CN105731476A - Preparation method of pillared saponite - Google Patents
Preparation method of pillared saponite Download PDFInfo
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- CN105731476A CN105731476A CN201410766178.7A CN201410766178A CN105731476A CN 105731476 A CN105731476 A CN 105731476A CN 201410766178 A CN201410766178 A CN 201410766178A CN 105731476 A CN105731476 A CN 105731476A
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Abstract
The invention discloses a preparation method of a pillared saponite, which includes the steps of: mixing an alkali source, a silicon source, an aluminium source, a magnesium source and water, and obtaining an initial gel; after the initial gel is thermally crystallized, filtering and washing obtained crystallization products, and obtaining a saponite filter cake; carrying out filtration after the acid treatment is carried out on the saponite filter cake in an acid solution, and obtaining an acid treated saponite; carrying out filtration after ammonium exchange is carried out on the acid treated saponite in an ammonium salt solution, and obtaining an ammonium exchange saponite; and carrying out aluminium crosslinking treatment on the ammonium exchange saponite by using an aluminium crosslinking agent, filtering and washing crosslinking products, and obtaining the pillared saponite. The preparation method of the pillared saponite is easy to operate. The obtained product has large specific surface and is suitable for large scale production.
Description
Technical field
The preparation method that the present invention relates to a kind of layer of post saponite.
Background technology
Layer post saponite is a kind of molecular sieve analog poromerics, there is two-dimentional gallery pore passage structure and suitable acid centre, its heat stability is high, and possesses the B-acid center required for the such as catalytic reaction such as isomerization, cracking and alkylation, obtains in acid catalysis field and studies widely.
Zhao Xiaohong et al. reports a kind of method that hydro-thermal prepares layer post saponite, and the method includes silicon source, aluminum source and magnesium source crystallization under hydrothermal conditions are generated saponite, then by the saponite of preparation through washing, ammonium exchange, the step such as dry and pillared, is prepared for a layer post saponite.Layer post saponite prepared by the method has good catalysis activity in n-decane hysomer.Yao Ming et al. also reports a layer hydrothermal preparing process for post saponite, and also discovery layer post saponite has layer unexistent strong acid center of post montmorillonite.
In current layer post saponite preparation method, preparation process is more, preparation method is also all more complicated, and it is fine to operate requirement, it is required in the middle of preparation process being dried or the step such as roasting, not only have impact on the performance of product, and because the intermediate after drying steps is required for when carrying out next preparation process being ground processing, to ensure the requirement of relatively high dispersive, not only complex steps, and add preparation cost.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of layer of post saponite, the method is simple compared with the preparation method of existing layer post saponite, step is few, and without refinement, relatively high-ratio surface and large hole can be kept to hold, and saponite crosslinked after without the sodium content layer post saponite not higher than 0.05% can be obtained through ammonium exchange.
To achieve these goals, the preparation method that the present invention provides a kind of layer of post saponite, the method includes: a, according to certain proportioning raw materials by alkali source, silicon source, aluminum source, magnesium source and water mix, obtain Primogel；Wherein 0.2≤x≤2；B, by after the Primogel hydrothermal crystallizing of gained in step a, the crystallization product filtration washing that will obtain, obtain saponite filter cake；C, carry out the saponite filter cake of gained in step b filtering after acid treatment in acid solution, obtain acid treatment saponite；D, carry out the acid treatment saponite of gained in step c filtering after ammonium exchange in ammonium salt solution, obtain ammonium exchange saponite；E, by step d gained ammonium exchange saponite aluminum crosslinker carry out aluminium cross-linked process, by cross-linking products filtration washing, obtain a layer post saponite.
Preferably, wherein, in step b, the described saponite filter cake of gained was not dried process before carrying out acid treatment described in step c.
Preferably, wherein, in step c, the described acid treatment saponite of gained was not dried process before carrying out ammonium exchange described in step d.
