WO2013072809A1 - Process for ion exchange on zeolites - Google Patents
Process for ion exchange on zeolites Download PDFInfo
- Publication number
- WO2013072809A1 WO2013072809A1 PCT/IB2012/056206 IB2012056206W WO2013072809A1 WO 2013072809 A1 WO2013072809 A1 WO 2013072809A1 IB 2012056206 W IB2012056206 W IB 2012056206W WO 2013072809 A1 WO2013072809 A1 WO 2013072809A1
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- WIPO (PCT)
- Prior art keywords
- ammonium
- zeolite
- sodium
- solution
- ammonium carbonate
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B39/026—After-treatment
Definitions
- the present invention relates to an improved process for exchanging alkali metal or alkaline earth metal ions in zeolites for ammonium ions.
- aqueous solutions of ammonium salts for example ammonium sulfate, ammonium nitrate or ammonium chloride, are currently being used.
- ammonium zeolites are calcined to convert them, with release of ammonia, to the H form of the zeolites suitable as a catalyst.
- ammonium carbonate instead of the ammonium compounds mentioned. Since excess ammonium carbonate, in contrast to the nitrates, sulfates or chlorides, can be recycled in the form of carbon dioxide and ammonia, the amount of salt which has to be discharged is lowered significantly.
- the high demand in petrochemistry for lower hydrocarbons such as saturated and unsaturated aliphatic, cycloaliphatic or aromatic hydrocarbons is satisfied by conversion processes such as catalytic cracking, hydrocracking or thermal cracking.
- the feedstocks used are crude oils or relatively high-boiling crude oil distillate fractions.
- zeolites In catalytic cracking, preference is given to working with fluidized beds consisting of zeolites (FCC processes).
- FCC processes zeolites
- the zeolites are used in the H form, which can be produced by heating corresponding zeolites comprising ammonium ions to about 400°C (Hans-Jurgen Arpe, Industrielle organische Chemie [Industrial Organic Chemistry], 6th edition, 2007, Wiley-VCH publishers, pages 64 to 65).
- US 3,966,882 describes the exchange of Na for NH4 ions.
- Ammonium carbonate is not mentioned.
- US Re28,629 and US 4,346,067 disclose using ammonium chloride, ammonium nitrate or ammonium sulfate for ion exchange.
- CN 102623650 mentions that ammonium carbonate is used for ion exchange.
- the zeolite has to be treated several times in succession, preferably at temperatures of 70°C to 100°C, in some cases to 200°C, with an excess of aqueous ammonium nitrate relative to the sodium ions.
- the salt solution is generally separated from the zeolite.
- the solid zeolite can subsequently be washed with water in order to remove salts. After each ion exchange step, it is calcined at 200°C to 600°C. In the course of this, ammonia release forms the desired H form of the zeolite (Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, volume 39, 2003, Wiley-VCH publishers, pages 638 to 640).
- the Y zeolite in the H form and an aqueous salt solution comprising a mixture of sodium nitrate and unconverted ammonium nitrate are obtained. Since the replacement of the sodium ions by the ammonium ions is incomplete, ammonium compounds are present alongside the sodium compounds in the mother liquor.
- figure 1 shows that ammonia and water are first released from ammonium hydrogencarbonate/sodium carbonate mixtures and the remaining sodium hydrogencarbonate is converted to sodium carbonate with release of carbon dioxide.
- ammoniumcarbonat it is known that ammonium carbonate can be produced by introducing carbon dioxide into aqueous ammonia.
- One disadvantage in the prior art processes is that large amounts of aqueous sodium nitrate and ammonium nitrate solution, sodium sulfate and ammonium sulfate solution or sodium chloride and ammonium chloride solution are formed, which are obtained, for example, in the case of use of ammonium nitrate, ammonium sulfate or ammonium chloride for the ion exchange of zeolites comprising sodium ions.
- the salt solutions can in principle be used for production of fertilizers. However, this means only a low level of added value. Moreover, the economic viability of utilization as a fertilizer depends on the site.
- the ammonia bound in the ammonium salts can be released by addition of at least equimolar amounts of sodium hydroxide solution, removed by stripping or distillation and reused for the preparation of the ammonium salts.
- this addition of value is reduced by the consumption of sodium hydroxide solution.
- the known processes require high circulation rates with a considerable energy requirement, which constitutes an economic disadvantage.
