CN103055805B - Synthesis method of interface micro-pore sequence structure LSX (low-silica X-zeolite) molecular sieve for spatially dividing oxygen-enriched adsorbent - Google Patents
Synthesis method of interface micro-pore sequence structure LSX (low-silica X-zeolite) molecular sieve for spatially dividing oxygen-enriched adsorbent Download PDFInfo
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Abstract
The invention discloses a synthesis method of an interface micro-pore sequence structure LSX (low-silica X-zeolite) molecular sieve for spatially dividing oxygen-enriched adsorbent. The method comprises the following steps: A1, synthesizing molecular sieve raw powder; and A2, carrying out lithium ion exchange, namely, firstly exchanging the prepared Na-LSX molecular sieve with the NH<4+>, and then exchanging with the Li<+1> after roasting. The molecular sieve with an interface micro-pore structure is prepared by adopting an one-step method synthesis process, based on the oleophylic and hydrophilic characters, the amphipathic macromolecule is used as a template agent of the synthesis of the molecular sieve, a set of advanced production process which is simpler, more environment-friendly, and lower in energy consumption is explored, the product production process is simple and easy to control, and the energy consumption is reduced over 50%.
Description
Technical field
The present invention relates to the method that preparation has the LSX molecular sieve of Jie's microporous layers sequence structure, in particular a kind of synthetic method being used as Jie's microporous layers sequence structure LSX molecular sieve of space-division oxygen-enriching adsorbent.
Background technology
Oxygen is widely used in medical treatment, metallurgy, papermaking, wastewater treatment, Metal Cutting and the industry such as welding, chemical industry due to its strong oxidizing property and the characteristic that sustains life, and along with science and technology and the improving constantly of industrial level, the demand of oxygen is the trend risen year by year.Before pressure swing adsorption occurs, air-separating oxygen-making nitrogen is frozen isolation technics always and monopolizes, and this situation is maintained to the seventies; Pressure swing adsorption starts to be applied to air separation domain variability and obtains swift and violent development afterwards, and the output that current pressure swing adsorption air is separated duty divides about 20% of total output, and still in growth.
Compared with freezing separation technology, pressure swing adsorption has the advantages such as flow process is simple, small investment, efficiency are high, compact conformation, and its shortcoming is that energy consumption is slightly high, oxygen yield is lower.At present in extensive air separation field, pressure swing adsorption still cannot be competed with freezing separation method, but in middle and small scale air separation field, the comprehensive benefit of air separation by PSA technology will obviously be better than freezing separation method, therefore divides pressure swing adsorption to be widely used at middle and small scale sky.
The key of PSA making oxygen by air separation technology is the research and development of oxygen enrichment adsorbent.We know, cation on zeolite molecular sieve and the effect between the quadrupole moment of nitrogen molecular stronger, therefore nitrogen adsorption capacity over a molecular sieve stronger than oxygen (ratio of pure component adsorbance is greater than 2), molecular sieve that Here it is can be used in the reason of PSA making oxygen by air separation.Obviously, adsorbent is determine the scale of PSA oxygenerator and the factor of technical-economic index most critical to the adsorbance of nitrogen and nitrogen oxygen separating coefficient; Traditional oxygen enrichment adsorbent 5A and 13X molecular sieve, because its nitrogen adsorption amount is little, nitrogen oxygen separating coefficient is lower, seriously fettered the development of PSA oxygenerating technology.Based on this situation, the research and development that external many companies all actively carry out novel oxygen enrichment adsorbent as the U.S. UCC, APCI, Praxair etc., have applied for a large amount of patents.From document, the development of novel oxygen enrichment adsorbent has achieved breakthrough and has been applied.Compared with traditional oxygen enrichment adsorbent, the separation of novel space-division oxygen-enriching adsorbent to the adsorption capacity of nitrogen and oxygen, nitrogen increases substantially, and makes the overall economics index of PSA oxygenerator have qualitative leap.
