CN1058682C - High efficiency manufacture of NaY zeolite - Google Patents

High efficiency manufacture of NaY zeolite Download PDF

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CN1058682C
CN1058682C CN96114271A CN96114271A CN1058682C CN 1058682 C CN1058682 C CN 1058682C CN 96114271 A CN96114271 A CN 96114271A CN 96114271 A CN96114271 A CN 96114271A CN 1058682 C CN1058682 C CN 1058682C
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nay
preparation
directed agents
sio
preparing
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CN1185996A (en
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杨小明
舒兴田
冯强
罗京娥
何鸣元
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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China Petrochemical Corp
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Abstract

The present invention relates to a method for preparing NaY zeolites. In the method, guiding agents are prepared with a method in conventional NaY preparation methods for preparing guiding agents, and hydrothermal crystallization is carried out according to conventional methods after the guiding agents, aluminate and aluminum salt are uniformly mixed with water glass whose temperature is from 40 to 100 DEG C. The molar composition of the reaction mixture accords with the proportion of (1.8-4.0)Na2O to Al2O3 to (7-12)SiO2 to (100-180)H2O, and Al2O3 in the guiding agents takes 1 to 10 W% of the total Al2O3 of mixed materials. The method provided in the present invention can greatly increase the single-kettle yield of NaY, and the quality the obtained NaY products is equivalent to that of NaY products prepared with conventional methods.

