CN103028372A - Binderless zeolite adsorbent and preparation method thereof - Google Patents
Binderless zeolite adsorbent and preparation method thereof Download PDFInfo
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- CN103028372A CN103028372A CN2011102935397A CN201110293539A CN103028372A CN 103028372 A CN103028372 A CN 103028372A CN 2011102935397 A CN2011102935397 A CN 2011102935397A CN 201110293539 A CN201110293539 A CN 201110293539A CN 103028372 A CN103028372 A CN 103028372A
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Abstract
The present invention relates to a binderless zeolite adsorbent and a preparation method thereof, and is mainly to solve the problem of small adsorbent capacity, low adsorption rate, and high impurity content in the adsorbent in the prior art. A technical solution solves the technical problems well. According to the present invention, the binderless zeolite adsorbent has particle size of 16-40 meshes, and strength >= 60 N/ particle. At room temperature and the solid-liquid ratio of 3:5, the adsorption capacity of the binderless zeolite adsorbent for n-hexane in a cyclohexane solution containing 10% of n-hexane by weight is greater than 0.11 g per gram of the adsorbent, and the adsorption rate is greater than 16 mg/gram of the adsorbent/minute in initial 5 minutes. The binderless zeolite adsorbent can be used for adsorption and separation of n-alkanes in naphtha.
Description
Technical field
The present invention relates to a kind of binder free zeolite adsorbents and preparation method thereof.
Background technology
Naphtha is by the compositions of mixtures of the multiple hydro carbons such as n-alkane, isoparaffin, cycloalkane and aromatic hydrocarbons.For steam cracking ethene, different types of hydrocarbon is different to the contribution that ethene generates.The yield of ethene of n-alkane is the highest, secondly is cycloalkane, isoparaffin, and aromatic hydrocarbons generates without contribution ethene.On the other hand, as catalytic reforming raw material, the n-alkane dehydrocyclization becomes the reaction rate of aromatic hydrocarbons very slow, low conversion rate.Therefore, adopting adsorbent of molecular sieve that n-alkane in the naphtha is separated is the effective ways that take full advantage of naphtha.
The most effective adsorbent of separating normal alkane is the 5A molecular sieve.Its average pore size is
The n-alkane molecular diameter is about
Can enter in the molecular sieve pore passage, and non-n-alkane molecular dimension be greater than molecular sieve pore passage, can not be adsorbed.
The 5A adsorbent of molecular sieve of early application, adopting the grain size of general synthetic method preparation is that the former powder of 1～5 μ m mixes with a certain amount of binding agent, makes with calcium ion-exchanged after traditional forming method moulding such as extrusion.Binding agent is the invalid components of adsorbing separation, and it adds affiliation descends adsorption capacity, reduces simultaneously the selective of the rate of adsorption and absorption, makes the adsorption and desorption degradation.Molding adhesive is generally selected the inorganic oxygen-containing compounds such as aluminium oxide, kaolin, certain catalytic activity is arranged, under the process conditions of adsorbing separation, can make part alkane generation cracking reaction, or make part unsaturated hydrocarbons generation polymerization, thereby affect the service life of adsorbent.
Some companies research and develop out the binderless A type adsorbent of molecular sieve in succession both at home and abroad.Adsorption test result take n-alkane as adsorbate shows that the conventional rate of adsorption that contains binding agent 5A adsorbent of molecular sieve of the rate of adsorption of such adsorbent increases, and the Static Adsorption capacity has also increased.
Such as US Patent No. 3119659, it is that binding agent is adhesion-molded with molecular sieve that this patent adopts clay, in the NaOH of finite concentration and temperature solution, binding agent is turned brilliant afterwards, generate the adsorbent of binder free, but clay class binding agent contains metal or the nonmetallic inclusions such as a large amount of iron, and the adsorbent of the method preparation can affect separating effect in follow-up adsorbing separation application process.
US Patent No. 4058586 adopts similar method, and difference is work simplification, as, the binding agent of employing is kaolin, adds a certain amount of alkali and water during moulding, directly heating turns brilliant, has saved hydro-thermal and has turned brilliant step.But the problem of introducing impurity effect adsorbing separation effect in the preparation process does not solve.
The method that US Patent No. 4818508 adopts binding agent to turn crystalline substance prepares the binderless A type zeolite adsorbent, binding agent adopts kaolin or halloysite, powder granule size to binding agent has been made specific requirement, and in forming process, add pore creating material, and stipulated the pore creating material particle size, this patent does not solve the problem of using natural clay to introduce impurity effect adsorbing separation effect equally.
