CN103663486A - Synthetic method of agglomerate Beta-zeolite - Google Patents
Synthetic method of agglomerate Beta-zeolite Download PDFInfo
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- CN103663486A CN103663486A CN201210528706.6A CN201210528706A CN103663486A CN 103663486 A CN103663486 A CN 103663486A CN 201210528706 A CN201210528706 A CN 201210528706A CN 103663486 A CN103663486 A CN 103663486A
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Abstract
The invention provides a synthetic method of agglomerate Beta-zeolite. Disodium hydrogen phosphate or sodium dihydrogen phosphate is introduced into synthetic reactants, so that the crystals are piled up in the crystallization process; as a result, the filter efficiency of the fine granulated beta-zeolite can be improved, and secondary pores also can be formed so that beneficial diffusion pores are provided for the catalytic products. The agglomerate Beta-zeolite is possible to show excellent prospect as the catalyst in fluid catalytic cracking of crude oil, etherification of cracked light gasoline and isomerization reaction of straight-chain paraffin.
Description
Technical field
The invention belongs to catalytic chemistry field, is exactly a kind of method of the Beta of reunion zeolite molecular sieve specifically.
Background technology
First β zeolite Shi You U.S. Mobil oil company researched and developed in 1967, there is three-dimensional twelve-ring intersection pore passage structure, the characteristic with high silica alumina ratio, and can to the scope of hundreds of, carry out modulation tens, in a series of catalyzed reactions, there is good heat and hydrothermal stability, acid resistance, anti-coking and catalytic activity, and aspect absorption, also show good performance, developed rapidly in recent years and become a kind of novel catalytic material.Yet β zeolite grain is thinner, sintetics is filtered, in washing process, makes filtration resistance increase because crystal grain is too careful, cause that the production efficiency of β zeolite is low.Therefore, its crystal is piled up in crystallization process, not only can be improved the filtration efficiency of beta zeolite in small crystal grain, can also form secondary pore, for its catalysate provides useful diffusion duct.
By add tensio-active agent cetyl trimethylammonium bromide in system, can realize the reunion of synthetic product.But experimental result shows.The method exists two unfavorable factors: the first, need to add tensio-active agent cetyl trimethylammonium bromide; The second, adding of tensio-active agent makes crystallization time extend to more than 10 days by 3-5 days.
Summary of the invention
The reunite synthetic method of Beta zeolite, has following steps: mixed alkali metal oxide source, alumina source, silica source and water stir synthetic initial gel; Add organic formwork agent and agglomerator, stirring at room, to evenly, packs in reactor again, and 140～170 ℃ of crystallization of temperature 24～80 hours, quenching was to room temperature, washing, filters, and obtains beta-zeolite molecular sieve; The mol ratio of preparing the various raw materials of initial gel is: SiO
2/ Al
2o
3=28.8～55, Na
2o/SiO
2=0.076～0.160, H
2o/SiO
2=4～7, organic formwork agent/SiO
2=0.08～0.15, agglomerator/Al
2o
3=0.1～0.2.
Described silica source can be white carbon black, and alkali metal hydroxide source is sodium hydroxide, and alumina source is NaAlO
2or pseudo-boehmite (Al
2o
3mass content 65.25%), organic formwork agent is tetraethyl ammonium hydroxide, and water is deionized water, and described agglomerator is SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic, and agglomerator add-on is NaH
2pO
4/ Al
2o
3=0.1～0.2, or Na
2hPO
4/ Al
2o
3=0.1.
Of the present invention by adding inorganic salt SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic in the synthetic system to Beta zeolite molecular sieve, make the state of aggregation of synthetic product evenly controlled, yield improves, for industrial development brings better application prospect.
Accompanying drawing explanation
Fig. 1 is the XRD figure (XRD figure of embodiment 3 synthetic Beta molecular sieve product as shown in Figure 1) of the embodiment of the present invention 1 synthesized sample.