Description

A kind of high-efficiency synthesis method of NaY zeolite
The present invention relates to NaY prepare zeolite method.
The NaY zeolite is the main raw material of preparation catalyst of cracking petroleum.The chemical formula of the NaY zeolite described in the USP 3103007 is 0.9 ± 0.2Na 2O: Al 2O 3: wSiO 2: xH 2O, w=3～6 wherein, x can reach 9, and as its w value of NaY zeolite general requirement (being silica alumina ratio) of catalyst of cracking petroleum raw material greater than 4.5, more preferably greater than 5.0.The method of present industrial production NaY zeolite all is that (USP 3639099 for the directing agent method that adopts U.S. Grace company to be proposed basically, USP 3671191), the method for preparing the NaY zeolite that is proposed among the USP 3639099 is that sodium silicate solution, sodium aluminate solution and aluminum salt solution and composition are approximately (15～17) Na 2O: Al 2O 3: (14～16) SiO 2: (280～360) H 2The crystal grain of O mixes less than the directed agents of 0.1 μ m, and then in about 100 ℃ of following crystallization, wherein the mole compositing range of reaction mixture is (3～6) Na 2O: Al 2O 3: (8～12) SiO 2: (120～200) H 2O; This method is because the basicity that feeds intake is bigger, and the silica alumina ratio of the NaY zeolite of preparing is generally 4.0～4.5; And when adopting low basicity (Na 2O/Al 2O 3During=3～4) with raising product silica alumina ratio, then owing to the low colloid of the water yield needs vigorous stirring (seeing embodiment 5 wherein) than thickness; Therefore Grace company improves this method in USP 3671191, promptly improves the silica alumina ratio that feeds intake, and increases the water yield that feeds intake, and to obtain silica alumina ratio greater than 5.0 NaY product, wherein the proportioning of reaction mixture is (3.5～7) Na 2O: Al 2O 3: (10～16) SiO 2: (140～280) H 2O, the method that is proposed among at present industrial most employing USP3671191 is produced the NaY zeolite, and the method for bibliographical information was also all similar therewith afterwards, and its shortcoming is that the water yield that feeds intake is higher so single still efficient (output) is lower, and the silica alumina ratio that feeds intake is higher, so SiO in the mother liquor 2Quantity discharged is higher, has reduced the utilization ratio of silicon.For many years the production method of NaY finalizes the design almost, how to reduce the water yield that feeds intake to improve single still efficient, can make the NaY product have higher silica alumina ratio again simultaneously.Just become people's striving direction.
The method for preparing the NaY zeolite that proposes among the USP4436708 is the NaY crystal seed to be mixed with water glass stir about 5 hours postcooling and make the water glass system to-5～0 ℃, join in the above-mentioned system after again sodium aluminate solution being cooled to 0 ℃, the gained mixture is in about 0 ℃ of ageing for some time to the room temperature, be heated to 80～120 ℃ then and carry out crystallization, wherein the mole compositing range of reaction mixture is (4.4～8.5) Na 2O: Al 2O 3: (10.1～16.0) SiO 2: (145～200) H 2O.The method for preparing the NaY zeolite that proposes among the USP 4576807 is to add under the room temperature to have synthesized the also NaY crystal seed of porphyrize in water glass, under about 100 ℃, boil the active silicic acid sodium system of making more than 4 hours then, be cooled to room temperature then, add sodium aluminate again and make reaction mixture, and then once be warming up to about 100 ℃ of stirring crystallization more than 12 hours, wherein the mole compositing range of reaction mixture is (5.0～8.5) Na 2O: Al 2O 3: (15～25) SiO 2: (100～180) H 2O.Thereby the water yield decreases and has improved single still efficient though these two kinds of methods feed intake, and its processing step is complicated, and running cost increases, and all is to adopt high basicity to become glue and the SiO that feeds intake 2/ Al 2O 3Higher, thereby its SiO 2Utilization ratio lower.
The inventor finds, if improve the temperature of raw water glass, then when its with other raw materials mixing such as sodium aluminate after become the colloidal viscosity to reduce greatly, thereby might reduce the water yield that feeds intake, improve single still efficient.
The synthetic method that the purpose of this invention is to provide a kind of NaY zeolite is not to change the single still combined coefficient that improves NaY under original NaY preparation technology and the product quality premise basically.
The synthetic method of NaY zeolite provided by the present invention comprises:
(1) prepares directed agents according to the method for preparing directed agents that is adopted among the conventional NaY preparation method;
(2) above-mentioned directed agents and aluminate, aluminium salt and water being joined temperature is to mix in 40～100 ℃ the water glass, the mole of gained mixture is formed met (1.8～4.0) Na 2O: Al 2O 3: (7～12) SiO 2: (100～180) H 2The proportioning of O, the wherein Al in the directed agents 2O 3Account for the total Al of mixture 2O 31～10 heavy % of amount, preferred 3～8 heavy %;
