CN101633507B - Ammonium ion exchange method for Y-type molecular sieve - Google Patents
Ammonium ion exchange method for Y-type molecular sieve Download PDFInfo
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Abstract
The invention discloses an ammonium ion exchange and ultra-stabilization method for a molecular sieve, which comprises the following steps: mixing Na-type molecular sieve and ammonium salt evenly according to a weight ratio of the molecular sieve to the ammonium salt of 1: (0.1-1.0), heating the mixed material to between 90 and 300 DEG C, keeping the temperature for at least 1 hour in a rotary or static state, cooling the mixed material to the room temperature, then mixing and beating the mixed material and deionized or decationized water according to a weight ratio of the molecular sieve to the water of 1: (1-10), filtering the slurry, and drying a filter cake to obtain the molecular sieve after ammonium ion exchange; and baking the obtained molecular sieve after the ammonium ion exchange for at least 0.5 hour at the temperature of between 400 and 700 DEG C under complete water vapor atmosphere to obtain the ultra-stabilized Y-type molecular sieve. The ammonium ion exchange and ultra-stabilization method provided by the invention reduces the using amount of the ammonium salt and the water, and reduces the cost.
Description
Technical field
The present invention relates to a kind of ammonium ion exchange method and molecular sieve super stabilizing method of molecular sieve.
Background technology
Y zeolite is the active ingredient commonly used of catalyzer.In the catalyzer, prepare by the NaY molecular sieve as Y zeolite contained in the hydrocarbon cracking catalyzer.General synthetic molecular sieve does not almost have catalytic performance under original state, need carry out modification to it, so that it has specific catalytic performance.The ion exchange method of molecular sieve is a method of modifying relatively more commonly used.Utilize the ion-exchange performance of molecular sieve can in molecular sieve, introduce other ion and change electric field, surface acidity in molecular sieve crystal, thereby change the character of molecular sieve, regulate the absorption property and the catalytic performance of molecular sieve.
The most frequently used method of molecular sieve ion-exchange is that the salt with exchange ion is made into the certain density aqueous solution (the also available non-aqueous solution of Special Circumstances) and molecular sieve joins in the interchanger by a certain percentage, heating while stirring, under preset temperature, the exchange certain hour; Also can repeatedly exchange as required, to reach the exchange degree that needs.Industrial application also be this ionic liquid phase exchange process mostly.But this method has certain limitation, the one, some metallic cation forms the bigger hydrated cation of volume in the aqueous solution, cause steric restriction, is difficult to exchange in the molecular sieve pore passage, need carry out the centre roasting, thereby impel the positively charged ion dehydration to move in the duct of molecular sieve; The 2nd, exchange ion solubleness in the aqueous solution is less can the cationic exchange capacity of restriction.
The mode that adopts the aqueous solution to exchange is carried out the ammonium ion exchange method of molecular sieve.Exchange liquid after the exchange contains sodium, ammonium ion and molecular sieve fine powder and a small amount of rare earth element, and the race of molecular sieve is decreased has not only increased manufacturing cost, and contaminate environment.The waste water that contains foreign ion can cause water pollution.
In the Industrial processes belt filter being changed in the still formula exchange of traditional ammonium ion solution exchanges continuously, improve production efficiency, reduced operator's labor capacity, but, still can produce the waste water of a large amount of foreign ions from remaining the ionic fluid exchange in essence.
The seventies, the researchist finds to do when mixing sample Na at 400 ℃ of thermal treatment NaCl and molecular sieve (CaY, ZnY, BaY or LaY etc.)
+Can exchange out the H+ in the molecular sieve surface acidity OH group.After this a new way has been opened up in the solid ionic modification and the saltus step that are exchanged for molecular sieve.
More bibliographical information H type or NH are arranged
4Solid ionic permutoid reaction between type Y molecular sieve and IA, IIA, IB, IIB and transition metal muriate, the oxide compound, report are thought in the solid state reaction process, owing to generate HCl, H
2O, NH
3Etc. the gas of easy volatile and help the carrying out of permutoid reaction.It is generally acknowledged that can't carry out the solid ionic exchange between Na type molecular sieve and the ammonium salt obtains ammonium type molecular sieve.