Fig. 2 is the stereoscan photograph (stereoscan photograph of embodiment 5 synthetic Beta molecular sieve product as shown in Figure 2) of the embodiment of the present invention 2 synthetic Beta molecular sieve product.
embodiment
Embodiment 1
At 25 ℃, 4.26 milliliters of NaOH solution getting 3.98 mol/L, add 1.16 grams of solid sodium metaaluminates, then add 12.3 grams of white carbon blacks, stir 45 minutes rapidly, and then splash into while stirring 14.26 milliliter of 25% tetraethyl ammonium hydroxide, then add 5.6 milliliters of deionized waters, then add 0.17 gram of SODIUM PHOSPHATE, MONOBASIC, stir and after evenly, move in stainless steel cauldron for 30 minutes, in 150 ℃ of crystallization 48 hours, then collect, wash, dry, obtain product.
At 25 ℃, 4.26 milliliters of NaOH solution getting 3.98 mol/L, add 1.74 grams of pseudo-boehmites, then add 12.3 grams of white carbon blacks, stir 45 minutes rapidly, and then splash into while stirring 14.26 milliliter of 25% tetraethyl ammonium hydroxide, then add 5.6 milliliters of deionized waters, then add 0.268 gram of SODIUM PHOSPHATE, MONOBASIC, stir and after evenly, move in stainless steel cauldron for 30 minutes, in 150 ℃ of crystallization 52 hours, then collect, wash, dry, obtain product.
Embodiment 3
At 25 ℃, 4.26 milliliters of NaOH solution getting 3.98 mol/L, add 1.16 grams of solid sodium metaaluminates, then add 12.3 grams of white carbon blacks, stir 45 minutes rapidly, and then splash into while stirring 14.26 milliliter of 25% tetraethyl ammonium hydroxide, then add 5.6 milliliters of deionized waters, then add 0.1 gram of Sodium phosphate dibasic, stir and after evenly, move in stainless steel cauldron for 30 minutes, in 150 ℃ of crystallization 72 hours, then collect, wash, dry, obtain product.
Embodiment 4
At 25 ℃, 4.26 milliliters of NaOH solution getting 3.98 mol/L, add 1.74 grams of pseudo-boehmites, then add 12.3 grams of white carbon blacks, stir 45 minutes rapidly, and then splash into while stirring 14.26 milliliter of 25% tetraethyl ammonium hydroxide, then add 5.6 milliliters of deionized waters, then add 0.085 gram of SODIUM PHOSPHATE, MONOBASIC, stir and after evenly, move in stainless steel cauldron for 30 minutes, in 140 ℃ of crystallization 80 hours, then collect, wash, dry, obtain product.
At 25 ℃, 4.26 milliliters of NaOH solution getting 3.98 mol/L, add 1.74 grams of pseudo-boehmites, then add 12.3 grams of white carbon blacks, stir 45 minutes rapidly, and then splash into while stirring 14.26 milliliter of 25% tetraethyl ammonium hydroxide, then add 5.6 milliliters of deionized waters, then add 0.085 gram of SODIUM PHOSPHATE, MONOBASIC, stir and after evenly, move in stainless steel cauldron for 30 minutes, in 150 ℃ of crystallization 52 hours, then collect, wash, dry, obtain product.
Embodiment 6
At 25 ℃, get 4.26 milliliters of the NaOH solution of 3.98 mol/L, add 1.16 grams of solid sodium metaaluminates, add again 12.3 grams of white carbon blacks, stir 45 minutes rapidly, and then splash into while stirring 14.26 milliliter of 25% tetraethyl ammonium hydroxide, then add 5.6 milliliters of deionized waters, then add 0.085 gram of SODIUM PHOSPHATE, MONOBASIC, stir and after evenly, move in stainless steel cauldron for 30 minutes,, in 160 ℃ of crystallization 42 hours, then collect, wash, be dried, obtain product.
