CN103359760A - Method for removing sodium from sodium zeolite molecular sieve through ion exchange - Google Patents
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Abstract
The invention relates to a method for removing sodium from a sodium zeolite molecular sieve through ion exchange, which comprises the following steps: (1) exchanging the sodium zeolite molecular sieve by using an acid solution and filtering; (2) exchanging the zeolite molecular sieve obtained in the step (1) with an ammonium ion and/or rare earth ion aqueous solution(s). Compared with the prior art, the method disclosed by the invention can greatly reduce the amount of ammonium ion compounds required for exchange on the premise that achieving the same sodium removing level is achieved and the molecular sieve structure is hardly broken.
Description
Technical field
The present invention relates to the method that sodium is taken off in a kind of sodium type zeolite molecular sieves ion-exchange, the method for taking off sodium more specifically to the acid exchange of a kind of zeolite molecular sieve and ammonium ion and/or the exchange of the rare earth ion aqueous solution.
Background technology
Na type molecular sieve comprises faujusite, the β zeolite, mordenite, Y zeolite during ZSM series zeolite, especially catalytic cracking catalyst are produced, traditional technology all adopts the method for ammonium salt and rare earth exchanged to reduce sodium content, to improve the active and stable of zeolite [molecular sieve.The sodium content that makes zeolite molecular sieve and contain the molecular sieve active constituent catalyst satisfies service requirements, often needs to adopt excessive ammonium salt exchange modification, therefore produces the trade effluent that contains a large amount of ammonia nitrogen substances.Ammonia-nitrogen content is generally 4000～1000mg/L in the ammonium exchange process filtered liquid, and ammonia-nitrogen content is 150～1500mg/L in the rear washing water of exchange.If directly enter water body, easily cause algae and other microorganism amount reproductions in the water, cause body eutrophication.Ammonia nitrogen in the water can change into nitrite under certain condition, and nitrite and protein bound can form nitrosamine, is a kind of strong carcinogen, and is totally unfavorable to HUMAN HEALTH.The ecotope aspect, ammonia nitrogen pollutes water body, and aquatic animals and plants is poisoned and death.Therefore, all stipulated the concentration limit of ammonia nitrogen in the existing surface water of China, underground water, integrated wastewater discharge standard and the water quality standard for fishery, national grade one discharge standard is 15mg/L, and secondary discharge standard is 50mg/L.
Many researchers adopts the ammonia nitrogen amount in the several different methods reduction trade effluent.Chinese patent CN1948191A adopts reverse osmosis and membrane sepn combining method to process the catalyzer ammonia nitrogen waste water.Chinese patent CN1485281A adopts the 13X molecular sieve to process ammonia nitrogen waste water, and molecular sieve adopts the regeneration of 20% sodium chloride solution.Industrial catalyzer mesolite molecular sieve after ammonium ion exchange, NH in the zeolite
4 +NH is sloughed in thermolysis more subsequently
3, stay H
+If directly use H
+Proton exchange, both the conservation cost can fundamentally solve the ammonia and nitrogen pollution problem again.At present, nearly all document all thinks, for y-type zeolite or generally low Si/Al can not be with acid exchange or acid treatment dealuminzation than zeolite, otherwise the destruction that will cause crystalline structure.(work such as Xu Ruren, " molecular sieve is in the porous material chemistry ", the 443rd page, Beijing Science Press, 2004; The Chen Junwu chief editor, " catalytic cracking process and engineering " second edition, the 193rd page of the first volume, Beijing: Sinopec press; The Huang Zhongtao chief editor, " Industrial Catalysis ", Teaching Materials at College level, the 45th page, Beijing: Chemical Industry Press, 1994).
Summary of the invention
The object of the invention is to provide a kind of Na type zeolite molecular sieve to exchange, exchange the method for taking off sodium with ammonium ion and/or the rare earth ion aqueous solution again with acid solution first, thereby the consumption that reduces the ammonium ion compound is not even used ammonium ion exchange, and avoids the zeolite molecular sieve crystal structural damage.
The method that sodium is taken off in sodium type zeolite molecular sieves ion-exchange of the present invention may further comprise the steps: with acid solution exchange 0.1 second～72 hours, then filter sodium type zeolite molecular sieves (1); (2) step (1) gained zeolite molecular sieve filter cake is exchanged with ammonium ion and/or the rare earth ion aqueous solution.
