CN104030315B - A kind of method utilizing natural ore soil to synthesize heteroatoms aluminium phosphate molecular sieve - Google Patents

A kind of method utilizing natural ore soil to synthesize heteroatoms aluminium phosphate molecular sieve Download PDF

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CN104030315B
CN104030315B CN201410291270.2A CN201410291270A CN104030315B CN 104030315 B CN104030315 B CN 104030315B CN 201410291270 A CN201410291270 A CN 201410291270A CN 104030315 B CN104030315 B CN 104030315B
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molecular sieve
natural ore
heteroatoms
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ore soil
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CN104030315A (en
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韶晖
陈晶晶
冷一欣
钟璟
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Changzhou University
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Abstract

The invention belongs to the preparing technical field of heteroatoms aluminium phosphate molecular sieve, be specifically related to a kind of method utilizing natural ore soil to synthesize heteroatoms aluminium phosphate molecular sieve.Natural ore soil through pulverizing, purifying, after activation treatment and auxiliary aluminum source, phosphorus source, fluorion, water and structure directing agent are mixed and made into slip and aging; Slip after aging is placed in hydrothermal reaction kettle, and hydrothermal crystallizing under certain temperature and time, obtains molecular screen primary powder; Molecular screen primary powder calcines removing structure directing agent under certain temperature, can obtain heteroatoms aluminium phosphate molecular sieve.Utilize cheap natural ore soil as silicon source and part aluminium source, greatly can reduce production cost; Source metal in natural ore soil is doped in molecular sieve, strengthens its acid and oxidation susceptibility.

