CN104340990B - A kind of synthetic method of y-type zeolite - Google Patents
A kind of synthetic method of y-type zeolite Download PDFInfo
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- CN104340990B CN104340990B CN201310328800.1A CN201310328800A CN104340990B CN 104340990 B CN104340990 B CN 104340990B CN 201310328800 A CN201310328800 A CN 201310328800A CN 104340990 B CN104340990 B CN 104340990B
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
A kind of synthetic method of y-type zeolite, it is that kaolin is calcined into dehydration at 500 860 DEG C to change into metakaolin, crush, the metakaolin powder that particle diameter is less than 230 microns is made again, by metakaolin powder with reclaiming mother liquor, directed agents, sodium hydroxide solution, water and optional waterglass, mol ratio, which is made, is（1‑2.5）Na2O：Al2O3：（4‑9）SiO2：（40‑450）H2O reacting material mixture, crystallization under described reacting material mixture is stirred at 80 100 DEG C, then filters and dries, it is characterised in that described reclaims building-up process of the mother liquor from gel method y-type zeolite, and its concentration is SiO2≤ 150g/L, Na2O≤70g/L, SO4 2‑≤100g/L.The synthetic method for the y-type zeolite that the present invention is provided, is effectively utilized silicon and sodium in the mother liquor of gel method synthesis y-type zeolite, reduces the discharge of the pollutant of containing sulfate radicals in mother liquor, gel method synthesis mother liquid is utilized without anticipating, directly.
Description
Technical field
The present invention relates to a kind of synthetic method of y-type zeolite, y-type zeolite synthesis furtherly the present invention relates to the use of female
The method that liquid synthesizes y-type zeolite.
Background technology
Y-type zeolite is the maximum molecular sieve of petrochemical industry application amount, and the annual production capacity of China's y-type zeolite has reached 50,000
More than ton, and in the gesture of growth.At present, the manufacturing technique method of y-type zeolite has gel directing agent method（Grace companies of the U.S.,
USP3,639,099 and USP4,166,099）, kaolin microsphere in-situ crystallization method（BASF AG, USP4,493,902）And height
The former powder in-situ crystallization method of ridge soil（Sinopec, CN15333982A）.Gel method uses NaOH, sodium aluminate, sodium metasilicate（Water glass
Glass）, aluminum sulfate etc. be raw material, it is possible to additionally incorporate 5-10% directed agents, hydrothermal crystallization method synthesis obtains molecular sieve.Kaolin microsphere
In-situ crystallization method is that kaolin first is spray dried into microballoon, and kaolin microsphere is mixed with waterglass, liquid caustic soda, directed agents, hydro-thermal
Crystallization synthesis obtains molecular sieve.Kaolin original powder in-situ crystallization method is directly using kaolin powder and waterglass, liquid caustic soda, directed agents
Mixing, hydrothermal crystallizing synthesis obtains molecular sieve.In three kinds of above-mentioned synthetic methods, in order to improve the silica alumina ratio of product, it feeds intake
Silica alumina ratio is all higher, and highest is even up to more than 9, and the silica alumina ratio of generally product is generally 5 or so, therefore, and about 40% or so
Silicon it is not utilized, these silicon after filtration enter synthesis mother liquid in, the amount of silicon is larger in mother liquor, and the concentration of silicon is not high, typically
Less than 100g/L, modulus is relatively low, and substantial amounts of sulfate radical is also contained in generally less than 3.0, particularly gel method.
For the recycling of synthesis mother liquid, GRACE companies are disclosed in US4164551 conventional GPC method NaY synthesis
Mother liquor is collected, acid aluminium salt such as aluminum sulfate is then added into mother liquor, regulation pH value forms Alusil, then is back to use routine
In the synthesis of gel method NaY zeolite.This method and follow-up improved method solve the Utilizing question of silicon source in mother liquor, but greatly
The waste water of amount sulfur acid sodium stills need outer row, and Alusil can not ensure all of superfluous Alusil is also needed further
Processing.
