CN103539150A - Low-silica-alumina-ratio X-type zeolite molecular sieve [(Li,Ca)-LSX] preparation method - Google Patents
Low-silica-alumina-ratio X-type zeolite molecular sieve [(Li,Ca)-LSX] preparation method Download PDFInfo
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Abstract
The invention relates to a low-silica-alumina-ratio X-type zeolite molecular sieve [(Li,Ca)-LSX] preparation method, and belongs to various fields such as microporous material, nitrogen-oxygen separation, ion exchange, and the like. According to the invention, through lithium ion exchange, sodium-type low-silica-alumina-ratio X-type zeolite molecular sieve (Na-LSX) is provided with certain lithium ion exchange degree; and through calcium ion exchange, low-silica-alumina-ratio X-type zeolite molecular sieve [(Li,Ca)-LSX] is obtained, wherein a final product composition is LixCa(48-0.5x)Si96Al96O384. Compared with a single lithium ion exchange process, with the method provided by the invention, lithium ion dose is reduced, production cost is reduced, and production process is simple. Compared with Li-LSX, he prepared (Li,Ca)-LSX zeolite molecular sieve has higher absorption capacity, and has wide application potential in the fields such as fine chemicals, absorption exchange, nitrogen-oxygen separation, and the like.
Description
Technical field:
The invention belongs to the multiple fields such as catalysis, absorption, the separation of nitrogen oxygen and ion-exchange, be specifically related to the preparation method of a kind of low silica-alumina ratio X-type zeolite molecular sieve [(Li, Ca)-LSX].
Background technology:
The X-type zeolite molecular sieve of silica alumina ratio between 1.0-1.2 is called as low silica-alumina ratio X-type zeolite molecular sieve (LSX).It is reported, due to Li
+radius is minimum, and electric density is maximum, than Na
+, Mg
2+, Ag
+formed other zeolite molecular sieve of plasma, Li-LSX zeolite molecular sieve has good Oxygen Enrichment and nitrogen oxygen separating power (USP5268023,1993; US5962358,1997), thereby aspect gas delivery, show superiority and in sepn process (EP0769320B1, the 1996) fields such as separated (PSA) separated with Vacuum Pressure Swing Adsorption (VSA) of pressure-variable adsorption, be used widely thus.
The people such as Guan Lili (Acta Phys.Chim.Sin., 2002,18:998～1004) are once by carrying out Ca to Na-LSX molecular sieve
2+exchange, result shows along with Ca
2+the increase of exchange degree, prepared (Ca, Na)-LSX molecular sieve is to the adsorptive capacity of nitrogen rising tendency linearly, and the Ca on different positions in framework of molecular sieve
2+not obvious to nitrogen adsorption performance impact, work as Ca
2+when exchange degree is 97.1%, Ca-LSX molecular sieve reaches 28.3ml/g to the adsorptive capacity of nitrogen.On this basis, the people such as Sicar (USP4557763,1996) utilize rare earth ion (Sr
2+) Ca-LSX molecular sieve is carried out to modification, obtain Ca
2+exchange degree is 5～45% and Sr
2+exchange degree is (Ca, Sr)-LSX molecular sieve of 60～95%, and finds to introduce the nitrogen adsorption capacity that rare earth ion can improve LSX molecular sieve.The people such as Coe (USP4481081,2002) utilize again the alkaline earth metal cations such as magnesium, calcium, strontium and barium further to carry out ion-exchange to Na-LSX molecular sieve, although result shows these positively charged ions and all can improve the absorption property to nitrogen, but than Li-LSX and Ag-LSX equimolecular sieve, alkaline-earth metal type LSX molecular sieve is due to more difficult to nitrogen desorb, thereby increased the energy consumption in air separation process.
The people such as Robert (US7300899,2005) find to only have the Li of working as in Li-LSX molecular sieve
+when exchange degree is greater than 75%, its nitrogen adsorption capacity just can increase sharply, and nitrogen adsorption is conciliate to the Li that picks up keying action
+mainly be arranged in FAU skeleton structure S III position, but because this part positively charged ion is very difficult exchanged, a large amount of lithium salts of unavoidable waste when the Li-LSX molecular sieve of the high exchange degree of preparation.Chinese invention patent (CN101289196A, 2008) passes through K
+, NH
4 +and Li
+the utilization ratio that is conducive to improve lithium salts etc. continuous exchange process.We once proposed a kind of Li that aqueous solution exchange is combined with solid phase fusion exchange
+switching method (CN101125664A, 2008), has further reduced lithium salts consumption, has improved Li simultaneously
+exchange degree.But these method complex process, complex operation, production cost is very high.The people such as Hutson (AIChE Journal, 1999,45 (4): 724-734) once by introduce a small amount of Ag in Li-LSX molecular sieve
+obtained (Li, Ag)-LSX molecular sieve, result shows that this molecular sieve under high pressure has higher selectivity, and under low pressure shows very low selectivity, and because silver salt price is higher and exchange process more complicated, cannot realize suitability for industrialized production.
