
5) with the former powder of metal-modified SAPO-34 molecular sieve at 450-650 ℃ of following roasting 4-8 hour, metal-modified SAPO-34 molecular sieve.
2, method according to claim 1 is characterized in that, described template is tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine or their any mixture.
3, according to claims 1 described method, it is characterized in that, described metallic element is Ag, Cu, Mg, Co, Ni, Ca, Ba, Sr, Fe, Zn or their any mixture, and the content of wherein said metallic element is 0.01~1.0% of molecular sieve weight.
4, method according to claim 1 is characterized in that, described silicon source is the silicon sol, silicic acid, silicon-dioxide, white carbon black, water glass, tetraethoxy of 40 weight % or they mixture arbitrarily.
5, method according to claim 1 is characterized in that, described phosphorus source is phosphoric acid, phosphoric acid salt or phosphite or they mixture arbitrarily; Preferred phosphorus source is a phosphoric acid, and described phosphoric acid to contain be 85% ortho-phosphoric acid by weight.
6, method according to claim 1 is characterized in that, described aluminium source is pseudo-boehmite, aluminum isopropylate, aluminum oxide, aluminium hydroxide or they mixture arbitrarily.
7, a kind of metal-modified SAPO-34 molecular sieve Preparation of catalysts method is characterized in that described method comprises the steps: with A) and quality summation meter B),
A) quality is the former powder of metal-modified SAPO-34 molecular sieve that 10~100% the arbitrary described method of claim 1-6 makes; With
B) 0~90% binding agent;
Mix, 50~150 ℃ of dryings in 350~650 ℃ of roastings moulding in 1~8 hour, promptly make the metal-modified SAPO-34 molecular sieve catalyzer then.
8, method according to claim 7 is characterized in that, described method comprises the steps: with A) and quality summation meter B),
A) quality is the former powder of metal-modified SAPO-34 molecular sieve that 30~80% the arbitrary described method of claim 1-6 makes, and wherein, the content of described metallic element is 0.01~1.0% of molecular sieve weight; With
B) 20~70% binding agent;
Mix, 50 ℃~150 ℃ dryings in 350 ℃~650 ℃ roastings moulding in 1~8 hour, promptly make the metal-modified SAPO-34 molecular sieve catalyzer then.
9, method according to claim 8 is characterized in that, described binding agent is that make up arbitrarily aluminum oxide, aluminium hydroxide, aluminum phosphate, pure aluminium silicate, silicon oxide, magnesium oxide or they.
10, method according to claim 9 is characterized in that, described method also comprises the adding pore-forming material, and described pore-forming material is sesbania powder, carboxymethyl cellulose or starch; The consumption of pore-forming material is 1~15% of a metal-modified SAPO-34 molecular sieve catalyst quality.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200910082917XA CN101555022B (en) | 2009-04-22 | 2009-04-22 | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200910082917XA CN101555022B (en) | 2009-04-22 | 2009-04-22 | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101555022A true CN101555022A (en) | 2009-10-14 |
CN101555022B CN101555022B (en) | 2011-06-08 |
Family
ID=41173335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200910082917XA Active CN101555022B (en) | 2009-04-22 | 2009-04-22 | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101555022B (en) |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102259892A (en) * | 2011-06-09 | 2011-11-30 | 浙江大学 | Method for synthesizing silicoaluminophosphate molecular sieve by use of metal-amine-complex as template agent |