Sodium type zeolite molecular sieves of the present invention comprises Y zeolite, X-type molecular sieve, ZSM Series Molecules sieve, mordenite molecular sieve, one or more in the beta-zeolite molecular sieve.Described Y zeolite is NaY molecular sieve and one friendship one roasting Y zeolite and the two friendships two roasting Y zeolites synthetic with kaolin in-situ crystallization that comprise that gel method is synthetic.The synthetic NaY molecular sieve of described kaolin in-situ crystallization is blended in the degree of crystallinity of acquisition in 70-120 ℃ of lower crystallization 8-72 hour at the crystallization product of 15-85% for the kaolin microsphere (particle diameter 20-150 micron accounts for more than 60%) through 600-1000 ℃ of roasting with water glass, sodium hydroxide and NaY directed agents and water.Described one hands over a roasting and two to hand over two roasting Y zeolites to comprise ultra-steady Y molecular sieve, rare-earth Y molecular sieve, rare earth HY molecular sieve and hydrogen Y molecular sieve.
Acid solution of the present invention comprises hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, formic acid, acetic acid, propionic acid, tartrate, silicofluoric acid, one or more among the H4EDTA.
One of sour exchanged form of the present invention is that sodium type zeolite molecular sieves is mixed with water and/or acid solution, be interrupted or the continuous adding acid solution, it is between any two pH values of 0.01～1.0 0.1 second～48 hours that slurry pH value is stabilized in pH difference between the 2.5-6.5, preferably is between any two pH values of 0.01～0.5 0.1 second～12 hours in the pH difference between 2.8～4.5 with the pH value stabilization of slurry.Described acid solution exchange times is 1～20 time, preferred 1～5 time.
The pH value of above-mentioned acid exchange slurry can adopt the interpolation speed of the automatic pH meter control of numerical control acid exchange solution to regulate.The automatic pH meter of described numerical control comprises potential electrode, digital-controlled instrument and topworks.
Two of the mode of acid exchange of the present invention is that sodium type zeolite molecular sieves is mixed more than 0.1 second with the acid solution of pH=1.0～6.0, makes slurry pH value more than or equal to 2.5.Described acid solution exchange times is 1～20 time, preferred 1～8 time.The liquid-solid mass ratio of each exchange (exchange liquid: be 1.5～200 sodium type zeolite molecular sieves), preferred 5～50.
Three of the mode of acid exchange of the present invention is to carry out multistage at the belt vacuum filter with 1～20 section to exchange and filter and realize, every section exchange liquid is the acid solution of the preferred pH=2.0 in pH=1.0～6.0～3.5.Multistage exchange and filtration are known technologies on the belt vacuum filter, can adopt mobile disc type or adhesive tape type vacuum filter.Preferred 1～12 section belt vacuum filter.
Slurry exchange temperature of the present invention is 0-100 ℃.
The compound of ammonium ion of the present invention comprises one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, the ammonium hydroxide; The compound of described rare earth ion comprises rare earth chloride, a kind of in the rare earth nitrate or two kinds; Described ammonium ion and/or rare earth ion aqueous solution pH=2.0-12.0.
Zeolite molecular sieve ammonium ion of the present invention and/or rare earth ion aqueous solution switching method are known technology, can adopt tank exchange and/or band filter exchange.
Exchange and filter with ammonium ion and/or the rare earth ion aqueous solution again after zeolite molecular sieve acid exchange of the present invention and the filtration, gained filtrate sodium ions content is low, can recycle or apply mechanically when repeatedly hydrothermal chemistry is processed zeolite molecular sieve, namely after once exchange exchange filtrate can as or preparation before once exchange liquid.
Compared with prior art, Na type zeolite molecular sieve ion-exchange method for removing Na provided by the invention can reach the consumption that reduces clearing house need ammonium ion compound under the prerequisite of taking off on an equal basis the sodium level and substantially not destroying the zeolite molecular sieve crystal structure, even exchange with the ammonium ion compound, thereby reduce even the elimination ammonia and nitrogen pollution.
Embodiment
The below further specifies the present invention with embodiment, but does not therefore limit the present invention.
Embodiment 1
Get 200g kaolin in-situ crystallization NaY material (degree of crystallinity=38.3%, silica alumina ratio=5.13, Na
2O=5.5wt%, Shanghai is received auxiliary agent company limited of section and is produced), the deionized water that adds 10 times of pH=3.5, drip 2%HCl solution, stop during pH=3.0 dripping, when pH＞3.2, continue to drip, when slurry pH is stabilized in after time between 3.0～3.2 surpasses 20 minutes, filter, washing. blot.Filter cake is pulled an oar again, adds 30g ammonium chloride, stirs, and regulating the pH value is 3.3～3.5, and 85 ℃ of lower exchanges 1 hour, filter cake was 600 ℃ of lower roastings 2 hours after filtering, and recording degree of crystallinity is 33.1%, Na
2O content is 1.95wt%.