Therefore,, in order to overcome in Na-LSX framework of molecular sieve the problem such as the more difficult exchange of sodium ion and lithium salts price continuous rise on indivedual positions, the present invention, on CN101125664A patent basis, has reported a kind of Li that simultaneously introduces in Na-LSX molecular sieve
+and Ca
2+thereby prepare (Li, Ca)-LSX molecular sieve, wishes to reduce by this lithium salts consumption, simplifies technique, and improve the adsorptive capacity to nitrogen.
Summary of the invention:
The present invention is directed in current industrial production the problems such as the complicated and price of Li-LSX preparation of molecular sieve is higher, on Chinese invention patent (CN101125664A, 2008) basis, further propose the preparation method of a kind of (Li, Ca)-LSX molecular sieve.
1, a preparation method for low silica-alumina ratio X-type zeolite molecular sieve [(Li, Ca)-LSX], is characterized in that, comprises the following steps:
1) activation: sodium type low silica-alumina ratio X-type zeolite molecular sieve (Na-LSX) is put into retort furnace, be dried 2 hours at 100 ℃, roasting, after 1 hour, is placed in moisture eliminator cooling standby at 550 ℃;
2) lithium exchange: the Na-LSX zeolite molecular sieve of getting after activation mixes with the lithium salt solution of 0.4mol/L, and in described Na-LSX zeolite molecular sieve, sodium ion and lithium ion mol ratio are 1:0.5-1:2; And in 90 ℃ of water-baths, stir after 2 hours suction filtration washing; Sample after washing is rejoined to above-mentioned lithium salt solution, then repeat 2-4 time; Na-LSX zeolite molecular sieve and the lithium salt solution solid-liquid mass ratio of each exchange are 1:20-1:100; After exchange finishes, sample is dried to 2 hours at 100 ℃, at 450 ℃, roasting obtains having (Li, Na)-LSX type zeolite molecular sieve of certain lithium ion exchanged degree after 1 hour; Measure the sodium ions content not exchanging in (Li, Na)-LSX type zeolite molecular sieve;
3) calcium exchange: get the calcium salt soln that above-mentioned whole (Li, Na)-LSX type zeolite molecular sieve is placed in 1mol/L, in described (Li, Na)-LSX type zeolite molecular sieve, sodium ion and the calcium salt mol ratio of exchange are not 1:0.2-1:1; And in 90 ℃ of water-baths, stir after 2 hours suction filtration washing; Sample after washing is rejoined in above-mentioned calcium salt soln, then repeat 1-2 time; (Li, Na)-LSX zeolite molecular sieve and the calcium salt soln solid-liquid mass ratio of each exchange are 1:20-1:100; After exchange finishes, final sample is dried to 2 hours at 100 ℃, at 450 ℃, roasting obtains (Li, Ca)-LSX type zeolite molecular sieve for 1 hour;
Or by step 2) (the Li that obtains, Na)-LSX type zeolite molecular sieve mixes with calcium salt powder and stirs to grind well and is placed in retort furnace, in described (Li, Na)-LSX type zeolite molecular sieve, sodium ion and the calcium salt mol ratio of exchange are not 1:0.2-1:1; Temperature programming is set to: at ambient temperature, with the speed of 1 ℃/min, be warmed up to 120 ℃, constant temperature 2 hours; Then the speed with 2 ℃/min is warmed up to 200 ℃, constant temperature 2 hours; Then the speed with 4 ℃/min is warmed up to 550 ℃, and constant temperature is naturally cooling after 4 hours, and taking-up is dried 6 hours after washing and filtering at 150 ℃, naturally cools to room temperature, also can obtain (Li, Ca)-LSX type zeolite molecular sieve.