CN102464324A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Forming method for molecular sieve |
CN102614910A (en) * | 2012-03-16 | 2012-08-01 | 北京工业大学 | Ammonia-selective preparation method of SAPO-34 supported Cu-Fe catalyst for catalytically removing NOx |
CN103224241A (en) * | 2013-04-27 | 2013-07-31 | 陕西师范大学 | Preparation method of cobalt-silicoaluminophosphate molecular sieve |
CN103241746A (en) * | 2013-05-02 | 2013-08-14 | 西南化工研究设计院有限公司 | In-situ synthetic method of modified molecular sieve for preparing ethylene by transforming ethanol |
CN103420388A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Metal ion-containing silicon-phosphorus-aluminum molecular sieve preparation method |
CN104495870A (en) * | 2014-12-18 | 2015-04-08 | 山东齐鲁华信高科有限公司 | Method for preparing metal modified SAPO-34 molecular sieve |
CN104549478A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing MgO modified SAPO-34 molecular sieve |
CN105080601A (en) * | 2015-09-11 | 2015-11-25 | 宁波海越新材料有限公司 | Catalyst for preparing methyl ethyl ketone by dehydration of 2,3-butanediol, and preparation method of catalyst |
CN105688981A (en) * | 2016-04-13 | 2016-06-22 | 贵州大学 | Preparation method of modified SAPO-34 molecular sieve catalyst |
CN105772065A (en) * | 2016-04-13 | 2016-07-20 | 贵州大学 | Modified ZSM-5 molecular sieve based catalyst and preparing method thereof |
CN105772063A (en) * | 2016-04-13 | 2016-07-20 | 贵州大学 | Modified ZSM-5 molecular sieve based catalyst and preparing method thereof |
CN105854931A (en) * | 2016-04-13 | 2016-08-17 | 贵州大学 | Preparation method of modified SAPO-34 molecular sieve catalyst |
CN106540744A (en) * | 2015-09-22 | 2017-03-29 | 正大能源材料(大连)有限公司 | A kind of reuse method of sial phosphorus molecular sieve catalyst |
CN106732765A (en) * | 2016-12-14 | 2017-05-31 | 中国石油天然气股份有限公司 | Catalyst for preparing propylene from butylene and preparation method thereof |
CN107244679A (en) * | 2017-05-17 | 2017-10-13 | 汕头大学 | A kind of molecular sieves of spherical heteroatom Ni SAPO 34 and its preparation and application |
CN107899620A (en) * | 2015-06-29 | 2018-04-13 | 宣乐 | A kind of preparation method of MTO catalyst carrier |
CN108203102A (en) * | 2016-12-16 | 2018-06-26 | 中国石油天然气股份有限公司 | Composite modified SAPO-34 molecular sieve and preparation method thereof |
CN108602684A (en) * | 2016-03-16 | 2018-09-28 | 沙特基础工业全球技术公司 | The synthesis of SAPO-34 and the application in chloromethanes olefine reaction |
WO2019010815A1 (en) * | 2017-07-12 | 2019-01-17 | 中国科学院大连化学物理研究所 | Cu-sapo-34 molecular sieve synthesis method, and synthesized cu-sapo molecular sieve and application thereof |
CN110548538A (en) * | 2018-06-04 | 2019-12-10 | 中国科学院大连化学物理研究所 | Preparation method and application of metal modified SAPO-34 molecular sieve |
CN110801862A (en) * | 2019-10-24 | 2020-02-18 | 杜成荣 | Catalyst for preparing low-carbon olefin from methanol |
CN111013649A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Preparation method of Ni-SAPO-34 molecular sieve, prepared molecular sieve and application thereof |
CN111013650A (en) * | 2019-12-25 | 2020-04-17 | 山东江岳科技开发股份有限公司 | SAPO-34 molecular sieve thin-layer catalyst and preparation method thereof |
CN111744548A (en) * | 2020-07-09 | 2020-10-09 | 鲍周艳 | Ce-Ni/Ca-SAPO-34 catalyst and preparation method thereof |
CN112209405A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve and synthetic method and application thereof |
