CN102616800B - Method for removing organic amine template in molecular sieve - Google Patents
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Abstract
A method for removing an organic amine template in molecular sieve is provided. The method is characterized in that the method comprises the following steps: carrying out contact mixing on the molecular sieve containing the organic amine template and an aqueous solution or gel of a compound containing a metal M at room temperature, drying, heating to 200-450DEG C, roasting for 1-8h, carrying out contact mixing on the obtained roasted products and an aqueous solution of an ammonium salt, filtering, and washing the resulting filter cake to remove metal ions, wherein the metal M comprises one or more of Cu, Ag, Zn, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co and Ni, and the charging mole ratio of the compound containing the metal M (by the metal M) to the molecular sieve containing the organic amine template (by Al) is 1:1-10:1. The method provided in the invention is especially suitable for deamination of silicon aluminum molecular sieve containing the organic amine template. The method allows the organic amine template to be effectively removed at a low temperature, and the thermostability of the skeleton of the molecular sieve to be improved because of the introduction of metal cations in the deamination roasting process.
Description
Technical field
The invention relates to a kind of method that molecular sieve is processed, further say the method that removes organic amine template in molecular sieve about a kind of.
Background technology
Organic amine molecule is widely used in synthesizing of the porous materials such as molecular sieve as template or structure directing agent, owing to forming hydrogen bond, Van der Waals force between these organic object species and the inorganic main body framework of molecular sieve and joining in some cases key, exist, most amine ions occupies cation-bit with stable form and is set up, and the most of bag of amine molecule is stayed in molecular sieve pore passage and cage.In order to make the inorganic main body of molecular sieve obtain catalytic activity, meet the functions such as absorption, separation, these organic amine species must be removed from inorganic duct to regular to form, open structure.
It is high temperature thermal bake-out method (CN1268403A) that organic amine guest molecule is deviate to the traditional method of framework of molecular sieve.Be about to the synthetic molecular sieve obtaining and be directly placed in retort furnace or tube furnace at air, or high-temperature roasting under other oxygenous atmosphere (common 500～600 ℃).Organic amine molecular oxidation is decomposed into inertia small molecules on the one hand, and with gas form effusion guest molecule sieve skeleton frame, by the Roasting Decomposition of amine ion, some molecular sieves can activate formation hydrogen type molecular sieve on the other hand.The temperature of this traditional method roasting is high, and roasting time is long, is effective, as ZSM-5 molecular sieve for the de-amine of constitutionally stable molecular sieve.But it is not good for the molecular sieve that some structural stabilities are poor, the method not only can cause framework of molecular sieve to shrink the destruction of caving in, degree of crystallinity significantly declines by (as BEA type molecular sieve, SAPO-20 molecular sieve), even also can make molecular sieve turn brilliant (as VPI-5 and AlPO
4-8).Therefore develop a kind of method that new type low temperature removes organic amine template and just seem particularly important.
CN1117472A discloses the removal methods of organic amine in a kind of mesopore and macropore Si-Al zeolite or its composition, the method is included in zeolite or adds the oxygenant that is selected from perchloric acid, hypochlorous acid, perchloric acid or hypochlorous sylvite, sodium salt, ammonium salt and aluminium salt containing zeolite weight 1～40% containing in the composition of zeolite, and in 300～500 ℃ of air, roasting is 1～5 hour.
CN1138007A discloses a kind of employing and take hydrogen peroxide and urge the method that removes organic formwork agent in super macroporous molecular sieve into roasting method as oxygenant, the method is first that said molecular sieve is wetting with aqueous hydrogen peroxide solution, then this wetting molecular sieve is heated to 200～500 ℃ with temperature programming at a slow speed in stoving oven and keeps 2～10 hours.
Above-mentioned two kinds of methods all belong to together with oxygenant and promote roasting, are the improvement of thermal bake-out method, but the amplitude that maturing temperature reduces little also only limits to remove the organic amine template in mesopore and large pore molecular sieve.