X-type molecular sieve and faujasite have identical silicon (aluminium) oxygen skeleton structure, and the mineral of spontaneous growth are faujasite, and the molecular sieve of Prof. Du Yucang is then according to silica alumina ratio (SiO
2/ Al
2o
3) difference and have X-type molecular sieve and Y zeolite point.Traditionally, SiO
2/ Al
2o
3mol ratio be greater than 3.0 be Y zeolite, SiO
2/ Al
2o
3mol ratio between 2.2-3.0, be X-type molecular sieve.X-type molecular sieve belongs to cubic system, and cell parameter a is 2.486-2.502nm, and X-type molecular sieve is structurally similar with natural faujasite, and it is connected like that by adamantine crystal.Replace the C atom in diamond lattic structure with β cage, connected by hexagonal prism cage between adjacent β cage, each like this β cage four hexatomic rings connect with other β cage by tetrahedron direction, just define the three-dimensional framework of faujasite.Octahedral zeolite cage (becoming supercage again) is defined by β cage and hexagonal prism cage.Be connected by twelve-ring between octahedral zeolite cage, just become the main channel of faujasite, aperture is
Because on skeleton, aluminium atom is trivalent, so there is the valence electron of an oxygen atom not neutralized in aluminum-oxygen tetrahedron, so just make whole aluminum-oxygen tetrahedron with a negative electrical charge.For keeping electroneutral, the metal cation (M that positively charged must be had near aluminum-oxygen tetrahedron
+) offset negative electrical charge.Generally, in synthetic zeolite, metal cation is sodium (or potassium) ion, and these cations are easy to by other ion-exchange out.Molecular sieve after exchange shows excellent absorption property.X-type zeolite molecular sieve belongs to low silicone zeolite (silica alumina ratio is less than 3), and the X-type zeolite molecular sieve being 2 ~ 2.2 silica alumina ratio traditionally calls low Si-Al zeolite molecular sieve (LSX), and this is
the minimum silica alumina ratio that rule allows.Due to the silica alumina ratio that X-type molecular sieve is lower, can there is more cation can be exchanged, thus show better absorption property.Baksh etc. find that the adsorption capacity of LiX molecular sieve to nitrogen exceeds 50% than NaX, and Li-LSX has larger N2 adsorption capacity and oxygen N2 adsorption ability than common X molecular sieve.
Domestic separating oxygen from air by means of pressure swing adsorption technology has in recent years and develops fast, particularly in the research and development of new adsorbent.But oxygenerator domestic at present is substantially also using traditional 5A and 13X molecular sieve as oxygen enrichment adsorbent, novel efficient adsorbent is needing further to be developed.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method preparing the LSX molecular sieve with Jie's microporous layers sequence structure for the deficiencies in the prior art.
Technical scheme of the present invention is as follows:
As the synthetic method of Jie's microporous layers sequence structure LSX molecular sieve of space-division oxygen-enriching adsorbent, comprise the following steps:
The former powder of A1, synthesis of molecular sieve; Concrete steps:
First dissolve 5.55g sodium metaaluminate is stirred to entirely molten in water, then dissolves 6.06g KOH and 8.65g NaOH and is stirred to entirely molten in water.Above-mentioned two kinds of solution are mixed, and adds the waterglass of 12.31g, then add amphipathy macromolecule PEG400 and water, fully mix to gel under stirring; Gel is transferred to in teflon-lined stainless steel cauldron, put into air dry oven ageing 24h at 40 DEG C, then crystallization 6h at 100 DEG C; Be cooled to room temperature after reaction terminates, take out material, product is through centrifugal, washing extremely neutrality; Product is transferred in surface plate, puts into air dry oven, in 100 DEG C of dried overnight; Dried sample is ground to form tiny powder particle, puts into crucible, obtain final sample Na-LSX molecular sieve in tube furnace Program intensification roasting; During synthesis of molecular sieve, the proportioning of various material is as follows:
2SiO
2: Al
2o
3: 7.5 (Na
2o+K
2o): 125H
2o:xPolymer(mol ratio); Polymer is amphipathy macromolecule;
Na
2o/ (Na
2o+K
2o)=0.77(mol ratio); m
h2O/ m
polymer=5 or 10 or 15 or 20 or 25(mass ratio);
A2, lithium ion exchanged:
By the Na-LSX molecular sieve elder generation of preparation and NH
4 +exchange, after roasting again with Li
+exchange, concrete steps are as follows:
First, Na-LSX molecular sieve and NH
4 +carry out ion-exchange:
(1) precise 5g Na-LSX sieve sample is in beaker, adds 1mol/L NH
4nO
3solution 40ml stirring and dissolving, is placed in after temperature control magnetic stirring apparatus stirs 2h at 90 DEG C by beaker, stop stirring, and carries out ion-exchange 3 times continuously again after suction filtration, and suction filtration after completing is also dry at 100 DEG C;
(2) dried sample is ground to form tiny powder particle, put into crucible, obtain H-LSX sieve sample in tube furnace Program intensification roasting; Concrete heating schedule is as follows: keep 3 hours from room temperature with the ramp to 250 of 5 DEG C/min DEG C constant temperature; Be warming up to 400 DEG C of constant temperature from 250 DEG C with the speed of 5 DEG C/min and keep 1 hour; Be warming up to 550 DEG C of constant temperature from 400 DEG C with the speed of 5 DEG C/min and keep 5 hours;
Secondly, H-LSX molecular sieve and Li
+carry out ion-exchange:
(1) sample after above-mentioned roasting is transferred in beaker, adds the LiCl solution 30ml of 1.0mol/L, stirring and dissolving, beaker is placed in after temperature control magnetic stirring apparatus stirs 2h at 90 DEG C, stop stirring, carry out ion-exchange 3 times continuously again after suction filtration, suction filtration after completing is also dry at 100 DEG C;
(2) dried sample is ground to form tiny powder particle, put into crucible, obtain Li-LSX sieve sample in tube furnace Program intensification roasting.
The present invention has following beneficial effect:
1) by adding a kind of amphipathy macromolecule, in sieve synthesis procedure, the formation of microcellular structure is not affected, but the existence of macromolecular material, play the effect of " soft template ", make the molecular sieve of formation have Jie's microporous layers sequence structure.
2) material synthesized by has micro-mesoporous sequence structure.Namely the skeleton of molecular sieve is made up of micropore X-type molecular sieve, there is meso-hole structure simultaneously, thus there is larger duct and spacious opening structure, larger duct and spacious opening structure are that cation diffusion in molecular sieve and the velocity ratio that exchanges are very fast, thus more lithium ion exchanged is switched in molecular sieve pore passage, shows better nitrogen adsorption performance, is thus separated in oxygen at pressure swing adsorption air and is conducive to absorption nitrogen better, adsorption capacity is large, and nitrogen oxygen separating is than high.The micro porous molecular sieves such as current industrial frequent use 5A or 13X, general employing pressure ratio is more than or equal to 4, occur that oxygen yield declines rapidly (when pressure ratio is 3 lower than 4, oxygen yield is only about 40%), if and adopt Jie micropore sequence Li-LSX zeolite molecular sieve, even if pressure ratio is down to about 2, oxygen yield is now still about 60%.
3) one-step synthesis process preparation is adopted to have the molecular sieve of Jie's microcellular structure, based on amphipathy macromolecule, there is oleophylic and hydrophilic double properties, it can be used as the template of Zeolite synthesis, explore a set of more simply, more environmental protection, vanguard technology that energy consumption is lower, process of producing product is simple and easy to control, and its power consumption decreases beyond 50%.
Accompanying drawing explanation
Fig. 1 is the flow chart that lithium ion exchanged prepares Li-LSX molecular sieve
Fig. 2 is the different amphipathy macromolecule measured synthesizes the molecular sieve obtained adsorption/desorption isotherms and pore size distribution as template;
Fig. 3 is the XRD spectra of Jie's LiLSX microporous layers sequence structure molecular sieve;
Fig. 4 is the shape appearance figure of Jie's LiLSX microporous layers sequence structure molecular sieve;
Fig. 5 is the molecular sieve nitrogen Static Adsorption thermoisopleth at room temperature before and after lithium ion exchanged;
To be Jie's microcellular structure Li-LSX compare at 0.101MPa, Nitrogen adsorption capacity at 0 DEG C with micropore Li-LSX molecular sieve Fig. 6.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
One, the former powder of synthesis of molecular sieve
The present embodiment adopts static hydrothermal synthesis method, with waterglass (SiO
226%, Na
2o8.2%) be silicon source, with sodium metaaluminate (Al
2o
349%, Na
2o38%) be aluminium source, in synthesis, add a certain amount of amphipathy macromolecule polymer, a series of sieve sample of static monitor in stainless steel cauldron.