Embodiment 7
At 25 ℃, 4.26 milliliters of NaOH solution getting 3.98 mol/L, add 1.74 grams of pseudo-boehmites, then add 12.3 grams of white carbon blacks, stir 45 minutes rapidly, and then splash into while stirring 14.26 milliliter of 25% tetraethyl ammonium hydroxide, then add 5.6 milliliters of deionized waters, then add 0.134 gram of SODIUM PHOSPHATE, MONOBASIC, stir and after evenly, move in stainless steel cauldron for 30 minutes, in 160 ℃ of crystallization 48 hours, then collect, wash, dry, obtain product.
Embodiment 8
At 25 ℃, 4.26 milliliters of NaOH solution getting 3.98 mol/L, add 1.16 grams of solid sodium metaaluminates, then add 12.3 grams of white carbon blacks, stir 45 minutes rapidly, and then splash into while stirring 14.26 milliliter of 25% tetraethyl ammonium hydroxide, then add 5.6 milliliters of deionized waters, then add 0.085 gram of SODIUM PHOSPHATE, MONOBASIC, stir and after evenly, move in stainless steel cauldron for 30 minutes, in 150 ℃ of crystallization 48 hours, then collect, wash, dry, obtain product.
Embodiment 9
At 25 ℃, 4.26 milliliters of NaOH solution getting 3.98 mol/L, add 1.74 grams of pseudo-boehmites, then add 12.3 grams of white carbon blacks, stir 45 minutes rapidly, and then splash into while stirring 14.26 milliliter of 25% tetraethyl ammonium hydroxide, then add 5.6 milliliters of deionized waters, then add 0.134 gram of SODIUM PHOSPHATE, MONOBASIC, stir and after evenly, move in stainless steel cauldron for 30 minutes, in 150 ℃ of crystallization 52 hours, then collect, wash, dry, obtain product.
Claims (3)
1. the reunite synthetic method of Beta zeolite, has following steps: mixed alkali metal oxide source, alumina source, silica source and water stir synthetic initial gel; Add organic formwork agent and agglomerator, stirring at room, to evenly, packs in reactor again, and 140～170 ℃ of crystallization of temperature 24～80 hours, quenching was to room temperature, washing, filters, and obtains beta-zeolite molecular sieve; The mol ratio of preparing the various raw materials of initial gel is: SiO
2/ Al
2o
3=28.8～55, Na
2o/SiO
2=0.076～0.160, H
2o/SiO
2=4～7, organic formwork agent/SiO
2=0.08～0.15, agglomerator/Al
2o
3=0.1～0.2.
2. according to claim 1, described silica source can be white carbon black, and alkali metal hydroxide source is sodium hydroxide, and alumina source is NaAlO
2or pseudo-boehmite (Al
2o
3mass content 65.25%), organic formwork agent is tetraethyl ammonium hydroxide, and water is deionized water.
3. according to claim 1, described agglomerator is SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic, and agglomerator add-on is NaH
2pO
4/ Al
2o
3=0.1～0.2, or Na
2hPO
4/ Al
2o
3=0.1.
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| CN201210528706.6A CN103663486A (en) | 2012-12-11 | 2012-12-11 | Synthetic method of agglomerate Beta-zeolite |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107804856A (en) * | 2017-12-13 | 2018-03-16 | 山东齐鲁华信高科有限公司 | The direct synthesis method of high silica alumina ratio Beta molecular sieves |
| CN108203100A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | Method for improving filtering speed of Y-type molecular sieve |
-
2012
- 2012-12-11 CN CN201210528706.6A patent/CN103663486A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108203100A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | Method for improving filtering speed of Y-type molecular sieve |
| CN108203100B (en) * | 2016-12-20 | 2020-07-14 | 中国石油天然气股份有限公司 | Method for improving filtering speed of Y-type molecular sieve |
| CN107804856A (en) * | 2017-12-13 | 2018-03-16 | 山东齐鲁华信高科有限公司 | The direct synthesis method of high silica alumina ratio Beta molecular sieves |
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Application publication date: 20140326 |