US6645899B disclose a kind of under solvent vapo(u)r atmosphere roasting remove molecular sieve in the method for template.It is 20～100% organic vapor atmosphere that the method is placed in volumetric molar concentration by described molecular sieve, is warming up to 250～380 ℃ of roastings 0.25～72 hour, and wherein organic solvent used mainly comprises methyl alcohol, fatty acid methyl ester and methyl halide.Although the method has reduced organic amine maturing temperature,, owing to having used organic solvent, increase the cost that removes organic amine template, in addition, a large amount of organic steams exist, and also increase the danger of baking operation.
Other methods that remove template in molecular sieve are as Microwave Digestion, ultraviolet/hydrogen peroxide oxidation method (CN1772613A), although the treatment time is short, but reaction conditions is violent, and conventionally under acidic medium, carry out, this is helpless for the less molecular sieve in not acid resistance and duct.
Summary of the invention
The object of the present invention is to provide a kind of method that removes organic amine template in molecular sieve that is different from prior art, the method just can remove organic amine template (200～450 ℃) at lower temperature in roasting, and molecular sieve can also keep its structural stability and good crystallinity and specific surface area in the process of de-amine.
The method that removes organic amine template in molecular sieve provided by the invention, it is characterized in that the method is at room temperature to contact mixing containing the molecular sieve of organic amine template and the aqueous solution of the compound that contains metal M or gel, dry post-heating to 200～450 ℃ roasting 1～8 hour, again product of roasting is contacted to mixing with ammonium salt aqueous solution, filter, filter cake is removed metal ion through washing, wherein, said metal M is Cu, Ag, Zn, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, one or more in Mn, the said compound that contains metal M is 1: 1～10: 1 with mole proportioning that feeds intake that contains the molecular sieve of organic amine template, the compound that contains metal M is in metal M, contain the molecular sieve of organic amine template in aluminium.
In method provided by the invention, described molecular sieve can be Si-Al zeolite, can be also sial mesopore molecular sieve, such as but not limited to X-type zeolite, y-type zeolite, A type zeolite, ZSM-5, β zeolite, mordenite, MCM series mesoporous material etc.Method provided by the invention is specially adapted to remove organic amine template in β zeolite (synthetic according to technology such as US3308069, EP159846, EP164208), to produce high-crystallinity and high-specific surface area, and the beta-molecular sieve that skeleton stability is good.
In method provided by the invention, described template refers to the organic amine compound of introducing in sieve synthesis procedure, it can be tetraethyl-oxyammonia, tetraethyl-amine bromide, tetraethyl-ammonia chloride, tetramethyl-oxyammonia, one or more of tetramethyl-amine bromide etc., be preferably tetraethyl-oxyammonia, tetraethyl-amine bromide, one or more of tetraethyl-ammonia chloride.
Metal M described in method provided by the invention is selected from one or more in metal Cu, Ag, Zn, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Mn, and preferred metal M is Fe, Cu or Ag, and preferred metal M is Cu.
In method provided by the invention, described metal M compound is selected from nitrate, villaumite, vitriol, the acetate of metal M, one or more of oxyhydroxide.Be preferably muriate, nitrate, acetate, oxyhydroxide etc. are containing monovalence, and one or more of divalence or trivalent iron compound, as CuCl
2, AgNO
3, FeCl
3, Fe (OH)
3deng.The compound of the metal of high oxidation valence state preferably wherein, as CuCl
2, Fe (OH)
3deng.
In method provided by the invention, also comprise the raffinate of the containing metal M of filtration is reclaimed, is mixed with the aqueous solution of the compound that contains metal M or the step of gel recycling.In method provided by the invention, the solution of the compound of described containing metal M and gel can be the also raffinate of the containing metal M of recovery preparations of above-mentioned fresh feed preparation, from cost-saving angle, more preferably take off the raffinate of the containing metal M reclaiming amine process.
In method provided by the invention, described gel process for preparing is the alkaline solutions such as ammoniacal liquor dropwise to be added to the aqueous solution of metal M according to certain stoichiometric ratio, forms the cotton-shaped gel that contains metal M oxyhydroxide, as Cu (OH)
2, and Fe (OH)
3deng.