(3) with (2) gained mixture hydrothermal crystallizing according to a conventional method.
Directed agents (crystal seed) in the step in the method provided by the present invention (1) can prepare by the whole bag of tricks of preparation faujusite directed agents in the prior art, but be that the method for preparing directed agents that is adopted among the conventional preparation method of NaY prepares preferably according to industrial common employing at present, for example according to USP3639099, USP 3671191, the method for preparing directed agents that is proposed among USP 4166099 and the CN 1081425A prepares, and can not change the synthesis technique of existing NaY like this and need not increase equipment; The compositing range of the directed agents of preparing according to these ordinary methods is (11～18) Na 2O: Al 2O 3: (10～17) SiO 2: (200～350) H 2O.
The said aluminium salt of step in the method provided by the present invention (2) can be Tai-Ace S 150, aluminum phosphate, aluminum chloride or aluminum nitrate, the Al when its aluminium in aluminate and directed agents synthesizes as NaY 2O 3Source, and the SiO when synthetic as NaY together of the silicon in water glass and the directed agents 2The source; Tart aluminium salt can be used to the basicity of conditioned reaction system with the aluminate of alkalescence, and the consumption of aluminium salt and aluminate meets (1.8～4.0) Na according to its mole composition with gained mixture after step (1) gained directed agents and water glass mix 2O: Al 2O 3: (7～12) SiO 2: (100～180) H 2O, preferably (2.0～3.0) Na 2O: Al 2O 3: (8～10) SiO 2: (100～150) H 2The proportioning of O decides; Na in this proportioning 2O represents the basicity of mixture, and it does not comprise the part that is neutralized by acid.In addition, except with the aluminium in aluminium salt and aluminate and the directed agents as compound Al 2O 3Beyond the source, the Al in the time of also can using aluminium salt separately or synthesize NaY with the aluminium conduct of aluminate in directed agents separately 2O 3The source needs other exogenously added alkali or acid to come the basicity of conditioned reaction system this moment, the Al when therefore preferably adopting aluminium salt and the aluminate aluminium in directed agents as synthetic NaY 2O 3The source.
Said water glass its temperature when it mixes with directed agents and aluminium source should remain on 40～100 ℃ in the method provided by the present invention, preferably remains on 60～95 ℃.
The condition of said hydrothermal crystallizing is that temperature is 95～120 ℃ in the method provided by the present invention, and the time is 8～40 hours.
The advantage of method provided by the present invention is not change substantially under the situation of existing conventional NaY production technique and equipment, can make single still efficient of synthetic NaY improve 30～80%, and the quality of the NaY that the quality of gained NaY product and ordinary method are prepared is suitable, and its silica alumina ratio is greater than 5.0.
The following examples will the present invention is described further.
In each embodiment and Comparative Examples, the relative crystallinity of the NaY zeolite that synthesizes is measured according to the RIPP146-90 standard method and (is seen " petrochemical complex analytical procedure (RIPP test method) ", Yang Cui waits volume surely, Science Press, nineteen ninety version), the mensuration of silica alumina ratio is the lattice constant a that records earlier the NaY zeolite by RIPP 145-90 standard method (the same) o, calculate silica alumina ratio according to following formula then:
Figure C9611427100051
The specific surface of zeolite low temperature N 2Determination of adsorption method (GB/T5816-1995), the temperature failure temperature is measured with differential thermal analysis (DTA).
Output per single reactor in the table 2 is that the commercial tank output with Comparative Examples 1 is 1.0 tons, calculates by the same industry kettle is long-pending.
Embodiment 1
Get 7.7ml water glass (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.252, SiO 2Content 227 grams per liters, modulus 2.9) put into a beaker, (producer is the same, Al to add the high sodium aluminate solution of 5.0ml 2O 3Content 40 grams per liters, Na 2O concentration 281.5 grams per liters, proportion 1.36) mix back ageing 24 hours under room temperature, making mole proportioning is 16.7Na 2O: Al 2O 3: 14.9SiO 2: 345H 2The directed agents of O.
Get 100ml concentrated sodium silicate solution (Nanjing inorganic chemical industry factory product, proportion 1.38, SiO 2The heavy % of content 26.7, modulus 3.13) be heated to 95 ℃ after, stop heating, then under agitation to wherein adding 42.4ml low sodium aluminate solution (Chang Ling oil-refining chemical factory catalyst plant product, Al 2O 3Content 106 grams per liters, Na 2O concentration 157 grams per liters, proportion 1.25), 34ml alum liquor (Chang Ling oil-refining chemical factory catalyst plant, Al 2O 3Content 92.6 grams per liters, proportion 1.283) and above-mentioned directed agents pack into after mixing (colloid cumulative volume 193ml) in the stainless steel cauldron, in 100 ℃ of following crystallization 24 hours, washing after filtration,, dry that product 28.6 restrains (butt), recording its silica alumina ratio is 5.0, degree of crystallinity 90%, the physical and chemical performance data of product are listed in table 1, preparation process analysis in table 2.
