CN1157398C - A molecular sieve type organic iron phosphonate crystal with pore structure and preparation method thereof - Google Patents
A molecular sieve type organic iron phosphonate crystal with pore structure and preparation method thereof Download PDFInfo
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- CN1157398C CN1157398C CNB011206861A CN01120686A CN1157398C CN 1157398 C CN1157398 C CN 1157398C CN B011206861 A CNB011206861 A CN B011206861A CN 01120686 A CN01120686 A CN 01120686A CN 1157398 C CN1157398 C CN 1157398C
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Abstract
一种具有孔道结构的分子筛型有机膦酸铁晶体，其特征在于无水化学组成由下述化学式(1)表示：化学式(1)：(Fe2O3)·(RPO2)x，其中R表示与磷原子相连的C1-C4烷基，x为RPO2的数目，其范围为2.0≤x≤3.6。具有良好的热稳定性，其孔径和孔道形状可通过改变原料种类加以控制。这种晶体可用作分离吸附剂、催化剂、填料和色谱柱担体等。另外，该有机膦酸铁晶体的制备方法是采用水热合成方法，在密闭合成釜内使合成原料铁源、磷源在溶剂存在下于80-350℃温度内进行晶化反应。A molecular sieve type organic iron phosphonate crystal with a pore structure, characterized in that the anhydrous chemical composition is represented by the following chemical formula (1): chemical formula (1): (Fe 2 O 3 )·(RPO 2 ) x , where R Represents the C 1 -C 4 alkyl group connected to the phosphorus atom, x is the number of RPO 2 , and its range is 2.0≤x≤3.6. It has good thermal stability, and its pore size and channel shape can be controlled by changing the type of raw material. This crystal can be used as separation adsorbent, catalyst, filler and chromatographic column support, etc. In addition, the preparation method of the organic iron phosphonate crystal adopts a hydrothermal synthesis method, and the synthesis raw material iron source and phosphorus source are crystallized at a temperature of 80-350 DEG C in the presence of a solvent in a closed synthesis kettle.
Description
Technical field
The present invention relates to the porousness organic ferric phosphonate crystal of its aperture of a class and duct controllable shapes system.
Background technology
Molecular sieve is the inorganic poromerics that a class has the regular pore canal structure, except that the Si-Al zeolite molecular sieve of natural formation, the sial type zeolite molecular sieve of existing tens of kinds of synthetic, because they on structure and performance, have been widely used in every field such as catalysis, absorption and ion-exchange.In application, molecular screen material is constantly proposed the new performance and the requirement of structure, promoted the development of novel molecular sieve type poromerics again.
By the AlPO of kind surplus in the of synthetic 20 first such as S.T.Wilson
4-n series phosphate aluminium molecular sieve, its skeleton is made of phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron fully, broken the tradition that zeolite-type molecular sieves is made of silicon-oxy tetrahedron and aluminum-oxygen tetrahedron, in its building-up process, add different template, can synthesize different skeleton structures (U.S.Patent No.4,310,440; 1982).The effective pore radius of these phosphate aluminium molecular sieves is 0.3～1.0nm, can be used as sorbent material and porous catalyst carrier.After this, there is multiple phosphate aluminium molecular sieve to be synthesized out again.
Have again thereafter report synthesize SAPO series molecular sieve (U.S.Patent 4,440,871; 1984), the AlPO molecular sieve of multiple Transition metal substituted (U.S.Patent 4,554,143; 1985) and multiple phosphate molecule sieve etc.In these molecular sieves, B, As, Si, Be, Zn, Co, Mn, V, Cr, Ti, Ga partly or entirely replace aluminium atom in the skeleton, all useful as catalysts, sorbent material and ion-exchanger etc.
(JP 68026/94 for organic phospho acid aluminum molecular screen by report such as K.Maeda in 1994; 1994 and EP 0671,403, A1; 1995) be the complex type molecular sieve that a class has inorganic phosphorus aluminium skeleton and the duct inwall that organic group was constituted that links to each other with skeleton with covalent linkage, can be used as organic sorbent material, chromatogram carrier and catalyzer etc.