Preferably, wherein, in step d, the described ammonium exchange saponite of gained was not dried process before carrying out crosslinking Treatment described in step e.
Preferably, wherein, described alkali source is at least one in sodium hydroxide, sodium bicarbonate and sodium carbonate；Described silicon source is sodium silicate and/or sodium metasilicate；Source of aluminium is at least one in aluminum sulfate, aluminum nitrate, aluminum chloride and sodium metaaluminate；Described magnesium source is at least one in magnesium chloride, magnesium sulfate, magnesium nitrate, magnesium hydroxide and magnesium oxide.
Preferably, wherein silicon source, aluminum source, magnesium source is respectively with SiO2、Al2O3, MgO meter, its each feed molar proportioning is: (8.0-x) SiO2:(x/2)Al2O3:6.0MgO:(400-1000)H2O, wherein 0.2≤x≤2,
The amount of alkali source is be enough to make the mixture 10 < pH < 11 of step (a)；
It is highly preferred that wherein alkali source, silicon source, aluminum source, magnesium source is respectively with Na2O、SiO2、Al2O3, MgO meter, its each feed molar proportioning is: 0.65Na2O:(8.0-x)SiO2:(x/2)Al2O3:6.0MgO:(400-1000)H2O, wherein 0.2≤x≤2.
Preferably, wherein, the condition of hydrothermal crystallizing described in step b is: crystallization temperature is 100-400 DEG C, and crystallization time is 2-72 hour.
Preferably, wherein, acid solution described in step c is at least one in hydrochloric acid solution, sulfuric acid solution and salpeter solution, and in acid solution, proton molar concentration is 0.1-2mol/L.
Preferably, wherein, the condition of acid treatment described in step c is: H in acid solution+With the mol ratio 0.2-5 of Al in saponite, it is preferable that 1.75-3.5, acid treatment temperature be room temperature to 60 DEG C, the acid treatment time is 0.5-2 hour.
Preferably, wherein, ammonium salt described in step d is at least one in ammonium sulfate, ammonium chloride and ammonium nitrate.
Preferably, wherein, described in step d, the condition of ammonium exchange is: NH4 +: the Al that described acid treatment saponite is total2O3: the mol ratio of water is (5-20): 1:(100-1000), it is preferable that (6-12): 1:500, ammonium exchange temperature be room temperature to 90 DEG C, ammonium swap time is 0.5-2 hour.
Preferably, wherein, aluminum crosslinker described in step e is Al13 7+The aqueous solution of polymerizing cationically, in aluminum crosslinker, the concentration of Al is 0.1-0.4mol/L.
Preferably, wherein, the preparation process of described aluminum crosslinker includes: be slowly added dropwise in the liquor alumini chloridi of 0.1-2mol/L by the sodium hydroxide solution of 0.1-2mol/L, then stirs 2-48 hour at 30-80 DEG C, wherein, the pH controlling obtained aluminum crosslinker is 4.1-4.4.
Preferably, wherein, the condition of crosslinking Treatment described in step e includes: the mol ratio of the silicon in saponite and the aluminum in aluminum crosslinker is (0.2-5): 1, and saponite crosslinking temperature is 60-90 DEG C, and crosslinking time is 1-2 hour.