In method provided by the invention, the said compound that contains metal M is 1: 1～10: 1 with mole proportioning that feeds intake that contains the molecular sieve of organic amine template, be preferably 1: 1～3: 1, the compound that contains metal M, in metal M, contains the molecular sieve of organic amine template in aluminium.
Described in method provided by the invention, maturing temperature is 200～450 ℃, is preferably 300～400 ℃ of maturing temperatures, and the time of roasting is 1～8 hour, is preferably 2～6 hours, and calcination atmosphere can air, nitrogen or pure oxygen atmosphere.Be preferably air and oxygen atmosphere.According to a preferred scheme of the present invention, roasting method comprises, under air atmosphere, with the temperature rise rate of 0.5～10 ℃/min, from room temperature, rise to 200～450 ℃, be preferably 300～450 ℃, then roasting 2～8 hours at 300～450 ℃, is preferably 2～6 hours.Adopt this roasting method, can further improve the degree of crystallinity of de-amine molecule sieve, reduce heat collapse.
Described in method provided by the invention, ammonium salt is selected from one or more in ammonium acetate, ammonium chloride, ammonium nitrate, ammonium sulfate, more preferably one or more in ammonium acetate, ammonium chloride, ammonium nitrate.The pH value of ammonium salt aqueous solution between 4～10, preferably 5～9, more preferably 5～7; Concentration range is 0.1～50wt%, is preferably 10～20wt%.
The stirring dipping time of described product of roasting and ammonium salt aqueous solution is 10～180 minutes, more preferably 120～180 minutes.
Method provided by the invention is specially adapted to the de-amine of Si-Al molecular sieve containing organic amine template.Employing this method can be by organic amine template removal at lower temperature, simultaneously in de-amine roasting process due to metallic cation introducing, improve the thermostability of framework of molecular sieve, thereby made molecular sieve can keep its structural stability and good crystallinity and specific surface area in the process of de-amine.
Method provided by the invention and conventional high-temperature thermal bake-out method, with CN104161818C, CN1138007A, the disclosed method of US6645899B is compared, and maturing temperature is low, and roasting time is short, can effectively remove organic amine template in molecular sieve or molecular sieve at low temperatures, the complete degree of crystallinity of molecular sieve structure is high, and working method is simple, and selected reagent can be recycled.
Accompanying drawing explanation
Fig. 1 is thermogravimetric (TG) and differential thermogravimetric (DTG) analysis chart.
Fig. 2 is thermogravimetric (TG) analysis chart.
Fig. 3 is infrared spectrum, wherein 1350～1600cm
-1for the flexural vibration spectrum peak of C-H, 2800～3000cm
-1stretching vibration spectrum peak for C-H.
Embodiment
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
Thermogravimetric analysis instrument is the SDT Q600 of U.S. TA company type thermogravimetric analyzer, and temperature rise rate is 10 ℃/min, air atmosphere.
The FTS 3000 type Fourier infrared spectrographs of infrared spectrometric analyzer Qi Wei U.S. BIO-RAD company.
Thing phase and degree of crystallinity are measured with Rigaku D/Max-3 type X-ray diffractometer.
With measuring in U.S. VARI-AN INOVA300 NMR spectrometer with superconducting magnet
29si,
27al intensity, calculates sial skeleton ratio referring to < < Petrochemical Engineering Analysis method (RIPP experimental technique) > >, Science Press, P405,1990.
Molecular sieve relative crystallinity is calculated as follows: relative crystallinity=(the de-last sample degree of crystallinity of amine)/(degree of crystallinity of background sample S0 before de-amine) * 100%.
The ammonium type beta-molecular sieve containing organic amine template using in comparative example and embodiment is that Sinopec is built long catalyst Co. production, and template is tetraethyl-oxyammonia.Al wherein
2o
3massfraction 7.28%, SiO
2content massfraction 92.5%, Na
2o massfraction 0.034%, framework si-al ratio is 11.26.
Comparative example 1
This comparative example illustrates that traditional high-temperature roasting method removes the process of organic amine template in molecular sieve.
