CN101941714B - Method for synthesizing molecular sieve by modified kaolin - Google Patents
Method for synthesizing molecular sieve by modified kaolin Download PDFInfo
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- CN101941714B CN101941714B CN 200910012480 CN200910012480A CN101941714B CN 101941714 B CN101941714 B CN 101941714B CN 200910012480 CN200910012480 CN 200910012480 CN 200910012480 A CN200910012480 A CN 200910012480A CN 101941714 B CN101941714 B CN 101941714B
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Abstract
The invention discloses a method for synthesizing a molecular sieve by modified kaolin. The method comprises the following steps of: dividing the raw powder of kaolin into two parts, roasting one part of raw powder of kaolin at the temperature of between 300 and 600 DEG C for 1 to 5 hours to obtain roasted soil, performing acid treatment on the obtained roasted soil, filtrating, washing and drying, and then roasting at the temperature of between 700 and 900 DEG C for 1 to 5 hours to obtain secondary roasted soil; roasting the other part of raw powder of kaolin at the temperature of between 920 and 1,050 DEG C to obtain kaolin; and mixing the secondary roasted soil and the kaolin in a weight ratio of 5:1-1:5 to prepare the synthetic raw materials, crystallizing the synthetic raw materials to obtain the products containing an NaY molecular sieve. By the method, the kaolin is properly modified, and the NaY molecular sieve is synthesized in situ by the modified kaolin, so that the NaY molecular sieve content of the crystallized products is improved.
Description
Technical field
The invention belongs to the synthetic field of molecular sieve, specifically a kind of is that raw material is handled through modification with kaolin, then the method for synthetic NaY molecular sieve.
Background technology
Usually the method for preparing the NaY molecular sieve is to adopt alkaline silica-alumina gel system synthetic.The general raw material that adopts be water glass, Tai-Ace S 150, sodium metaaluminate, directed agents as raw material, synthesis of molecular sieve has molecular sieve content height, characteristics that silica alumina ratio is high like this, adopts different method of modifying, can make modified molecular screen have multiple reaction characteristics.
In the catalytic cracking field, the NaY molecular sieve remains topmost active ingredient and originates, and particularly the kaolin in-situ compound method is the important technology of catalytic cracking catalyst preparation.USP3506594, USP3503900, USP3647718 is on the high mountain range to be the technology that raw material prepares the in-situ crystallization zeolite of active constituent and matrix simultaneously, the FCC catalyzer that obtains with the in-situ crystallization method is called the kaolin type catalyzer, also claims full clay catalyst.Be active ingredient with gel method synthetic Y zeolite; Adopt the FCC catalyzer of semi-synthesizing technology preparation to compare; It is strong that full clay catalyst has the preventing from heavy metal pollution ability; It is flexible that advantages such as activity index is high, and hydrothermal stability, structural stability are good, shortcoming are that the adjustable sex change of active ingredient and matrix is not so good as semi-synthesis method.
When synthesizing the NaY molecular sieve with kaolin in early days, generally use metakaolin (hereinafter to be referred as inclined to one side soil) microballoon.UK1271450 has described kaolin has been become metakaolin in roasting below 704 ℃, again with the synthetic Y zeolite of reaction such as water glass; What USP3377006 described is to synthesize Y zeolite with special thin native partially powder.
USP3367886; USP3367887, USP3506594, USP3647718; USP3657154; USP3663165, the silica alumina ratio of Y zeolite is higher in the whole uses of proposition such as the USP3932268 in-situ crystallization product that high-temperature roasting kaolin (hereinafter to be referred as high soil) prepares more than 900 ℃, but percent crystallinity is generally between 20%-30%.
USP4493902 has described the technology that in same microballoon, contains inclined to one side soil and high soil and the synthetic high zeolite content crystallization product of crystal seed simultaneously; Crystallization product percent crystallinity is higher than 40%; But it is very high in should technology to the used ingredient requirement of spray shaping; Use high soil of super-refinement and super-refinement original soil ASP～600, this ultra-fine soil costs an arm and a leg, and is difficult on the market buying.
In above method, the synthetic of molecular sieve is that microballoon carries out later at the kaolin spray shaping, during the preparation catalyzer, and the modulation very flexible of component.