Compared with the preparation method of existing layer post saponite, the preparation method of the present invention does not include drying steps in preparation process, not only shorten preparation flow, avoid saponite agglomeration in dry run, from without process of lapping, and before aluminium cross-linked process introduce acid treatment step and ammonium exchange step makes saponite swelling and synusia peel off, the non-framework aluminum in saponite can be removed on the one hand, the Na ion in saponite can be removed and reduce the impact of strong alkaline substance on the other hand, thus improving aluminium cross-linked efficiency, improve the hole structural property of aluminum post saponite.Layer post saponite prepared by the inventive method, after aluminium cross-linked process, it is not necessary to again carry out ammonium exchange, can be down to the Na content in saponite not higher than 0.05%, and operation fineness is less demanding, and products obtained therefrom specific surface is big, is suitable for large-scale production.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The preparation method that the present invention provides a kind of layer of post saponite, the method includes: a, according to certain proportioning raw materials by alkali source, silicon source, aluminum source, magnesium source and water mix, obtain Primogel；Wherein 0.2≤x≤2；B, by after the Primogel hydrothermal crystallizing of gained in step a, the crystallization product filtration washing that will obtain, obtain saponite filter cake；C, carry out the saponite filter cake of gained in step b filtering after acid treatment in acid solution, obtain acid treatment saponite；D, carry out the acid treatment saponite of gained in step c filtering after ammonium exchange in ammonium salt solution, obtain ammonium exchange saponite；E, by step d gained ammonium exchange saponite aluminum crosslinker carry out aluminium cross-linked process, by cross-linking products filtration washing, obtain a layer post saponite.
Owing to the layer post saponite of synthetic belongs to bloating tendency clay-like material, can with water generation imbibition, filter cake solid content after filtration is very low by (about 20%, apparent expansion degree and determine), after dry, volume contraction is violent, and in lump shape, need to additionally grind, saponite is processed the work such as modification application to reality and brings a lot of inconvenience by this.Therefore, according to the specific embodiment of the present invention, in step b, the described saponite filter cake of gained can not be dried process before carrying out acid treatment described in step c；In step c, the described acid treatment saponite of gained can not be dried process before carrying out ammonium exchange described in step d；In step d, the described ammonium exchange saponite of gained can not be dried process before carrying out crosslinking Treatment described in step e；In step e the layer post saponite of gained due to its Na content relatively low, it is possible to be directly used in the preparation of catalyst, it is also possible to store for future use.
According to the present invention, described alkali source, aluminum source, magnesium source and silicon source are well known to those skilled in the art, and there is no particular limitation to it for the present invention；Such as, described alkali source can be at least one in sodium hydroxide, sodium bicarbonate and sodium carbonate；Described silicon source can be sodium silicate and/or sodium metasilicate；Source of aluminium can be at least one in aluminum sulfate, aluminum nitrate, aluminum chloride and sodium metaaluminate；Described magnesium source can be at least one in magnesium chloride, magnesium sulfate, magnesium nitrate, magnesium hydroxide and magnesium oxide.
Wherein silicon source, aluminum source, magnesium source is respectively with SiO2、Al2O3, MgO meter, its each feed molar proportioning is: (8.0-x) SiO2:(x/2)Al2O3:6.0MgO:(400-1000)H2O, wherein 0.2≤x≤2,
The amount of alkali source is be enough to make the mixture 10 < pH < 11 of step (a)；
It is highly preferred that wherein alkali source, silicon source, aluminum source, magnesium source is respectively with Na2O、SiO2、Al2O3, MgO meter, its each feed molar proportioning is: 0.65Na2O:(8.0-x) SiO2:(x/2)Al2O3:6.0MgO:(400-1000)H2O, wherein 0.2≤x≤2.
Wherein it is desired to illustrate, the proportioning raw materials 0.65Na in the present invention2O:(8.0-x)SiO2:(x/2)Al2O3:6.0MgO:(400-1000)H2Na in O2What O represented is the basicity of mixture, and it does not include the part neutralized by acid, is not namely represent Na content actual in Primogel (but the Na that the XRF elementary analysis of the last layer post saponite product prepared obtains2O content refers to the Na content that product is actual), this is well-known to those skilled in the art；Additionally, those skilled in the art also will appreciate that, above-mentioned silicon source, aluminum source, magnesium source proportioning system determine according to the composition according to saponite, change in actual certain limit.X in ratio proportioning raw materials represents the layer charge number of saponite, 0.2≤x≤2, the ion-exchange capacity of the more big explanation saponite of numerical value more strong.By changing saponite synthesis condition, it is possible to obtain the product of different x value.