Take 20g ammonium type beta-molecular sieve (brief note for background sample S0), be placed in retort furnace, in air atmosphere, by room temperature, through 2 hours, be warming up to 400 ℃, roasting 2 hours, is warming up to 600 ℃ of roastings 5 hours again for 2 hours.After cooling, obtain comparative sample D1.
The degree of crystallinity of comparative sample D1, specific surface area and framework si-al ratio data are listed in table 1.
The analyses of the thermogravimetric (TG) of background sample S0 and differential thermogravimetric (DTG) are seen Fig. 1.Fig. 1 shows, in the partial heat multigraph of background sample S0, show three weightless peaks, it near 150 ℃, is mainly the desorption peaks of physical absorption water, near two weightless peaks 400 ℃ and 600 ℃ come from the decomposition of organic amine template, can find out that the template in beta-molecular sieve could be removed completely when temperature reaches more than 700 ℃.
Fig. 2 is shown in the thermogravimetric analysis of comparative sample D1, and infrared spectrum is shown in Fig. 3.Fig. 2 shows that wherein organic amine template removes, and in the C-H vibration infrared spectrum of the residual organic amine in its result and Fig. 3, information matches, and interpret sample is through the roasting in lower 5 hours of 600 ℃ of temperature, and organic amine species remove totally.
Comparative example 2
Take 20g background sample S0, be placed in retort furnace, in air atmosphere, by room temperature, through 1 hour, be warming up to 350 ℃, 350 ℃ of constant temperature calcinings 4 hours, obtain comparative sample D2 after cooling.
Comparative sample D2 is black, and thermogravimetric spectrogram is shown in Fig. 2.Fig. 2 shows between 500 ℃～650 ℃, still there is the weightless step of a very large organism; Infrared spectrum is shown in Fig. 3, Fig. 3 demonstration, and in comparative sample D2, the C-H flexural vibration peak of residual organic amine is quite obvious, shows that comparative sample D2 is not deviate from totally at 350 ℃ of organic amine species of low temperature.
Embodiment 1
Take 2.43g copper chloride dihydrate, add water 500mL and form copper chloride solution, dropwise add 1.94g massfraction and be 25% strong aqua, be mixed with copper hydroxide gel.
Taking 20g background sample S0 is at room temperature uniformly mixed with copper hydroxide gel, filter, filter cake repeatedly washs with deionized water, after 110 ℃ of oven dry, obtain middle sample S10 (Fig. 1), middle sample S10 is placed in to retort furnace, in air atmosphere, by room temperature, through 1 hour, is warming up to 350 ℃, 350 ℃ of constant temperature calcinings 4 hours, obtain middle sample S11 after cooling.
The thermogravimetric analysis figure of S11 is shown in Fig. 2, and Fig. 2 shows that in S11, organic amine template has removed totally, and this point is further confirmed by the C-H flexural vibration peak disappearance of S11 in Fig. 3 infrared spectrum.
Sample S11 after roasting is ground in quartz grinds powdered, adding massfraction is 10% ammonium acetate aqueous solution 100mL, with ammoniacal liquor, regulates pH in 7.0 left and right.Stirring at room 120～180 minutes, filters out cupric raffinate.Finally with deionized water, repeatedly wash, after being dried, obtain sample S12.
The degree of crystallinity of sample S12, specific surface area and framework si-al ratio data are listed in table 1.
Embodiment 2
Take the nitrate trihydrate copper of 1.72g, add water 500mL and form copper nitrate aqueous solution, dropwise add 0.97g massfraction and be 25% strong aqua, be mixed with copper hydroxide gel.
Taking 20g background sample S0 is at room temperature uniformly mixed with copper hydroxide gel, filter, filter cake repeatedly washs with deionized water, 110 ℃ of oven dry are placed in retort furnace, in air atmosphere, by room temperature, through 1 hour, be warming up to 400 ℃, 400 ℃ of constant temperature calcinings 4 hours, obtain middle sample S21 after cooling.
The thermogravimetric analysis figure of sample S21 is shown in Fig. 2, and Fig. 2 shows that organic amine template has removed totally.
