CN1112248C - Preparation of superstable Y-type molecular sieve - Google Patents
Preparation of superstable Y-type molecular sieve Download PDFInfo
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- CN1112248C CN1112248C CN 99125504 CN99125504A CN1112248C CN 1112248 C CN1112248 C CN 1112248C CN 99125504 CN99125504 CN 99125504 CN 99125504 A CN99125504 A CN 99125504A CN 1112248 C CN1112248 C CN 1112248C
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Abstract
The present invention discloses a preparing method of ultrlstable Y type molecular sieves, which uses Y type molecular sieves whose sodium oxide content is larger than 10 wt% as raw materials. The method comprises the following steps: uniformly mixing the molecular sieves, ammonium salt solution, metal salt solution, titanium oxide and mixed rare earth chloride in a weight ratio of 1: (0.2 to 2): (0.01 to 0.5): (0 to 0.2): (0 to 0.1); stirring the mixture for 0.5 to 4 hours at a pH value of 3.8 to 10.8 and a temperature of 20 to 90 DEG C; carrying out filtration and washing; calcining the mixture for 0.5 to 4 hours at 550 to 750 DEG C in a 100% steam atmosphere. The method can shorten procedures, increase the yield of the ultrastable Y type molecular sieves and reduce production cost.
Description
The invention relates to a kind of preparation method of super-stable Y molecular sieves.
In modern petroleum refining industry, along with the wide material sources of crude oil type with to the variation of oil fuel kind demand, and the proposition of the friendly oil fuel prescription of environmental protection, people have proposed more and more higher requirement to being used for the refining of petroleum catalyzer.In order to satisfy multiple class, multi-level different requirements to catalyzer, prepare suitable oil or petrochemical industry catalyzer, people have carried out many modification work to the catalyzer constituent element.
Y zeolite has regular crystalline structure, and the positively charged ion of pore structure, bigger serface, balance skeleton electric charge can be substituted isostructuralism matter uniformly, is highly effective catalyzer constituent element.
Super-stable Y molecular sieves (brief note for USY) is the product that people carry out modification to Y zeolite, and because of the structure super stabilizing, the thermostability height has good selectivity and becomes various oil or petrochemical process activity of such catalysts constituent element more and more.
The preparation method of super-stable Y molecular sieves has hydrothermal method, EDTA complexometry, silicon tetrachloride dealumination complement silicon method, ammonium silicofluoride aluminium-eliminating and silicon-replenishing method and hydro-thermal acidic treatment etc.USP3293172, USP3402996, USP3449070 at first disclose high-temperature vapor and have handled Y zeolite to obtain the method for super-stable Y molecular sieves, and this also is the method for the present industrial preparation USY that extensively adopts both at home and abroad.The primary feature of super stabilizing is that structure cell shrinks, and with respect to original NaY molecular sieve, its shrinkage amplitude is 1.0～1.5%.If sodium content in the NaY molecular sieve (in sodium oxide weight) height, then structure cell shrinks few; Sodium content is low, and then the amplitude of structure cell contraction is big.
In the process of Hydrothermal Preparation USY molecular sieve, in order to reduce sodium content to 0.5 (weight) below the %, shrink to obtain bigger structure cell, generally all need the NaY molecular sieve is carried out several times ammonium ion exchange and hydrothermal calcine, after being ion-exchange of NaY molecular sieve through ammonium and filtration, carry out hydrothermal calcine again.So repeat the process of ion-exchange and hydrothermal calcine, respectively once claim " one hands over a roasting ", respectively carry out twice title " two hand over two roastings ", hand over a roasting method as adopting two among the EP667185A1, CN1031030A, CN1060977A etc. adopt two to hand over two roasting methods.
Do not see so far at original NaY molecular sieve and adopt one to hand over the method for a roasting to make molecular sieve have big structure cell to shrink and keep the report of high crystallization reservation degree, do not see the report of when one hands over a roasting, in ultra-steady Y molecular sieve, introducing metallic element yet.
The objective of the invention is to provide on the basis of existing technology a kind of preparation method than the more simple containing metal super-stable Y molecular sieves of prior art.
Method provided by the invention be with Y zeolite in ammonium ion exchange, add metal ion solution and also carry out hydrothermal calcine.