Summary of the invention
One of technical problem to be solved by this invention is that the adsorption capacity owing to using clay class binding agent to cause of existing binderfreeadsorbent existence is little, the problem that the rate of adsorption is low, a kind of new binderless A type zeolite adsorbent is provided, it is large that this adsorbent has adsorption capacity, the advantage that the rate of adsorption is high.Two of technical problem to be solved by this invention provides the preparation method of the corresponding adsorbent of one of technical problem with solving.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: adopt a kind of new binderless A type zeolite adsorbent, the adsorbent granularity is 16～40 orders, intensity 〉=60 newton/; Under the room temperature, solid-to-liquid ratio is 3: 5 o'clock, to the n-hexane adsorption capacity in the cyclohexane solution that contains by weight percentage 10% n-hexane greater than 0.11 gram/gram adsorbent, initial 5 minutes rates of adsorption greater than 16 milligrams/gram adsorbent/minute.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: adopt a kind of preparation method of binder free zeolite adsorbents, may further comprise the steps: A) forming step, take NaA type zeolite powder as raw material, Ludox or sodium metasilicate are made binding agent, make the moulding of NaA zeolite; B) turn brilliant pre-treatment step, moulded zeolite is with containing by weight percentage Al
2O
3Be that 5%～35% alkaline aqueous solution soaks, make in the formed absorbent aluminium in the silicon in the binding agent and solution mol ratio be: Si/Al=1.0～2.5, Na
2O/SiO
2=0.50～1.6; C) binding agent turns brilliant, and three sections substeps turn brilliant, and binding agent in the formed absorbent is converted into binder free NaA type zeolite fully; D) binder free NaA calcium exchange step will turn brilliant NaA zeolite calcium exchange and be converted into the CaA molecular sieve, namely get required product.
In the technique scheme, the silicon source of NaA type zeolite powder synthesis material is at least a in Ludox, waterglass, silester, amorphous silica, silica gel, the diatomite; The aluminium source is at least a in aluminum sulfate, sodium aluminate, aluminium hydroxide, aluminium isopropoxide, aluminium secondary butylate, aluminum nitrate, the aluminium oxide; FeO, MgO, K in the raw material
2O, TiO
2Deng impurity content less than 100ppm; The mole proportioning of synthesis material is: Si/Al=1.0～2.5, Na
2O/SiO
2=0.75～1.6, H
2O/Na
2O=10～60.
In the technique scheme, in the NaA powder forming process, consumption of binder is 5%～25% of NaA molecular sieve by weight percentage.Binding agent adopts three sections fractional crystallizations, and three sections fractional crystallization temperature are respectively 20～60 ℃, 40～80 ℃ and 60～100 ℃; Time was respectively 2～48 hours, 1～48 hour and 1～24 hour, turned brilliant rear adsorbent mesolite average crystal grain less than 600 nanometers.
The present invention adopts the binding agent rotating crystal method to prepare the binder free zeolite adsorbents, owing to do not use natural clay or other clay class material to carry out forming processes, so eliminated the problem that traditional forming method causes adsorbent duct Partial Blocking to cause the adsorbent absorption property to reduce because adding clay-type substance, introduce FeO, MgO, K when also having eliminated simultaneously owing to such material of interpolation
2O, TiO
2The negative effect that causes Deng impurity, these impurity have certain catalytic activity, in naphtha under the n-alkane adsorptive separation technology condition, can make part alkane generation cracking reaction, or make part unsaturated hydrocarbons generation polymerization, coking, finally cause the reduction of adsorbent adsorption capacity, affect separating effect.
Adopt binder free zeolite adsorbents provided by the invention and preparation method thereof, when the adsorbent granularity is 16～40 order, its intensity 〉=60 newton/; Under the room temperature, solid-to-liquid ratio is 3: 5 o'clock, can reach 0.12 gram/more than the gram adsorbent to the saturated adsorption capacity maximum of the n-hexane in the cyclohexane solution that contains by weight percentage 10% n-hexane, initial 5 minutes rates of adsorption greater than 16 milligrams/gram adsorbent/minute, obtained preferably technique effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Take by weighing sodium aluminate and (by weight percentage, contain Al
2O
3Be 41%) 200 grams, in 3000 ml beakers, add again 1000 milliliters of stirring and dissolving of water, add a certain amount of NaOH or sulfuric acid, keep Na
2O/SiO
2=0.75～1.6, after add Ludox (40wt%) 250 gram, move in 4000 milliliters of reactors 70 ℃ of crystallization 10 hours.Take out product and wash neutrality with deionized water, in 120 ℃ of dryings 10 hours, get the 4A molecular sieve.Be that 10% sodium metasilicate mixes with this molecular sieve and weight ratio, roller forming namely gets formed absorbent of the present invention.Formed absorbent with contain by weight percentage Al
2O
3Be that 15% alkaline sodium aluminate aqueous solution mixes, making mol ratio total in the mixed system is Si/Al=1.0～2.5, Na
2O/SiO
2=0.50～1.6, soaked 6 hours, the heating substep turns brilliant in the immigration closed container, by dry, 10wt%CaCl
2Exchange, washing, dry, roasting namely get the adsorbent product.Zeolite synthesis material proportioning sees Table 1, Al in binding agent kind, consumption and the alkaline aqueous solution
2O
3Concentration see Table 2, substep turns crystal bar spare and sees Table 3.After the adsorbent drying, through 350 ℃ of activation 2 hours, the absorption property of cool to room temperature post-evaluation adsorbent in drier.