Summary of the invention
To the deficiency of prior art, the present invention provides that a kind of compound method is simple, in the crystallization product NaY molecular sieve content high be the method for the directly synthetic NaY molecular sieve of raw material with kaolin.
The present invention comprises following content with the method for modified kaolin synthesis of molecular sieve: the former powder of kaolin is divided into two portions; The former powder of part kaolin obtains roasting soil at 300 ℃ of-600 ℃ of roasting 1h-5h; Then the roasting soil that obtains is carried out s.t.; Filtration, washing, drying obtain re-baking soil (secondary is soil partially) at 700 ℃ of-900 ℃ of roasting 1h-5h then; The high soil that the former powder of another part kaolin obtains 920 ℃ of-1050 ℃ of roastings.With the inclined to one side soil of secondary and high soil by weight 5: 1-1: 5 mixed prepares synthesis material, obtains containing the product of NaY molecular sieve after the crystallization.
In the inventive method, synthesis material adds suitable component according to the conventional knowledge in this area, and like sodium hydroxide, water, directed agents, water glass etc., mixture ratio is: (4.0-4.5) Na
2O: (8-12) SiO
2: Al
2O
3: (160-210) H
2O.Crystallization condition is at 90 ℃ of-100 ℃ of crystallization 16h-36h.
In the inventive method; Key is the former powder of part kaolin is carried out lower temperature calcination, carry out s.t. then and remove activated alumina, and then roasting obtains secondary soil partially; Be characterized in that maturing temperature is 300 ℃-600 ℃ for the first time; Roasting time is 1h-5h, and maturing temperature is 920 ℃-1050 ℃ for the second time, and roasting time is 1h-5h.S.t. can be adopted monoprotic acid or diprotic acid; Monoprotic acid can be selected from one or more in the inorganic monoprotic acid, example hydrochloric acid, nitric acid etc., and said diprotic acid is selected from one or more in the inorganic diprotic acid; Preferably sulfuric acid wherein, the preferred 0.5-4.0mol/L of the concentration of said acid solution.Also can adopt the mixing acid of monoprotic acid and diprotic acid, the mol ratio of monoprotic acid and diprotic acid is preferably 2.0-6.0 in the mix acid liquor.Acid solution volumetric usage (ml) during s.t. is preferably 5-15 times of kaolin weight (g).The temperature of kaolin and acid-respons is 90 ℃-150 ℃ after the roasting, and the time is 4h-40h.
In the inventive method, described directed agents can be formed for this area is conventional, like a kind of concrete composition (mol ratio) is: (14-16) SiO
2: (0.7-1.3) Al
2O
3: (14-16) Na
2O: (300-330) H
2O.
Directed agents can adopt the conventional feedstock production in this area, and like sodium hydroxide, water glass, sodium metaaluminate, water etc., directed agents is pressed material rate preparation back at 25 ℃ of-45 ℃ of ageing 20h-30h, obtains directed agents.
The inventive method synthetic product has the characteristic spectrogram of the X light powder diffraction (XRD) of Y zeolite, and wherein NaY zeolite weight content is generally 30%-50%.
The inventive method utilizes the modified kaolin original position to synthesize the NaY molecular sieve through modification that kaolin is suited then.It is big that the kaolin of the inventive method modification (secondary is soil partially) has specific surface area; Pore volume is big; Characteristics such as pore size distribution is concentrated just provide more reaction touch opportunity like this in the process of synthetic NaY molecular sieve, help improving the content of NaY molecular sieve in the crystallization product.
Description of drawings
Fig. 1 is the XRD diffractogram of the embodiment of the invention 6 sinteticses.
Embodiment
The present invention is following with a kind of concrete grammar of modified kaolin synthesis of molecular sieve: be raw material with kaolin, the former powder of a part of kaolin obtained roasting soil at 300 ℃ of-600 ℃ of roasting 1h-5h, then with the roasting soil and the acid-respons that obtain; Filter; Use the deionized water wash product, the product after the dry washing obtains re-baking soil (secondary is soil partially) at 700 ℃ of-900 ℃ of roasting 1h-5h, the high soil that another part kaolin obtains 920 ℃ of-1050 ℃ of roastings; Two kinds of roasting kaolins are pressed 5: 1-1: after 5 the mixed; Add sodium hydroxide, chemical water, directed agents, water glass etc.,, remove by filter mother liquor in 90 ℃ of-100 ℃ of crystallization 16h-36h; It is below 9 that cakes with deionized water is washed till pH, obtains the molecular sieve of a kind of NaY of comprising after the drying.