- the object is achieved in accordance with the invention by the provision of a process for exchanging sodium ions in sodium-comprising zeolites for ammonium ions, which comprises a) treating the sodium-comprising zeolite with a solution comprising water and ammonium carbonate, b) separating the zeolite from the solution (mother liquor) comprising aqueous sodium carbonate and ammonium carbonate, and c) thermally treating the mother liquor to release ammonia and carbon dioxide.
- natural or synthetic crystalline zeolites which comprise alkali metal or alkaline earth metal ions are suitable.
- All zeolites comprising alkali metal and alkaline earth metal ions are suitable in principle.
- Preferred zeolites are those of the ZSM type, especially ZSM-5, and also X, Y, A and L zeolites.
- Other options are naturally occurring zeolites such as faujasite, chabazite, erionite, mordenite, offretite (US 4,346,067, column 1 , lines 43 to 57).
- Y zeolites in the sodium form.
- the alkali metal content of the zeolite should be lowered by ion exchange to less than 10% by weight, preferably less than 5% by weight, more preferably less than 1 % by weight.
- the solution comprising water and ammonium carbonate is preferably prepared from water and ammonium carbonate and optionally further compounds.
- ammonium carbonate is used for the ion exchange as an aqueous solution of strength 0.1 % by weight up to the solubility limit, preferably 5 to 35% by weight and more preferably 10 to 25% by weight.
- Ammonium carbonate is understood to mean (NhU ⁇ COs, NH4HCO3 and mixtures thereof.
- ammonium carbonate or in a mixture with ammonium carbonate
- compounds which form ammonium carbonate in aqueous solution under the reaction conditions are urea and ammonium carbamate.
- reaction of, for example, urea and/or ammonium carbamate with water can be effected in a separate reaction step prior to the ion exchange.
- reaction of urea and/or ammonium carbonate and the ion exchange it is also possible to conduct the reaction of urea and/or ammonium carbonate and the ion exchange in the same process step.
- the ion exchange is performed at temperatures of 0°C to 200°C, preferably 20°C to 100°C, and more preferably 50°C to 80°C, and total pressures of 1 to 300 bar, preferably 1 to 50 bar, and more preferably 1 to 10 bar.
- the ion exchange can be effected batchwise or continuously.
- the zeolite can be suspended in the aqueous stirred ammonium carbonate solution.
- the zeolite and the ammonium carbonate solution can flow through a tube, particular preference being given to conducting the solution in countercurrent to the zeolite.
- the ion exchange is conducted in one or more belt filters.
- the mother liquor from the downstream filter can be recycled in countercurrent to the previous filter.
- the ion exchange is performed in a combination of one or more stirred tanks or one or more flow tubes and one or more belt filters in succession and in countercurrent.
- the reaction time needed for the ion exchange is 0.1 second to 10 hours, preferably 1 second to 2 hours and more preferably 1 second to 1 hour.
- Zeolite suspended in aqueous ammonium carbonate solution can be removed, for example, by filtration or centrifugation.
- the zeolite In order to remove salts adhering to the zeolite, it can be washed once or more than once, preferably one to three times, with water.
- the amount of water is 1 to 1000 g of water per g of zeolite.
- the wash water can be combined with the salt solution removed from the zeolite.
- the calcined zeolite can optionally be passed onward into a second ion exchange stage a).
- the cycle sequence of ion exchange, zeolite removal and calcination is optionally repeated until the sodium content of the zeolite has fallen to the desired value. In general, 1 to 3 cycles and especially 1 to 2 cycles are needed for this purpose.
- the excess ammonium carbonate solution which has been removed from the zeolite after the ion exchange additionally comprises sodium carbonate.
- This solution can be combined with the wash water if the zeolite has been washed with water.
- the mixture of ammonium carbonate solution and sodium carbonate solution and water is heated to a temperature above 50°C, preferably above 60°C. There is in principle no upper limit to the temperature, but temperatures above 100°C may require an elevated pressure.
- the heating can be performed batchwise or continuously. Evaporation of a portion of the liquid results in escape of carbon dioxide and possibly ammonia.
- the mixture is supplied continuously to a distillation column.
- the liquid in the bottom of the column is heated and partly evaporated by introduction of heat or steam.
- Ammonium carbonate decomposes along the plates of the column, and carbon dioxide and ammonia formed are stripped out of the liquid by the ascending vapor.
- a solution depleted of ammonium carbonate is obtained. More preferably, the bottoms comprise barely any or no ammonium carbonate.
- the thermal release is effected with addition of a base.