According to the present invention, the condition of described hydrothermal crystallizing is well-known to those skilled in the art, and there is no particular limitation to it for the present invention；Such as, the condition of hydrothermal crystallizing described in step b can be: crystallization temperature is 100-400 DEG C, and crystallization time is 2-72 hour.The crystallization product of gained carries out repeatedly washing and filtering, and wherein, the pH value of the last filtrate filtered can at about 6-11.
According to the present invention, described acid treatment refers to and is distributed in acid solution and carries out pickling by the described saponite filter cake prepared by step b, the alkalescence of described saponite can be reduced, remove the part Na ion in saponite, and the non-framework aluminum in saponite can be removed, even elimination part framework aluminum, aluminium cross-linked ready in step e.Wherein, acid solution described in step c can be at least one in hydrochloric acid solution, sulfuric acid solution and salpeter solution, and in acid solution, proton molar concentration can be 0.1-2mol/L.The condition of described acid treatment can be: H in acid solution+Be 0.2-5 with the mol ratio of Al in saponite, acid treatment temperature be room temperature to 60 DEG C, the acid treatment time is 0.5-2 hour.
According to the present invention, the exchange of described ammonium is also well-known to those skilled in the art, refers to and is dispersed in ammonium salt solution and carries out ammonium exchange by the described acid treatment saponite obtained in step c, it is possible to the Na ion in elimination saponite further.Wherein, described ammonium salt can be at least one in ammonium sulfate, ammonium chloride and ammonium nitrate, and the condition of ammonium exchange can be: NH4 +: the Al that described acid treatment saponite is total2O3: the mol ratio of water is (5-20): 1:(100-1000), it is preferable that (6-12): 1:500, ammonium exchange temperature be room temperature to 90 DEG C, ammonium swap time is 0.5-2 hour.
According to the present invention, described aluminium cross-linked process is well-known to those skilled in the art, refers to and is dispersed in aluminum crosslinker to carry out aluminium cross-linked by the ammonium exchange saponite of gained in step d, and wherein, described aluminum crosslinker can be Al13 7+The aqueous solution of polymerizing cationically, wherein, Al13 7+Polymerizing cationically is generally with chemical formula [Al13O4(OH)24(H2O)12]7+Representing, in aluminum crosslinker, the concentration of Al is generally 0.1-0.4mol/L.The preparation method of described aluminum crosslinker is also well-known to those skilled in the art, for instance, it is possible to the sodium hydroxide solution of 0.1-2mol/L is slowly added dropwise in the liquor alumini chloridi of 0.1-2mol/L, then at 30-80 DEG C, stirs preparation in 2-48 hour and obtain.In general, the pH of gained aluminum crosslinker controls at about 4.1-4.4.The condition of described crosslinking Treatment can be: the mol ratio of the silicon in saponite and the aluminum in aluminum crosslinker is (0.2-5): 1, and saponite crosslinking temperature is 60-90 DEG C, and crosslinking time is 1-2 hour.
Following by embodiment, the detailed description of the invention of the inventive method is further detailed, but therefore the present invention is not limited to.In the embodiment of the present invention, agents useful for same is analytical pure, and instrument equipment is laboratory routine instrument device.
In each embodiment and comparative example, total specific surface area S of the layer post saponite product preparedtotal, micropore specific area Smicro, total pore volume VtotalWith micropore pore volume VmicroMeasuring by the method for nitrogen adsorption-desorption, and calculated by BET and t-plot analysis method, concrete grammar is referred to " Pore Characterization of porous material and analysis thereof ", author: Cui Jingjie, He Wen, Liao Shijun, Xia Xi, periodical: material Leader, reign title and reel number: the 23rd volume the 7th phase in 2009.Constituent content Na2O、MgO、SiO2And Al2O3Method X-ray fluorescence spectra analytic process (XRF) measures, and concrete grammar is referred to " synthesis and sign " containing magnesium smelting, author: Zhao Qian, Qiao Xiuli, WANG Xiaohong, Jiang Yinhua, Zheng Ningning, periodical: mining industry research and development, reign title and reel number: the 26th volume the 3rd phase in 2006.