Adsorbent appreciation condition: room temperature, adsorbent: under adsorption liquid=3: 5 (weight ratio) condition, the cyclohexane solution that contains by weight percentage 10% n-hexane is adsorbent evaluation criterion liquid, under the rapid stirring condition, measure adsorbent to the adsorbance of n-alkane in the titer, and the initial 5 minutes rates of adsorption.
Performance of the adsorbent and evaluation result see Table 4.
[embodiment 2～9]
The preparation method of embodiment 2～9 and embodiment 1 are identical, just Al in raw material proportioning, binding agent kind, consumption, the alkaline aqueous solution
2O
3Concentration and specifically to turn crystal bar spare different.Concrete Zeolite synthesis raw material proportioning sees Table 1, Al in binding agent kind, consumption and the alkaline aqueous solution
2O
3Concentration see Table 2, substep turns crystal bar spare and sees Table 3.After the adsorbent drying, through 350 ℃ of activation 2 hours, the absorption property of cool to room temperature post-evaluation adsorbent in drier.Adsorbent appreciation condition and embodiment 1 are identical, and performance of the adsorbent and evaluation result see Table 4.
[comparative example 1]
The preparation method of comparative example 1 and embodiment 1 are identical, brilliant (95 ℃ of the temperature of alkali lye (PH is 12) transfer are adopted in just different with binding agent, the synthetic NaA molecular sieve kaolin moulding of moulding after the moulding, 4 hours time) preparation Adhesive-free Molecular Sieve gets adsorbent after the calcium exchange.Concrete Zeolite synthesis raw material proportioning sees Table 1, and binding agent kind and consumption see Table 2, and substep turns crystal bar spare and sees Table 3.After the adsorbent drying, through 350 ℃ of activation 2 hours, the absorption property of cool to room temperature post-evaluation adsorbent in drier.Adsorbent appreciation condition and embodiment 1 are identical, and performance of the adsorbent and evaluation result see Table 4.
[comparative example 2]
The preparation method of comparative example 2 and embodiment 1 are identical, just turn brilliant process and adopt a step to turn brilliant, and concrete Zeolite synthesis raw material proportioning sees Table 1, Al in binding agent kind and consumption, the alkaline aqueous solution
2O
3Concentration see Table 2, substep turns crystal bar spare and sees Table 3.After the adsorbent drying, through 350 ℃ of activation 2 hours, the absorption property of cool to room temperature post-evaluation adsorbent in drier.Adsorbent appreciation condition and embodiment 1 are identical, and performance of the adsorbent and evaluation result see Table 4.
Table 1
| The silicon source | The aluminium source | Si/Al* | Na 2O/SiO 2* | H 2O/SiO 2* | |
| Embodiment 1 | Ludox | Sodium aluminate | 1.04 | 1.14 | 35 |
| Embodiment 2 | Ludox | Aluminium secondary butylate | 1.20 | 0.85 | 20 |
| Embodiment 3 | Silica gel | Aluminium oxide | 1.50 | 1.00 | 50 |
| Embodiment 4 | Amorphous silica | Sodium aluminate | 1.73 | 1.60 | 40 |
| Embodiment 5 | Sodium metasilicate | Aluminium hydroxide | 1.34 | 1.30 | 60 |
| Embodiment 6 | Diatomite | Aluminum nitrate | 2.00 | 1.20 | 45 |
| Embodiment 7 | Silester | Aluminium isopropoxide | 1.00 | 1.60 | 10 |
| Embodiment 8 | Sodium metasilicate | Aluminum sulfate | 1.80 | 1.40 | 30 |
| Embodiment 9 | Sodium metasilicate | Aluminium oxide | 1.40 | 1.50 | 25 |
| Comparative example 1 | Ludox | Sodium aluminate | 1.04 | 1.14 | 35 |
| Comparative example 2 | Ludox | Sodium aluminate | 1.04 | 1.14 | 35 |
* mol ratio
Table 2
* impurity refers to FeO, MgO, K
2O, TiO
2Deng total amount
Table 3
Table 4
* adsorption process is at room temperature carried out, and adsorption liquid contains the cyclohexane solution of 10% n-hexane by weight percentage;
* 20-40 order spheric granules, data are the arithmetic mean of instantaneous value of 10 measurement results in the table;
Adsorbent: adsorption liquid=3: 5 (weight ratio)
Claims (5)
1. binder free zeolite adsorbents, the adsorbent granularity is 16～40 orders, intensity 〉=60 newton/; Under the room temperature, solid-to-liquid ratio is 3: 5 o'clock, to the n-hexane adsorption capacity in the cyclohexane solution that contains by weight percentage 10% n-hexane greater than 0.11 gram/gram adsorbent, initial 5 minutes rates of adsorption greater than 16 milligrams/gram adsorbent/minute.