2, a preparation method for low silica-alumina ratio X-type zeolite molecular sieve [(Li, Ca)-LSX], is characterized in that, comprises the following steps:
1) activation: sodium type low silica-alumina ratio X-type zeolite molecular sieve (Na-LSX) is put into retort furnace, be dried 2 hours at 100 ℃, roasting, after 1 hour, is placed in moisture eliminator cooling standby at 550 ℃;
2) the Na-LSX zeolite molecular sieve of getting after a certain amount of activation mixes with the ammonium salt solution of a certain amount of 1mol/L, and in described Na-LSX type zeolite molecular sieve, sodium ion and ammonium salt mol ratio are 1:0.2-1:2; And in the water-bath of 70 ℃, exchange after 2 hours suction filtration washing; Sample after washing is rejoined to above-mentioned ammonium salt solution, then after 2-4 end of repeated exchanged, final sample is dried to 2 hours at 70 ℃, obtain having (the NH of certain exchange degree
4, Na)-LSX type zeolite molecular sieve; Measure the sodium ion and the NH that in (Li, Na)-LSX type zeolite molecular sieve, do not exchange
4 +ion content;
3) lithium and calcium exchange: by above-mentioned all (NH
4, Na)-LSX type zeolite molecular sieve mixes with the pressed powder of lithium salts and calcium salt, described (NH
4, in Na)-LSX type zeolite molecular sieve, NH
4 +ion and lithium salts mol ratio are 1:0.5-1:2, and sodium ion and the calcium salt mol ratio of exchange are not 1:0.2-1:1; Stir and grind well, in retort furnace, temperature programming is set to: at ambient temperature, with the speed of 1 ℃/min, be warmed up to 120 ℃, constant temperature 2 hours; Then the speed with 2 ℃/min is warmed up to 200 ℃, constant temperature 2 hours; Then the speed with 4 ℃/min is warmed up to 550 ℃, and constant temperature is after 4 hours, take out and wash and filter, under 150 ℃ of conditions constant temperature after 6 hours naturally cooling obtain (Li, Ca)-LSX type zeolite molecular sieve;
Or get above-mentioned all (NH
4, Na)-LSX type zeolite molecular sieve mixes with lithium salts and calcium salt mixing solutions, described (NH
4, in Na)-LSX type zeolite molecular sieve, NH
4 +ion and lithium salts mol ratio are 1:0.5-1:2, and sodium ion and the calcium salt mol ratio of exchange are not 1:0.2-1:1; And the water-bath that is placed in 90 ℃ exchanges after 2 hours, suction filtration washing; Sample after washing is rejoined to above-mentioned mixing solutions, then repeated exchanged 1-2 time; (the NH of each exchange
4, Na)-LSX zeolite molecular sieve and lithium salts and calcium salt mixing solutions solid-liquid mass ratio are 1:20-1:100; After end, at 100 ℃, be dried 2 hours, at 450 ℃, roasting obtains (Li, Ca)-LSX type zeolite molecular sieve for 1 hour.
Described lithium salts is LiCl, LiOH, LiNO
3one of, calcium salt is respectively CaCl
2, Ca (NO
3)
2one of.
The advantages such as the present invention compares with single lithium ion exchanged technique, has lithium ion consumption and reduces, and production cost reduction and production technique are simple.It is larger that prepared (Li, Ca)-LSX type zeolite molecular sieve and Li-LSX compare loading capacity, in the fields such as fine chemistry industry, absorption exchange and the separation of nitrogen oxygen, shows application potential widely.
Accompanying drawing explanation:
Fig. 1: each example nitrogen adsorption kinetic curve.
Embodiment
The activation of the step 1) of each examples of implementation is all identical: sodium type low silica-alumina ratio X-type zeolite molecular sieve (Na-LSX) is put into retort furnace, at 100 ℃, be dried 2 hours, at 550 ℃, roasting, after 1 hour, is placed in moisture eliminator cooling standby.
Embodiment 1:
Lithium exchange: the Na-LSX zeolite molecular sieve of getting after 5g activation mixes with the LiCl solution 100mL of 0.4mol/L, and stirs after 2 hours in 90 ℃ of water-baths, suction filtration washing; Sample after washing is rejoined to above-mentioned lithium salt solution, after repeating again to finish for 4 times, final sample is dried to 2 hours at 100 ℃, and at 450 ℃, roasting obtains having (Li, Na)-LSX type zeolite molecular sieve of certain lithium ion exchanged degree after 1 hour.