Concrete steps:
First dissolve 5.55g sodium metaaluminate is stirred to entirely molten in water, then dissolves 6.06g KOH and 8.65g NaOH and is stirred to entirely molten in water.Above-mentioned two kinds of solution are mixed, and add the waterglass of 12.31g, then add amphipathy macromolecule PEG400(polyethylene glycol) and water, fully mix to gel under stirring; Gel is transferred to in teflon-lined stainless steel cauldron, put into air dry oven ageing 24h at 40 DEG C, then crystallization 6h at 100 DEG C; Be cooled to room temperature after reaction terminates, take out material, product is through centrifugal, washing extremely neutrality; Product is transferred in surface plate, puts into air dry oven, in 100 DEG C of dried overnight; Dried sample is ground to form tiny powder particle, puts into crucible, obtain final sample Na-LSX molecular sieve in tube furnace Program intensification roasting.
During synthesis of molecular sieve, the proportioning of various material is as follows:
2SiO
2: Al
2o
3: 7.5 (Na
2o+K
2o): 125H
2o:xPolymer(mol ratio); Polymer is amphipathy macromolecule;
Na
2o/ (Na
2o+K
2o)=0.77(mol ratio); m
h2O/ m
polymer=5 or 10 or 15 or 20 or 25(mass ratio);
Two, lithium ion exchanged
The lithium ion exchanged method that pressure swing adsorption air is separated in oxygen molecular sieve has aqueous solution exchange process, melting exchange process etc.Wherein, aqueous solution exchange process can reach higher exchange degree through repeatedly exchanging or exchanging continuously, and give-and-take conditions are comparatively gentle, easily realize industrialization; so be most widely used in large-scale production at present, the present invention's lithium ion exchanged method used is aqueous solution exchange process.By the Na-LSX molecular sieve elder generation of preparation and NH
4 +exchange, after roasting again with Li
+exchange, concrete steps are as follows:
First, Na-LSX molecular sieve and NH
4 +carry out ion-exchange:
(1) precise 5g Na-LSX sieve sample is in beaker, adds 1mol/L NH
4nO
3solution 40ml stirring and dissolving, is placed in after temperature control magnetic stirring apparatus stirs 2h at 90 DEG C by beaker, stop stirring, and carries out ion-exchange 3 times continuously again after suction filtration, and suction filtration after completing is also dry at 100 DEG C;
(2) dried sample is ground to form tiny powder particle, put into crucible, obtain H-LSX sieve sample in tube furnace Program intensification roasting.Concrete heating schedule is as follows: keep 3 hours from room temperature with the ramp to 250 of 5 DEG C/min DEG C constant temperature; Be warming up to 400 DEG C of constant temperature from 250 DEG C with the speed of 5 DEG C/min and keep 1 hour; Be warming up to 550 DEG C of constant temperature from 400 DEG C with the speed of 5 DEG C/min and keep 5 hours.
Secondly, H-LSX molecular sieve and Li+ carry out ion-exchange:
(1) sample after above-mentioned roasting is transferred in beaker, adds the LiCl solution 30ml of 1.0mol/L, stirring and dissolving, beaker is placed in after temperature control magnetic stirring apparatus stirs 2h at 90 DEG C, stop stirring, carry out ion-exchange 3 times continuously again after suction filtration, suction filtration after completing is also dry at 100 DEG C;
(2) dried sample is ground to form tiny powder particle, put into crucible, obtain Li-LSX sieve sample in tube furnace Program intensification roasting.
Fig. 2 is adsorption/desorption isotherms and the pore size distribution of synthesizing the molecular sieve obtained by adding the different amphipathy macromolecule measured.As can be seen from pore size distribution figure, all molecular sieves all have micropore and meso-hole structure, and the molecular sieve synthesized by explanation belongs to Jie's microcellular structure molecular sieve.
The specific area of LSX molecular sieve and pore volume data are in table 1.The total specific area of BET of this LSX molecular sieve is 503m
2g
-1, wherein micropore specific area reaches 756.1m
2g
-1; Middle pore specific surface area 24-35m
2g
-1.As shown in Figure 2, the adsorption/desorption curve of LSX molecular sieve belongs to the I type thermoisopleth in Brunauer adsorption isotherm, shows that in molecular sieve, micropore distribution height is concentrated, and exists regular microcellular structure; Combined hole distribution map can be found out, all samples all have multi-stage artery structure, illustrates and synthesized molecular sieve can be made to produce multistage pore canal after macromolecule adds.