So far, existing comprise that the multiple element of carbon can enter the skeleton of molecular sieve, wherein multiple metallic cation can be used as the main component of skeleton.Yet ferro element enters framework of molecular sieve as a kind of minor consistuent always, and except that a kind of cacoxenite with pore passage structure of natural generation, artificial the synthesizing with iron of not appearing in the newspapers is the molecular sieve of main skeleton formation element.
Summary of the invention
The present inventor has in depth studied the porousness organic ferric phosphonate crystal of its aperture and duct controllable shapes system, discovery with organic phospho acid and iron-bearing material with water or/and organic solvent mix, and mixture placed the pressurized vessel internal heating, but crystallization is the porousness organic ferric phosphonate crystal of a series of its apertures and duct controllable shapes system under autogenous pressure, its duct inwall is made up of the organic group ordered arrangement, and these organic groups connect with inorganic skeleton with covalent linkage.The present invention is fully with the above-mentioned basis that is found to be, specifically,
The invention provides:
(1) a kind of heat-stable molecular sieve type organic ferric phosphonate crystal with cellular structure is characterized in that chemical constitution represents with chemical formula (I):
Chemical formula (I) (Fe
2O
3) (RPO
2)
x
Wherein R represents the alkyl that links to each other with phosphorus atom, and x is RPO
2Number, its scope is
2.0≤x≤3.6。
And, having the pore passage structure of homogeneous in the crystalline structure, the diameter range in duct is for approximately
0.26nm to 1.2nm.
(2) molecular sieve type organic ferric phosphonate crystal of indication in above-mentioned (1), it is the 1-4 alkyl that the alkyl R in its chemical formula (I) represents carbon number, for example, methyl, ethyl, propyl group or butyl, and be preferably methyl.
(3) the best scope of X of indication is 2.4≤X≤3.2 in above-mentioned (1).
(4) molecular sieve type organic ferric phosphonate crystal of indication in above-mentioned (1)-(3) is characterized in that the feature d value among the X ray polycrystalline diffraction result shown in table 1 or table 2.
Table 1
| 2θ | d | Relative intensity |
| 6.75-7.05 7.58-7.88 13.78-20.08 14.22-14.52 15.42-15.72 22.25-22.55 25.14-25.44 | 12.96-12.36 11.61-11.21 6.43-6.27 6.23-6.08 5.74-5.62 3.99-3.92 3.53-3.48 | 1000 80-600 70-500 70-500 100-800 60-400 60-400 |
Table 2
| 2θ | d | Relative intensity |
| 11.07-11.77 18.63-19.33 19.51-20.21 24.70-25.40 28.06-28.76 | 7.86-7.66 4.72-4.64 4.52-4.44 3.58-3.53 3.15-3.10 | 1000 50-200 200-500 50-200 50-150 |
In the present invention, " organic ferric phosphonate " refers in particular to a kind of molysite of oxygen acid of phosphorus, and in the oxygen acid of this phosphorus, the former covalent linkage that gives of phosphorus links to each other with an organic group.
In organic ferric phosphonate crystal of the present invention, inner pore passage structure links to each other with covalent linkage with inorganic skeleton by organic group and is built into.The pore structure of traditional molecular sieve is determined by the Sauerstoffatom number of forming the duct inwall, and the intervention of organic group makes that the generation type of pore structure is more flexible and diversified; Organic group is arranged in the inwall in duct, and links to each other with the inorganic phosphorus iron skeleton with covalent linkage, guarantees that its crystalline structure has certain thermostability; Iron ion has multiple ligancy and becomes the key mode with multiple.These all make organic ferric phosphonate crystal be synthesized under hydrothermal condition, and the size in hole is easy to regulation and control.