Further specify preparation process of the present invention below in conjunction with embodiment.
Embodiment 1-5 is the modifying kaolin scheme
Embodiment 1
500g Suzhou kaolin at 450 ℃ of roasting 3h, is taken by weighing kaolin 60.0g and the reaction of 120.0ml mixed acid solution after the roasting, and mixed acid solution is prepared with the 20.0ml 37wt% hydrochloric acid and the 3.4ml 98wt% vitriol oil; Temperature of reaction is 100 ℃, and the reaction times is 26 hours, filters; With deionized water wash to there not being acid group; Drying then 850 ℃ of roastings 2 hours, obtains secondary soil 1 partially.
500g Suzhou kaolin at 550 ℃ of roasting 2h, is taken by weighing kaolin 60.0g and the reaction of 120.0ml hydrochloric acid soln after the roasting, and the salt salts solution adopts the preparation of 30.0ml 37wt% hydrochloric acid; 100 ℃ of reactions 26 hours; Filter, with deionized water wash to not having acid group, drying; 850 ℃ of roastings 2 hours, obtain secondary soil 2 partially then.
Embodiment 3
500g Suzhou kaolin at 550 ℃ of roasting 2h, is taken by weighing kaolin 60.0g and the reaction of 120.0ml sulphuric acid soln after the roasting, and sulphuric acid soln adopts the preparation of the 4.0ml 98wt% vitriol oil; 100 ℃ of reactions 24 hours; Filter, with deionized water wash to not having acid group, drying; 830 ℃ of roastings 2 hours, obtain secondary soil 3 partially then.
Embodiment 4
500g Suzhou kaolin at 550 ℃ of roasting 3h, is taken by weighing kaolin 60.0g and the reaction of 120.0ml mixed acid solution after the roasting, and mixed acid solution adopts 20.0ml 37wt% hydrochloric acid and 2.7ml 60wt% nitric acid to prepare; 120 ℃ of reactions 10 hours; Filter, with deionized water wash to not having acid group, drying; 820 ℃ of roastings 2 hours, obtain secondary soil 4 partially then.
Embodiment 5
500g Suzhou kaolin at 600 ℃ of roasting 3h, is taken by weighing kaolin 60.0g and the reaction of 120.0ml mixed acid solution after the roasting, and mixed acid solution adopts the 30.0ml 37wt% hydrochloric acid and the 5.0ml 98wt% vitriol oil to prepare; Temperature of reaction is 90 ℃, and the reaction times is 8 hours, filters; With deionized water wash to there not being acid group; Drying then 850 ℃ of roastings 2 hours, obtains secondary soil 5 partially.
The kaolinic main character of table 1 typical modification
| The kaolin sample | The kaolin original soil | Embodiment 1 secondary is soil 1 partially | Embodiment 3 secondaries are soil 3 partially | Embodiment 5 secondaries are soil 5 partially |
| Specific surface (m 2/g) | 25 | ?155 | ?75 | ?130 |
| Pore volume (ml/g) | 0.11 | ?0.24 | ?0.16 | ?0.20 |
The molecular sieve synthetic schemes
Embodiment 6
With former Suzhou kaolin is raw material, gets 3g 950 ℃ of roastings in muffle furnace and obtains high soil in 2 hours, and other gets native partially 1 thorough mixing of 3g secondary.Successively with water glass 10.0ml, sodium hydroxide 0.92g, directed agents 5.0ml, deionized water 30ml and the high soil that mixes and secondary partially soil 1 drop in the stainless steel reactor, be warmed up to 100 ℃ and thermostatic crystallization 24 hours.Crystallization removes by filter mother liquor after finishing, and washing, dry cake obtain crystallization product.Measure through X-ray diffraction, contain 30% NaY zeolite in the crystallization product.
Embodiment 7
With former Suzhou kaolin is raw material, gets 4g 1000 ℃ of roastings in muffle furnace and obtains high soil in 2 hours, and other gets native partially 1 thorough mixing of 2g secondary.Successively with water glass 7.5ml, sodium hydroxide 1.25g, directed agents 5.0ml, deionized water 32.5ml and the high soil that mixes and secondary partially soil drop in the stainless steel reactor, be warmed up to 100 ℃ and thermostatic crystallization 24 hours.Crystallization removes by filter mother liquor after finishing, and washing, dry cake obtain crystallization product.Measure through X-ray diffraction, contain 27% NaY zeolite in the crystallization product.