Sodium in conventional GPC method NaY mother liquors has two kinds of forms, sodium hydroxide and sodium sulphate, by mother liquor in handling process
Acid adding is neutralized to pH value 9.5, then solution is cooled into 5-25 DEG C, now, and sodium sulphate saturated crystallization is separated out, separating sodium sulfate crystal
And filtrate, product sodium sulphate is Na2SO4·10H2O, can as other techniques raw material.A filtrate part directly profit containing gel
Consumption for feed intake middle waterglass and liquid caustic soda in NaY synthesis, can be reduced；Another part can be used for preparing catalyst, utilize
The silicon concentrated in filtrate as catalyst binding agent.But the discharge that these processing modes only partly solve sulfur acid waste liquor of sodium is asked
Topic, and high energy consumption.
Microballoon is prepared using kaolin is carried out into high and low temperature roasting respectively in US4493902, utilizes microballoon in-situ crystallization to close
Into y-type zeolite, and realize the reuse of mother liquor.The mother liquor Treatment for Reuse of the technique is by being concentrated by evaporation.But, because in mother liquor
The concentration ratio of silicon is relatively low, and the discharge rate of mother liquor is larger, so the workload of concentration is larger, high energy consumption.
CN1709794A uses kaolin for raw material, synthesizes y-type zeolite composite by in-situ crystallization technology and realizes
The direct reuse of filtrated stock is with instead of liquid caustic soda and part waterglass after technique synthesis.
The content of the invention
The present inventor is by many experiments it was unexpectedly observed that the synthesis mother liquid that gel method is obtained can be without place
Manage, be directly used in the method for the former powder in-situ crystallization method synthesis y-type zeolite of kaolin, reduce the discharge of gel method synthesis mother liquid and makes
Into pollution, and change after acid aluminium salt to be added manufacture Alusil could circulating and recovering to gel method y-type zeolite conjunction
Into the conventional treatment mode of process.Based on this, the present invention is formed.
The synthetic method for the y-type zeolite that the present invention is provided, be by kaolin 500-860 DEG C be calcined dehydration change into it is higher
Ridge soil, is crushed, then the metakaolin powder that particle diameter is less than 230 microns is made, by metakaolin powder with reclaiming mother liquor, directed agents, hydrogen
Sodium hydroxide solution, water and optional waterglass, mol ratio, which is made, is（1-2.5）Na2O：Al2O3：（4-9）SiO2：（40-450）
H2O reacting material mixture, crystallization under described reacting material mixture is stirred at 80-100 DEG C, then filters and does
It is dry, it is characterised in that described reclaims building-up process of the mother liquor from gel method y-type zeolite, and its concentration is SiO2≤ 150g/L,
Na2O≤70g/L, SO4 2-≤100g/L。
The synthetic method for the y-type zeolite that the present invention is provided, can obtain the former powder in-situ crystallization method synthesis of conventional kaolin
Y-type zeolite, the advantage of this method is：
1st, silicon and sodium in the mother liquor of gel method synthesis y-type zeolite are effectively utilized.
2nd, the discharge of the pollutant of containing sulfate radicals in the mother liquor of gel method synthesis y-type zeolite is reduced.
3rd, the mother liquor of gel method synthesis y-type zeolite is without anticipating, can be directly used for the former powder in-situ crystallization method of kaolin
Y-type zeolite is synthesized, mother liquid disposal and synthesis step is simplified.
Embodiment
The synthetic method for the y-type zeolite that the present invention is provided, be by kaolin 500-860 DEG C be calcined dehydration change into it is higher
Ridge soil, is crushed, then the metakaolin powder that particle diameter is less than 230 microns is made, by metakaolin powder with reclaiming mother liquor, directed agents, hydrogen
Sodium hydroxide solution, water and optional waterglass, mol ratio, which is made, is（1-2.5）Na2O：Al2O3：（4-9）SiO2：（40-450）
H2O reacting material mixture, crystallization under described reacting material mixture is stirred at 80-100 DEG C, then filters and does
It is dry, it is characterised in that described reclaims building-up process of the mother liquor from gel method y-type zeolite, and its concentration is SiO2≤ 150g/L,
Na2O≤70g/L, SO4 2-≤100g/L。
In the method that the present invention is provided, described kaolin is selected from hard kaolin or soft kaolin；Its crystalline content should be big
In 75 heavy %, preferably greater than 85 heavy %, its average grain diameter is less than 4 microns, so being the original soil without forming processes.
