CN114408941A - Industrial method for preparing lithium X molecular sieve by countercurrent exchange and lithium X molecular sieve prepared by same - Google Patents
Industrial method for preparing lithium X molecular sieve by countercurrent exchange and lithium X molecular sieve prepared by same Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/22—Type X
Abstract
The invention discloses an industrial method for preparing a lithium X molecular sieve by countercurrent exchange and the lithium X molecular sieve prepared by the method. The method comprises the following steps: mixing X molecular sieve with Li+Mixing the recovered liquid, pre-exchanging and filtering; with Li content+The exchange liquid carries out 9-15 times of countercurrent exchange treatment on the pre-exchanged X molecular sieve under the vacuum condition, and the filtrate generated after each time of countercurrent exchange treatment is recovered and used as the Li-containing solution+Carrying out next countercurrent exchange treatment on the exchange solution, and recovering the filtrate generated after the last countercurrent exchange treatment to be used as a recovery solution; drying the X molecular sieve obtained after the countercurrent exchange treatment. The method utilizes the exchange medium which is quickly separated under the action of vacuum to push the reaction balance to move, and more effectively utilizes Li+A source. The lithium X molecular sieve prepared by the method has high ion exchange degree, better nitrogen adsorption and no ammonia nitrogen environmental pollution.
Description
Technical Field
The invention belongs to the technical field of molecular sieves, and particularly relates to an industrial method for preparing a lithium X molecular sieve by countercurrent exchange and the lithium X molecular sieve prepared by the same.
Background
The molecular sieve is a kind of synthetic hydrated aluminosilicate (zeolite) or natural zeolite with adsorption and separation function. The chemical general formula is (M' 2M) O.Al2O3·xSiO2·yH2O, M', M are respectively monovalent and divalent cations such as K+、Na+And Ca2+、Ba2+And the like.
The molecular sieves having a faujasite structure (FAU) and a silica to alumina molar ratio of 2.0 to 3.0 among the molecular sieves are collectively referred to as an X-type molecular sieve, wherein the molecular sieve having a silica to alumina molar ratio of 2.2 to 3.0 is a general silica to alumina X-type molecular sieve, and the molecular sieve having a silica to alumina molar ratio of 2.0 to 2.2 is a low silica to alumina X-type molecular sieve (LSX). Li+The radius is minimum, the charge density is large, and the lithium-exchanged LSX molecular sieve and nitrogen molecules have stronger interaction, so that the LSX molecular sieve shows stronger adsorption performance to nitrogen; the X molecular sieve is of FAU structure type, the higher the aluminum atom content is, the more the cation number is, the more the framework is, and therefore Li+Compared with the common X type molecular sieve, the exchanged LSX type molecular sieve has higher nitrogen adsorption capacity and stronger nitrogen-oxygen separation capacity. The adsorption capacity of Li-LSX to nitrogen is 2-3 times higher than that of common X-type molecular sieve and CaA molecular sieve, and the Li-LSX molecular sieve as a novel adsorbent has better economic benefit in the field of pressure swing adsorption oxygen production.
Chinese patent CN 101289196A discloses a preparation method of Li-LSX molecular sieve, firstly LSX and K+By substitution 5 times to form K-LSX, and reaction with NH4 +By substitution 5 times to form NH4 +-LSX，NH4 +-LSX with hydrogen hydroxideExchanging lithium into Li-LSX, and using air to expel ammonia gas generated by lithium exchange by utilizing reaction equilibrium movement principle. The method has the advantages of multiple exchange procedures, long time and complicated process, can generate a large amount of ammonia nitrogen wastewater and ammonia-containing waste gas, and is not environment-friendly.
Disclosure of Invention
Aiming at the problems that the ion exchange degree and the adsorption value of the existing lithium X molecular sieve are not high and ammonia nitrogen exists in the process, the invention provides an industrial method for preparing the lithium X molecular sieve by countercurrent exchange+A source. The lithium X molecular sieve prepared by the method has high ion exchange degree, better nitrogen adsorption and no ammonia nitrogen environmental pollution.