Sample S21 after roasting is ground in quartz grinds powdered, adding massfraction is 10% aqueous ammonium chloride solution 100mL, with ammoniacal liquor, regulates pH in 7.0 left and right.Stirring at room 120～180 minutes, filters out cupric raffinate.Finally with deionized water, repeatedly wash, after being dried, obtain sample S22.
The degree of crystallinity of sample S22, specific surface area and framework si-al ratio data are listed in table 1.
Embodiment 3
Take 2.43g copper chloride dihydrate, add water 20mL and form copper chloride solution, taking 20g background sample S0 is at room temperature uniformly mixed with copper chloride solution, 110 ℃ of oven dry are placed in retort furnace, in air atmosphere, by room temperature, through 1 hour, be warming up to 350 ℃, 350 ℃ of constant temperature calcinings 4 hours, obtain middle sample S31 after cooling.
The thermogravimetric analysis figure of S31 is shown in Fig. 2, and Fig. 2 shows that organic amine template has removed totally.
S31 is ground in quartz grinds powdered, adding massfraction is 10% ammonium acetate aqueous solution 100mL, with ammoniacal liquor, regulates pH in 7.0 left and right.Stirring at room 120～180 minutes, filters out cupric raffinate.Finally with deionized water, repeatedly wash, after being dried, obtain sample S32.
The degree of crystallinity of sample S32, specific surface area and framework si-al ratio data are listed in table 1.
Embodiment 4
Take 2g Silver Nitrate, add water 20mL and form silver nitrate aqueous solution, taking 20g ammonium type beta-molecular sieve is at room temperature uniformly mixed with silver nitrate aqueous solution, 110 ℃ of oven dry are placed in retort furnace, in air atmosphere, by room temperature, through 1 hour, be warming up to 400 ℃, 400 ℃ of constant temperature calcinings 4 hours, obtain middle sample S41 after cooling.
The thermogravimetric analysis figure of S41 is shown in Fig. 2, and Fig. 2 shows that organic amine template has removed totally.
S41 after roasting is ground in quartz grinds powdered, adding massfraction is 10% aqueous ammonium nitrate solution 100mL, with nitre acid for adjusting pH in 4.0 left and right.Stirring at room 120～180 minutes, filters out cupric raffinate.Finally with deionized water, repeatedly wash, after being dried, obtain sample S42.
The degree of crystallinity of sample S42, specific surface area and framework si-al ratio data are listed in table 1.
Embodiment 5
Take the FERRIC CHLORIDE ANHYDROUS of 2.31g, add water 500mL and form ferric chloride aqueous solutions, dropwise add 1.94g massfraction and be 25% strong aqua, be mixed with ironic hydroxide gel.Take 20g background sample S0 and be at room temperature uniformly mixed with it, filter, filter cake repeatedly washs with deionized water, 110 ℃ of oven dry are placed in retort furnace, in air atmosphere, by room temperature, through 1 hour, are warming up to 400 ℃, 400 ℃ of constant temperature calcinings 4 hours, obtain middle sample S51 after cooling.
The thermogravimetric analysis figure of S51 is shown in Fig. 2, and Fig. 2 shows that organic amine template has removed totally.
S51 is ground in quartz grinds powdered, adding massfraction is 10% ammonium oxalate aqueous solution 100mL, with careless acid for adjusting pH in 5.0 left and right.Stirring at room 120～180 minutes, filters out cupric raffinate.Finally with deionized water, repeatedly wash, after being dried, obtain sample S52.
The degree of crystallinity of sample S52, specific surface area and framework si-al ratio data are listed in table 1.
Table 1
Known by data in table 1: method provided by the invention has not only improved organic amine decreasing ratio at low temperatures, simultaneously because de-amine temperature is low, and in de-amine roasting process because metallic cation is synchronously introduced, significantly reduced the destruction of hot de-amine, improved the thermostability of framework of molecular sieve, crystallization reservation degree is high.