Embodiment 2
Get 200g kaolin in-situ crystallization NaY material (degree of crystallinity=38.3%, silica alumina ratio=5.13, Na
2O=5.5wt%, Shanghai is received auxiliary agent company limited of section and is produced), add the deionized water of 10 times of pH=3.5, drip 2%HNO
3Solution stops during pH=3.3 dripping.When pH＞3.5, continue to drip, when slurry pH is stabilized in after time between the 3.3-3.5 surpasses 2 hours, filter, wash, blot.Filter cake is pulled an oar again, adds the 25g rare earth chloride, stirs, and regulating the pH value is 3.8～4.0, and 90 ℃ of lower exchanges 1 hour, filter cake was 550 ℃ of lower roastings 2 hours after filtering, and recording degree of crystallinity is 34.1%, Na
2O content is 2.56wt%.
Embodiment 3
Get 200g kaolin in-situ crystallization NaY material (degree of crystallinity=38.3%, silica alumina ratio=5.13, Na
2O=5.5wt%, Shanghai is received auxiliary agent company limited of section and is produced), add the deionized water of 10 times of pH=3.5, drip 1% oxalic acid solution, stop during pH=5.0 dripping.When pH＞5.5, continue to drip, when slurry pH is stabilized in after time between 5.0～5.5 surpasses 3 hours, filter, wash, blot.Filter cake is pulled an oar again, adds 20g ammonium chloride and 15g rare earth chloride, stirs, and regulating the pH value is 3.5～3.8, and 90 ℃ of lower exchanges 1 hour, filter cake was 650 ℃ of lower roastings 2 hours after filtering, and recording degree of crystallinity is 33.3%, Na
2O content is 1.85wt%.
Embodiment 4
Get 200g kaolin in-situ crystallization NaY material (degree of crystallinity=38.3%, silica alumina ratio=5.13, Na
2O=5.5wt%, Shanghai is received auxiliary agent company limited of section and is produced), add the deionized water of 10 times of pH=3.5, drip 1%H
2SO
4Solution stops during pH=4.0 dripping.When pH＞4.5, continue to drip, when slurry pH is stabilized in after time between the 4.0-4.5 surpasses 25 hours, filter, wash, blot.Filter cake is pressed said procedure acid again and is handed over twice, and then making beating, add 70 milliliters of ammoniacal liquor, 50 ℃ of lower exchanges 1 hour, again making beating after filtering, washing and blot, add the 20g rare earth chloride, stir, regulating the pH value is 3.8～4.0,95 ℃ of lower exchanges 1 hour, filter cake was 500 ℃ of lower roastings 3 hours after filtering, and recording degree of crystallinity is 32.5%, Na
2O content is 1.56wt%.
Comparative Examples 1
Get 200g kaolin in-situ crystallization NaY material (degree of crystallinity=38.3%, silica alumina ratio=5.13, Na
2O=5.5wt%, Shanghai is received auxiliary agent company limited of section and is produced), adds 10 times of deionized waters, 60g ammonium chloride stirs, and regulating pH value is 3.3～3.8, filters, washs, blots after descending to exchange 1 hour at 90 ℃.Filter cake is pulled an oar again, adds the 25g rare earth chloride, stirs, and regulating the pH value is 3.8～4.0, and 95 ℃ of lower exchanges 1 hour, filter cake was 600 ℃ of lower roastings 2 hours after filtering, and recording degree of crystallinity is 33.8%, Na
2O content is 2.26wt%.
Comparative Examples 2
Get 200g kaolin in-situ crystallization NaY material (degree of crystallinity=38.3%, silica alumina ratio=5.13, Na
2O=5.5wt%, Shanghai is received auxiliary agent company limited of section and is produced), add the deionized water of 10 times of pH=2.5, drip 1% HCl solution, stop during pH=3.3 dripping.When pH＞3.5, continue to drip, when slurry pH is stabilized in after time between the 3.3-3.5 surpasses 2 hours, filter, wash, blot.Filter cake was 600 ℃ of roastings 2 hours.Recording degree of crystallinity is 26.6%, Na
2O content is 2.61wt%.