The invention is realized by the following technical scheme:
in a first aspect, the present invention provides an industrial process for the preparation of lithium X molecular sieves by countercurrent exchange, comprising:
mixing X molecular sieve with Li+Mixing the recovered liquid, pre-exchanging and filtering;
with Li content+The exchange liquid carries out 9-15 times of countercurrent exchange treatment on the pre-exchanged X molecular sieve under the vacuum condition, and the filtrate generated after each time of countercurrent exchange treatment is recovered and used as the Li-containing solution+Carrying out next countercurrent exchange treatment on the exchange solution, and recovering the filtrate generated after the last countercurrent exchange treatment to be used as a recovery solution;
drying the X molecular sieve obtained after the countercurrent exchange treatment.
Further, in a preferred embodiment of the present invention, after the step of performing the counter-current exchange treatment, the method further comprises the step of performing 2-4 times of counter-current water washing on the X molecular sieve, and in the process of counter-current water washing, the washing liquid generated after each time of counter-current water washing is recovered for preparing the high-concentration Li-containing solution+And (4) exchanging the liquid.
Further, in the preferred embodiment of the present invention, the temperature of the pre-exchange is 80-95 ℃ and the exchange time is 30-60 min.
Further, in the preferred embodiment of the present inventionIn the pre-exchange process, X molecular sieve and Li+The solid content of the mixed solution formed by mixing the recovery liquid is 120-130 g/L.
Further, in a preferred embodiment of the invention, during the countercurrent exchange treatment, Li is contained+The temperature of the exchange liquid is 80-95 ℃, and the Li is firstly exchanged+The concentration of the exchange liquid is 110-120 g/L.
Further, in a preferred embodiment of the present invention, Li is contained during the first counter-current exchange treatment+The mass ratio of the exchange liquid to the X molecular sieve dry basis is 0.32-0.35: 1.
Further, in the preferred embodiment of the present invention, the countercurrent exchange process is performed by using a tape type vacuum filter, wherein the dry basis weight of the X molecular sieve processed by the tape type vacuum filter is 450-550 Kg/h.
Further, in a preferred embodiment of the present invention, the adhesive tape type vacuum filter has 9-15 stages of filtrate conveying pipelines, a filtrate conveying pump is disposed in each stage of filtrate conveying pipeline, and a heat exchanger is disposed at an outlet of the filtrate conveying pump.
Further, in the preferred embodiment of the invention, the water used in the countercurrent washing process is the washing water regenerated by the filter cloth of the adhesive tape type vacuum filter, and the temperature of the washing water is 80-95 ℃.
In a second aspect, the present invention provides a lithium X molecular sieve prepared by the above industrial process.
Compared with the prior art, the invention at least has the following technical effects:
the invention provides an industrial method for preparing a lithium X molecular sieve by countercurrent exchange, wherein the X molecular sieve is subjected to countercurrent exchange for 9-15 times under vacuum after being pre-exchanged. In the 9-15 exchanges, from the 1 st time to the 9 th-15 th time, the sodium and potassium contents in the X molecular sieve filter cake are gradually reduced, and the lithium content is gradually increased. And (4) from 9 th to 15 th to 1 st in reverse direction, gradually enriching the sodium and potassium content in the exchange filtrate, and gradually reducing the lithium content. In the ion exchange process, each time of exchange is strictly partitioned, no liquid cross is generated, and 9-15 ion exchange concentration gradients are formed. 9-15 times of counter-current exchange, and exchange formed by utilizing ion concentration gradient to the maximum extentAnd (4) power. The exchanged sodium and potassium ions are taken away along with the filtrate in time, the forward movement of the reaction is promoted, the reverse exchange is avoided, and the stability of the lithium content exchanged to the molecular sieve is ensured. And the filtrate after the last exchange is used as a recovery liquid for pre-exchanging the X molecular sieve, so that lithium ions are recycled, and the using amount of a lithium chloride solution is reduced. After the pre-exchange treatment, Li in the filtrate is produced+Has the lowest content of Na+、K+Is enriched.
Therefore, the method provided by the invention utilizes the exchange medium which is rapidly separated under the action of vacuum to push the equilibrium movement of the reaction, and more effectively utilizes Li+A source. The lithium X molecular sieve prepared by the method has high ion exchange degree, better nitrogen adsorption and no ammonia nitrogen environmental pollution.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail with reference to the following examples, but those skilled in the art will understand that the following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the present invention, and that the specific conditions not specified in the examples are carried out according to conventional conditions or conditions suggested by the manufacturer, and that the reagents or equipment used are not specified by the manufacturer, and are all conventional products available through commercial purchase.