Summary of the invention
The ammonium ion exchange and the super stabilizing method that the purpose of this invention is to provide a kind of molecular sieve are simplified Production Flow Chart, are reduced discharge of wastewater.
The present inventor finds at work, different with the understanding of people in the prior art, adopting ammonium salt and Na type molecular sieve to carry out the solid ionic exchange energy at a lower temperature accesses ammonium type molecular sieve and reaches satisfied transformation efficiency, thereby further roasting obtains hydrogen type molecular sieve, super stable molecular sieve, and a kind of method of easier industrial production hydrogen type molecular sieve is provided.
A kind of ammonium ion exchange method of molecular sieve, according to molecular sieve: ammonium salt=1: the weight ratio of (0.1～1.0) mixes Na type molecular sieve and ammonium salt, mixture is heated to 90～300 ℃ also to be kept 1 hour at least, cool to room temperature then, according to molecular sieve: water=1: the mixture that the weight ratio of (1～10) will contain molecular sieve and ammonium salt mixes making beating with deionized water, filter slurries, obtain the molecular sieve after the ammonium ion exchange behind the filtration cakes torrefaction.
A kind of super stabilizing method of molecular sieve, according to molecular sieve: ammonium salt=1: the weight ratio of (0.1～1.0) mixes Na type molecular sieve and ammonium salt, mixture is heated to 150～280 ℃ also to be kept 1 hour at least, cool to room temperature then, according to molecular sieve: water=1: the mixture that the weight ratio of (1～10) will contain molecular sieve and ammonium salt mixes making beating with deionized water, filter slurries, obtain the molecular sieve after the ammonium ion exchange behind the filtration cakes torrefaction, with the molecular sieve after the ammonium ion exchange at 400～700 ℃, roasting is at least 0.5 hour under 100% water vapour atmosphere, obtains the Y zeolite of super stabilizing.
Compared with prior art, the present invention has following beneficial effect:
Ammonium ion exchange method provided by the invention is compared with traditional liquid phase exchange, has reduced the consumption of ammonium salt, the consumption of water.In the liquid phase ammonium ion exchange process, the weight feed ratio of molecular sieve and ammonium salt was generally 1: 1, the consumption of water often is 10～20 times of molecular sieve, the consumption of the water of belt filter exchange is also between 10～15 times, and the weight ratio of molecular sieve of the present invention and ammonium salt is 1: (0.2～0.6) just can reach same exchange effect, and the consumption of water is about 5 times of molecular sieve quality.Compare with the method for modifying of molecular sieve solid phase of the prior art ion-exchange, carry out the solid phase exchange under lower temperature, it is higher to obtain ammonium type molecular sieve and transformation efficiency, follow-up hydrogen type molecular sieve, the super stable molecular sieve of obtaining.
Embodiment
The ammonium ion exchange method of molecular sieve provided by the invention, with Na type molecular sieve and ammonium salt according to molecular sieve: ammonium salt=1: (0.1～1.0), preferred 1: the weight ratio of (0.1～0.6) mixes, material is heated under 90～300 ℃, preferred 150～280 ℃ temperature kept at least 1 hour, cool to room temperature then, according to weight ratio=1 of molecular sieve with water: (1～10), preferred 1: the ratio of (2～6) is mixed making beating with material with deionized water, filter slurries, obtain the molecular sieve after the ammonium ion exchange behind the filtration cakes torrefaction.
At 400～700 ℃, preferred 500～650 ℃, roasting at least 0.5 hour under 100% water vapour atmosphere, preferred 1.5～2.5 hours obtains the Y zeolite of super stabilizing with the molecular sieve after the ammonium ion exchange.
In the method provided by the invention, described molecular sieve is various types of Na type molecular sieves, the molecular sieve of pending ammonium ion exchange, and wherein preferred NaY molecular sieve, is handed over a roasting Y zeolite.
In the method provided by the invention, described ammonium salt is selected from one or more in ammonium chloride, ammonium sulfate and the ammonium nitrate.
