CN1069552C - Preparation of super-stable Y molecular sieves - Google Patents
Preparation of super-stable Y molecular sieves Download PDFInfo
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- CN1069552C CN1069552C CN97116833A CN97116833A CN1069552C CN 1069552 C CN1069552 C CN 1069552C CN 97116833 A CN97116833 A CN 97116833A CN 97116833 A CN97116833 A CN 97116833A CN 1069552 C CN1069552 C CN 1069552C
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Abstract
The present invention provides a preparing method of ultrastable Y type molecular sieves. The method comprises the following steps: carrying out an ammonium ion exchange of NaY molecular sieves by using a conventional method; putting filtered cakes after filtration into a calcining furnace to calcine for 1 to 4 hours at 500 to 700 DEG C in a 100% steam atmosphere; circularly returning 10 to 40% of calcined products into the next batch of ammonium exchange slurry to continue the previous operation; continuously carrying out the operation in such as manner. The method shortens technology steps and reduces cost, and the obtained products are high in crystallization reserving degree and reach the crystal cell shrinking level of ultrastable Y type molecular sieves.
Description
The invention relates to a kind of preparation method of crystalline aluminosilicate zeolite, more specifically say the preparation method about a kind of superstable gamma-type faujasite.
The catalytic cracking of petroleum hydrocarbon is the Main Means of producing gasoline, diesel oil; the current subject matter that faces is; require on the one hand the more and more heavier feedstock oil of catalyzed cracking processing to improve the economic benefit of oil plant; because of society the needs of environmental protection are required to use unleaded gas on the other hand; therefore in the urgent need to mixing the Cracking catalyst of refining residual oil and energy producing high-octane gasoline, one of solutions is to replace widely used rare earth Y type molecular sieve as the active component of Cracking catalyst with super steady Y (USY) type molecular sieve more.
The method for preparing ultrastable in the prior art is existing multiple, such as silicon tetrachloride gas chemistry method (USP4701313), fluosilicic acid liquid chemical method (USP4503023) etc., but because the difficult operation of said method or environmental pollution are serious, the method for the at present industrial production ultra-steady Y molecular sieve that generally adopts remains the hydro-thermal method of early succeeding in developing. The earliest the method for production ultra-steady Y molecular sieve of report be by people such as C.V. McDaniel at USP3, the heat treating process of report namely exchanges to Na with the NaY raw material first in 449,0702O content is 1～4 heavy %, and then roasting under at least 700 ℃ high temperature obtains the overstable gamma zeolite that lattice constant is 2.440～2.455nm; The method is because sintering temperature is too high, and is larger to the structural deterioration of molecular sieve, and energy consumption is large, to having relatively high expectations of equipment. The people such as P.E.Zberly are at USP3,591, the method that proposes in 488 similarly, but in roasting process, introduce water vapour, can strengthen the structure cell shrinkage amplitude like this, reduce sintering temperature, obtain preferably effect, thereby this hydrothermal calcine method becomes the Main Means of present production super-stable Y molecular sieves.
Prepare in the method for super-stable Y molecular sieves at hydrothermal calcine, its key is must be with the Na of zeolite before hydrothermal calcine2The O content just can make to lower level the unit cell size of zeolite when hydrothermal calcine, obtain by a relatively large margin contraction and super stabilizing, simultaneously roasting can impel again the sodium ion that is in the zeolite sodalite cage mobile and be easy to exchangedly get off in the supercage. USP3 requires the Na of the Y zeolite before the hydrothermal calcine in the method that proposes in 591,488 and USP4,036,7392The level of the heavy % in O content to 1～4, but those skilled in the art knows the Na that can't make the NaY zeolite according to conventional method by an ammonium ion exchange2O reaches so low level, must be through twice above ammonium ion exchange, therefore general what is called " the two friendships two roast " technique (such as CN 1060976A) that adopts ammonium exchange → hydrothermal calcine → ammonium exchange → hydrothermal calcine during present industrial production super-stable Y molecular sieves, or adopt one to hand over a roasting to add again what is called " hydro-thermal-chemical method " technique (such as CN 1088247A) that a step chemical method is taken out aluminium, flow process is longer, and cost is also higher.