In each embodiment and comparative example, the preparation process of the aluminum crosslinker used is: under Electromagnetic Heating stirring condition, and the NaOH solution of 0.4mol/L is slowly added dropwise 80 DEG C, the AlCl of 1.0mol/L3In solution, making pH is between 4.1-4.4, stirs 24h, is cooled to room temperature standby.The Al concentration of obtained aluminum crosslinker is 0.14mol/L.
Embodiment 1
The preparation method that embodiment 1 is the layer post saponite according to the present invention is prepared a layer post saponite, according to 17.9NaOH:15.6NaHCO3:7.0Na2SiO3:1.0AlCl3:6.0MgCl2:600H2O (wherein Na2The computational methods of O and basicity are: 1 mole of AlCl3Consume 3 moles of NaOH and generate Al2O3·3H2O, 6 moles of MgCl2Consume 12 moles of NaOH and generate MgO H2O, remaining 17.9-15=2.9 moles of NaOH；7.0Na2SiO3Modulus is 1, is equivalent to 7.0Na2O:7.0SiO2, 7Na2O+14NaHCO3=14Na2CO3, remaining 15.6-14=1.6 mole of NaHCO3React with NaOH；1.6NaOH+1.6NaHCO3=1.6Na2CO3, remaining 2.9-1.6=1.3NaOH, it is 0.65Na2Sodium hydroxide, sodium metasilicate, sodium bicarbonate and proportioning are that 500 deionized waters are configured to solution A by proportioning raw materials O), it is that 100 deionized waters are configured to solution B by aluminum chloride, magnesium chloride and proportioning again, under 60 DEG C of water bath condition, B is joined in A, stir 1 hour, obtain Primogel；Primogel is put in reactor hydrothermal crystallizing 24 hours at 300 DEG C, and the crystallization product deionized water obtained carries out repeatedly washing and filters, it is ensured that the pH value of filtrate is less than 11；It is dispersed in the hydrochloric acid solution of 0.5mol/L by the saponite filter cake of gained at room temperature to stir 1 hour, H in acid solution+It is 1.75 with the mol ratio of Al in saponite, the suspension after acid treatment is filtered, obtain acid treatment saponite；Acid treatment saponite is dispersed in ammonium chloride solution, and is warmed up to 80 DEG C of stirrings 0.5 hour, NH therein4 +: the Al that described acid treatment saponite is total2O3: the mol ratio of water is 6:1:360, and the suspension after being exchanged by ammonium filters, and obtains ammonium exchange saponite；Ammonium is exchanged saponite and at 120 DEG C, is dried process no less than 12 hours, the block saponite obtained is dispersed in the aluminum crosslinker prepared after being ground, it is warmed up to 80 DEG C to stir 1 hour, the mol ratio of the silicon in saponite and the aluminum in aluminum crosslinker is 1, suspension after crosslinking is filtered, then filtering with after deionized water wash 1 time, the pH value of filtrate is 4.3, obtains a layer post saponite S1 again.BET and the XRF data of prepared layer post saponite S1 are as shown in table 1.