In the method that the present invention is provided, described kaolin can also be the kaolinite obtained through peracid or alkali or salt treatment
Soil, described acid can be the inorganic acids such as hydrochloric acid, nitric acid, acetic acid, ethanedioic acid, oxalic acid, sulfuric acid, phosphoric acid and organic acid, wherein excellent
Select hydrochloric acid and nitric acid；Described alkali can be sodium hydroxide, potassium hydroxide, ammoniacal liquor etc., wherein it is preferred that sodium hydroxide；Described salt
Selected from sodium carbonate or sodium acid carbonate.
The kaolinic sintering temperature be 500~900 DEG C, preferably 500~700 DEG C, more preferably 640~680 DEG C, typically
Roasting time be 1~10 hour.
Described directed agents can be synthesized conventionally, such as according to USP3574538, USP3639099,
USP3671191, USP4166099 and EUP0435625 preparation method synthesis.The composition of directed agents is preferably：（10-17）
SiO2：（0.7-1.3）Al2O3：（1-18）Na2O：（200-450）H2O.Described directed agents are preferably obtained through aging at 4~20 DEG C
Arrive.
Building-up process of the mother liquor from gel method y-type zeolite is reclaimed described in the present invention, is the first-time filtrate being filtrated to get,
It can also be the mixed solution of first-time filtrate and follow-up cleaning fluid.Described filter type can be centrifugation, belt type filter
Machine etc..Described gel method reclaims mother liquor, and its concentration is SiO2≤ 150g/L, Na2O≤70g/L, SO4 2-≤100g/L；Preferred
In the case of, described gel method reclaims mother liquor, and its concentration is SiO220~100g/L, Na2O 15~70g/L, SO4 2-5~
100g/L；In the case of further preferably, described gel method reclaims mother liquor, and its concentration is SiO220~50g/L, Na2O
18~30g/L, SO4 2-5~60g/L.For example, in the specific embodiment of the present invention, its concentration can be SiO2
28.5g/L, Na2O 22.6g/L, SO4 2-25g/L；In another specific embodiment of the present invention, its concentration can be
SiO220.2g/L, Na2O 18.6g/L, SO4 2-40g/L；In another specific embodiment of the present invention, its concentration can
Think SiO238.5g/L, Na2O 28.6g/L, SO4 2- 60g/L。
Described waterglass be the need for being matched according to reacting material mixture determine if add reaction raw materials mix
In compound.
Described crystallization can be carried out under stirring or standing.If crystallization under agitation, mixing speed is
100-1000 revs/min, preferably 400-600 revs/min, the time is 16-48 hours, preferably 24-32 hours.Zeolite after crystallization
Drying temperature is 100-120 DEG C.
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
The NaY contents of zeolite are drawn according to the relative crystallinity that RIPP146-90 standard methods are determined in embodiment；It is brilliant
Born of the same parents' constant a0Determined according to RIPP145-90 standard methods.
Zeolite data are calculated according to following formula and obtained：
SiO2/Al2O3（Mol ratio）=2×（2.5858-a0）/（a0-2.4191）, wherein, lattice constant a0Unit is nm.
Embodiment 1
The preparation of directed agents：Take 250 grams of sodium silicate solutions（SiO containing 20.05 weight %2, 6.41 weight % Na2O）, 30 DEG C fast
120 grams of sodium aluminate solutions are slowly added under speed stirring（Al containing 3.15 weight %2O3, 21.1 weight % Na2O）, 30 DEG C of stirrings of constant temperature
Static aging 24 hours, obtain directed agents at 1 hour, 20 DEG C.Directed agents composition is 16Na2O：Al2O3：15SiO2：320H2O。
By the kaolin that average grain diameter is 4 μm（Suzhou, Yangshan board, China Kaolin Co., Ltd, crystalline content is 80 heavy %）,
It is calcined 3 hours at 660 DEG C, obtains metakaolin powder, is crushed and the metakaolin powder that particle diameter is less than 230 μm is made.