The specific area of table 1.LSX molecular sieve and pore volume data
As can be seen from Fig. 3, Fig. 4, be exchanged into Li-LSX sample by the former powder of LSX, the peak position that its XRD composes and peak intensity there occurs certain change, which show the impact of cation on framework of molecular sieve.
Fig. 5 is the molecular sieve nitrogen Static Adsorption thermoisopleth at room temperature before and after lithium ion exchanged.Under can finding out the pressure measured through the molecular sieve that lithium ion exchanged is modified, the adsorbance of nitrogen is all increased.The molecular sieve adsorbance to nitrogen modified through three lithium ion exchangeds obviously increases.Because lithium ion exchanged degree only reaches after more than 70%, the adsorbance of nitrogen just can increase considerably, and therefore only have after exchanging when three times, lithium ion exchanged degree just can reach more than 70%.Be in cost consideration, lithium ion exchanged number of times is too much unsuitable.In the industrial production of common omnibus control system, usually adopt pressure to adsorb a little more than under 3.0MPa, then adopt low pressure or vacuum desorption, so only to the air work of absorption, to reduce energy consumption.
To be Jie's microcellular structure Li-LSX compare at 0.101MPa, Nitrogen adsorption capacity at 0 DEG C with micropore Li-LSX molecular sieve Fig. 6.Wherein meso-LSX is the sample of the modified Li-LSX of Jie's microcellular structure.Result shows, the N2 adsorption capacity of micro porous molecular sieve is also smaller, uses the PSA oxygen preparation energy consumption of these molecular sieves and invests relatively high.Jie's microcellular structure Li-LSX adsorbent studied herein, possesses higher adsorption capacity.For the optimization of separating oxygen from air by means of pressure swing adsorption process provides the foundation.
The making oxygen by air separation molecular sieve of exploitation both at home and abroad at present, adopts the low silica-alumina ratio X-type molecular sieve of lithium ion exchanged mostly.Li
+exchange degree determines the adsorption capacity of zeolite molecular sieve.The LSX molecular sieve with Jie's microporous layers sequence structure of the present invention's synthesis, due to its larger duct and spacious opening structure, cation diffusion velocity wherein and exchange velocity, than very fast, therefore more easily carry out lithium ion exchanged.The LSX molecular sieve of Jie's microporous layers sequence structure and the Performance comparision of other company's sample have been shown in table 2.The adsorptive selectivity of molecular sieve refers to N
2adsorbance and O
2adsorbance ratio.Adsorptive selectivity is higher, and the separating property of nitrogen and oxygen is better.Can obviously find out, the adsorbing separation ratio of LSX molecular sieve to nitrogen and oxygen of Jie's microporous layers sequence structure increases substantially, and reaches 7.34, than other company's high value greatly close to 1.This is because the LSX molecular sieve of Jie's microporous layers sequence structure has higher lithium ion exchanged degree, demonstrates significant superiority in air separation.