Embodiment 2
The preparation method that embodiment 2 is the layer post saponite according to the present invention is prepared a layer post saponite, according to 17.9NaOH:15.6NaHCO3:7.0Na2SiO3:1.0AlCl3:6.0MgCl2:600H2Sodium hydroxide, sodium metasilicate, sodium bicarbonate and proportioning are that 500 deionized waters are configured to solution A by the proportioning raw materials of O, it is that 100 deionized waters are configured to solution B by aluminum chloride, magnesium chloride and proportioning again, under 60 DEG C of water bath condition, B is joined in A, stir 1 hour, obtain Primogel；Primogel is put in reactor hydrothermal crystallizing 24 hours at 300 DEG C, and the crystallization product deionized water obtained carries out repeatedly washing and filters, it is ensured that the pH value of filtrate is less than 11；The saponite filter cake obtained is dispersed in the hydrochloric acid solution of 1mol/L, is warmed up to 50 DEG C and stirs 1 hour, H in acid solution+It is 3.5 with the mol ratio of Al in saponite, the suspension after acid treatment is filtered, obtain acid treatment saponite；Acid treatment saponite is dispersed in ammonium chloride solution, and is warmed up to 80 DEG C of stirrings 0.5 hour, NH4 +: the Al that described acid treatment saponite is total2O3: the mol ratio of water is 12:1:360, and the suspension after being exchanged by ammonium filters, and obtains ammonium exchange saponite；Ammonium is exchanged saponite and is dispersed in the aluminum crosslinker prepared, it is warmed up to 80 DEG C to stir 1 hour, the mol ratio of the silicon in saponite and the aluminum in aluminum crosslinker is 1, suspension after crosslinking is filtered, then filter with after deionized water wash 1 time, the pH value of filtrate is 4.2, obtains a layer post saponite S2.BET and the XRF data of prepared layer post saponite S2 are as shown in table 1.
Comparative example 1
Comparative example 1 adopts traditional method to prepare layer post saponite, specifically comprises the following steps that saponite synthesis, washing and filtering, dry, grinding distribution, aluminium cross-linked, drying and roasting, ammonium exchange and drying and roasting.According to 17.9NaOH:15.6NaHCO3:7.0Na2SiO3:1.0AlCl3:6.0MgCl2:600H2Sodium hydroxide, sodium metasilicate, sodium bicarbonate and proportioning are that 500 deionized waters are configured to solution A by the proportioning raw materials of O, it is that 100 deionized waters are configured to solution B by aluminum chloride, magnesium chloride and proportioning again, under 60 DEG C of water bath condition, B is joined in A, stir 1 hour, obtain Primogel；Primogel is put in reactor hydrothermal crystallizing 24 hours at 300 DEG C, and the crystallization product deionized water obtained carries out repeatedly washing and filters, it is ensured that the pH value of filtrate is less than 9；Process will be dried no less than 12 hours at the saponite filter cake 120 DEG C obtained, the block saponite obtained is dispersed in the aluminum crosslinker prepared after being ground, it is warmed up to 80 DEG C to stir 1 hour, the mol ratio of the silicon in saponite and the aluminum in aluminum crosslinker is 1, suspension after crosslinking is filtered, then it is dried at 120 DEG C after no less than 12 hours, at 500 DEG C, carries out roasting 2 hours；Saponite after roasting is dispersed in ammonium chloride solution, and is warmed up to 80 DEG C of stirrings 0.5 hour, NH4 +: the Al that described acid treatment saponite is total2O3: the mol ratio of water is 12:1:360, and the suspension after being exchanged by ammonium filters, and is then dried at 120 DEG C no less than 12 hours, obtains a layer post saponite D1 at 500 DEG C after carrying out roasting 2 hours.BET and the XRF data of prepared layer post saponite D1 are as shown in table 1.
Comparative example 2
Comparative example 2 adopts wet feed method directly to prepare a layer post saponite by the method for comparative example 1, specifically comprises the following steps that saponite synthesis, washing and filtering, dispersion, aluminium cross-linked, ammonium exchange and drying and roasting.According to 17.9NaOH:15.6NaHCO3:7.0Na2SiO3:1.0AlCl3:6.0MgCl2:600H2Sodium hydroxide, sodium metasilicate, sodium bicarbonate and proportioning are that 500 deionized waters are configured to solution A by the proportioning raw materials of O, it is that 100 deionized waters are configured to solution B by aluminum chloride, magnesium chloride and proportioning again, under 60 DEG C of water bath condition, B is joined in A, stir 1 hour, obtain Primogel；Primogel is put in reactor hydrothermal crystallizing 24 hours at 300 DEG C, and the crystallization product deionized water obtained carries out repeatedly washing and filters, it is ensured that the pH value of filtrate is less than 9；Being dispersed in the aluminum crosslinker prepared by the saponite filter cake obtained, be warmed up to 80 DEG C and stir 1 hour, the mol ratio of the silicon in saponite and the aluminum in aluminum crosslinker is 1, suspension after crosslinking is filtered, filter cake is dispersed in ammonium chloride solution, and is warmed up to 80 DEG C of stirrings 0.5 hour, NH4 +: the Al that described acid treatment saponite is total2O3: the mol ratio of water is 12:1:360, and the suspension after being exchanged by ammonium filters, and is then dried at 120 DEG C no less than 12 hours, obtains a layer post saponite D2 at 500 DEG C after carrying out roasting 2 hours.BET and the XRF data of prepared layer post saponite D2 are as shown in table 1.