In the method provided by the invention, described material being heated under 90～300 ℃ the temperature kept 1 hour at least, wherein, soaking time is relevant with the exchange temperature, change to some extent with the difference of exchange temperature, at least will reach the exchange equilibrium time of exchange temperature correspondence, their corresponding relation is as shown in the table:
| The exchange temperature, ℃ | 150 | 200 | 250 | 300 |
| The exchange equilibrium time, h | 2.5-3.4 | 2.0-2.8 | 1.6-2.1 | 1.0-1.3 |
In the method provided by the invention, described mixing step can be finished in optional mixing equipment, as batch-mixed equipment or continous way mixing equipment.
In the method provided by the invention, can stir material in the described heat-processed, also can make material keep static.Heat-processed can be finished in optional heating installation, and as baking oven, retort furnace, tube furnace or other heating installation, as long as can reach Heating temperature and keep time enough, the present invention is not subjected to the restriction of institute's use heating installation.
In the method provided by the invention, described making beating, filtration step can carry out in optional making beating, filter plant equipment, and the present invention is not subjected to the restriction of the equipment that uses.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Employed NaY molecular sieve is produced by catalyzer Shandong branch office of limited-liability company of China Petrochemical Industry in embodiment and the Comparative Examples, and relative crystallinity is 92%, and lattice constant 24.67 dusts, initial water content are 31wt%, initial Na
2O content is 13.7wt%.The a friendship one roasting Y zeolite that uses is produced by catalyzer Shandong branch office of limited-liability company of China Petrochemical Industry, and relative crystallinity is 84%, Na
2O content 6.3wt%, lattice constant are 24.63 dusts, and initial water content is 17wt%.
Embodiment 1
Take by weighing the NH of 20 grams
4The NaY of Cl and 100 grams carries out mechanical mill in agate mortar mixes, then the sample that mixes is forwarded in the crucible, in tube furnace, heated 3.0 hours under 220 ℃ of temperature, after the reaction sample is taken out, then according to water: molecular sieve (weight ratio)=5: 1 pairs of samples wash, filter oven dry at last.Analytic sample Na
2O content is 4.8wt%.
Embodiment 2
Take by weighing (the NH of 40 grams
4)
2SO
4Handing over a roasting Y zeolite to carry out mechanical mill in agate mortar with one of 100 grams mixes, is ground into powder as far as possible for the fine grained chippings after the roasting.Then the sample that mixes is forwarded in the crucible, in tube furnace, heats, arrive 220 ℃ after constant temperature 2 hours.Sample is taken out according to water: molecular sieve (weight ratio)=5: 1 pairs of samples wash, and filter oven dry, analytic sample, Na at last
2O content 2.3wt%
Embodiment 3
Take by weighing the NH of 40 grams
4NO
3Handing over a roasting Y zeolite to carry out mechanical mill in agate mortar with one of 100 grams mixes, is ground into powder as far as possible for the fine grained chippings after the roasting.Then the sample that mixes is forwarded in the crucible, in tube furnace, heats, arrive 180 ℃ after constant temperature 5 hours.Sample is taken out according to water: molecular sieve (weight ratio)=5: 1 pairs of samples wash, and filter oven dry, analytic sample, Na at last
2O content 2.0wt%
Embodiment 4
Take by weighing the NH of 40 grams
4One of Cl and 100 grams hand over a roasting Y zeolite to carry out the mechanical mill mixing in agate mortar, are ground into powder as far as possible for the fine grained chippings after the roasting.Then the sample that mixes is forwarded in the converter and heats, arrive 280 ℃ after, rotate heating 2 hours.Sample is taken out according to water: molecular sieve (weight ratio)=5: 1 pairs of samples wash, and filter oven dry, analytic sample, Na at last
2O content 1.9wt%
Embodiment 5
Take by weighing the NH of 30 grams
4The NaY of Cl and 100 grams carries out mechanical mill in agate mortar mixes, then the sample that mixes is forwarded in the crucible, in retort furnace, heated 3.0 hours under 150 ℃ of temperature, after the reaction sample is taken out, then according to water: molecular sieve (weight ratio)=5: 1 pairs of samples wash, filter oven dry at last.Analytic sample Na
2O content is 5.3wt%.Sample is directly put into the tubular type stoving oven, in stoving oven, be full of water vapour, be warmed up to 500 ℃ of roastings 2 hours, cooling post analysis sample.Lattice constant is 24.66 dusts, and relative crystallinity is 80%.