Calcium exchange: get the CaCl that above-mentioned all (Li, Na)-LSX type zeolite molecular sieves are placed in 1mol/L
2in solution 100mL, and stir after 2 hours suction filtration washing in 90 ℃ of water-baths; Sample after washing is rejoined in above-mentioned calcium salt soln, then after repeating to finish for 2 times, final sample is dried to 2 hours at 100 ℃, at 450 ℃, roasting obtains (Li, Ca)-LSX type zeolite molecular sieve for 1 hour.
Embodiment 2:
Lithium exchange: the Na-LSX zeolite molecular sieve of getting after 5g activation mixes with the LiCl solution 100mL of 0.4mol/L, and stirs after 2 hours in 90 ℃ of water-baths, suction filtration washing; Sample after washing is rejoined to above-mentioned lithium salt solution, after repeating again to finish for 4 times, final sample is dried to 2 hours at 100 ℃, and at 450 ℃, roasting obtains having (Li, Na)-LSX type zeolite molecular sieve of certain lithium ion exchanged degree after 1 hour.
Calcium exchange: get above-mentioned all (Li, Na)-LSX type zeolite molecular sieve and 0.717g CaCl
2powder mixes and stirs to grind well and is placed in retort furnace, and temperature programming is set to: at ambient temperature, with the speed of 1 ℃/min, be warmed up to 120 ℃, constant temperature 2 hours; Then the speed with 2 ℃/min is warmed up to 200 ℃, constant temperature 2 hours; Then the speed with 4 ℃/min is warmed up to 550 ℃, and constant temperature is naturally cooling after 4 hours, and taking-up is dried 6 hours after washing and filtering at 150 ℃, naturally cools to room temperature, also can obtain (Li, Ca)-LSX type zeolite molecular sieve.
Embodiment 3:
NH
4 +exchange: get Na-LSX zeolite molecular sieve and 100ml after 5g activation, the NH of 1mol/L
4cl solution mixes, and in the water-bath of 70 ℃, exchanges after 2 hours, suction filtration washing; Sample after washing is rejoined to above-mentioned ammonium salt solution, then after 4 end of repeated exchanged, final sample is dried to 2 hours at 70 ℃, obtain having (the NH of certain exchange degree
4, Na)-LSX type zeolite molecular sieve.
Lithium and calcium exchange: get above-mentioned all (NH
4, LiCl and the 1mol/LCaCl of Na)-LSX type zeolite molecular sieve and 0.4mol/L
2mixing solutions 100ml exchanges, and is placed in the water-bath of 90 ℃ and exchanges after 2 hours, suction filtration washing; Sample after washing is rejoined to above-mentioned calcium salt and lithium salts mixing solutions, then after 1-2 end of repeated exchanged, at 100 ℃, be dried 2 hours, at 450 ℃, roasting obtains (Li, Ca)-LSX type zeolite molecular sieve for 1 hour.
Embodiment 4:
NH
4 +exchange: get Na-LSX zeolite molecular sieve and 100ml after 5g activation, the NH of 1mol/L
4cl solution mixes, and in the water-bath of 70 ℃, exchanges after 2 hours, suction filtration washing; Sample after washing is rejoined to above-mentioned ammonium salt solution, then after 4 end of repeated exchanged, final sample is dried to 2 hours at 70 ℃, obtain having (the NH of certain exchange degree
4, Na)-LSX type zeolite molecular sieve.
Lithium and calcium exchange: by above-mentioned all (NH
4, Na)-LSX type zeolite molecular sieve and 0.293g LiCl and 0.179g CaCl
2pressed powder mixes, and stirs and grinds well, and in retort furnace, temperature programming is set to: at ambient temperature, with the speed of 1 ℃/min, be warmed up to 120 ℃, constant temperature 2 hours; Then the speed with 2 ℃/min is warmed up to 200 ℃, constant temperature 2 hours; Then the speed with 4 ℃/min is warmed up to 550 ℃, and constant temperature is after 4 hours, take out and wash and filter, under 150 ℃ of conditions constant temperature after 6 hours naturally cooling obtain (Li, Ca)-LSX type zeolite molecular sieve.
To the above-mentioned (Li preparing, Ca)-LSX type zeolite molecular sieve material is tested, and it is larger that its result and Li-LSX compare loading capacity, compares with single lithium ion exchanged technique, there is lithium ion consumption and reduce, the advantage such as production cost reduces and production technique is simple.As seen from Figure 1, prepared (Li, the Ca)-LSX molecular sieve nitrogen adsorption maximum value of each example is all between Li-LSX and Ca-LSX.