The purpose of this invention is to provide and a kind ofly prepare the method for super-stable Y molecular sieves by hydrothermal calcine, so that adopt better simply processing step just can prepare lattice constant a. Be not more than the super-stable Y molecular sieves of 2460nm.
Fig. 1 is the process flow diagram according to preparation super-stable Y molecular sieves of the present invention.
According to Fig. 1, the preparation method of super-stable Y molecular sieves provided by the present invention comprises: the NaY molecular sieve is carried out the exchange of ammonium ion according to conventional method, and the filter cake after it filters entered in the roaster under 500～700 ℃, the condition of 100% water vapour atmosphere roasting 1～4 hour; With 10～40% of the product after the roasting, described operation above preferred 15～30% circulations are returned and continued in the next group ammonium exchange slurries is carried out so continuously.
The condition of said ammonium ion exchange is in the method provided by the present invention: according to NaY: inorganic ammonium salt: H2O=1: (0.5～2.0): the weight ratio of (5～30) with the making beating of NaY molecular sieve and a kind of inorganic ammonium salt water evenly is adjusted to 2.3～6.5 with the PH of slurries, and 60～95 ℃ of lower exchanges 0.5～2 hour.
Said inorganic ammonium salt is ammonium sulfate, ammonium chloride or ammonium nitrate in the method provided by the present invention, wherein preferably ammonium sulfate or ammonium chloride.
In the method provided by the present invention after the said roasting 10～40%, preferred 15～30% cycle stock can carry out the ammonium exchange with the NaY slurries, all add when being the exchange of each ammonium 10～40% through the cycle stock of a hydrothermal calcine, can take full advantage of like this exchange capacity of residue ammonium salt in the NaY ammonium exchange equilibrium rear slurry, the structure cell of molecular sieve be shunk and reduces the Na of molecular sieve2O content is all beneficial.
Can be directly used in the preparation catalytic cracking catalyst according to the prepared super steady Y of the present invention (USY) type molecular sieve, perhaps further reduce Na through step ammonium ion exchange again2For the preparation of catalytic cracking catalyst, also can be combined with the more excellent super-stable Y molecular sieves of processability with chemical aluminium-eliminating and silicon-replenishing method behind the O.
The method for preparing super-stable Y molecular sieves provided by the present invention is characterised in that to be returned the product circulation behind the part hydrothermal calcine in the slurries of next group ammonium exchange, can take full advantage of so on the one hand the exchange potentiality of ammonium ion more than needed in the ammonium exchange slurries, make the Na of molecular sieve2O content further reduces. On the other hand because some molecular sieve has passed through above hydrothermal calcine twice, and the structure cell shrinkage amplitude improves, and to the Na of further reduction molecular sieve2O is beneficial, therefore can prepare lattice constant a with " once handing over a roasting " of the present invention technique. Be not more than the super-stable Y molecular sieves of 2.460nm, traditional " two hand over two roastings " technological process is simplified, reduced equipment investment, energy consumption and cost have been reduced, and products obtained therefrom has reached the requirement of super-stable Y molecular sieves, owing to reduced by an one-step baking step, the crystallization reservation degree of product is higher than the crystallization reservation degree of " two hand over two roastings " products obtained therefrom.
The following examples will be done to the present invention the explanation in a step. In each embodiment and Comparative Examples, the cell parameter of molecular sieve, crystallization reservation degree (take the NaY raw material as benchmark) and Na2O content is measured according to RIPP 145-90,146-90 and 127-90 standard method in " Petrochemical Engineering Analysis method " (RIPP test method) (nineteen ninety publishes for the volume such as Yang Cuiding, Science Press) respectively; The temperature failure temperature of molecular sieve is measured with DuPont 999 thermal analyzers.