Claims (13)
1. a method that removes organic amine template in molecular sieve, it is characterized in that the method is at room temperature to contact mixing containing the molecular sieve of organic amine template and the aqueous solution of the compound that contains metal M or gel, dry post-heating to 200～450 ℃ roasting 1～8 hour, again product of roasting is contacted to mixing with ammonium salt aqueous solution, filter, filter cake is removed metal ion through washing, wherein, said organic amine template is selected from tetraethyl ammonium hydroxide, tetraethylammonium bromide, etamon chloride, Tetramethylammonium hydroxide, one or more in 4 bromide, said metal M is Cu, Ag, Zn, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, one or more in Ni, the said compound that contains metal M is 1:1～10:1 with mole proportioning that feeds intake that contains the molecular sieve of organic amine template, the compound that contains metal M is in metal M, contain the molecular sieve of organic amine template in aluminium.
2. according to the process of claim 1 wherein, said molecular sieve is that backbone element is micro porous molecular sieve or the mesopore molecular sieve of silicon, aluminium.
3. according to the method for claim 2, wherein, said micro porous molecular sieve is X-type zeolite, y-type zeolite, A type zeolite, ZSM-5, β zeolite, mordenite, and said mesopore molecular sieve is MCM series.
4. according to the process of claim 1 wherein, said organic amine template is the organic amine compound that molecular sieve is introduced in synthesis of molecular sieve process.
5. according to the process of claim 1 wherein, said metal M is selected from Fe, Cu or Ag.
6. according to the process of claim 1 wherein, the said compound that contains metal M is selected from one or more in nitrate, villaumite, vitriol, acetate and the oxyhydroxide of metal M.
7. according to the process of claim 1 wherein, said roasting, its atmosphere is air, nitrogen or pure oxygen.
8. according to the process of claim 1 wherein, said maturing temperature is 350～400 ℃.
9. according to the process of claim 1 wherein, said roasting comprises, under air atmosphere, with the temperature rise rate of 0.5～10 ℃/min, from room temperature, rises to 200～450 ℃, roasting 2～8 hours.
10. according to the process of claim 1 wherein, said ammonium salt is selected from one or more in ammonium acetate, ammonium chloride, ammonium oxalate, ammonium nitrate and ammonium sulfate.
11. according to the process of claim 1 wherein, the pH value of said ammonium salt aqueous solution is between 4～10, and said ammonium salt aqueous solution mass concentration is 0.1～50%.
12. according to the process of claim 1 wherein, the solid-liquid mass ratio that product of roasting contacts with ammonium salt aqueous solution while mixing is 5～10, and the time that contact mixes is 10～180 minutes, and the temperature that contact mixes is room temperature to 90 ℃.
13. according to the process of claim 1 wherein, the method also comprises the step of the raffinate recovery of filtration, the aqueous solution that is mixed with the compound that contains metal M or gel recycling.
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Citations (3)
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|---|---|---|---|---|
| US4335020A (en) * | 1981-01-06 | 1982-06-15 | Mobil Oil Corporation | Method of preparation of composite zeolite catalysts |
| CN1117472A (en) * | 1994-08-22 | 1996-02-28 | 中国石油化工总公司石油化工科学研究院 | Method No.1 for removing organic amine from silica-alumina zeolite or its compound |
| CN1268403A (en) * | 1999-03-30 | 2000-10-04 | 中国石油化工集团公司 | Rapid deaminatio activating method of beta-zeolite containing organic ammonium |
-
2011
- 2011-01-27 CN CN201110028908.XA patent/CN102616800B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4335020A (en) * | 1981-01-06 | 1982-06-15 | Mobil Oil Corporation | Method of preparation of composite zeolite catalysts |
| CN1117472A (en) * | 1994-08-22 | 1996-02-28 | 中国石油化工总公司石油化工科学研究院 | Method No.1 for removing organic amine from silica-alumina zeolite or its compound |
| CN1268403A (en) * | 1999-03-30 | 2000-10-04 | 中国石油化工集团公司 | Rapid deaminatio activating method of beta-zeolite containing organic ammonium |
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| 周仲承 等.有序介孔材料制备过程中模板剂脱除方法研究进展.《材料导报》.2005,第19卷(第8期),36-39. |
| 有序介孔材料制备过程中模板剂脱除方法研究进展;周仲承 等;《材料导报》;20050831;第19卷(第8期);36-39 * |
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