Comparative example 3
The preparation method according to the layer post saponite of the present invention of the preparation method of the layer post saponite of comparative example 3 and previous embodiment 1 is distinctive in that and does not include acid treatment step, after gained saponite sample washing and filtering, do not dry, it is made directly aluminium cross-linked step, other preparation process is identical with embodiment 1 with condition, and BET and the XRF data of prepared layer post saponite D3 are as shown in table 1.
Comparative example 4
The preparation method according to the layer post saponite of the present invention of the preparation method of the layer post saponite of comparative example 4 and previous embodiment 2 is distinctive in that and does not include acid treatment step, after gained saponite sample washing and filtering, do not dry, it is made directly aluminium cross-linked step, other preparation process is identical with embodiment 2 with condition, and BET and the XRF data of prepared layer post saponite D4 are as shown in table 1.
From table 1 data it can be seen that in comparative example 1,2, ammonium friendship processes in the last step, the Na of product D1 and D22Although O content is very low, but its specific surface character is less better, and its preparation process is complicated, controls to require height to operation, and in comparative example 3,4, ammonium friendship processes before being put into the crosslinking of aluminum post, the Na of product D3 and D42O content is all higher, and their specific surface and pore volume character are all relatively poor.Adopt layer post saponite prepared by the inventive method, there is specific surface area and pore volume is big and sodium content is relatively low feature simultaneously, and preparation process is simple, operation controls easily, it is easy to carry out industrialized production.
Table 1
| S1 | S2 | D1 | D2 | D3 | D4 | |
| BET | ||||||
| Total specific surface area (m2/g) | 340.0 | 346.2 | 292.9 | 235.3 | 284.7 | 289.5 |
| Micropore specific area (m2/g) | 97.5 | 102.9 | 87.4 | 60.2 | 78.6 | 85.4 |
| Total pore volume (cm3/g) | 0.275 | 0.289 | 0.248 | 0.272 | 0.280 | 0.267 |
| Micropore pore volume (cm3/g) | 0.030 | 0.035 | 0.029 | 0.018 | 0.025 | 0.022 |
| XRF | ||||||
| Na2O (%) | 0.03 | 0.03 | 0.01 | 0.05 | 0.55 | 0.23 |
| MgO (%) | 26.71 | 26.27 | 27.59 | 28.15 | 27.74 | 27.32 |
| SiO2(%) | 50.10 | 49.47 | 51.05 | 51.29 | 48.51 | 50.27 |
| Al2O3(%) | 22.45 | 23.39 | 20.73 | 19.38 | 21.98 | 21.21 |
Claims (13)
1. a preparation method for layer post saponite, the method includes:
A, according to certain proportioning raw materials by alkali source, silicon source, aluminum source, magnesium source and water mix, obtain Primogel；
B, by after the Primogel hydrothermal crystallizing of gained in step a, the crystallization product filtration washing that will obtain, obtain saponite filter cake；
C, carry out the saponite filter cake of gained in step b filtering after acid treatment in acid solution, obtain acid treatment saponite；
D, carry out the acid treatment saponite of gained in step c filtering after ammonium exchange in ammonium salt solution, obtain ammonium exchange saponite；
E, by step d gained ammonium exchange saponite aluminum crosslinker carry out aluminium cross-linked process, by cross-linking products filtration washing, obtain a layer post saponite.