CN112973782A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Bimetal modified catalyst and preparation method and application thereof |
CN113213506A (en) * | 2021-06-01 | 2021-08-06 | 江西师范大学 | Preparation method and application of metal modified SAPO-34 molecular sieve |
CN113600230A (en) * | 2021-08-02 | 2021-11-05 | 大连理工大学 | Efficient monatomic molecular sieve forming catalyst and preparation method thereof |
CN114887586A (en) * | 2022-05-07 | 2022-08-12 | 西南化工研究设计院有限公司 | Production method of lithium molecular sieve with low silicon-aluminum ratio |
CN115283009A (en) * | 2022-08-11 | 2022-11-04 | 扬州晨化新材料股份有限公司 | SAPO-34-containing molecular sieve composition for continuously synthesizing tertiary amine catalyst for polyurethane and preparation method thereof |
-
2009
- 2009-04-22 CN CN200910082917XA patent/CN101555022B/en active Active
Cited By (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102464324A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Forming method for molecular sieve |
CN102259892A (en) * | 2011-06-09 | 2011-11-30 | 浙江大学 | Method for synthesizing silicoaluminophosphate molecular sieve by use of metal-amine-complex as template agent |
CN102259892B (en) * | 2011-06-09 | 2013-04-03 | 浙江大学 | Method for synthesizing silicoaluminophosphate molecular sieve by use of metal-amine-complex as template agent |
CN102614910A (en) * | 2012-03-16 | 2012-08-01 | 北京工业大学 | Ammonia-selective preparation method of SAPO-34 supported Cu-Fe catalyst for catalytically removing NOx |
CN102614910B (en) * | 2012-03-16 | 2014-01-01 | 北京工业大学 | Ammonia-selective preparation method of SAPO-34 supported Cu-Fe catalyst for catalytically removing NOx |
CN103420388A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Metal ion-containing silicon-phosphorus-aluminum molecular sieve preparation method |
CN103224241A (en) * | 2013-04-27 | 2013-07-31 | 陕西师范大学 | Preparation method of cobalt-silicoaluminophosphate molecular sieve |
CN103224241B (en) * | 2013-04-27 | 2015-01-21 | 陕西师范大学 | Preparation method of cobalt-silicoaluminophosphate molecular sieve |
CN103241746A (en) * | 2013-05-02 | 2013-08-14 | 西南化工研究设计院有限公司 | In-situ synthetic method of modified molecular sieve for preparing ethylene by transforming ethanol |
CN103241746B (en) * | 2013-05-02 | 2015-06-17 | 西南化工研究设计院有限公司 | In-situ synthetic method of modified molecular sieve for preparing ethylene by transforming ethanol |
CN104549478A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing MgO modified SAPO-34 molecular sieve |
CN104549478B (en) * | 2013-10-28 | 2017-02-08 | 中国石油化工股份有限公司 | Method for preparing MgO modified SAPO-34 molecular sieve |
CN104495870A (en) * | 2014-12-18 | 2015-04-08 | 山东齐鲁华信高科有限公司 | Method for preparing metal modified SAPO-34 molecular sieve |
CN104495870B (en) * | 2014-12-18 | 2016-03-23 | 山东齐鲁华信高科有限公司 | A kind of preparation method of metal-modified SAPO-34 molecular sieve |
CN107971020A (en) * | 2015-06-29 | 2018-05-01 | 宣乐 | A kind of preparation method of MTO catalyst carrier |
CN107971021A (en) * | 2015-06-29 | 2018-05-01 | 宣乐 | A kind of preparation method of MTO catalyst carrier |
CN107930685A (en) * | 2015-06-29 | 2018-04-20 | 宣乐 | A kind of method for preparing MTO catalyst carrier |
CN107899610A (en) * | 2015-06-29 | 2018-04-13 | 宣乐 | A kind of preparation method of MTO catalyst carrier |
CN107899620A (en) * | 2015-06-29 | 2018-04-13 | 宣乐 | A kind of preparation method of MTO catalyst carrier |
CN105080601A (en) * | 2015-09-11 | 2015-11-25 | 宁波海越新材料有限公司 | Catalyst for preparing methyl ethyl ketone by dehydration of 2,3-butanediol, and preparation method of catalyst |