Embodiment 2
With 1.81 premium on currency glass (Chang Ling oil-refining chemical factory catalyst plant product, SiO 2Content 250 grams per liters, modulus 3.13, proportion 1.252) be heated to after 75 ℃ to wherein adding directed agents that 235.4 grams make according to the method among the embodiment 1 and 600ml alum liquor (with example 1) and 409ml and hang down sodium aluminate solution (with example 1) and mix, with in gained mixture (cumulative volume 3000ml) stainless steel cauldron of packing in 100 ℃ of following crystallization 24 hours, get NaY product (butt) 475 grams after washing after filtration,, the drying, its physical and chemical performance data are listed in table 1, preparation process analysis in table 2.
Embodiment 3
The preparation method is with embodiment 1, and the temperature of water glass raw material was 65 ℃ when difference was into glue, gets NaY product (butt) 28.0 grams, and its product performance are listed in table 1, preparation process analysis in table 2.
Embodiment 4
With 1.75 premium on currency glass (Chang Ling oil-refining chemical factory catalyst plant, SiO 2Content 252.8 grams per liters, modulus 3.16, proportion 1.253) be heated to after 70 ℃ to wherein adding directed agents and 482ml low sodium aluminate solution (Chang Ling oil-refining chemical factory catalyst plant, the Al that 392.3 grams make according to the method among the embodiment 1 2O 3Content 99.2 grams per liters, Na 2O concentration 148.8 grams per liters, proportion 1.25) and the 545ml alum liquor (producer is the same, Al 2O 3Content 91 grams per liters, proportion 1.27)) mix, with in gained mixture (cumulative volume 3140ml) stainless steel cauldron of packing in 105 ℃ of crystallization 30 hours, get NaY product (butt) 470 grams after washing after filtration,, the drying, its physical and chemical performance data are listed in table 1, preparation process analysis in table 2.
Embodiment 5
According to the method preparation of embodiment 4, the temperature of water glass raw material was 85 ℃ when difference was into glue, got NaY product (butt) 469 grams, and its product performance data are listed in table 1, preparation process analysis in table 2.
Comparative Examples 1
The explanation of this Comparative Examples prepares the effect of NaY molecular sieve with reference to the method for USP3671191.
Get 102.5ml water glass (Chang Ling oil-refining chemical factory product, SiO 2Content 227 grams per liters, modulus 2.9, proportion 1.25) put into a container, under agitation adding the low sodium aluminate solution (with example 1) of directed agents, 26.6ml, 22.3ml alum liquor (with example 1) and the 31.1ml water that 11.3 grams make according to the method among the embodiment 1 mixes, with in gained mixture (cumulative volume 193ml) stainless steel cauldron of packing in 100 ℃ of following crystallization 24 hours, get NaY product (butt) 18 grams after washing after filtration,, the drying, its physical and chemical performance data are listed in table 1, preparation process analysis in table 2.To prepare single still efficient of NaY lower for this method as can be seen.
Comparative Examples 2
The explanation of this Comparative Examples prepares the effect of NaY zeolite with reference to the method for USP3639099.
Under vigorous stirring, restrain concentrated sodium silicate (Nanjing inorganic chemical industry factory products to 2190, with embodiment 1) in add directed agents that 235.4 grams make according to the method among the embodiment 1 and 356ml alum liquor (with embodiment 1) and 622ml and hang down sodium aluminate solution (with embodiment 1) and mix, with in gained mixture (cumulative volume 2746ml) stainless steel cauldron of packing in 100 ℃ of following crystallization 24 hours, get product NaY (butt) 302.8 grams after washing after filtration,, the drying, its physical and chemical performance data are listed in the table 1, and wherein the mole of reaction mixture consists of 4.2Na 2O: Al 2O 3: 10.2 SiO 2: 144H 2O.Though single still efficient was suitable with the present invention when this method prepared NaY as can be seen, the silica alumina ratio of gained NaY product is lower.
Table 1
Product performance Relative crystallinity (%) Silica alumina ratio The temperature failure temperature (℃) BET specific surface (m%)
Embodiment 1 90 5.3 968 780
Embodiment 2 87 5.3 990 764
Embodiment 3 90 5.0 970 776
Embodiment 4 89 5.1 974 767
Embodiment 5 89 5.0 969 770
Comparative Examples 1 91 5.1 970 783
Comparative Examples 2 90 4.1 970 772
Table 2
Water is heavy in the product NaY weight/synthetic system Every liter of gel volume gets NaY product (gram, butt) Output per single reactor (ton, commercial tank)
Embodiment 1 0.2 148 1.67
Embodiment 2 0.17 158 1.70
Embodiment 3 0.20 145 1.67
Embodiment 4 0.16 150 1.33
Embodiment 5 0.16 149 1.33
Comparative Examples 1 0.12 93 1.00
Comparative Examples 2 0.16 149 1.33