The embodiment provides a lithium X molecular sieve, and the preparation method of the lithium X molecular sieve is as follows:
step S1: mixing X molecular sieve with Li+Mixing the recovered liquid, pre-exchanging and filtering;
with Li content+The recovered solution carries out pre-exchange on the X molecular sieve, recycles lithium ions and reduces Li+The dosage of the solution can be increased to the maximum extent+The utilization ratio of (2). Na in the X molecular sieve is obtained through pre-exchange+、K+Is subjected to preliminary exchange. After the molecular sieve is mixed with the pre-exchange liquid with high ion concentration, a filter cake with high porosity can be formed during filtration, which is beneficial to the exchange of the subsequent exchange liquid and the filter cakeAnd (4) quickly separating.
Further, the temperature of the pre-exchange is 80-95 ℃, and the exchange time is 30-60 min. Preferably, the temperature of the pre-exchange is 83-90 ℃, and the exchange time is 40-50 min. When containing Li+The temperature of the recovered solution is 80-95 ℃, and Li is+The exchange efficiency of (2) is high. Above this temperature, the materials of the existing equipment cannot withstand; below this temperature, the exchange rate is lower.
Further, in the pre-exchange process, the X molecular sieve and Li-containing material+The mixed solution formed by mixing the recovery solution has a solid content of 120-130g/L, preferably 122-128 g/L. When the solid content is within the range, the pre-exchange and the subsequent countercurrent exchange treatment steps can fully treat the X molecular sieve, so that the lithium molecular sieve with uniform quality can be obtained.
Step S2: with Li content+The exchange liquid carries out 9-15 times of countercurrent exchange treatment on the pre-exchanged X molecular sieve under the vacuum condition, and the filtrate generated after each time of countercurrent exchange treatment is recovered and used as the Li-containing solution+Carrying out next countercurrent exchange treatment on the exchange solution; and recovering the filtrate generated after the last countercurrent exchange treatment to be used as a recovered solution.
Carrying out 9-15 times of countercurrent exchange treatment on the X molecular sieve under a vacuum condition, and recovering filtrate generated after each time of countercurrent exchange for use as Li-containing liquid in the next countercurrent exchange treatment process+The exchange solution recycles the lithium ion solution, which is beneficial to reducing the using amount of the lithium solution. And (4) recovering the filtrate generated after the last countercurrent exchange treatment, and using the recovered filtrate as a recovered solution in the pre-exchange process.
Further, in a preferred embodiment of the invention, during the countercurrent exchange treatment, Li is contained+The mass ratio of the exchange liquid to the X molecular sieve dry basis is 0.32-0.35: 1.
Preferably, the lithium source comprises lithium chloride, lithium sulfate, lithium acetate, lithium citrate, lithium oxalate, lithium nitrate. In the embodiment of the present invention, lithium chloride is preferably used as the lithium source.
Further, the countercurrent exchange treatment is completed by using a tape type vacuum filter, the dry basis amount of the tape type vacuum filter for treating the X molecular sieve is 550Kg/h, preferably 480 Kg/h and 530 Kg/h.
For preparing the high-quality lithium molecular sieve, the number of the countercurrent exchange treatment is at least 9, and the best number is 9-15. The belt type vacuum filter is divided into 9-15 stages, the molecular sieve materials move from the inlet end to the outlet end step by step, and the exchange liquid circulates from the last stage to the previous stage step by step, so that the countercurrent exchange of the molecular sieve is realized. The example was carried out with 9 countercurrent exchanges, fresh lithium chloride solution being added to the 9 th exchange. And collecting the filtrate after the 9 th exchange, conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump, and performing the 8 th exchange. And collecting the filtrate after the 8 th exchange, conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump, and performing the 7 th exchange. Collecting the filtrate after 7 th exchange, and pumping to the front stage of the adhesive tape type vacuum filter for 6 th exchange. Collecting the filtrate after the 6 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 5 th exchange. Collecting the filtrate after the 5 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 4 th exchange. Collecting the filtrate after the 4 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 3 rd exchange. Collecting the filtrate after the 3 rd exchange, and pumping the filtrate to the front stage of the adhesive tape type vacuum filter for the 2 nd exchange. Collecting the filtrate after the 2 nd exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 1 st exchange. And collecting the filtrate after the 1 st exchange, and conveying the filtrate to a pre-exchange tank in front of the adhesive tape type vacuum filter by using a pump for pre-exchange.