Comparative Examples 1
10 times deionized waters are joined in the stainless steel exchanging container, under agitation condition, drop into 100 gram NaY molecular sieves, add the NH of 100 grams again
4Cl is warmed up to 90 ℃ of constant temperature and stirred 2 hours, and cooling is filtered, and filter cake is with 5 times deionized water wash, the Na after the exchange
2O content is 6.8wt%.
Comparative Examples 2
Take by weighing the NH of 20 grams
4The NaY of Cl and 100 grams carry out mechanical mill in agate mortar mixes, and according to water: molecular sieve (weight ratio)=5: 1 pairs of samples wash, and filter oven dry at last.Analytic sample Na
2O content is 8.5wt%.
By embodiment 1～5 as seen, adopt ammonium ion exchange method provided by the invention, use the ammonium salt of 0.2～0.4 times of weight, 5 times deionized water wash, the Na of sieve sample after the ammonium ion exchange
2O content is 1.9wt%～5.3wt%, compares with the liquid phase exchange of Comparative Examples 1, adopts the ammonium salt of 1 times of weight, 15 times deionized water, the Na of exchange back sieve sample
2O content is 6.8wt%, and the consumption while exchange efficiency of having saved ammonium salt and deionized water is higher.Comparative Examples 2 is for exchanging the Na of sieve sample after the washing and drying without the mechanically mixing that adds heat exchange
2O content is 8.5wt%, illustrates that the ammonium ion exchange of molecular sieve is not to occur in the washing process in the method provided by the invention.
Claims (4)
1. the ammonium ion exchange method of a molecular sieve, it is characterized in that according to molecular sieve: ammonium salt=1: the weight ratio of (0.1～0.6) mixes Na type molecular sieve and ammonium salt, mixture is heated to 150～280 ℃ also to be kept 1 hour at least, cool to room temperature then, according to molecular sieve: water=1: the mixture that the weight ratio of (1～10) will contain molecular sieve and ammonium salt mixes making beating with deionized water, filter slurries, obtain the molecular sieve after the ammonium ion exchange behind the filtration cakes torrefaction.
2. according to the method for claim 1, it is characterized in that described Na type molecular sieve is that NaY molecular sieve or is handed over a roasting Y zeolite.
3. according to the method for claim 1, it is characterized in that described ammonium salt is selected from one or more in ammonium chloride, ammonium sulfate and the ammonium nitrate.
4. the roasting at least 0.5 hour under 400～700 ℃, 100% water vapour atmosphere of the super stabilizing method of a molecular sieve, the molecular sieve after the ammonium ion exchange that it is characterized in that obtaining in the claim 1～3 obtains the Y zeolite of super stabilizing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102502695B (en) * | 2011-10-27 | 2014-08-27 | 湖南大学 | NaY molecular sieve modifying method |
| CN105366690B (en) * | 2014-08-15 | 2018-01-19 | 中国石油天然气集团公司 | A kind of y-type zeolite with transgranular multi-stage porous and preparation method and application |
| CN106538519A (en) * | 2016-11-01 | 2017-03-29 | 山东理工大学 | A kind of method that ion exchange prepares silver molecular sieve high-efficient antibacterial agent admittedly |
| CN113522207B (en) * | 2020-04-13 | 2023-06-16 | 中国石油化工股份有限公司 | Molecular sieve ion exchange method, preparation method and application of ion exchange type rare earth molecular sieve |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415439A (en) * | 1980-10-28 | 1983-11-15 | W. R. Grace & Co. | Catalytic cracking catalyst |
| 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 |
| CN1060977A (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 aluminum silicide |
| CN1676577A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Petroleum hydrocarbon cracking catalys containing rare earth superstable Y-type zeolite |
-
2008
- 2008-07-24 CN CN2008101171007A patent/CN101633507B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415439A (en) * | 1980-10-28 | 1983-11-15 | W. R. Grace & Co. | Catalytic cracking catalyst |
| 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 |
| CN1060977A (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 aluminum silicide |
| CN1676577A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Petroleum hydrocarbon cracking catalys containing rare earth superstable Y-type zeolite |
Non-Patent Citations (1)
| Title |
|---|
| JP特开200636616A 2006.02.09 |
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