80 grams of metakaolin powder are taken, stirring is lower to add 2600 grams of regular industrial gel method NaY synthesis mother liquids（Containing SiO2
28.5g/L, Na2O 22.6g/L, SO4 2-25g/L）, 60 grams of directed agents, 80 grams of concentration are 5 weight % sodium hydroxide solution.Heating
Crystallization is stirred to 90 DEG C of constant temperature 28 hours, and speed of agitator is 400 revs/min when charging and crystallization.After crystallization terminates, by crystallization tank
Cooling, filtering is washed to washing lotion pH value less than 10.120 DEG C of dryings 2 hours, obtain zeolite Y -1.
It is 72.4 heavy % that X-ray diffraction, which determines NaY contents in Y-1, and lattice constant is 2.472nm.Zeolite is
4.30。
Embodiment 2
80 grams of metakaolin powder are taken, stirring is lower to add 2900 grams of regular industrial gel method NaY synthesis mother liquids（Containing SiO2
20.2g/L, Na2O 18.6g/L, SO4 2-40g/L）, directed agents prepared by 60 grams of embodiments 1,76 grams of concentration are 5 weight % hydrogen-oxygen
Change sodium solution.It is warming up to 90 DEG C of constant temperature and stirs crystallization 28 hours, speed of agitator is 400 revs/min when charging and crystallization.Crystallization knot
Shu Hou, crystallization tank is cooled down, filtering,
Washing lotion pH value is washed to less than 10.120 DEG C of dryings 2 hours, obtain zeolite Y -2.
It is 75.4 heavy % that X-ray diffraction, which determines NaY contents in Y-2, and lattice constant is 2.469nm.Zeolite is
4.67。
Embodiment 3
80 grams of metakaolin powder are taken, stirring is lower to add 1800 grams of regular industrial gel method NaY synthesis mother liquids（Containing SiO2
38.5g/L, Na2O 28.6g/L, SO4 2-60g/L）, directed agents prepared by 60 grams of embodiments 1,75 grams of industrial waterglass（Containing SiO2
258.5g/L, Na2O 80.6g/L）, 75 grams of concentration are 5 weight % sodium hydroxide solution.It is warming up to 90 DEG C of constant temperature stirring crystallization 26
Hour, speed of agitator is 400 revs/min when charging and crystallization.After crystallization terminates, crystallization tank is cooled down, filters, is washed to washing lotion
PH value is less than 10.120 DEG C of dryings 2 hours, obtain zeolite Y -3.
It is 72.9 heavy % that X-ray diffraction, which determines NaY contents in Y-3, and lattice constant is 2.471nm.Zeolite is
4.42。
Embodiment 4
80 grams of metakaolin powder are taken, stirring is lower to add 1400 grams of regular industrial gel method NaY synthesis mother liquids（Containing SiO2
38.5g/L, Na2O 28.6g/L, SO4 2-60g/L）, directed agents prepared by 60 grams of embodiments 1,81 grams of industrial waterglass（Containing SiO2
258.5g/L, Na2O 80.6g/L）, 78 grams of concentration are 5 weight % sodium hydroxide solution.It is warming up to 90 DEG C of constant temperature stirring crystallization 26
Hour, speed of agitator is 400 revs/min when charging and crystallization.After crystallization terminates, crystallization tank is cooled down, filters, is washed to washing lotion
PH value is less than 10.120 DEG C of dryings 2 hours, obtain zeolite Y -4.
It is 75.9 heavy % that X-ray diffraction, which determines NaY contents in Y-4, and lattice constant is 2.468nm.Zeolite is
4.82。
Embodiment 5
80 grams of metakaolin powder are taken, stirring is lower to add 1000 grams of regular industrial gel method NaY synthesis mother liquids（Containing SiO2
38.5g/L, Na2O 28.6g/L, SO4 2-60g/L）, directed agents prepared by 60 grams of embodiments 1,170 grams of industrial waterglass（Contain
SiO2258.5g/L, Na2O 80.6g/L）, 94 grams of concentration are 5 weight % sodium hydroxide solution.It is warming up to 90 DEG C of constant temperature stirrings brilliant
Change 26 hours, charging speed of agitator is 400 revs/min, stands crystallization.After crystallization terminates, crystallization tank is cooled down, filtered, washing
It is less than 10 to washing lotion pH value.120 DEG C of dryings 2 hours, obtain zeolite Y -5.