CN105080601B (en) * | 2015-09-11 | 2017-12-26 | 宁波海越新材料有限公司 | A kind of preparation method of 2,3 Butanediol preparing ethyl methyl ketone catalyst |
CN106540744A (en) * | 2015-09-22 | 2017-03-29 | 正大能源材料(大连)有限公司 | A kind of reuse method of sial phosphorus molecular sieve catalyst |
CN108602684A (en) * | 2016-03-16 | 2018-09-28 | 沙特基础工业全球技术公司 | The synthesis of SAPO-34 and the application in chloromethanes olefine reaction |
CN105772063B (en) * | 2016-04-13 | 2018-01-30 | 贵州大学 | A kind of molecular sieve catalyst of modified ZSM-5 5 and preparation method thereof |
CN105772065B (en) * | 2016-04-13 | 2018-01-30 | 贵州大学 | A kind of molecular sieve catalyst of modified ZSM-5 5 and preparation method thereof |
CN105854931B (en) * | 2016-04-13 | 2018-01-30 | 贵州大学 | A kind of preparation method of the molecular sieve catalysts of modified SAPO 34 |
CN105688981B (en) * | 2016-04-13 | 2018-02-09 | 贵州大学 | A kind of preparation method of the molecular sieve catalysts of modified SAPO 34 |
CN105854931A (en) * | 2016-04-13 | 2016-08-17 | 贵州大学 | Preparation method of modified SAPO-34 molecular sieve catalyst |
CN105772063A (en) * | 2016-04-13 | 2016-07-20 | 贵州大学 | Modified ZSM-5 molecular sieve based catalyst and preparing method thereof |
CN105772065A (en) * | 2016-04-13 | 2016-07-20 | 贵州大学 | Modified ZSM-5 molecular sieve based catalyst and preparing method thereof |
CN105688981A (en) * | 2016-04-13 | 2016-06-22 | 贵州大学 | Preparation method of modified SAPO-34 molecular sieve catalyst |
CN106732765A (en) * | 2016-12-14 | 2017-05-31 | 中国石油天然气股份有限公司 | Catalyst for preparing propylene from butylene and preparation method thereof |
CN108203102A (en) * | 2016-12-16 | 2018-06-26 | 中国石油天然气股份有限公司 | Composite modified SAPO-34 molecular sieve and preparation method thereof |
CN108203102B (en) * | 2016-12-16 | 2019-11-08 | 中国石油天然气股份有限公司 | Composite modified SAPO-34 molecular sieve and preparation method thereof |
CN107244679A (en) * | 2017-05-17 | 2017-10-13 | 汕头大学 | A kind of molecular sieves of spherical heteroatom Ni SAPO 34 and its preparation and application |
WO2019010815A1 (en) * | 2017-07-12 | 2019-01-17 | 中国科学院大连化学物理研究所 | Cu-sapo-34 molecular sieve synthesis method, and synthesized cu-sapo molecular sieve and application thereof |
CN110548538A (en) * | 2018-06-04 | 2019-12-10 | 中国科学院大连化学物理研究所 | Preparation method and application of metal modified SAPO-34 molecular sieve |
CN111013649A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Preparation method of Ni-SAPO-34 molecular sieve, prepared molecular sieve and application thereof |
CN111013649B (en) * | 2018-10-10 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of Ni-SAPO-34 molecular sieve, prepared molecular sieve and application thereof |
CN112209405A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve and synthetic method and application thereof |
CN110801862A (en) * | 2019-10-24 | 2020-02-18 | 杜成荣 | Catalyst for preparing low-carbon olefin from methanol |
CN112973782A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Bimetal modified catalyst and preparation method and application thereof |
CN111013650A (en) * | 2019-12-25 | 2020-04-17 | 山东江岳科技开发股份有限公司 | SAPO-34 molecular sieve thin-layer catalyst and preparation method thereof |
CN111744548A (en) * | 2020-07-09 | 2020-10-09 | 鲍周艳 | Ce-Ni/Ca-SAPO-34 catalyst and preparation method thereof |
CN113213506A (en) * | 2021-06-01 | 2021-08-06 | 江西师范大学 | Preparation method and application of metal modified SAPO-34 molecular sieve |