According to method provided by the invention, the concrete steps of preparation super-stable Y molecular sieves are as follows: is raw material with sodium oxide content greater than the Y zeolite of 10 (weight) %, according to molecular sieve: ammonium salt: metal-salt: titanium oxide: the weight ratio of mixed chlorinated rare earth=1: 0.2～2: 0.01～0.5: 0～0.2: 0～0.1, with molecular sieve, ammonium salt solution, metal salt solution, titanium oxide, mixed chlorinated rare earth mixes, at pH value is 3.8～10.8,20-90 ℃ was stirred 0.5-4 hour down, after filtration, the washing back is at 550～750 ℃, in 100% the steam atmosphere roasting 0.5-4 hour, wherein said metal-salt was selected from Al, Ba, Ca, Mg, Sr, Sn, Sb, Zn, one of the salt of metals such as Zr or the mixture of two or more metal-salt wherein.
Said ammonium salt can be selected from ammonium chloride, ammonium sulfate or ammonium nitrate, wherein preferred ammonium chloride.
The optimum ratio of said molecular sieve, ammonium salt, metal-salt, titanium oxide, mixed chlorinated rare earth is 1: 1.0～1.8: 0.1～0.3: 0～0.1: 0～0.07.
The pH value preferable range is 5.0～7.0, and general available ammoniacal liquor or hydrochloric acid are regulated.
Adopt ordinary method to carry out the molecular sieve of a friendship one roasting Hydrothermal Preparation, though its structure cell has certain contraction, more than 24.50 , crystallization reservation degree is below 87% basically; Adopt two of ordinary method to hand over the USY molecular sieve of two roasting Hydrothermal Preparation, though its lattice constant below 24.5 , crystallization reservation degree has only about 70%.And method provided by the invention is to NaO
2Content has been taked in ammonium ion exchange greater than the Y zeolite of 10 (weight) %, the technical measures that also exchange with molecular sieve with the metal ion of IIA, IIIA, IVA, VA, IIB, IVB family, only carry out hydrothermal calcine one time, just can reach conventional hydrothermal method two and hand over just accessible structure cell shrinkage amplitude of two roastings, lattice constant is less than 24.48 , and crystallization reservation degree is higher, can remain on more than 90%.Therefore, method provided by the invention has shortened operation, can increase the output of USY, reduces production costs.
The USY molecular sieve that the inventive method is prepared, as the catalyzer constituent element, not only have ultra-steady Y molecular sieve inherent high hydrothermal stability, but also can provide owing to introducing other catalytic performance that metal ion brings, to satisfy the needs of different oil or petrochemical process.As contain the USY of Mg, Ca, Sr, Ba, can be used as anti-vanadium catalyst constituent element in the catalytic cracking process; The USY that contains metal ions such as Mg, Ca, Zn, Al can be used as catalytic reforming and isomerization catalyst constituent element and uses; Introduce the USY of above-mentioned metal ion and rare earth element, can be applied to the alkylated reaction of benzene; Introduce the USY of Zn, in shortening, also have the effect of removing the impurity nitride; Introduce the USY of Zr, can be used in the reactions such as decomposition of hydrocarbons, isomerization, alkylation.
Following example will be described further USY molecular sieve preparation method provided by the invention.
In the example in the molecular sieve content of sodium oxide, aluminum oxide and silicon-dioxide measure by 3271 type fluorescence analysers, the lattice constant of molecular sieve and crystallization reservation degree are measured by SIEMENS D5005D X-ray diffractometer, wherein:
Used NaY molecular sieve is the catalyst plant production of Qilu Petrochemical company, sodium oxide content 14 (weight) %, and silica alumina ratio 4.9, degree of crystallinity is 93%.
Agents useful for same is the chemically pure reagent that the Beijing Chemical Plant produces, and wherein ammonia concn is 25～28 (weight) %.
Used mixed chlorinated rare earth (RECl
x) produce by Inner Mongol Baotou rare earth factory, content of rare earth is counted 46 (weight) %, wherein La with rare earth oxide
2O
3=24.5 (weight) %, Ce
2O=6.0 (weight) %, Pr
6O
3=6.0 (weight) %, Nd
2O
3=9.5 (weight) %.Use preceding through 800 ℃ of roastings 1 hour.