Embodiment 8
With former Suzhou kaolin is raw material, gets 2g 950 ℃ of roastings in muffle furnace and obtains high soil in 2 hours, and other gets native partially 2 thorough mixing of 4g secondary.Successively with water glass 12.5ml, sodium hydroxide 0.58g, directed agents 5.0ml, deionized water 27.5ml and the high soil that mixes and secondary partially soil drop in the stainless steel reactor, be warmed up to 100 ℃ and thermostatic crystallization 24 hours.Crystallization removes by filter mother liquor after finishing, and washing, dry cake obtain crystallization product.Measure through X-ray diffraction, contain 45% NaY zeolite in the crystallization product.
Embodiment 9
With former Suzhou kaolin is raw material, gets 0.5g 950 ℃ of roastings in muffle furnace and obtains high soil in 2 hours, and other gets native partially 1 thorough mixing of 5.5g secondary.Successively with water glass 12.5ml, sodium hydroxide 0.58g, directed agents 5.0ml, deionized water 27.5ml and the high soil that mixes and secondary partially soil drop in the stainless steel reactor, be warmed up to 100 ℃ and thermostatic crystallization 24 hours.Crystallization removes by filter mother liquor after finishing, and washing, dry cake obtain crystallization product.Measure through X-ray diffraction, contain 50% NaY zeolite in the crystallization product.
With former Suzhou kaolin is raw material, gets 3g 950 ℃ of roastings in muffle furnace and obtains high soil in 2 hours, and other gets native partially 3 thorough mixing of 3g secondary.Successively with water glass 10.0ml, sodium hydroxide 0.92g, directed agents 5.0ml, deionized water 30ml and the high soil that mixes and secondary partially soil drop in the stainless steel reactor, be warmed up to 90 ℃ and thermostatic crystallization 24 hours.Crystallization removes by filter mother liquor after finishing, and washing, dry cake obtain crystallization product.Measure through X-ray diffraction, contain 35% NaY zeolite in the crystallization product.
Embodiment 11
With former Suzhou kaolin is raw material, gets 3g 950 ℃ of roastings in muffle furnace and obtains high soil in 2 hours, and other gets native partially 3 thorough mixing of 3g secondary.High soil that successively water glass 5.0ml, sodium hydroxide 1.63g, directed agents 5.0ml, deionized water 35ml is mixed and secondary soil partially drop in the stainless steel reactor, are warmed up to 90 ℃ and thermostatic crystallization 28 hours.Crystallization removes by filter mother liquor after finishing, and washing, dry cake obtain crystallization product.Measure through X-ray diffraction, contain 30% NaY zeolite in the crystallization product.
Embodiment 12
With former Suzhou kaolin is raw material, gets 3g 950 ℃ of roastings in muffle furnace and obtains high soil in 2 hours, and other gets native partially 4 thorough mixing of 3g secondary.Successively with water glass 5.0ml, sodium hydroxide 1.63g, directed agents 5.0ml, deionized water 35ml and the high soil that mixes and secondary partially soil drop in the stainless steel reactor, be warmed up to 100 ℃ and thermostatic crystallization 20 hours.Crystallization removes by filter mother liquor after finishing, and washing, dry cake obtain crystallization product.Measure through X-ray diffraction, contain 33% NaY zeolite in the crystallization product.
Embodiment 13
With former Suzhou kaolin is raw material, gets 1g 950 ℃ of roastings in muffle furnace and obtains high soil in 2 hours, and other gets native partially 5 thorough mixing of 5g secondary.Successively with water glass 10.0ml, sodium hydroxide 0.92g, directed agents 5.0ml, deionized water 30ml and the high soil that mixes and secondary partially soil drop in the stainless steel reactor, be warmed up to 90 ℃ and thermostatic crystallization 24 hours.Crystallization removes by filter mother liquor after finishing, and washing, dry cake obtain crystallization product.Measure through X-ray diffraction, contain 50% NaY zeolite in the crystallization product.