Embodiment 5
Get 100g NaY molecular sieve (degree of crystallinity=90.0%, silica alumina ratio=5.10, Na
2O=13.2wt%, Shanghai is received auxiliary agent company limited of section and is produced), add the deionized water of 10 times of pH=3.5, stop during pH=3.3 dripping.When pH＞3.5, continue to drip, when slurry pH is stabilized in after time between the 3.3-3.5 surpasses 2 hours, filter, wash, blot.Filter cake is pulled an oar with 5 times of water, adds that ammonium hydroxide carries out ammonium ion exchange until system is kept pH about 10.0 1.5 hours, and filter cake was 600 ℃ of roastings 3 hours after filtering, and recording molecular sieve crystallinity is 80.0%, Na
2O content is 4.97wt%.
Comparative Examples 3
Get 100gNaY molecular sieve (degree of crystallinity=90.0%, silica alumina ratio=5.10, Na
2O=13.2wt%, Shanghai is received auxiliary agent company limited of section and is produced), add the deionized water of 10 times of pH=3.5, add 50g ammonium chloride, stir, regulate pH at 3.3-3.5, filter, wash, blot after 1 hour 90 ℃ of lower exchanges.Filter cake was 600 ℃ of roastings 3 hours, and recording molecular sieve crystallinity is 80.1%, Na
2O content is 4.90wt%.
Embodiment 6
Get 200g in-situ crystallization REHNaY two roasting material (degree of crystallinity=32.5%, silica alumina ratio=5.83, Na
2O=0.8wt%, Shanghai is received auxiliary agent company limited of section and is produced), add the deionized water of 10 times of pH=2.5, drip 1% HNO
3Solution stops during pH=3.1 dripping, and pH＞3.3 an o'clock continuation drips, after making slurry pH be stabilized in time more than 30 minutes between the 3.1-3.3, filter washing, blotting rear filter cake pulls an oar again, add 10g ammonium nitrate, stir, regulate pH at 3.3-3.5,90 ℃ of lower exchanges 1 hour, filter, wash, blot rear drying, recording degree of crystallinity is 31.5%, Na
2O content is 0.25wt%, and micro-activity (17 hours, 800 ℃) is 70.1.
Comparative Examples 4
Get 200g in-situ crystallization REHNaY two roasting material (degree of crystallinity=32.5%, silica alumina ratio=5.83, Na
2O=0.8wt%, Shanghai is received auxiliary agent company limited of section and is produced), adds 5 times of deionized waters, add 30g ammonium nitrate, stir, regulate pH at 3.3-3.5, exchange 1 hour down at 90 ℃, filter, wash, blot rear drying, recording degree of crystallinity is 31.8%, Na
2O content is 0.30wt%, and micro-activity (17 hours, 800 ℃) is 68.4.
Embodiment 7
Get 200g in-situ crystallization REHNaY one roasting material (degree of crystallinity=35.3%, silica alumina ratio=5.51, Na
2O=2.8wt%, Shanghai is received auxiliary agent company limited of section and is produced), add the deionized water of 10 times of pH=3.5, drip 1%HCl solution, stop during pH=3.3 dripping.When pH＞3.5, continue to drip, when slurry pH is stabilized in after time between the 3.3-3.5 surpasses 2 hours, filter, wash, blot.Filter cake is with ammonium nitrate exchange filtrate making beating among the embodiment 6 and add 10g ammonium chloride 90 ℃ of lower exchanges 1 hour, and in 580 ℃ of roastings 3 hours, recording degree of crystallinity was 32.6%, Na after filtering, wash, blotting
2O content is 0.83wt%.
Comparative Examples 5
Get 200g in-situ crystallization REHNaY one roasting material (degree of crystallinity=35.34%, silica alumina ratio=5.51, Na
2O=2.8wt%, Shanghai is received auxiliary agent company limited of section and is produced), add the deionized water making beating of 5 times of pH=3.5, add 60g ammonium chloride, stir, regulate pH at 3.3-3.5, filter cake was in 580 ℃ of roastings 3 hours after 90 ℃ of lower exchanges were filtered, washed, blot after 1 hour.Recording degree of crystallinity is 32.9%, Na
2O content is 0.92wt%.
Embodiment 8
Get 200g kaolin in-situ crystallization NaY material (degree of crystallinity=38.3%, silica alumina ratio=5.13, Na
2O=5.5wt%, Shanghai is received auxiliary agent company limited of section and is produced), the deionized water that adds 10 times of pH=3.5, drip 2% HCl solution, stop during pH=3.0 dripping, when pH＞3.2, continue to drip, when slurry pH is stabilized in after time between the 3.0-3.2 surpasses 40 minutes, filter, wash, blot.The filter cake making beating adds ammonium hydroxide exchange filtrate making beating among the embodiment 5, and adds 25g ammonium nitrate, regulates pH at 3.3-3.5, and 90 ℃ of lower exchanges 1 hour, 600 ℃ of lower roastings 2 hours, recording degree of crystallinity was 33.4%, Na after filtering
2O=1.98wt%.