- bases are alkali metal hydroxide and/or alkaline earth metal hydroxide. These can be added in solid form or as a solution, preferably as an aqueous solution. If a base is added as an aqueous solution, a concentration of 0.1 % by weight to 50% by weight is preferred, particular preference being given to a concentration of 10% by weight to 50% by weight.
- an aqueous solution of sodium hydroxide (sodium hydroxide solution) with a concentration of 0.1 % by weight to 50% by weight.
- an aqueous solution of sodium hydroxide (sodium hydroxide solution) with a concentration of 10% by weight to 50% by weight is used.
- Carbon dioxide and ammonia which are obtained as low boilers from the thermal treatment, can be recombined by cooling for recovery. They are preferably recombined in aqueous solution. Particular preference is given to recovery by condensation and cooling of the liquid stream, the liquid stream being used for absorption of gaseous carbon dioxide and ammonia.
- the aqueous ammonium carbonate solution can be reused for the ion exchange.
- the bottom product obtained from the thermal treatment is aqueous sodium carbonate solution, which is discharged from the process.
- Sodium carbonate (soda) is one of the most important products in the large-scale chemical industry, which is optionally used instead of NaOH. Annual global production is on the
- Figure 1 shows a preferred embodiment of the process according to the invention.
- the sodium zeolite is treated in an ion exchanger stage with an aqueous ammonium carbonate solution. Thereafter, treated zeolite and mother liquor are separated by a suitable process, for example filtration, and optionally dried.
- the zeolite thus pretreated is calcined in a furnace, releasing ammonia. These stages can be conducted twice or more in succession.
- the mother liquor from the removal stage is supplied to a column which comprises a stripping section and is heated at the bottom with an evaporator or by direct addition of steam.
- the temperature increase drives out ammonia and carbon dioxide, entraining water in the form of steam.
- the vaporous mixture is condensed in a direct or indirect condenser, and ammonia and carbon dioxide recombine with water to give aqueous ammonium carbonate.
- the ammonium carbonate solution thus obtained is recycled into the ion exchange stage.
- an aqueous sodium carbonate solution is discharged.
- the ammonia from the calcining furnace is optionally conducted with supplementary ammonia and carbon dioxide into the column upstream of the condenser.
- the examples which follow describe the inventive sodium exchange in zeolite Y using ammonium carbonate.
- the zeolite Y used having a sodium content of 7.3% by weight, was purchased under the CBV 100 brand name from Zeolyst.
- USY (X6503, Engelhardt) with a sodium content of 3.1 % by weight was used.
- Chemical analyses of the ammonium carbonate or ammonium nitrate solutions used, prior to treatment of the zeolite, showed a sodium content of ⁇ 0.01 % by weight. All sodium contents specified hereinafter were determined analogously by means of chemical analysis.
- the zeolite used in each case was calcined at 500°C for 5 hours. XRD analyses of selected samples on completion of treatment confirmed that the zeolite structure was intact after the ion exchange.
- the sodium content was determined by means of flame atomic absorption spectrometry, and the ammonium content according to Kjeldahl.
- the inorganic carbon was determined as carbon dioxide by means of thermal conductivity measurements after combustion of the sample in an oxygen stream.
- the filtrate had a sodium content of 0.1 % by weight.
- the filtercake was dried at 120°C for 4 hours and then calcined at 500°C for 5 hours.
- the sodium content of the zeolite after calcination was 2.7% by weight.
- Example 1 The procedure corresponded to Example 1. The treatment of the zeolite with the ammonium carbonate solution was extended both times from 2 hours to 14 hours. The sodium content of the zeolite thereafter was 2.5% by weight.
- Example 1 The procedure corresponded to Example 1 .
- the treatment of the zeolite with the ammonium carbonate solution was conducted both times at 60°C rather than 80°C.
- the sodium content of the zeolite thereafter was 2.5% by weight.
- the procedure corresponded to Examples 1 to 3, except that the treatment of the zeolite was performed with ammonium nitrate solutions.
- the sodium contents of the ammonium nitrate solutions after treatment of the zeolite were in all cases comparable with the sodium contents of the ammonium carbonate solutions.
- the sodium content of the zeolite after treatment with ammonium nitrate was 2.3-2.6% by weight.
- Example 7 The procedure corresponded to Example 5, except that the treatment of the zeolite was performed with ammonium oxalate. The sodium content of the zeolite after the calcination was 2.6% by weight. Comparative Example 7
- Example 8 The procedure corresponded to Example 5, except that the treatment of the zeolite was performed with ammonium nitrate. The sodium contents of the filtrates were 0.5% and 0.1 % by weight. The sodium content of the zeolite after the calcination was 2.3% by weight.