2. the preparation method of the described binder free zeolite adsorbents of claim 1 may further comprise the steps: A) forming step, and take NaA type zeolite powder as raw material, Ludox or sodium metasilicate are made binding agent, make the moulding of NaA zeolite; B) turn brilliant pre-treatment step, moulded zeolite is with containing by weight percentage Al
2O
3Be that 5%～35% alkaline aqueous solution soaks, make in the formed absorbent that the mol ratio of aluminium is in the silicon in the binding agent and solution: Si/Al=1.0～2.5, Na
2O/SiO
2=0.50～1.6; C) binding agent turns brilliant, and three sections substeps turn brilliant, and binding agent in the formed absorbent is converted into binder free NaA type zeolite fully; D) binder free NaA calcium exchange step will turn brilliant NaA zeolite calcium exchange and be converted into the CaA molecular sieve, namely get required product.
3. the preparation method of described binder free zeolite adsorbents according to claim 2, the silicon source that it is characterized in that NaA type zeolite powder synthesis material is at least a in Ludox, waterglass, silester, amorphous silica, silica gel, the diatomite; The aluminium source is at least a in aluminum sulfate, sodium aluminate, aluminium hydroxide, aluminium isopropoxide, aluminium secondary butylate, aluminum nitrate, the aluminium oxide; FeO, MgO, K in the raw material
2O, TiO
2Deng impurity content less than 100ppm; The mole proportioning of synthesis material is: Si/Al=1.0～2.5, Na
2O/SiO
2=0.75～1.6, H
2O/Na
2O=10～60.
4. the preparation method of described binder free zeolite adsorbents according to claim 2 is characterized in that in the NaA powder forming process that consumption of binder is 5%～25% of NaA molecular sieve by weight percentage.
5. the preparation method of described binder free zeolite adsorbents according to claim 2 is characterized in that three sections fractional crystallizations, and three sections fractional crystallization temperature are respectively 20～60 ℃, 40～80 ℃ and 60～100 ℃; Time was respectively 2～48 hours, 1～48 hour and 1～24 hour, turned brilliant rear adsorbent mesolite average crystal grain less than 600 nanometers.
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| CN104477937A (en) * | 2014-12-05 | 2015-04-01 | 上海绿强新材料有限公司 | Mesoporous X-type molecular sieve, adsorbent based on molecular sieve, and preparation and application thereof |
| CN104876239A (en) * | 2015-05-22 | 2015-09-02 | 山东理工大学 | Method for preparing small-particle diameter NaA molecular sieve by use of solid silica gel and water glass as silicon source |
| CN108940188A (en) * | 2018-06-29 | 2018-12-07 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of binder free Siliceous MCM-41 adsorbent of molecular sieve |
| CN112316897A (en) * | 2020-10-15 | 2021-02-05 | 西安近代化学研究所 | Adsorbent for separating 1,2, 4-butanetriol in fermentation liquor, preparation method and application |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104477937A (en) * | 2014-12-05 | 2015-04-01 | 上海绿强新材料有限公司 | Mesoporous X-type molecular sieve, adsorbent based on molecular sieve, and preparation and application thereof |
| CN104876239A (en) * | 2015-05-22 | 2015-09-02 | 山东理工大学 | Method for preparing small-particle diameter NaA molecular sieve by use of solid silica gel and water glass as silicon source |
| CN108940188A (en) * | 2018-06-29 | 2018-12-07 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of binder free Siliceous MCM-41 adsorbent of molecular sieve |
| CN108940188B (en) * | 2018-06-29 | 2021-07-13 | 中海油天津化工研究设计院有限公司 | Preparation method of binder-free all-silicon MCM-41 molecular sieve adsorbent |
| CN112316897A (en) * | 2020-10-15 | 2021-02-05 | 西安近代化学研究所 | Adsorbent for separating 1,2, 4-butanetriol in fermentation liquor, preparation method and application |
| CN112316897B (en) * | 2020-10-15 | 2023-04-18 | 西安近代化学研究所 | Adsorbent for separating 1,2, 4-butanetriol in fermentation liquor, preparation method and application |
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