Further, after the step of countercurrent exchange treatment, the method also comprises the step of carrying out countercurrent washing on the X molecular sieve for 2-4 times, and in the process of countercurrent washing, the washing liquid generated after each countercurrent washing is recovered and used for preparing high-concentration Li-containing materials+And (4) exchanging the liquid.
And carrying out countercurrent washing after the last countercurrent exchange on the X molecular sieve, gradually enriching the lithium chloride remained in the filter cake by the countercurrent washing, collecting the filter cake in a lithium source dissolving tank, and preparing a fresh lithium source solution for the first countercurrent exchange. The step of counter-current water washing is performed at least 2 times, preferably 2-4 times. Furthermore, water used in the process of countercurrent water washing is washing water regenerated by the filter cloth of the adhesive tape type vacuum filter. Taking 2 times of countercurrent water washing as an example, collecting chemical water at 80-95 ℃ for regeneration washing of filter cloth of a DU-type rubber belt type vacuum filter, and adding the chemical water to the 2 nd time of water washing; collecting the filtrate after the 2 nd water washing, conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump, and carrying out the 1 st water washing. And collecting the filtrate after the 1 st washing, and conveying the filtrate to a lithium chloride dissolving tank by using a pump for dissolving solid lithium chloride.
Further, in a preferred embodiment of the invention, during the countercurrent exchange treatment, Li is contained+The temperature of the exchange liquid is 80-95 ℃ (preferably 83-90 ℃), and Li contained in the exchange liquid is exchanged for the first time+The concentration of the exchange liquid is 110-120 g/L. Namely, the concentration of the fresh lithium chloride solution used in the 9 th exchange is 110-120g/L, preferably, the concentration is 112-117 g/L.
Further, in the preferred embodiment of the present invention, the countercurrent exchange process is performed by using a tape type vacuum filter, wherein the dry basis weight of the X molecular sieve processed by the tape type vacuum filter is 450-550 Kg/h.
Further, in a preferred embodiment of the present invention, the adhesive tape type vacuum filter has 9-15 stages of filtrate conveying pipelines, a filtrate conveying pump is disposed in each stage of filtrate conveying pipeline, and a heat exchanger is disposed at an outlet of the filtrate conveying pump. The heat exchanger is arranged, so that the filtrate after each countercurrent exchange, the washing liquid after countercurrent water washing and the chemical water after filter cloth regeneration all pass through the heat exchanger, the temperature is maintained at 80-95 ℃, and the Li is improved+Exchange efficiency, improve the washing effect.
Step S3: drying the X molecular sieve obtained after the countercurrent exchange treatment.
And drying to obtain the improved lithium X molecular sieve raw powder. The product exchange degree, nitrogen adsorption and nitrogen-oxygen adsorption time difference of the lithium X molecular sieve are all better.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1 reference is made to FIG. 1
This example provides an industrial method for preparing lithium X molecular sieve by countercurrent exchange, comprising the following steps:
(1) adding 23m into the exchange tank3Adding 3300Kg of X molecular sieve dry base into the lithium-containing exchange liquid, heating to 85 ℃ with steam, and adding chemical water to control the solid content of the pre-exchange slurry to be 125 g/L. The reaction is carried out at constant temperature for 60 minutes. And (3) sending the pre-exchanged slurry to a DU type rubber belt type vacuum filter, and treating the dry basis weight of the molecular sieve by 500 Kg/h.
(2) The mass ratio of the lithium chloride solution (with the concentration of 110g/L) for the 9 th exchange of the DU type rubber belt type vacuum filter to the X molecular sieve dry basis is 0.33:1, the filtrate after the 9 th exchange is collected and conveyed to the previous stage of the rubber belt type vacuum filter by a pump for the 8 th exchange. And collecting the filtrate after the 8 th exchange, conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump, and performing the 7 th exchange. Collecting the filtrate after 7 th exchange, and pumping to the front stage of the adhesive tape type vacuum filter for 6 th exchange. Collecting the filtrate after the 6 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 5 th exchange. Collecting the filtrate after the 5 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 4 th exchange. Collecting the filtrate after the 4 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 3 rd exchange. Collecting the filtrate after the 3 rd exchange, and pumping the filtrate to the front stage of the adhesive tape type vacuum filter for the 2 nd exchange. Collecting the filtrate after the 2 nd exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 1 st exchange.