In organic ferric phosphonate crystal of the present invention synthetic, the organic phospho acid for as the phosphorus source has adopted alkyl phosphonic acid, and its molecular formula is as follows:
RPO
3H
2
Wherein R represents alkyl, is C
1-C
4Alkyl such as methyl, ethyl, propyl group or butyl, and be preferably methyl etc., it links to each other with phosphorus atom.The derivative of these organic phospho acids also can be used as the phosphorus source as salt or ester etc. and uses.
On the other hand, preferably adopt iron nitrate or iron trichloride, but other various soluble ferric iron salt can be used all as alkoxide of ferric sulfate or iron etc. as source of iron.
Provided by the present invention, adopt in the synthetic system of organic ferric phosphonate of above-mentioned phosphorus source and source of iron, the solvent that adopts is preferably water, alcohol, polyvalent alcohol, ether and cyclic ethers and the mixture between them, the atomic ratio scope of iron is 4: 1 to 200: 1 in solvent that adds and the source of iron, and optimum range is 9: 1 to 100: 1.In addition, the solvent that is added is water and dioxane preferably, and the mol ratio of water and dioxane is 1.0: 0.5-1.0: 3.0, and be preferably 1.0: 1.0-1.0: 1.8.
For adjusting the pH value of above-mentioned synthetic system, also to add a certain amount of alkali.The alkali that adds can be alkali-metal oxyhydroxide or carbonate and ammoniacal liquor and organic amine etc.The atomic ratio of its add-on and iron is 0.5: 1.0～3.0: 1.0, and optimum range is 1.0: 1.0～1.8: 1.0.
Above-mentioned raw materials obtains the initial soln gel through suitable stirring or employing ultrasonic dispersing or after leaving standstill.
The skeleton of organic ferric phosphonate provided by the present invention generates under hydrothermal synthesizing condition.Reaction vessel can adopt the withstand voltage synthesis reactor of the stainless steel that has teflon lined.Crystallization temperature can be adjusted in 80 ℃ to 350 ℃ scopes, and optimum crystallization temperature is 100 ℃ to 250 ℃.Crystallization time is 0.5 hour to 1000 hours, and the best is 24 hours to 168 hours.Reaction pressure is the autogenous pressure in the synthesis reactor of sealing.The atomic ratio scope of iron is 1.0: 1.0 to 1.8: 1.0 in phosphorus in the phosphorus source and the source of iron, and optimum range is 1.2: 1.0 to 1.6: 1.0.
Solid product during methods such as employing filtration and centrifugation are synthesized hydro-thermal is separated, and can obtain organic ferric phosphonate crystal.Still mixing unreacted raw material and additive in the crystal this moment, needs water to clean separation repeatedly repeatedly.
Clean isolating organic ferric phosphonate crystal through above step, still have the molecule of water and organic additive in its duct, need in exsiccant air, nitrogen, argon gas or vacuum to be removed more than the heat drying to 200 ℃.Organic ferric phosphonate crystal provided by the present invention can be at 200 ℃ with interior maintenance Stability Analysis of Structures, in the time of 200 ℃ to 400 ℃, because P-C bond rupture and structure is caved in.
Organic ferric phosphonate crystal provided by the present invention is the porousness crystal, has 40～600m
2The specific surface area of/g, after 100～200 ℃ of processing, best specific surface area is 100～600m
2/ g.
The micropore of organic ferric phosphonate crystal provided by the present invention has the aperture of 0.20～1.2nm, and the optimum distribution scope is 0.25～0.9nm.
Organic ferric phosphonate crystal provided by the present invention, its inner pore passage structure link to each other with covalent linkage with inorganic skeleton by organic group and are built into.Can prepare the porousness crystal that has hydrophobic nature duct inwall and thermostability simultaneously according to the present invention.Furthermore, change the condition of crystallization, the organic ferric phosphonate crystal that can obtain having different skeleton structures and performance again.Organic ferric phosphonate crystal provided by the present invention serves many purposes, and for example can make separate sorbent, catalyzer, filler and chromatographic column carrier etc.Adopt different organic reagents that organic ferric phosphonate crystal provided by the present invention is carried out modification, make organo-functional groups different on its inner wall belt, then can obtain a series of novel organic-inorganic composite porous crystal.