CN113600230A (en) * | 2021-08-02 | 2021-11-05 | 大连理工大学 | Efficient monatomic molecular sieve forming catalyst and preparation method thereof |
CN113600230B (en) * | 2021-08-02 | 2023-11-07 | 大连理工大学 | Efficient monoatomic molecular sieve forming catalyst and preparation method thereof |
CN114887586A (en) * | 2022-05-07 | 2022-08-12 | 西南化工研究设计院有限公司 | Production method of lithium molecular sieve with low silicon-aluminum ratio |
CN115283009A (en) * | 2022-08-11 | 2022-11-04 | 扬州晨化新材料股份有限公司 | SAPO-34-containing molecular sieve composition for continuously synthesizing tertiary amine catalyst for polyurethane and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN101555022B (en) | 2011-06-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101555022B (en) | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve | |
CN100584758C (en) | Fast synthetic method for phosphorus-silicon-aluminum molecular sieve | |
CN101885493B (en) | Synthesis method of ZSM-5/beta nuclear shell-shaped molecular sieve | |
CN104226360B (en) | Holocrystalline ZSM-5 molecular sieve catalyst and its production and use | |
CN102633279B (en) | Aluminum silicophosphate molecular sieve with macro-porous structure and preparation method thereof | |
CN104828842B (en) | A kind of preparation method of the composite molecular screen of SAPO 5 and 34 symbiosis of SAPO | |
CN109201109B (en) | Catalyst for preparing olefin from methanol and preparation method thereof | |
CN101259431B (en) | Cobalt modification silicoaluminophosphate molecular sieve and its preparation and catalytic application in MTO | |
CN105417552A (en) | Hierarchical porous SAPO-18 molecular sieve, preparation method thereof and application thereof | |
CN103495436A (en) | Method for manufacturing ALPO-5/SAPO-34 composite molecular sieve for preparing catalyst of low carbon olefin made of organic oxygenated chemicals | |
CN102372291A (en) | Preparation method of SAPO-18 / SAPO-34 intergrowth molecular sieve | |
CN101205072A (en) | Method for synthesizing low silica-alumina ratio beta zeolite | |
CN104056654A (en) | ZSM-5 molecular sieve composition, preparation method and application thereof | |
CN101633509B (en) | Method for modifying silica alumina phosphate molecular sieve | |
CN102627297A (en) | Synthetic method for SAPO (Silicoaluminophosphate)-34 molecular sieve | |
CN103663483B (en) | A kind of synthetic method of SAPO-34 molecular sieve and catalyzer prepared therefrom | |
CN103030158B (en) | Synthetic method of SAPO-44 molecular sieve modified by rare earth metals | |
CN103058208A (en) | Preparation method of SAPO-56 molecular sieve | |
CN1268591C (en) | Method for preparing olefin by conversion of methanol | |
CN106276964B (en) | A kind of transgranular phosphorous ZSM-5 molecular sieve and preparation method thereof | |
CN100368086C (en) | Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve | |
CN111115655B (en) | Eutectic nano molecular sieve, preparation method and application thereof | |
CN106660026A (en) | Crystalline porous silicoaluminophosphates and metal-substituted silicoaluminophosphates with a hierarchical pore structure comprising micropores and mesopores, methods for making the same, and processes for converting oxygenates to olefins via reactions catalyzed by the same | |
CN112456511B (en) | SAPO-34 molecular sieve, and preparation method and application thereof | |
CN1274596C (en) | Process for preparing metallic-ion-containing Si-P-Al 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 |