Example 1
Get 50 gram NaY molecular sieves, be dispersed in the ammonium chloride solution of 200 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the magnesium chloride hexahydrate solution that adds 60 grams 20% (in magnesium chloride weight), the pH value of regulating the gained slurries with ammoniacal liquor is 6.5, is warming up to 90 ℃, stirs 2 hours, filter, to there not being acid group, put into aging equipment with 20 times decationized Y sieve water washings, be warming up to 600 ℃, the water vapour of feeding 100%, after the roasting 2 hours, with 20 times of deoxidation deionised water, oven dry, obtain the USY molecular sieve, numbering A.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Comparative Examples 1
Get 50 gram NaY molecular sieves, be dispersed in the ammonium chloride solution of 200 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the pH value of regulating the gained slurries with ammoniacal liquor is 6.5, is warming up to 90 ℃, stirs exchange 2 hours, filter, to there not being acid group, put into aging equipment with 20 times decationized Y sieve water washings, be warming up to 600 ℃, the water vapour of feeding 100%, roasting 2 hours obtains the USY molecular sieve, numbering A '.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Example 2
Getting 60 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 340 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the four water-calcium nitrate solution that adds 50 grams 25% (in nitrocalcite weight), the pH value of regulating the gained slurries with ammoniacal liquor is 6.0, be warming up to 85 ℃, stir exchange 2.5 hours, filter, to there not being acid group, put into aging equipment with 20 times decationized Y sieve water washings, be warming up to 640 ℃, the water vapour of feeding 100%, roasting is after 2 hours, with 20 times of deoxidation deionised water, oven dry obtains USY molecular sieve B.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Comparative Examples 2
Press the method preparation contrast molecular sieve for preparing molecular sieve B in the example 2, do not add ca nitrate soln when being ion-exchange, the molecular sieve that makes note is made B '.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Example 3
Get 50 gram NaY molecular sieves and be dispersed in the ammonium chloride solution of 200 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, add the alum liquor of 50 grams 11.2% (in Tai-Ace S 150 weight), the pH value of regulating the gained slurries with ammoniacal liquor is 6.8, filter, with 20 times decationized Y sieve water washings to there not being acid group, put into aging equipment, be warming up to 700 ℃, feed 100% water vapour, roasting is after 1.5 hours, with 20 times of deoxidation deionised water, oven dry,, the molecular sieve numbering C that obtains.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Comparative Examples 3
Press the method preparation contrast molecular sieve for preparing molecular sieve C in the example 3, do not add alum liquor when ion-exchange, the molecular sieve that obtains is numbered C '.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Example 4
Getting 50 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 150 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the zinc nitrate hexahydrate solution that adds 75 grams 30% (in zinc nitrate hexahydrate weight), the pH value of regulating the gained slurries with ammoniacal liquor is 5.2, be warming up to 80 ℃, stir exchange 2 hours, filter, with 20 times decationized Y sieve water washings to there not being acid group, put into aging equipment, be warming up to 620 ℃, feed 100% water vapour, roasting is after 2 hours, with 20 times of deoxidation deionised water, oven dry, the molecular sieve that obtains, numbering D.
Comparative Examples 4
Press the method preparation contrast molecular sieve for preparing molecular sieve D in the example 4, do not add zinc nitrate solution when ion-exchange, the molecular sieve that obtains is numbered D '.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Example 5
Getting 80 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 360 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the two water zirconium nitrate solutions that add 40 grams 20% (in two water zirconium nitrate weight), the magnesium chloride hexahydrate solution of 40 grams 20% (in magnesium chloride weight), the pH value of regulating slurries with ammoniacal liquor is 6.5, is warming up to 85 ℃, stirs exchange 2.0 hours, filter, to there not being acid group, put into aging equipment with 20 times decationized Y sieve water washings, be warming up to 660 ℃, the water vapour of feeding 100%, after the roasting 2 hours, with 20 times of deoxidation deionised water, oven dry, obtain the USY molecular sieve, numbering E.
The chemical constitution and the structural parameter of this molecular sieve of gained see Table 1.