Comparative Examples 1
With NaY molecular sieve (Chang Ling oil-refining chemical factory catalyst plant produce) and ammonium chloride and water according to NaY: NH4Cl∶H
2O=1: 1: 20 butt weight ratio making beating mixes, with watery hydrochloric acid the PH of slurries is adjusted to 3.0, then be warming up to 90 ℃ and also stir exchange 1 hour, filter filter cake and after the deionized water drip washing of NaY butt weight, put into pipe type calciner with 10 times, 560 ℃, (weight space velocity of water inlet is 2.0 o'clock to 100% water vapour-1) condition under roasting 2 hours, obtain conventional one and hand over the molecular sieve of a roasting, be designated as A-1, its performance is listed in the table 1. Acquired results shows that routinely one hands over molecular sieve lattice constant that a roasting flow process obtains greater than 2.460nm, does not reach the level of super-stable Y molecular sieves, and Na2O content is also higher.
Above-mentioned A-1 sample is sample as a comparison both, and the cycle stock that can be used as again back embodiment uses.
Comparative Examples 2
The effect of two roasting method gained molecular sieves is handed in this Comparative Examples explanation conventional two
Comparative Examples 1 gained sample A-1 is replaced the NaY raw material, repeat the step of an ammonium exchange, filtration, roasting according to the same procedure of Comparative Examples 1 again, just obtain conventional two and hand over the super-stable Y molecular sieves of two roastings, be designated as A-2, its performance is listed in the table 1.
Embodiment 1～7
With NaY molecular sieve (production of Chang Ling oil-refining chemical factory) and ammonium chloride and water according to NaY: NH4Cl∶H
2O=1: 1: 20 butt weight ratio making beating mixes, and behind the Comparative Examples 1 gained sample A-1 that wherein adds 25 heavy % (take the above-mentioned NaY raw material butt weight that adds as benchmark), with watery hydrochloric acid the PH of slurries is adjusted to 3.0, then be warming up to 90 ℃ and also stir exchange one hour, then filter, filter cake is put into the tubular type muffle furnace with 10 times after the deionized water drip washing of NaY butt weight, 560 ℃, (weight space velocity of water inlet is 2.0 o'clock to 100% water vapour-1) condition under roasting 2 hours, obtain the sample according to part circulation primary of the present invention, be designated as B-1.
Operating procedure above repeating once, difference is that used cycle stock changes above-mentioned sample B-1 into by A-1, obtains the sample according to part circulation secondary of the present invention, is designated as B-2.
Similarly again take the B-2 sample as cycle stock, repeat once described operating procedure, obtain the sample according to part of the present invention circulation three times, be designated as B-3.
So analogize, obtain respectively being designated as respectively B-4, B-5, B-6, B-7 according to circulation four of the present invention, five, six, seven times sample.
The performance of the above-mentioned sample of gained is listed in table-1.
Embodiment 8～12
With NaY molecular sieve and ammonium chloride and water according to NaY: NH4Cl∶H
2O=1: 1: 20 butt weight ratio making beating mixes, with dilute sulfuric acid (20 heavy %) PH of slurries is adjusted to 2.5, then be warming up to 90 ℃ and also stir exchange 30 minutes, behind the Comparative Examples 1 gained sample A-1 that wherein adds 25 heavy % (take the above-mentioned NaY raw material butt weight that adds as benchmark), continue exchange 30 minutes, then filter, filter cake is put into the tubular type muffle furnace with 10 times after the deionized water drip washing of NaY butt weight, roasting is 2 hours under 650 ℃, the condition of 100% water vapour atmosphere, obtain being designated as B-8 according to sample of the present invention.
Operating procedure above repeating, difference is that the PH of slurries is adjusted to respectively: (9) 3.5, (10) 4.0, (11) 4.5, (12) 5.0, obtain being designated as respectively B-9, B-10, B-11, B-12 according to sample of the present invention. The performance of these samples is listed in table-1.