Above example has been described in detail technical scheme of the present invention; be understood that this embodiment is only specific embodiments of the invention; be not limited to the present invention, all any modifications of making within the scope of principle of the present invention and improvement etc., within all should being included in protection scope of the present invention.
Claims (3)
1. a preparation method for low silica-alumina ratio X-type zeolite molecular sieve [(Li, Ca)-LSX], is characterized in that, comprises the following steps:
1) activation: sodium type low silica-alumina ratio X-type zeolite molecular sieve (Na-LSX) is put into retort furnace, be dried 2 hours at 100 ℃, roasting, after 1 hour, is placed in moisture eliminator cooling standby at 550 ℃;
2) lithium exchange: the Na-LSX zeolite molecular sieve of getting after activation mixes with the lithium salt solution of 0.4mol/L, and in described Na-LSX zeolite molecular sieve, sodium ion and lithium salts mol ratio are 1:0.5-1:2; And in 90 ℃ of water-baths, stir after 2 hours suction filtration washing; Sample after washing is rejoined to above-mentioned lithium salt solution, then repeat 2-4 time; Na-LSX zeolite molecular sieve and the lithium salt solution solid-liquid mass ratio of each exchange are 1:20-1:100; After exchange finishes, sample is dried to 2 hours at 100 ℃, at 450 ℃, roasting obtains having (Li, Na)-LSX type zeolite molecular sieve of certain lithium ion exchanged degree after 1 hour; Measure the sodium ions content not exchanging in (Li, Na)-LSX type zeolite molecular sieve;
3) calcium exchange: get the calcium salt soln that above-mentioned whole (Li, Na)-LSX type zeolite molecular sieve is placed in 1mol/L, in described (Li, Na)-LSX type zeolite molecular sieve, sodium ion and the calcium salt mol ratio of exchange are not 1:0.2-1:1; And in 90 ℃ of water-baths, stir after 2 hours suction filtration washing; Sample after washing is rejoined in above-mentioned calcium salt soln, then repeat 1-2 time; (Li, Na)-LSX zeolite molecular sieve and the calcium salt soln solid-liquid mass ratio of each exchange are 1:20-1:100; After exchange finishes, final sample is dried to 2 hours at 100 ℃, at 450 ℃, roasting obtains (Li, Ca)-LSX type zeolite molecular sieve for 1 hour;
Or by step 2) (the Li that obtains, Na)-LSX type zeolite molecular sieve mixes with calcium salt powder and stirs to grind well and is placed in retort furnace, in described (Li, Na)-LSX type zeolite molecular sieve, sodium ion and the calcium salt mol ratio of exchange are not 1:0.2-1:1; Temperature programming is set to: at ambient temperature, with the speed of 1 ℃/min, be warmed up to 120 ℃, constant temperature 2 hours; Then the speed with 2 ℃/min is warmed up to 200 ℃, constant temperature 2 hours; Then the speed with 4 ℃/min is warmed up to 550 ℃, and constant temperature is naturally cooling after 4 hours, and taking-up is dried 6 hours after washing and filtering at 150 ℃, naturally cools to room temperature, also can obtain (Li, Ca)-LSX type zeolite molecular sieve.