By the following examples the present invention is made detailed description, but the present invention is not limited to these
Embodiment.
Embodiment
The preparation of embodiment 1.FeMepO-1
(a) with 2.67gFe (NO
3)
39H
2O is dissolved in the 10ml dioxane, the 0.96g methyl-phosphorous acid is added the dissolving of this solution again and stirs 1 hour.0.35gNaOH is dissolved in the 1g distilled water, this NaOH solution slowly is added dropwise to the above-mentioned Fe of being dissolved with (NO while stirring
3)
39H
2In the dioxane solution of O and methyl-phosphorous acid.The suspension liquid that obtains is transferred in the stainless steel synthesis reactor that has teflon lined after stirring 1 hour and sealing, places in 140 ℃ the baking oven under the system autogenous pressure crystallization 48 hours.The solid product that obtains obtains acicular methyl-phosphorous acid iron crystal through repeatedly washing to separate after the oven dry again, and these crystalline X-ray powder diffraction data are as shown in table 3.Chemical analysis results shows that its chemical constitution is: C (wt.%)=10.48%, H (wt.%)=2.56%, Fe (wt.%)=22.97%, P (wt.%)=18.02%.This product called after FeMepO-1.
Table 3
| 2θ | d | Relative intensity |
| 6.95 7.79 9.83 12.55 13.97 14.37 15.57 22.42 25.30 27.84 31.52 | 12.71 11.33 9.00 7.04 6.33 6.15 5.67 3.96 3.51 3.20 2.83 | 1000 280 100 90 210 200 440 160 180 140 130 |
(b) with resulting methyl-phosphorous acid iron crystal FeMepO-1 in above-mentioned (a) through 200 ℃ of air roastings after 2 hours, basic identical before its X-ray powder diffraction data and the roasting.
(c) resulting methyl-phosphorous acid iron crystal FeMepO-1 in above-mentioned (a) is vacuumized under 200 ℃ (pressure is 1 * 10
-7Pa) handle after 6 hours, under 77K, measure its N
2Adsorption isothermal line.This adsorption isothermal line presents the feature of porousness adsorbate, and promptly adsorptive capacity has bigger rising when lower pressure.According to this crystalline Langmuir specific surface area 118m that adsorption isothermal line calculated
2/ g, the effective pore radius is about 0.5～0.7nm.
The preparation of embodiment 2.FeMepO-1
With 2.5gFe (NO
3)
39H
2O is dissolved in the 20ml dioxane.0.35gNaOH is dissolved in the 1g distilled water, again the 0.96g methyl-phosphorous acid is added the dissolving of this solution and stirred 1 hour, this solution slowly is added dropwise to the above-mentioned Fe of being dissolved with (NO while stirring
3)
39H
2In the O dioxane solution.The suspension liquid that obtains is transferred in the stainless steel synthesis reactor that has teflon lined after stirring 1 hour and sealing, places in 160 ℃ the baking oven under the system autogenous pressure crystallization 24 hours.The solid product that obtains obtains larger-size acicular methyl-phosphorous acid iron crystal through repeatedly washing to separate after the oven dry again, and is basic identical among these crystalline X-ray powder diffraction data and the embodiment 1.
The preparation of embodiment 3.FeMepO-1
With 2.5gFe (NO
3)
39H
2O is dissolved in the 20ml dioxane.0.30gNaOH is dissolved in the 4g propyl carbinol, again the 0.96g methyl-phosphorous acid is added the dissolving of this solution and stirred 1 hour, this solution slowly is added dropwise to the above-mentioned Fe of being dissolved with (NO while stirring
3)
39H
2In the O dioxane solution.The suspension liquid that obtains is transferred in the stainless steel synthesis reactor that has teflon lined after stirring 1 hour and sealing, places in 160 ℃ the baking oven under the system autogenous pressure crystallization 24 hours.The solid product that obtains obtains larger-size acicular methyl-phosphorous acid iron crystal through repeatedly washing to separate after the oven dry again, and is basic identical among these crystalline X-ray powder diffraction data and the embodiment 1.