Embodiment 13～16
With NaY molecular sieve and ammonium sulfate and water according to NaY: (NH4)
2SO
4∶H
2O=1: 1: 20 butt weight ratio making beating mixes, with dilute sulfuric acid the PH of slurries is adjusted to 3.0, then be warming up to 90 ℃ and also stir exchange 30 minutes, behind the Comparative Examples 1 gained sample A-1 that wherein adds 10 heavy % (take the above-mentioned NaY raw material butt weight that adds as benchmark), continue exchange 30 minutes, then filter, filter cake is put into the tubular type muffle furnace with 10 times after the deionized water drip washing of NaY butt weight, roasting is 2 hours under 650 ℃, the condition of 100% water vapour atmosphere, obtain being designated as B-13 according to sample of the present invention.
Operating procedure above repeating, difference is that the amount of the cycle stock A-1 of adding is respectively (14) 20%, (15) 30%, (16) 40% (all take NaY raw material butt weight as benchmark), obtain according to sample of the present invention, be designated as respectively B-14, B-15, B-16, the performance of these samples is listed in table-1.
Embodiment 17
With NaY molecular sieve and ammonium sulfate and water according to NaY: (NH4)
2SO
4∶H
2O=1: 0.75: 10 butt weight ratio making beating mixes, the Comparative Examples 1 gained sample A-1 that adds again 25 heavy % (take said NaY raw material butt weight as benchmark), after mixing, with dilute sulfuric acid the PH of slurries is adjusted to 3.0, then be warming up to 70 ℃ and also stir exchange 1 hour, then filter, filter cake is put into the tubular type muffle furnace, roasting is 1.5 hours under 600 ℃, the condition of 100% water vapour atmosphere, obtain according to sample of the present invention, be designated as B-17, its performance is listed in table-1.
Embodiment 18
With NaY molecular sieve and ammonium sulfate and water according to NaY: (NH4)
2SO
4∶H
2O=1: 1.5: 20 butt weight ratio making beating mixes, the Comparative Examples 1 gained sample A-1 that adds again 25 heavy % (take said NaY butt weight as benchmark), after mixing, with dilute sulfuric acid the PH of slurries is adjusted to 3.0, then be warming up to 80 ℃ and also stir exchange 1 hour, then filter, filter cake is put into the tubular type muffle furnace with 10 times after the deionized water drip washing of NaY butt weight, roasting is 3 hours under 600 ℃, the condition of 100% water vapour atmosphere, obtain according to sample of the present invention, be designated as B-18, its performance is listed in table-1.
Table 1
| Sample number into spectrum | Na 2O (heavy %) | Lattice constant a. (nm) | Crystallization reservation degree (%) | The temperature failure temperature (℃) | Crystallization reservation degree (%) behind 800 ℃/4 hours, 100% steam aging* |
| A-1 | 5.0 | 2.463 | 100 | 956 | 65 |
| A-2 | 0.83 | 2.452 | 82 | 994 | 63 |
| B-1 | 4.0 | 2.458 | 100 | 979 | 70 |
| B-2 | 3.8 | 2.458 | 100 | 974 | 69 |
| B-3 | 3.9 | 2.457 | 100 | 978 | 73 |
| B-4 | 4.0 | 2.458 | 100 | - | - |
| B-5 | 4.0 | 2.458 | 100 | - | - |
| B-6 | 4.0 | 2.457 | 100 | - | - |
| B-7 | 3.8 | 2.456 | 100 | - | - |
| B-8 | 3.8 | 2.453 | 100 | - | - |
| B-9 | 4.1 | 2.455 | 100 | - | - |
| B-10 | 4.0 | 2.455 | 100 | - | - |
| B-11 | 4.2 | 2.456 | 100 | - | - |
| B-12 | 4.1 | 2.457 | 100 | - | - |
| B-13 | 4.2 | 2.458 | 100 | - | - |
| B-14 | 4.1 | 2.458 | 100 | - | - |
| B-15 | 4.0 | 2.456 | 100 | - | - |
| B-16 | 3.9 | 2.455 | 100 | - | - |
| B-17 | 4.4 | 2.458 | 100 | - | - |
| B-18 | 3.8 | 2.457 | 98 | - | - |
*Compare with aging front sample
-do not measure
Claims (5)
1. method for preparing super-stable Y molecular sieves by hydrothermal calcine, it is characterized in that the method comprises that the NaY molecular sieve is carried out an ammonium ion according to conventional method to be exchanged, filter cake after it filters entered in the roaster under 500～700 ℃, the condition of 100% water vapour atmosphere roasting 1～4 hour, with 10～40% circulations of the product after the roasting return continue in the next group ammonium exchange slurries above described operation; Carry out so continuously.