(3) Collecting chemical water at 80 ℃ for regeneration and washing of filter cloth of the DU-type rubber belt type vacuum filter, adding the chemical water into the 2 nd water washing, collecting filtrate after the 2 nd water washing, and conveying the filtrate to a lithium chloride dissolving tank by a pump for dissolving solid lithium chloride. The fresh lithium chloride prepared was used for the 9 th lithium exchange.
(4) And drying the washed X molecular sieve to obtain the improved lithium X molecular sieve raw powder.
Example 2
This example provides an industrial method for preparing lithium X molecular sieve by countercurrent exchange, comprising the following steps:
(1) adding 22m into the exchange tank3Adding 3157Kg of X molecular sieve dry basis into the lithium-containing exchange liquid, heating to 90 ℃ by using steam, and adding chemical water to control the solid content of the pre-exchange slurry to be 120 g/L. The reaction was carried out at constant temperature for 30 minutes. And (3) sending the pre-exchanged slurry to a DU type rubber belt type vacuum filter, and treating the dry basis weight of the molecular sieve to be 590 Kg/h.
(2) The mass ratio of the 12 th-grade lithium chloride solution (the concentration is 115g/L) of the DU type rubber belt type vacuum filter to the X molecular sieve dry basis is 0.35:1, the filtrate after the 12 th exchange is collected and conveyed to the previous stage of the rubber belt type vacuum filter by a pump for the 11 th exchange. Collecting the filtrate after the 11 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 10 th exchange. Collecting the filtrate after the 10 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 9 th exchange. And collecting the filtrate after the 9 th exchange, conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump, and performing the 8 th exchange. And collecting the filtrate after the 8 th exchange, conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump, and performing the 7 th exchange. Collecting the filtrate after 7 th exchange, and pumping to the front stage of the adhesive tape type vacuum filter for 6 th exchange. Collecting the filtrate after the 6 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 5 th exchange. Collecting the filtrate after the 5 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 4 th exchange. Collecting the filtrate after the 4 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 3 rd exchange. Collecting the filtrate after the 3 rd exchange, and pumping the filtrate to the front stage of the adhesive tape type vacuum filter for the 2 nd exchange. Collecting the filtrate after the 2 nd exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 1 st exchange.
(3) Collecting 95 ℃ chemical water for regeneration and washing of DU type rubber belt type vacuum filter cloth, adding the chemical water into the 2 nd water washing, collecting the filtrate after the 2 nd water washing, and conveying the filtrate to a lithium chloride dissolving tank by a pump for dissolving solid lithium chloride. The fresh lithium chloride prepared was used for the 12 th lithium exchange.
(4) And drying the washed X molecular sieve to obtain the improved lithium X molecular sieve raw powder.
Example 3
This example provides an industrial method for preparing lithium X molecular sieve by countercurrent exchange, comprising the following steps:
(1) adding 24m into the exchange tank3Adding 3460Kg molecular sieve dry basis of X into the lithium-containing exchange liquid, heating to 95 ℃ with steam, and adding chemical water to control the solid content of the pre-exchange slurry to be 120 g/L. The reaction was carried out at constant temperature for 30 minutes. And (3) sending the pre-exchanged slurry to a DU type rubber belt type vacuum filter, and treating the dry basis weight of the molecular sieve to be 550 Kg/h.
(2) The mass ratio of the 15 th-grade lithium chloride solution (the concentration is 120g/L) of the DU type rubber belt type vacuum filter to the X molecular sieve dry basis is 0.32:1, the filtrate after the 15 th exchange is collected and conveyed to the previous stage of the rubber belt type vacuum filter by a pump for the 14 th exchange. And collecting the filtrate after the 14 th exchange, conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump, and performing the 13 th exchange. Collecting the filtrate after 13 th exchange, pumping to the front stage of the adhesive tape type vacuum filter, collecting the filtrate after 12 th exchange … … and 6 th exchange, pumping to the front stage of the adhesive tape type vacuum filter, and performing 5 th exchange. Collecting the filtrate after the 5 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 4 th exchange. Collecting the filtrate after the 4 th exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 3 rd exchange. Collecting the filtrate after the 3 rd exchange, and pumping the filtrate to the front stage of the adhesive tape type vacuum filter for the 2 nd exchange. Collecting the filtrate after the 2 nd exchange, and conveying the filtrate to the front stage of the adhesive tape type vacuum filter by using a pump to perform the 1 st exchange. Collecting 90 ℃ chemical water for regeneration and washing of DU type rubber belt type vacuum filter cloth, adding the chemical water into the 2 nd water washing, collecting the filtrate after the 2 nd water washing, and conveying the filtrate to a lithium chloride dissolving tank by a pump for dissolving solid lithium chloride. The fresh lithium chloride prepared was used for the 15 th lithium exchange.