- Example 8 The procedure corresponded to Example 5, except that the treatment of the zeolite was performed with ammonium nitrate. The sodium contents of the filtrates were 0.5% and 0.1 % by weight. The sodium content of the zeolite after the calcination was 2.3% by weight. Example 8
- Example 8 The procedure corresponded to Example 8. USY (X6503, Engelhardt, sodium content 3.1 % by weight) was used. The sodium content of the zeolite after the calcination was 1 .0% by weight.
- Example 8 The procedure corresponded to Example 8, except that the treatment of the zeolite was performed with ammonium oxalate.
- the sodium contents of the filtrates were 0.4% and 0.1 % by weight.
- the sodium content of the zeolite after the calcination was 2.0% by weight.
- Example 8 The procedure corresponded to Example 8, except that the treatment of the zeolite was performed with ammonium nitrate.
- the sodium contents of the filtrates were 0.4% and 0.1 % by weight.
- the sodium content of the zeolite at the end of the treatment was 1 .4% by weight.
- Example 15 The procedure corresponded to Example 13, except that 7% ammonia solution and 2 bar of CO2 were employed.
- the sodium content of the first filtrate was 0.2 to 0.3% by weight.
- the sodium content of the zeolite after the first calcination was 3.4 to 3.8% by weight.
- the sodium content of the second filtrate was 0.1 % by weight.
- the sodium content of the zeolite at the end of the treatment was 2.6% by weight.
- Example 13 The procedure corresponded to Example 13, except that 3% ammonia solution and 5 bar of CO2 were employed.
- the sodium content of the first filtrate was 0.3% by weight.
- the sodium content of the zeolite after the first calcination was 3.6% by weight.
- the sodium content of the second filtrate was 0.1 % by weight.
- the sodium content of the zeolite at the end of the treatment was 2.5% by weight.
- Example 13 The procedure corresponded to Example 13, except that 3% ammonia solution and 2 bar of CO2 were employed.
- the sodium content of the first filtrate was 0.2% by weight.
- the sodium content of the zeolite after the first calcination was 4.0% by weight.
- the sodium content of the second filtrate was 0.1 % by weight.
- the sodium content of the zeolite at the end of the treatment was 2.1 % by weight.
- Example 18 The procedure corresponded to Example 13, except that the treatment of the zeolite was performed with 3% ammonia solution and 1 bar of CO2. The sodium contents of the two filtrates were 0.2% and 0.1 % by weight. The sodium content of the zeolite at the end of the treatment was 3.4% by weight.
- Example 18 The procedure corresponded to Example 13, except that the treatment of the zeolite was performed with 3% ammonia solution and 1 bar of CO2. The sodium contents of the two filtrates were 0.2% and 0.1 % by weight. The sodium content of the zeolite at the end of the treatment was 3.4% by weight.
- Example 18 The procedure corresponded to Example 13, except that the treatment of the zeolite was performed with 3% ammonia solution and 1 bar of CO2. The sodium contents of the two filtrates were 0.2% and 0.1 % by weight. The sodium content of the zeolite at the end of the treatment was 3.4% by weight.
- Example 18 The procedure corresponded to Example 13, except that the treatment of the zeolite was performed with
- Example 13 The procedure corresponded to Example 13, except that the treatment of the zeolite was performed with 1 % ammonia solution and 1 bar of CO2. The sodium contents of the two filtrates were 0.2% and 0.1 % by weight. The sodium content of the zeolite at the end of the treatment was 3.2% by weight.