2. according to the process of claim 1 wherein that the condition of said ammonium ion exchange is: according to NaY: inorganic ammonium salt: H2O=1: (0.5～2.0): the weight ratio of (5～30) with the making beating of NaY molecular sieve and a kind of inorganic ammonium salt water evenly is adjusted to 2.3～6.5 with the PH of slurries, and 60～95 ℃ of lower exchanges 0.5～2 hour.
3. according to the method for claim 2, wherein said inorganic ammonium salt is ammonium sulfate, ammonium chloride or ammonium nitrate.
4. according to the method for claim 3, wherein said inorganic ammonium salt is ammonium sulfate or ammonium chloride.
5. according to the method for claim 1, it is characterized in that 15～30% circulations of the product after the roasting are returned in the next group ammonium exchange slurries.
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| CN97116833A CN1069552C (en) | 1997-08-29 | 1997-08-29 | Preparation of super-stable Y molecular sieves |
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| CN97116833A CN1069552C (en) | 1997-08-29 | 1997-08-29 | Preparation of super-stable Y molecular sieves |
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| CN1069552C true CN1069552C (en) | 2001-08-15 |
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| CN100404134C (en) * | 2005-08-09 | 2008-07-23 | 中国石油化工股份有限公司 | Ammonium ion exchange method of NaY molecular sieve |
| CN100439246C (en) * | 2005-08-26 | 2008-12-03 | 吉林大学 | Hard template synthetic composite hole zeolite molecular sieve and its preparing method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3945943A (en) * | 1971-10-20 | 1976-03-23 | Union Oil Company Of California | Zeolite containing compositions, catalysts and methods of making |
| US4036739A (en) * | 1971-10-20 | 1977-07-19 | Union Oil Company Of America | Catalytic cracking process using ammonia-stable zeolite catalyst |
| CN1042523A (en) * | 1989-06-15 | 1990-05-30 | 中国石油化工总公司兰州炼油化工总厂 | A kind of method for preparing high-silicon Y-Zeolite |
| CN1060976A (en) * | 1990-11-02 | 1992-05-13 | 中国石油化工总公司石油化工科学研究院 | The preparation method who contains the ultrastable of amorphous alumina |
| CN1121484A (en) * | 1994-10-25 | 1996-05-01 | 中国石油化工总公司石油化工科学研究院 | High-silicon zeolite preparation |
-
1997
- 1997-08-29 CN CN97116833A patent/CN1069552C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3945943A (en) * | 1971-10-20 | 1976-03-23 | Union Oil Company Of California | Zeolite containing compositions, catalysts and methods of making |
| US4036739A (en) * | 1971-10-20 | 1977-07-19 | Union Oil Company Of America | Catalytic cracking process using ammonia-stable zeolite catalyst |
| CN1042523A (en) * | 1989-06-15 | 1990-05-30 | 中国石油化工总公司兰州炼油化工总厂 | A kind of method for preparing high-silicon Y-Zeolite |
| CN1060976A (en) * | 1990-11-02 | 1992-05-13 | 中国石油化工总公司石油化工科学研究院 | The preparation method who contains the ultrastable of amorphous alumina |
| CN1121484A (en) * | 1994-10-25 | 1996-05-01 | 中国石油化工总公司石油化工科学研究院 | High-silicon zeolite preparation |
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