(4) And drying the washed X molecular sieve to obtain the improved lithium X molecular sieve raw powder.
Comparative example
This comparative example provides a lithium X molecular sieve prepared by the prior art method, the method being as follows:
LSX with K of 0.5M+The solution is displaced for 5 times to form K-LSX, which is then reacted with 1M NH4 +Solution displacement 5 times to form NH4-LSX，NH4-LSX is exchanged with a 5% lithium hydroxide solution to Li-LSX.
The improved lithium X molecular sieve prepared in the embodiment 1-3 of the invention is tested according to the following method:
firstly, the exchange degree:
it was analyzed by measuring the chemical composition using an X-ray fluorescence apparatus (model: Zsx Primus).
II, nitrogen adsorption:
a full-automatic specific surface and aperture analyzer (model TriStar3020) is adopted, and 79.1KPa is selected as a pressure point.
III, N2-O2Adsorption:
at room temperature and normal pressure, air passes through an oxygen-making molecular sieve adsorption column, gas after molecular sieve adsorption enters a mass spectrometer, the change of electric quantity is measured, and the peak top time difference is calculated according to the plotting of the time and the change of the electric quantity (representing concentration).
The performance test results are shown in table 1:
TABLE 1 Performance of the respective lithium-type molecular sieves
| Example 1 | Example 2 | Example 3 | Existing products | |
| SwitchingDegree of rotation | 99.1％ | 99.5％ | 99.2％ | 98.1％ |
| Nitrogen adsorption, 79.1KPa | 27.1 | 27.5 | 27.3 | 25.7 |
| N2-O2Adsorption peak time difference s | 112 | 116 | 113 | 91 |
As can be seen from Table 1, the product exchange degrees of the three lithium-type molecular sieves provided by the embodiment of the invention are all more than 99%, the nitrogen adsorption amounts are all more than 27, and N is2-O2The time difference of the adsorption peaks is above 112 s; compared with the existing products (the three parameters are respectively 98.1%, 25.7 and 91s), the product prepared by the method has the time difference of conversion, nitrogen adsorption and nitrogen-oxygen adsorption which are respectively improved by 1.4%, 7% and 27.5%. Therefore, the industrial method for preparing the lithium X molecular sieve by the countercurrent exchange has the advantages of high ion exchange degree, better nitrogen adsorption and better quality.
Finally, it should be noted that: the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An industrial method for preparing a lithium X molecular sieve by countercurrent exchange, which is characterized by comprising the following steps:
mixing X molecular sieve with Li+Mixing the recovered liquid, pre-exchanging and filtering;
with Li content+Carrying out 9-15 times of countercurrent exchange treatment on the pre-exchanged X molecular sieve under a vacuum condition by using an exchange liquid, and recovering filtrate generated after each time of countercurrent exchange treatment to serve as the Li-containing material+Carrying out next countercurrent exchange treatment on the exchange solution, and recovering the filtrate generated after the last countercurrent exchange treatment to be used as the recovery solution;
drying the X molecular sieve obtained after the countercurrent exchange treatment.
2. The industrial method for preparing the lithium X molecular sieve by the countercurrent exchange as claimed in claim 1, further comprising a step of performing countercurrent washing on the X molecular sieve for 2-4 times after the step of performing the countercurrent exchange treatment, wherein in the countercurrent washing process, a washing liquid generated after each time of the countercurrent washing is recovered for preparing the Li-containing molecular sieve with high concentration+And (4) exchanging the liquid.
3. The industrial method for preparing the lithium X molecular sieve by the countercurrent exchange according to claim 1 or 2, wherein the temperature of the pre-exchange is 80-95 ℃, and the exchange time is 30-60 min.