Table 2. is situated between the Performance comparision of microcellular structure Li-LSX and domestic and international other products
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (1)
1. be used as the synthetic method of Jie's microporous layers sequence structure LSX molecular sieve of space-division oxygen-enriching adsorbent, it is characterized in that, comprise the following steps:
The former powder of A1, synthesis of molecular sieve; Concrete steps:
First dissolve 5.55g sodium metaaluminate is stirred to entirely molten in water, then dissolves 6.06g KOH and 8.65g NaOH and is stirred to entirely molten in water; Above-mentioned two kinds of solution are mixed, and adds the waterglass of 12.31g, then add amphipathy macromolecule PEG400 and water, fully mix to gel under stirring; Gel is transferred to in teflon-lined stainless steel cauldron, put into air dry oven ageing 24h at 40 DEG C, then crystallization 6h at 100 DEG C; Be cooled to room temperature after reaction terminates, take out material, product is through centrifugal, washing extremely neutrality; Product is transferred in surface plate, puts into air dry oven, in 100 DEG C of dried overnight; Dried sample is ground to form tiny powder particle, puts into crucible, obtain final sample Na-LSX molecular sieve in tube furnace Program intensification roasting; During synthesis of molecular sieve, the proportioning of various material is as follows:
2SiO
2: Al
2o
3: 7.5 (Na
2o+K
2o): 125H
2o: xPolymer, this proportioning is mol ratio; Polymer is amphipathy macromolecule;
Na
2o/ (Na
2o+K
2o)=0.77, this proportioning is mol ratio; m
h2o/ m
polymer=5 or 10 or 15 or 20 or 25, this proportioning is mass ratio;
A2, lithium ion exchanged:
By the Na-LSX molecular sieve elder generation of preparation and NH
4 +exchange, after roasting again with Li
+exchange, concrete steps are as follows:
First, Na-LSX molecular sieve and NH
4 +carry out ion-exchange:
(1) precise 5gNa-LSX sieve sample is in beaker, adds 1mol/LNH
4nO
3solution 40ml stirring and dissolving, is placed in after temperature control magnetic stirring apparatus stirs 2h at 90 DEG C by beaker, stop stirring, and carries out ion-exchange 3 times continuously again after suction filtration, and suction filtration after completing is also dry at 100 DEG C;
(2) dried sample is ground to form tiny powder particle, put into crucible, obtain H-LSX sieve sample in tube furnace Program intensification roasting; Concrete heating schedule is as follows: keep 3 hours from room temperature with the ramp to 250 of 5 DEG C/min DEG C constant temperature; Be warming up to 400 DEG C of constant temperature from 250 DEG C with the speed of 5 DEG C/min and keep 1 hour; Be warming up to 550 DEG C of constant temperature from 400 DEG C with the speed of 5 DEG C/min and keep 5 hours;
Secondly, H-LSX molecular sieve and Li
+carry out ion-exchange:
(1) sample after above-mentioned roasting is transferred in beaker, add the LiCl solution 30ml of 1.0mol/L, stirring and dissolving, beaker is placed in after temperature control magnetic stirring apparatus stirs 2h at 90 DEG C, stop stirring, carry out ion-exchange 3 times continuously again after suction filtration, suction filtration after completing is also dry at 100 DEG C;
(2) dried sample is ground to form tiny powder particle, put into crucible, obtain Li-LSX sieve sample in tube furnace Program intensification roasting.
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| CN107970884A (en) * | 2017-12-08 | 2018-05-01 | 苏州思美特表面材料科技有限公司 | The preparation method of the low si molecular sieves load filler of lithium type |
| CN108273338B (en) * | 2018-02-08 | 2021-03-16 | 北京科技大学 | Adsorption method of ultrafine particles |
| CN113398877B (en) * | 2021-06-23 | 2023-05-26 | 南京永成分子筛有限公司 | Lithium-based molecular sieve with nitrogen-oxygen separation function, and preparation method and production equipment thereof |
| CN114082409A (en) * | 2021-11-25 | 2022-02-25 | 大连理工大学 | Hydrophobic LSX type molecular sieve for air separation oxygen enrichment, and preparation method and application thereof |
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| CN1981922A (en) * | 2005-12-14 | 2007-06-20 | 李宏愿 | Molecular-sieve removing adsorbent of low-fluorine sulfide impurities and its production |
| CN101289196A (en) * | 2008-06-13 | 2008-10-22 | 洛阳市建龙化工有限公司 | Method for preparing LiLSX molecular screen |
| CN101524637A (en) * | 2009-04-23 | 2009-09-09 | 中国海洋石油总公司 | Preparation method of LSX-molecular-sieve-rich cementing-agent-free absorbent |
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| CN1981922A (en) * | 2005-12-14 | 2007-06-20 | 李宏愿 | Molecular-sieve removing adsorbent of low-fluorine sulfide impurities and its production |
| CN101289196A (en) * | 2008-06-13 | 2008-10-22 | 洛阳市建龙化工有限公司 | Method for preparing LiLSX molecular screen |
| CN101524637A (en) * | 2009-04-23 | 2009-09-09 | 中国海洋石油总公司 | Preparation method of LSX-molecular-sieve-rich cementing-agent-free absorbent |
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