The preparation of embodiment 4.FeMepO-2
(a) with 2.64gFeCl
36H
2O is dissolved in the 10ml distilled water, again the 1.50g methyl-phosphorous acid is added the dissolving of this solution and stirred 1 hour, 0.35gNaOH is dissolved in this solution then, stir and transfer to after 1 hour in the stainless steel synthesis reactor that has teflon lined and sealing, placed in 150 ℃ the baking oven under the system autogenous pressure crystallization 72 hours.The solid product that obtains obtains acicular methyl-phosphorous acid iron crystal through repeatedly washing to separate after the oven dry again, and these crystalline X-ray powder diffraction data are as shown in table 4.Chemical analysis results shows that its chemical constitution is C (wt.%)=8.70%, H (wt.%)=2.65%, Fe (wt.%)=28.22%, P (wt.%)=22.48%.This product called after FeMepO-2.
Table 4
| 2θ | d | Relative intensity |
| 11.42 16.48 17.48 18.98 19.86 20.81 22.22 23.87 25.05 26.48 28.41 30.55 31.22 32.69 33.36 34.89 35.37 38.14 46.94 | 7.74 5.37 5.06 4.67 4.46 4.26 3.99 3.72 3.55 3.36 3.13 2.92 2.86 2.73 2.68 2.57 2.53 2.36 1.93 | 1000 20 20 80 250 20 60 40 100 30 80 30 50 30 30 40 40 40 30 |
(b) with resulting methyl-phosphorous acid iron crystal FeMepO-2 in above-mentioned (a) through 300 ℃ of air roastings after 2 hours, basic identical before its X-ray powder diffraction data and the roasting.
(c) resulting methyl-phosphorous acid iron crystal FeMepO-2 in above-mentioned (a) is vacuumized under 200 ℃ (pressure is 1 * 10
-7Pa) handle after 6 hours, at room temperature measure its H
2The O adsorption isothermal line.This adsorption isothermal line presents the feature of porousness adsorbate, and promptly adsorptive capacity has bigger rising when lower pressure.Its water regain at room temperature is 7.18%, and micropore size is between 0.26nm and 0.32nm.
The preparation of embodiment 5.FeMepO-2
With 2.0gFeSO
47H
2O is dissolved in the 10ml distilled water, the 1.0g methyl-phosphorous acid is added the dissolving of this solution again and stirs 1 hour, then 0.35gNaOH is dissolved in this solution restir 1 hour.This solution transferred in the stainless steel synthesis reactor that has teflon lined and sealing, placed in 160 ℃ the baking oven under the system autogenous pressure crystallization 24 hours.The solid product that obtains obtains acicular methyl-phosphorous acid iron crystal through repeatedly washing to separate after the oven dry again, and is basic identical among these crystalline X-ray powder diffraction data and the embodiment 4.
The preparation of embodiment 6.FeMepO-2
With 2.0gFeSO
47H
2O is dissolved in the 15ml Virahol, the 1.0g methyl-phosphorous acid is added the dissolving of this solution again and stirs 1 hour, then 0.25gNaOH is dissolved in this solution restir 1 hour.This solution transferred in the stainless steel synthesis reactor that has teflon lined and sealing, placed in 120 ℃ the baking oven under the system autogenous pressure crystallization 48 hours.The solid product that obtains obtains acicular methyl-phosphorous acid iron crystal through repeatedly washing to separate after the oven dry again, and is basic identical among these crystalline X-ray powder diffraction data and the embodiment 4.
Claims (9)
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