It is 71.9 heavy % that X-ray diffraction, which determines NaY contents in Y-5, and lattice constant is 2.468nm.Zeolite sial is 4.82.
Claims (11)
1. a kind of synthetic method of y-type zeolite, is that kaolin is calcined into dehydration at 500-860 DEG C to change into metakaolin, crushes,
Particle diameter is made again and is less than 230 microns of metakaolin powder, by metakaolin powder with reclaim mother liquor, directed agents, sodium hydroxide solution,
Water and with optional waterglass, mol ratio is made for (1-2.5) Na2O：Al2O3：(4-9)SiO2：(40-450)H2O reaction
Raw mixture, crystallization under described reacting material mixture is stirred at 80-100 DEG C, then filters and dries, and its feature exists
Building-up process of the mother liquor from gel method y-type zeolite is reclaimed in described, its concentration is SiO220~50g/L, Na2O18~30g/
L, SO4 2-5~60g/L.
2. according to the method for claim 1 wherein described kaolin is selected from hard kaolin, soft kaolin or gangue.
3. according to the method for claim 2, wherein, crystalline content is more than 75 heavy % in described kaolin.
4. according to the method for claim 3, wherein, crystalline content is more than 85 heavy % in described kaolin.
5. according to method any in Claims 1 to 4, wherein, described kaolin is to be obtained through peracid or alkali or salt treatment
Kaolin, the one kind or its mixture of described acid in hydrochloric acid, nitric acid, acetic acid, ethanedioic acid, oxalic acid, sulfuric acid, phosphoric acid,
The one kind or its mixture of described alkali in sodium hydroxide, potassium hydroxide, ammoniacal liquor, described salt are selected from sodium carbonate or carbonic acid
Hydrogen sodium.
6. according to the method for claim 5, wherein, described acid is hydrochloric acid or nitric acid.
7. according to the method for claim 5, wherein, described alkali is sodium hydroxide.
8. according to the method for claim 1 wherein, described kaolin, be calcined at 500~700 DEG C dehydrations change into it is higher
Ridge soil.
9. according to the method for claim 8, wherein, described kaolin, be calcined at 640~680 DEG C dehydrations change into it is higher
Ridge soil.
10. it is according to the method for claim 1 wherein, described directed agents, constituting：(10-17)SiO2：(0.7-1.3)
Al2O3：(1-18)Na2O：(200-450)H2O。
11. according to the method for claim 1 or 10, wherein, described directed agents are obtained through aging at 4~20 DEG C.
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| CN111320184A (en) * | 2018-12-13 | 2020-06-23 | 湖北赛因化工有限公司 | Method for preparing NaY molecular sieve by recycling NaY mother liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1709794A (en) * | 2004-06-16 | 2005-12-21 | 中国石油化工股份有限公司 | Method for synthesizing Y-zeolite composite material |
| CN101537368A (en) * | 2008-03-19 | 2009-09-23 | 中国石油天然气股份有限公司 | Method for preparing in situ crystallization type catalytic cracking catalyst |
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| CN1019094B (en) * | 1989-06-15 | 1992-11-18 | 中国石油化工总公司兰州炼油化工总厂 | Process for prepn. high silicon y zeolite |
| JP2003277046A (en) * | 2002-03-19 | 2003-10-02 | Nippon Oil Corp | Y type zeolite and method for manufacturing the same |
| CN101993092B (en) * | 2009-08-27 | 2014-04-30 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5 zeolite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1709794A (en) * | 2004-06-16 | 2005-12-21 | 中国石油化工股份有限公司 | Method for synthesizing Y-zeolite composite material |
| CN101537368A (en) * | 2008-03-19 | 2009-09-23 | 中国石油天然气股份有限公司 | Method for preparing in situ crystallization type catalytic cracking catalyst |
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