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- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
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Abstract
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020147016478A KR20140094009A (en) | 2011-11-18 | 2012-11-07 | Process for ion exchange on zeolites |
JP2014541781A JP2014533649A (en) | 2011-11-18 | 2012-11-07 | Ion exchange method |
EP12849861.5A EP2780285A4 (en) | 2011-11-18 | 2012-11-07 | Process for ion exchange on zeolites |
BR112014011299A BR112014011299A2 (en) | 2011-11-18 | 2012-11-07 | process for exchanging sodium ions in zeolites comprising sodium for ammonium ions |
CN201280056376.3A CN103946159A (en) | 2011-11-18 | 2012-11-07 | Process for ion exchange on zeolites |
IN3736CHN2014 IN2014CN03736A (en) | 2011-11-18 | 2012-11-07 | |
ZA2014/04333A ZA201404333B (en) | 2011-11-18 | 2014-06-13 | Process for ion exchange on zeolites |
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EP11189758 | 2011-11-18 | ||
EP11189758.3 | 2011-11-18 |
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WO2013072809A1 true WO2013072809A1 (en) | 2013-05-23 |
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PCT/IB2012/056206 WO2013072809A1 (en) | 2011-11-18 | 2012-11-07 | Process for ion exchange on zeolites |
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EP (1) | EP2780285A4 (en) |
JP (1) | JP2014533649A (en) |
KR (1) | KR20140094009A (en) |
CN (2) | CN103946159A (en) |
BR (1) | BR112014011299A2 (en) |
IN (1) | IN2014CN03736A (en) |
WO (1) | WO2013072809A1 (en) |
ZA (1) | ZA201404333B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1353086A (en) * | 2000-11-13 | 2002-06-12 | 中国石油化工股份有限公司 | Process for preparing Y-type molecular sieve |
CN1806908A (en) * | 2005-10-27 | 2006-07-26 | 复旦大学 | Macroporous zeolite absorbent and preparation method thereof |
WO2010139997A2 (en) * | 2009-06-03 | 2010-12-09 | University Of Manchester | Modified zeolites and their use in the recycling of plastics waste |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US3287255A (en) * | 1964-03-18 | 1966-11-22 | Exxon Research Engineering Co | Crystalline synthetic zeolites for the hydrocracking of hydrocarbons |
JPS50103473A (en) * | 1974-01-21 | 1975-08-15 | ||
JPS51126987A (en) * | 1975-04-30 | 1976-11-05 | Shokubai Kasei Kogyo Kk | Process for regenrating zeolite which has absorbed ammonical |
US4346067A (en) * | 1981-06-29 | 1982-08-24 | Exxon Research & Engineering Co. | Method of ion exchange zeolites |
US5256392A (en) * | 1989-06-23 | 1993-10-26 | Fina Technology, Inc. | Modified zeolite beta method of preparation |
CN100386280C (en) * | 2005-09-30 | 2008-05-07 | 山东理工大学 | Concrete additive for inhibiting alkali aggregate reaction and its production |
CN100422081C (en) * | 2005-10-19 | 2008-10-01 | 中国石油化工股份有限公司 | Modified Y zeolite and its preparation method |
WO2009036145A1 (en) * | 2007-09-11 | 2009-03-19 | Powerspan Corp. | Regeneration of ammonia and carbon dioxide after scrubbing carbon dioxide with ammonium carbonate |
CN102085488B (en) * | 2009-12-03 | 2012-10-17 | 中国石油天然气股份有限公司 | Catalyst for reducing cloud point of lubricating oil base oil and preparation method thereof |
-
2012
- 2012-11-07 KR KR1020147016478A patent/KR20140094009A/en not_active Application Discontinuation
- 2012-11-07 WO PCT/IB2012/056206 patent/WO2013072809A1/en active Application Filing
- 2012-11-07 IN IN3736CHN2014 patent/IN2014CN03736A/en unknown
- 2012-11-07 EP EP12849861.5A patent/EP2780285A4/en not_active Withdrawn
- 2012-11-07 JP JP2014541781A patent/JP2014533649A/en not_active Ceased
- 2012-11-07 CN CN201280056376.3A patent/CN103946159A/en active Pending
- 2012-11-07 BR BR112014011299A patent/BR112014011299A2/en not_active IP Right Cessation
- 2012-11-07 CN CN201710061479.3A patent/CN107021503A/en active Pending
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2014
- 2014-06-13 ZA ZA2014/04333A patent/ZA201404333B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1353086A (en) * | 2000-11-13 | 2002-06-12 | 中国石油化工股份有限公司 | Process for preparing Y-type molecular sieve |
CN1806908A (en) * | 2005-10-27 | 2006-07-26 | 复旦大学 | Macroporous zeolite absorbent and preparation method thereof |
WO2010139997A2 (en) * | 2009-06-03 | 2010-12-09 | University Of Manchester | Modified zeolites and their use in the recycling of plastics waste |
Non-Patent Citations (1)
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See also references of EP2780285A4 * |
Also Published As
Publication number | Publication date |
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KR20140094009A (en) | 2014-07-29 |
EP2780285A4 (en) | 2015-08-19 |
CN103946159A (en) | 2014-07-23 |
EP2780285A1 (en) | 2014-09-24 |
ZA201404333B (en) | 2015-08-26 |
JP2014533649A (en) | 2014-12-15 |
IN2014CN03736A (en) | 2015-09-04 |
CN107021503A (en) | 2017-08-08 |
BR112014011299A2 (en) | 2017-04-25 |
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