4. The industrial process for preparing lithium X molecular sieve by countercurrent exchange as claimed in claim 1, wherein during the pre-exchange, the X molecular sieve is mixed with Li+The solid content of the mixed solution formed by mixing the recovery liquid is 120-130 g/L.
5. The industrial process for preparing lithium X molecular sieve by countercurrent exchange according to claim 1, wherein during the countercurrent exchange treatment, the Li is contained+The temperature of the exchange liquid is 80-95 ℃, and the Li is firstly exchanged+The concentration of the exchange liquid is 110-120 g/L.
6. The industrial process for preparing lithium X molecular sieve by countercurrent exchange according to claim 5, wherein during the first countercurrent exchange treatment, the Li is contained+The mass ratio of the exchange liquid to the X molecular sieve dry basis is 0.32-0.35: 1.
7. The industrial method for preparing Li X molecular sieve by countercurrent exchange as claimed in claim 1, wherein the countercurrent exchange treatment is performed by a tape vacuum filter, and the dry basis weight of the tape vacuum filter for treating the X molecular sieve is 550 Kg/h.
8. The industrial method for preparing the lithium X molecular sieve by countercurrent exchange as claimed in claim 7, wherein the belt vacuum filter has 9-15 stages of filtrate conveying pipelines, each stage of filtrate conveying pipeline is provided with a filtrate conveying pump, and a heat exchanger is arranged at the outlet of the filtrate conveying pump.
9. The industrial method for preparing the lithium X molecular sieve by countercurrent exchange as claimed in claim 7, wherein the water used in the countercurrent water washing process is the water for washing the cloth regenerated from the filter cloth of the adhesive tape type vacuum filter, and the temperature of the water for washing is 80-95 ℃.
10. A lithium X molecular sieve prepared according to the industrial process of any one of claims 1 to 9.
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| CN101518749A (en) * | 2009-03-05 | 2009-09-02 | 华东理工大学 | Ion exchange process for multistage reverse flow zeolite molecular sieve of band filter |
| WO2010109477A2 (en) * | 2009-03-27 | 2010-09-30 | Council Of Scientific & Industrial Research | A process for the preparation of molecular sieve adsorbent for the size/shape selective adsorption of carbon dioxide from its gaseous mixture with nitrogen |
| CN102502694A (en) * | 2011-10-11 | 2012-06-20 | 于向真 | Li-modified X molecular sieve and preparation method thereof |
| CN102849754A (en) * | 2012-09-28 | 2013-01-02 | 上海恒业化工有限公司 | Ion exchange production method of molecular sieve |
| CN106732746A (en) * | 2016-12-07 | 2017-05-31 | 四川润和催化新材料股份有限公司 | A kind of method that catalytic cracking catalyst is prepared without ammonia process |
| CN111135787A (en) * | 2020-01-10 | 2020-05-12 | 四川润和催化新材料股份有限公司 | Preparation method of improved 3A molecular sieve raw powder |
| CN113772689A (en) * | 2021-09-23 | 2021-12-10 | 润和催化剂股份有限公司 | Preparation method of nitrogen-oxygen separation Li-LSX molecular sieve |
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| CN101518749A (en) * | 2009-03-05 | 2009-09-02 | 华东理工大学 | Ion exchange process for multistage reverse flow zeolite molecular sieve of band filter |
| WO2010109477A2 (en) * | 2009-03-27 | 2010-09-30 | Council Of Scientific & Industrial Research | A process for the preparation of molecular sieve adsorbent for the size/shape selective adsorption of carbon dioxide from its gaseous mixture with nitrogen |
| CN102502694A (en) * | 2011-10-11 | 2012-06-20 | 于向真 | Li-modified X molecular sieve and preparation method thereof |
| CN102849754A (en) * | 2012-09-28 | 2013-01-02 | 上海恒业化工有限公司 | Ion exchange production method of molecular sieve |
| CN106732746A (en) * | 2016-12-07 | 2017-05-31 | 四川润和催化新材料股份有限公司 | A kind of method that catalytic cracking catalyst is prepared without ammonia process |
| CN111135787A (en) * | 2020-01-10 | 2020-05-12 | 四川润和催化新材料股份有限公司 | Preparation method of improved 3A molecular sieve raw powder |
| CN113772689A (en) * | 2021-09-23 | 2021-12-10 | 润和催化剂股份有限公司 | Preparation method of nitrogen-oxygen separation Li-LSX molecular sieve |
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