Comparative Examples 5
Press the method preparation contrast molecular sieve for preparing molecular sieve E in the example 5, just when ion-exchange, do not add two water zirconium nitrate solutions and magnesium chloride hexahydrate solution, the molecular sieve that obtains, numbering E '.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Example 6
Getting 65 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 300 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the two water zirconium nitrate solutions that add 40 grams 20% (in two water zirconium nitrate weight), the re chloride that adds 15 grams 41.39% (mixed chlorinated rare earth weight meter), the pH value of regulating the gained slurries with ammoniacal liquor is 6.5, is warming up to 85 ℃, stirs exchange 2.0 hours, filter, to there not being acid group, put into aging equipment with 20 times decationized Y sieve water washings, be warming up to 680 ℃, the water vapour of feeding 100%, after the roasting 2.5 hours, with 20 times of deoxidation deionised water, oven dry, obtain the USY molecular sieve, numbering F.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Comparative Examples 6
Press the method preparation contrast molecular sieve for preparing molecular sieve F in the example 6, just do not add two water zirconium nitrate solution and re chlorides when ion-exchange, the molecular sieve that obtains is numbered F '.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
Example 7
Getting 80 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 360 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the two water zirconium nitrate solutions that add 25 grams 20% (in two water zirconium nitrate weight), the Adlerika of 30 grams 35% (in sal epsom weight), the mixed chlorinated rare earth solution that adds 10 grams, 41.39 heavy % (in mixed chlorinated rare earth weight), the pH value of regulating the gained slurries with ammoniacal liquor is 6.8, be warming up to 90 ℃, stir exchange 2.5 hours, filter, with 20 times decationized Y sieve water washings to there not being acid group, put into aging equipment, be warming up to 700 ℃, feed 100% water vapour, roasting is after 1.5 hours, with 20 times of deoxidation deionised water, oven dry obtains the USY molecular sieve, numbering G.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Comparative Examples 7
Press the method preparation contrast molecular sieve for preparing molecular sieve G in the example 7, do not add two water zirconium nitrate solutions, Adlerika and mixed chlorinated rare earth solution when ion-exchange, the molecular sieve that obtains is numbered G '.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Example 8
Getting 70 gram NaY molecular sieves is dispersed in the ammonium chloride solution of 310 grams 30% (in weight ammonium chloride), behind the stirring and evenly mixing, the titanium dioxide suspension liquid that adds 15 grams 30% (in titanium dioxide weight), the Adlerika of 40 grams 35% (in sal epsom weight), the mixed chlorinated rare earth solution that adds 10 grams 41.39% (in mixed chlorinated rare earth weight), the pH value of regulating the gained slurries with ammoniacal liquor is 6.0, be warming up to 90 ℃, stir exchange 2.0 hours, filter, with 20 times decationized Y sieve water washings to there not being acid group, put into aging equipment, be warming up to 680 ℃, feed 100% water vapour, roasting is after 2.5 hours, with 20 times of deoxidation deionised water, oven dry obtains the USY molecular sieve, numbering H.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Comparative Examples 8
Press the method preparation contrast molecular sieve for preparing molecular sieve H in the example 8, just do not add Adlerika, titanium dioxide suspension liquid and re chloride when ion-exchange, the molecular sieve that obtains is numbered H '.
The chemical constitution of gained molecular sieve and structural parameter the results are shown in Table 1.
Comparative Examples 9
Get the molecular sieve G ' of preparation in the Comparative Examples 7, replace the NaY molecular sieve, repeat the step of Comparative Examples 6, obtain two and hand over the molecular sieve of two roastings, be numbered G " with it.
The chemical constitution and the structural parameter of gained molecular sieve see Table 1.
As can be seen from Table 1, the USY molecular sieve that the present invention prepares is compared with adopting a molecular sieve of handing over a roasting hydrothermal method to make, bigger structure cell shrink grading is not only arranged, and crystallization reservation degree is higher; In addition as can be seen, though hydrothermal method routinely increases the contrast molecular sieve that the number of times of ion-exchange and hydrothermal calcine makes and also can reach bigger structure cell shrink grading, crystallization reservations degree is more much lower than the molecular sieve that the inventive method prepares.