2. method according to claim 1, wherein, in step b, the described saponite filter cake of gained was not dried process before carrying out acid treatment described in step c.
3. method according to claim 1, wherein, in step c, the described acid treatment saponite of gained was not dried process before carrying out ammonium exchange described in step d.
4. method according to claim 1, wherein, in step d, the described ammonium exchange saponite of gained was not dried process before carrying out crosslinking Treatment described in step e.
5. method according to claim 1, wherein, described alkali source is at least one in sodium hydroxide, sodium bicarbonate and sodium carbonate；Described silicon source is sodium silicate and/or sodium metasilicate；Source of aluminium is at least one in aluminum sulfate, aluminum nitrate, aluminum chloride and sodium metaaluminate；Described magnesium source is at least one in magnesium chloride, magnesium sulfate, magnesium nitrate, magnesium hydroxide and magnesium oxide；
Wherein silicon source, aluminum source, magnesium source is respectively with SiO2、Al2O3, MgO meter, its each feed molar proportioning is: (8.0-x) SiO2:(x/2)Al2O3:6.0MgO:(400-1000)H2O, wherein 0.2≤x≤2,
The amount of alkali source is be enough to make the mixture 10 < pH < 11 of step (a)；
Preferably, wherein alkali source, silicon source, aluminum source, magnesium source is respectively with Na2O、SiO2、Al2O3, MgO meter, its each feed molar proportioning is: 0.65Na2O:(8.0-x)SiO2:(x/2)Al2O3:6.0MgO:(400-1000)H2O, wherein 0.2≤x≤2.
6. method according to claim 1, wherein, the condition of hydrothermal crystallizing described in step b is: crystallization temperature is 100-400 DEG C, and crystallization time is 2-72 hour.
7. method according to claim 1, wherein, acid solution described in step c is at least one in hydrochloric acid solution, sulfuric acid solution and salpeter solution, and in acid solution, proton molar concentration is 0.1-2mol/L.
8. method according to claim 1, wherein, the condition of acid treatment described in step c is: H in acid solution+With the mol ratio 0.2-5 of Al in saponite, it is preferable that 1.75-3.5, acid treatment temperature be room temperature to 60 DEG C, the acid treatment time is 0.5-2 hour.
9. method according to claim 1, wherein, ammonium salt described in step d is at least one in ammonium sulfate, ammonium chloride and ammonium nitrate.
10. method according to claim 1, wherein, described in step d, the condition of ammonium exchange is: NH4 +: the Al that described acid treatment saponite is total2O3: the mol ratio of water is (5-20): 1:(100-1000), it is preferable that (6-12): 1:500, ammonium exchange temperature be room temperature to 90 DEG C, ammonium swap time is 0.5-2 hour.
11. method according to claim 1, wherein, aluminum crosslinker described in step e is Al13 7+The aqueous solution of polymerizing cationically, in aluminum crosslinker, the concentration of Al is 0.1-0.4mol/L.
12. the method according to claim 1 or 11, wherein, the preparation process of described aluminum crosslinker includes: be slowly added dropwise in the liquor alumini chloridi of 0.1-2mol/L by the sodium hydroxide solution of 0.1-2mol/L, then stir 2-48 hour at 30-80 DEG C, wherein, the pH controlling obtained aluminum crosslinker is 4.1-4.4.
13. method according to claim 1, wherein, the condition of crosslinking Treatment described in step e includes: the mol ratio of the silicon in saponite and the aluminum in aluminum crosslinker is (0.2-5): 1, and saponite crosslinking temperature is 60-90 DEG C, and crosslinking time is 1-2 hour.
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| CN108946749B (en) * | 2018-07-20 | 2021-04-02 | 东北大学 | Method for preparing saponite crystal under hydrothermal condition |
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