Embodiment 9
Get 200g gel method REHNaY one roasting material (degree of crystallinity=75.2%, silica alumina ratio=5.49, Na
2O=4.90wt%, Shanghai is received auxiliary agent company limited of section and is produced), adds 10 times of deionized waters, drip 1%HCl solution, stop dropping during pH=3.3.When pH＞3.5, continue to drip, when slurry pH is stabilized in after time between the 3.3-3.5 surpasses 10 minutes, filter, wash, blot.The filter cake making beating adds 25g ammonium chloride, stirs, and regulates pH at 3.3-3.5, and 90 ℃ of lower exchanges 1 hour, in 600 ℃ of roastings 2 hours, recording degree of crystallinity was 71.5%, Na after filtering, wash, blotting
2O content is 1.48wt%.
Comparative Examples 6
Get 200g gel method REHNaY one roasting material (degree of crystallinity=75.2%, silica alumina ratio=5.49, Na
2O=4.90wt%, Shanghai is received auxiliary agent company limited of section and is produced), adds 10 times of deionized waters making beating, add 35g ammonium chloride, stir, regulate pH at 3.3-3.5, filter, wash, blot after exchanging 1 hour down at 90 ℃.Filter cake was in 600 ℃ of roastings 2 hours, and recording degree of crystallinity is 71.8%, Na
2O content is 1.53wt%.
Claims (11)
1. method that sodium is taken off in sodium type zeolite molecular sieves ion-exchange is characterized in that the method may further comprise the steps: with acid solution exchange 0.1 second～72 hours, then filter sodium type zeolite molecular sieves (1); (2) step (1) gained zeolite molecular sieve filter cake is exchanged with ammonium ion and/or the rare earth ion aqueous solution.
2. method according to claim 1 is characterized in that, described sodium type zeolite molecular sieves comprises Y zeolite, X-type molecular sieve, ZSM Series Molecules sieve, mordenite molecular sieve, one or more in the beta-zeolite molecular sieve.
3. method according to claim 2 is characterized in that, described Y zeolite is NaY molecular sieve and one friendship one roasting Y zeolite and the two friendships two roasting Y zeolites synthetic with kaolin in-situ crystallization that comprise that gel method is synthetic.
4. method according to claim 3, it is characterized in that, the synthetic NaY molecular sieve of described kaolin in-situ crystallization is blended in the degree of crystallinity of acquisition in 70-120 ℃ of lower crystallization 8-72 hour at the crystallization product of 15-85% for the kaolin microsphere (particle diameter 20-150 micron accounts for more than 60%) through 600-1000 ℃ of roasting with water glass, sodium hydroxide and NaY directed agents and water.
5. method according to claim 3 is characterized in that, described one hands over a roasting and two to hand over two roasting Y zeolites to comprise ultra-steady Y molecular sieve, rare-earth Y molecular sieve, rare earth HY molecular sieve and hydrogen Y molecular sieve.
6. method according to claim 1 is characterized in that, described acid solution comprises hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, formic acid, acetic acid, propionic acid, tartrate, silicofluoric acid, H
4Among the EDTA one or more.
7. method according to claim 1, it is characterized in that, described acid solution exchange is that sodium type zeolite molecular sieves is mixed with water and/or acid solution, be interrupted or the continuous adding acid solution, it is between any two pH values of 0.01～1.0 0.1 second～48 hours that slurry pH value is stabilized in pH difference between the 2.5-6.5.
8. method according to claim 7 is characterized in that, the pH value stabilization of described slurry is between any two pH values of 0.01～0.5 0.1 second～12 hours in the pH difference between 2.8～4.5.
According to claim 1 with 7,8 described methods, it is characterized in that, described acid solution exchange times is 1～20 time.
10. method according to claim 1 is characterized in that, the compound of described ammonium ion comprises one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, the ammonium hydroxide; The compound of described rare earth ion comprises rare earth chloride, a kind of in the rare earth nitrate or two kinds.
11. method according to claim 1 is characterized in that, described ammonium ion and/or rare earth ion aqueous solution pH=2.0～12.0.
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Cited By (1)
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| CN103691491A (en) * | 2013-12-31 | 2014-04-02 | 中国天辰工程有限公司 | Method for removing sodium by silicon-aluminum-phosphor molecular sieve catalyst |
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Application publication date: 20131023 |