2. a preparation method for low silica-alumina ratio X-type zeolite molecular sieve [(Li, Ca)-LSX], is characterized in that, comprises the following steps:
1) activation: sodium type low silica-alumina ratio X-type zeolite molecular sieve (Na-LSX) is put into retort furnace, be dried 2 hours at 100 ℃, roasting, after 1 hour, is placed in moisture eliminator cooling standby at 550 ℃;
2) the Na-LSX zeolite molecular sieve of getting after a certain amount of activation mixes with the ammonium salt solution of a certain amount of 1mol/L, and in described Na-LSX type zeolite molecular sieve, sodium ion and ammonium salt mol ratio are 1:0.2-1:2; And in the water-bath of 70 ℃, exchange after 2 hours suction filtration washing; Sample after washing is rejoined to above-mentioned ammonium salt solution, then after 2-4 end of repeated exchanged, final sample is dried to 2 hours at 70 ℃, obtain having (the NH of certain exchange degree
4, Na)-LSX type zeolite molecular sieve; Measure the sodium ion and the NH that in (Li, Na)-LSX type zeolite molecular sieve, do not exchange
4 +ion content;
3) lithium and calcium exchange: by above-mentioned all (NH
4, Na)-LSX type zeolite molecular sieve mixes with the pressed powder of lithium salts and calcium salt, described (NH
4, in Na)-LSX type zeolite molecular sieve, NH
4 +ion and lithium salts mol ratio are 1:0.5-1:2, and sodium ion and the calcium salt mol ratio of exchange are not 1:0.2-1:1; Stir and grind well, in retort furnace, temperature programming is set to: at ambient temperature, with the speed of 1 ℃/min, be warmed up to 120 ℃, constant temperature 2 hours; Then the speed with 2 ℃/min is warmed up to 200 ℃, constant temperature 2 hours; Then the speed with 4 ℃/min is warmed up to 550 ℃, and constant temperature is after 4 hours, take out and wash and filter, under 150 ℃ of conditions constant temperature after 6 hours naturally cooling obtain (Li, Ca)-LSX type zeolite molecular sieve;
Or get above-mentioned all (NH
4, Na)-LSX type zeolite molecular sieve mixes with lithium salts and calcium salt mixing solutions, described (NH
4, in Na)-LSX type zeolite molecular sieve, NH
4 +ion and lithium salts mol ratio are 1:0.5-1:2, and sodium ion and the calcium salt mol ratio of exchange are not 1:0.2-1:1; And the water-bath that is placed in 90 ℃ exchanges after 2 hours, suction filtration washing; Sample after washing is rejoined to above-mentioned mixing solutions, then repeated exchanged 1-2 time; (the NH of each exchange
4, Na)-LSX zeolite molecular sieve and lithium salts and calcium salt mixing solutions solid-liquid mass ratio are 1:20-1:100; After end, at 100 ℃, be dried 2 hours, at 450 ℃, roasting obtains (Li, Ca)-LSX type zeolite molecular sieve for 1 hour.
3. preparation method according to claim 1 and 2, is characterized in that: described lithium salts is LiCl, LiOH, LiNO
3one of, calcium salt is respectively CaCl
2, Ca (NO
3)
2one of.
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| CN105327677A (en) * | 2015-12-11 | 2016-02-17 | 中国海洋石油总公司 | Adsorbent for separating bicyclo-arene in diesel oil and preparation method thereof |
| CN107486146A (en) * | 2017-09-06 | 2017-12-19 | 洛阳建龙微纳新材料股份有限公司 | A kind of mixed-cation LiCa LSX molecular sieves preparation methods and application |
| CN108117090A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of modified low silicon-aluminum is than X-type molecular sieve and its preparation method and application |
| CN108854947A (en) * | 2018-07-04 | 2018-11-23 | 洛阳建龙微纳新材料股份有限公司 | A kind of mixed-cation AgCa-LSX molecular sieve and its preparation method and application |
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| CN105327677A (en) * | 2015-12-11 | 2016-02-17 | 中国海洋石油总公司 | Adsorbent for separating bicyclo-arene in diesel oil and preparation method thereof |
| CN105327677B (en) * | 2015-12-11 | 2018-06-26 | 中海油天津化工研究设计院有限公司 | The adsorbent and preparation method of double ring arene in a kind of separation diesel oil |
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| CN108117090B (en) * | 2016-11-29 | 2021-07-27 | 中国科学院大连化学物理研究所 | Modified X-type molecular sieve with low silicon-aluminum ratio as well as preparation method and application thereof |
| CN107486146A (en) * | 2017-09-06 | 2017-12-19 | 洛阳建龙微纳新材料股份有限公司 | A kind of mixed-cation LiCa LSX molecular sieves preparation methods and application |
| EP3453677A1 (en) * | 2017-09-06 | 2019-03-13 | Luoyang Jalon Micro-Nano New Materials Co., Ltd. | Methods for preparing lica-lsx molecularsieves with mixed cations and applications thereof |
| CN108854947A (en) * | 2018-07-04 | 2018-11-23 | 洛阳建龙微纳新材料股份有限公司 | A kind of mixed-cation AgCa-LSX molecular sieve and its preparation method and application |
| CN108854947B (en) * | 2018-07-04 | 2021-08-17 | 洛阳建龙微纳新材料股份有限公司 | Mixed cation AgCa-LSX molecular sieve and preparation method and application thereof |
| CN113351157A (en) * | 2021-06-02 | 2021-09-07 | 昊华化工科技集团股份有限公司 | Modified lithium low-silicon zeolite molecular sieve and preparation method thereof |
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