Claims (7)

1. NaY prepare zeolite method is characterized in that this method comprises:
(1) preparing a mole compositing range according to the method for preparing directed agents that is adopted among the conventional NaY preparation method is (11～18) Na 2O: Al 2O 3: (10～17) SiO 2: (200～350) H 2The directed agents of O;
(2) be that 40～100 ℃ water glass mixes with above-mentioned directed agents and aluminate and aluminium salt and temperature, the mole of gained mixture formed met (1.8～4.0) Na 2O: Al 2O 3: (7～12) SiO 2: (100～180) H 2The proportioning of O, the wherein Al in the directed agents 2O 3Account for the total Al of mixture 2O 31～10 heavy % of amount;
(3) with (2) gained mixture 95～120 ℃ of following hydrothermal crystallizings 8～40 hours.
2. according to the preparation method of claim 1, wherein the said aluminate of step (2) is a sodium metaaluminate.
3. according to the preparation method of claim 1, wherein the said aluminium salt of step (2) is Tai-Ace S 150, aluminum phosphate, aluminum chloride or aluminum nitrate.
4. according to the preparation method of claim 3, wherein said aluminium salt is Tai-Ace S 150.
5. according to the preparation method of claim 1, wherein the mole proportioning of said mixture is (2.0～3.0) Na 2O: Al 2O 3: (8～10) SiO 2: (100～150) H 2O.
6. according to the preparation method of claim 1, the Al in the directed agents in the step (2) wherein 2O 3Account for the total Al of mixture 2O 33～8 heavy % of amount.
7. according to the preparation method of claim 1, wherein the temperature of water glass is 60～95 ℃ in the step (2).
CN96114271A 1996-12-25 1996-12-25 High efficiency manufacture of NaY zeolite Expired - Lifetime CN1058682C (en)

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Publication number Priority date Publication date Assignee Title
CN1323031C (en) * 2004-04-14 2007-06-27 中国石油化工股份有限公司 Process for preparing NaY molecular sieve
CN101863494A (en) * 2010-06-23 2010-10-20 深圳市海川实业股份有限公司 Method for preparing Y-zeolite by taking quartz sand as raw material
CN104773741B (en) * 2015-03-31 2017-03-08 中国石油天然气集团公司 A kind of big crystal grain NaY molecular sieve and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3347123A1 (en) * 1982-12-27 1984-07-05 W.R. Grace & Co., New York, N.Y. TYPE Y FAUJASITE WITH A HIGH SILICON DIOXIDE / ALUMINUM OXIDE RATIO
US4482530A (en) * 1982-12-29 1984-11-13 Ethyl Corporation Method of making zeolite Y
CN1079444A (en) * 1992-06-02 1993-12-15 中国石油化工总公司石油化工科学研究院 The preparation method of small crystal grain NaY molecular sieve
CN1081425A (en) * 1992-07-18 1994-02-02 中国石油化工总公司石油化工科学研究院 The preparation method of small crystal grain NaY molecular sieve

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3347123A1 (en) * 1982-12-27 1984-07-05 W.R. Grace & Co., New York, N.Y. TYPE Y FAUJASITE WITH A HIGH SILICON DIOXIDE / ALUMINUM OXIDE RATIO
US4482530A (en) * 1982-12-29 1984-11-13 Ethyl Corporation Method of making zeolite Y
CN1079444A (en) * 1992-06-02 1993-12-15 中国石油化工总公司石油化工科学研究院 The preparation method of small crystal grain NaY molecular sieve
CN1081425A (en) * 1992-07-18 1994-02-02 中国石油化工总公司石油化工科学研究院 The preparation method of small crystal grain NaY molecular sieve

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