Claims (10)
1. method with the modified kaolin synthesis of molecular sieve; It is characterized in that: the former powder of kaolin is divided into two portions; The former powder of part kaolin obtains roasting soil at 300 ℃ of-600 ℃ of roasting 1h-5h; Then the roasting soil that obtains is carried out s.t., filtration, washing, drying obtain secondary soil partially at 700 ℃ of-900 ℃ of roasting 1h-5h then; The high soil that the former powder of another part kaolin obtains 920 ℃ of-1050 ℃ of roastings; With the inclined to one side soil of secondary and high soil by weight 5: 1-1: 5 mixed prepares synthesis material, obtains containing the product of NaY molecular sieve after the synthesis material crystallization.
2. according to the described method of claim 1, it is characterized in that: comprise sodium hydroxide, water, directed agents and water glass in the described synthesis material, mixture ratio is (4.0-4.5) Na
2O: (8-12) SiO
2: Al
2O
3: (160-210) H
2O.
3. according to the described method of claim 1, it is characterized in that: the crystallization condition of synthesis material is at 90 ℃ of-100 ℃ of crystallization 16h-36h.
4. according to the described method of claim 1, it is characterized in that: the mixing acid of monoprotic acid, diprotic acid or monoprotic acid and diprotic acid is adopted in described s.t..
5. according to claim 1 or 4 described methods, it is characterized in that: the acid strength that the former powder s.t. of kaolin is used is 0.5-4.0mol/L.
6. according to the described method of claim 4, it is characterized in that: described monoprotic acid is hydrochloric acid or nitric acid, and described diprotic acid is a sulfuric acid.
7. according to the described method of claim 1, it is characterized in that: the acid-treated acid solution volumetric usage of the former powder of kaolin is counted kaolin weight 5-15 times with g in ml.
8. according to the described method of claim 1, it is characterized in that: described s.t. temperature of reaction is 90 ℃-150 ℃, and the time is 4h-40h.
9. according to the described method of claim 2, it is characterized in that: the mole of said directed agents consists of: (14-16) SiO
2: (0.7-1.3) Al
2O
3: (14-16) Na
2O: (300-330) H
2O.
10. according to the described method of claim 9, it is characterized in that: the raw material of preparation directed agents comprises sodium hydroxide, water glass, sodium metaaluminate, and directed agents is pressed material rate preparation back at 25 ℃ of-45 ℃ of ageing 20h-30h, obtains directed agents.
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| CN112919493B (en) * | 2021-02-05 | 2022-10-14 | 正大能源材料(大连)有限公司 | Method for preparing SSZ-13 molecular sieve at low cost and application thereof |
| CN115536036B (en) * | 2021-06-30 | 2024-03-12 | 中国石油化工股份有限公司 | Modified kaolin, preparation method thereof, method for synthesizing molecular sieve by in-situ crystallization and NaY molecular sieve |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4843052A (en) * | 1982-05-21 | 1989-06-27 | W. R. Grace & Co.-Conn. | Acid-reacted metakaolin catalyst and catalyst support compositions |
| CN1195014A (en) * | 1997-03-31 | 1998-10-07 | 中国石油化工总公司 | Process for modifying kaolin |
| US6004527A (en) * | 1997-09-29 | 1999-12-21 | Abb Lummus Global Inc. | Method for making molecular sieves and novel molecular sieve compositions |
| CN1334142A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for synthesizing molecular sieve from gaolin |
-
2009
- 2009-07-09 CN CN 200910012480 patent/CN101941714B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4843052A (en) * | 1982-05-21 | 1989-06-27 | W. R. Grace & Co.-Conn. | Acid-reacted metakaolin catalyst and catalyst support compositions |
| CN1195014A (en) * | 1997-03-31 | 1998-10-07 | 中国石油化工总公司 | Process for modifying kaolin |
| US6004527A (en) * | 1997-09-29 | 1999-12-21 | Abb Lummus Global Inc. | Method for making molecular sieves and novel molecular sieve compositions |
| CN1334142A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for synthesizing molecular sieve from gaolin |
Non-Patent Citations (2)
| Title |
|---|
| 刘从华等.酸改性高岭土基质FCC催化剂的反应性能.《工业催化》.2003,第11卷(第4期),49-52. * |
| 刘娟娟等.高岭土的改性及其用于合成分子筛的国内研究进展.《中外能源》.2008,第13卷(第5期),87-93. * |
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