The chemical constitution of table 1 molecular sieve and structural parameter
| Example number | The molecular sieve numbering | Chemical constitution, heavy % | Structural parameter | ||||
| Na 2O | Al 2O 3 | SiO 2 | Metal (in oxide compound) | Lattice constant | Crystallization reservation degree % | ||
| 1 | A | 2.0 | 20.5 | 74.9 | Mg，2.6 | 24.42 | 90.8 |
| 2 | B | 2.2 | 22.8 | 72.0 | Ca，3.0 | 24.45 | 90.0 |
| 3 | C | 2.3 | 24.5 | 73.2 | Al | 24.43 | 90.2 |
| 4 | D | 2.4 | 22.9 | 73.7 | Zn，1.0 | 24.48 | 90.4 |
| 5 | E | 2.3 | 21.5 | 72.6 | Zr，1.8 Mg，1.8 | 24.46 | 91.2 |
| 6 | F | 2.0 | 23.0 | 72.6 | Zr，1.3 RE，1.3 | 24.48 | 90.2 |
| 7 | G | 2.1 | 22.2 | 72.7 | Zr，1.1 Mg，0.9 RE，1.0 | 24.45 | 90.4 |
| 8 | H | 2.2 | 22.4 | 73.2 | Mg，0.7 Ti，0.7 RE，0.8 | 24.47 | 90.4 |
| Comparative Examples 1 | A’ | 2.8 | 23.6 | 74.6 | - | 24.54 | 84.7 |
| Comparative Examples 2 | B’ | 3.1 | 23.4 | 73.5 | - | 24.55 | 84.4 |
| Comparative Examples 3 | C’ | 2.9 | 24.1 | 73.0 | - | 24.51 | 84.8 |
| Comparative Examples 4 | D’ | 3.0 | 24.1 | 73.9 | - | 24.53 | 86.9 |
| Comparative Examples 5 | E’ | 3.1 | 24.4 | 73.5 | - | 24.52 | 80.8 |
| Comparative Examples 6 | F’ | 3.2 | 23.7 | 73.1 | - | 24.52 | 84.2 |
| Comparative Examples 7 | G’ | 3.0 | 23.5 | 73.5 | - | 24.51 | 85.6 |
| Comparative Examples 8 | H’ | 2.9 | 23.8 | 73.3 | - | 24.51 | 82.7 |
| Comparative Examples 9 | G” | 0.7 | 22.6 | 75.4 | - | 24.42 | 71.0 |
Claims (5)
1, a kind of preparation method of super-stable Y molecular sieves, it is characterized in that be raw material with sodium oxide content greater than 10 Y zeolites that weigh %, according to molecular sieve: ammonium salt: metal-salt: titanium oxide: the weight ratio of mixed chlorinated rare earth=1: 0.2～2: 0.01～0.5: 0～0.2: 0～0.1, with molecular sieve, ammonium salt solution, metal salt solution, titanium oxide, mixed chlorinated rare earth mixes, at pH value is 3.8-10.8,20-90 ℃ was stirred 0.5-4 hour down, after filtration, the washing back is at 550-750 ℃, in 100% the steam atmosphere roasting 0.5-4 hour, wherein said metal-salt was selected from Al, Ba, Ca, Mg, Sr, Sn, Sb, Zn, one of the metal-salt of Zr or the mixture of two or more metal-salt wherein.
2, in accordance with the method for claim 1, wherein said ammonium salt is selected from ammonium chloride, ammonium sulfate or ammonium nitrate.
3, in accordance with the method for claim 2, wherein said ammonium salt is an ammonium chloride.
4, in accordance with the method for claim 1, wherein said molecular sieve: ammonium salt: metal-salt: titanium oxide: the proportioning of mixed chlorinated rare earth is 1: 1.0～1.8: 0.1～0.3: 0～0.1: 0～0.07.
5, in accordance with the method for claim 1, wherein said pH value is 5～7.
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| CN 99125504 CN1112248C (en) | 1999-12-02 | 1999-12-02 | Preparation of superstable Y-type molecular sieve |
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|---|---|---|---|
| CN 99125504 CN1112248C (en) | 1999-12-02 | 1999-12-02 | Preparation of superstable Y-type molecular sieve |
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| CN1112248C true CN1112248C (en) | 2003-06-25 |
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Families Citing this family (6)
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| CN101134576B (en) * | 2006-09-01 | 2010-09-08 | 中国石油大学(北京) | Method for improving Y-shaped molecular sieve water heat stability by employing cage heteroatom |
| FR3012125A1 (en) * | 2013-10-22 | 2015-04-24 | China Petroleum & Chemical | |
| CN106145153B (en) * | 2015-03-31 | 2018-06-19 | 中国石油化工股份有限公司 | Modified y zeolite and its preparation and application |
| CN106145152B (en) * | 2015-03-31 | 2018-06-19 | 中国石油化工股份有限公司 | Modified Y zeolite and its preparation method and application |
| BR112018010444B1 (en) * | 2015-11-24 | 2021-10-05 | Basf Corporation | CATALYST, AND, METHOD FOR PRODUCING A MICROSPHERIC FLUID CATALYTIC CRACKING CATALYST |
| CN108201898A (en) * | 2016-12-20 | 2018-06-26 | 中国石油天然气股份有限公司 | Method for modifying Y-type molecular sieve |
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