Description

A kind of method utilizing natural ore soil to synthesize heteroatoms aluminium phosphate molecular sieve
Technical field
The invention belongs to the preparing technical field of heteroatoms aluminium phosphate molecular sieve, be specifically related to a kind of method utilizing natural ore soil to synthesize heteroatoms aluminium phosphate molecular sieve.
Background technology
Modern industry commonly use zeolite molecular sieve synthesis mainly with traditional chemical product for raw material, although technical maturity, quality product is high, but with the increase in demand of other industry to high reactivity raw material, prepare being becoming tight supply day of siliceous, aluminum-containing raw material needed for molecular sieve and alkali, price rises steadily, and causes production cost high, the technology of preparing of molecular sieve can not adapt to the requirement of its day by day wide Application Areas far away, and these problems constrain the development of molecular sieve.In order to address this problem, people start to pay close attention to the natural ore soil raw material being rich in sial.With natural ore soil synthetic zeolite, abundant raw material source, cheap, considerably reduce production cost.Make full use of natural ore soil resource, the synthesis for molecular sieve opens a new road, has vast potential for future development.
At present, be that the molecular sieve main Types of Material synthesis has Si-Al molecular sieve, aluminium silicophosphate molecular sieve and mesopore molecular sieve with natural ore soil.And the natural ore soil mentioned in current most of patent and document is commercially available natural ore soil, through the process of deironing and other metallic elements etc.
When patent or document utilization natural ore soil synthesis of molecular sieve, the metallic ore material existed in natural mineral is not utilized as impurity removing mostly.In recent years, along with the rise of Green Chemical Engineering Process tide, use nontoxic raw material in chemical process, Appropriate application starting material, employing less energy-consumption, oligosaprobic chemical reaction process productive target product have been trend of the times.Make full use of natural ore soil resource, can be used as the new direction in application this field of natural ore soil synthesis of molecular sieve.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of production cost lower, the technique of heteroatoms aluminium phosphate molecular sieve (MeSAPO molecular sieve) is prepared by natural ore soil, heteroatoms aluminium phosphate molecular sieve refers to: the aluminium phosphate molecular sieve that metallic ore material (Me) adulterates
Technique for: utilize natural ore soil to provide silicon source needed for molecular sieve, aluminium source and doping type metallic ore substance source, prepare MeSAPO molecular sieve through hydrothermal crystallizing.
Concrete operations are:
(1) to the natural ore soil after pulverizing, acidifying purification or calcining and activating process is carried out,
Natural ore soil is one or more the mixture in kaolin, diatomite, wilkinite, alum clay and attapulgite,
Natural ore soil after above-mentioned pulverizing refers to the powder of natural mineral, and particle diameter is less than 100 μm, and preferably at 1 ~ 50 μm, particle diameter is unfavorable for crystallization too greatly,
What above-mentioned acidifying was purified is operating as: by natural ore soil in 25 DEG C-60 DEG C, Solute mass fraction is in the sulphuric acid soln of 8-10% after (mass ratio of sulphuric acid soln and natural ore soil is 8:1) standing or magnetic agitation 4h, use distilled water to after natural ore soil washing to neutral (pH value is 6.0 ~ 7.0), natural ore soil is dried at 105 DEG C
Above-mentioned calcining and activating process refers to: natural ore soil is calcined 2h, naturally cooling at 700 DEG C-750 DEG C;
(2) acidifying in step (1) or the natural ore soil activated and auxiliary aluminum source (add or do not add), phosphorus source, fluorion (add or do not add), water and structure directing agent (representing with SDA below) are mixed with slip; In slip, the mol ratio of each composition and water is n si: n al: n p: n f: n me: n h2O=0.05 ~ 0.5:0.5 ~ 1.5:0.5 ~ 1.5:0 ~ 0.5:0.003 ~ 0.2:25 ~ 100, the mol ratio of structure directing agent and silicon, phosphorus, aluminium element sum is n sDA: (n si+ n al+ n p)=0.2 ~ 1.0,
Preparation synthesis slip process in, by acidifying or activate natural ore soil elder generation mix with phosphorus source, to the crystallization of system, there is certain help,
Wherein, Me represents the doping type metallic ore material in natural mineral, and as the metal such as magnesium, iron, and the metallic ore material in the natural mineral be entrained in is provided by natural ore soil itself, and concrete proportioning is determined according to metal content contained in natural ore soil,
In Middle molecule sieve structure unit of the present invention, silicon source is provided by natural ore soil, aluminium source provides the aluminium source of part or whole aluminium source by natural ore soil, remainder is provided by auxiliary aluminum source, therefore in step (2), need to select add or do not add auxiliary aluminum source, the mol ratio n of sial in natural ore soil according to the molar ratio of sial in natural ore soil si: n al=0 ~ 1, do not add auxiliary aluminum source; n si: n al=1 ~ 5, add auxiliary aluminum source,
Auxiliary aluminum source for intending thin water aluminium, aluminium hydroxide, activated alumina, aluminum isopropylate or bauxitic clay, and ensures that the ratio (Si/Al) of the active silica-alumina mole number in slip is between 0.1 ~ 1.0, preferably between 0.2 ~ 0.5;
In step (2), phosphorus source is phosphoric acid, aluminum phosphate or triethyl phosphate, and ensures that the ratio (P/Al) of the phosphorus aluminium mole number in slip is between 0.5 ~ 1.5, preferably between 0.8 ~ 1.2;
In step (2), the hydrofluoric acid solution of to be Solute mass fraction be in the source of fluorion 20wt%, and select to add or do not add hydrofluoric acid solution according to the molar ratio of metallic ore material and aluminium in natural ore soil: the mol ratio n of metallic ore material and aluminium in natural ore soil me: n al=0 ~ 0.2, do not add fluorion; n me: n al>=0.2, add fluorion, and the fluorine al mole ratio (F/Al) in guarantee slip is between 0 ~ 0.5, preferably between 0 ~ 0.3;
In step (2), structure directing agent is one or more the mixture in triethylamine, Diisopropylamine, di-n-propylamine, tripropyl amine, diethanolamine, tetraethyl ammonium hydroxide, TPAOH, TBAH,
Ratio (the n of the mole number of structure directing agent and silicon, phosphorus, aluminium element sum sDA: (n si+ n al+ n p)=0.2 ~ 1.0) between 0.2 ~ 1.0, preferably between 0.3 ~ 0.6;
In step (2), the ratio (H of the mole number of water and aluminium 2o/Al) between 25 ~ 100, preferably between 40 ~ 75, water has vital role in crystallization process, and water can make Si-O-Si bond rupture easily, promotes molecular recombination;
(3) after the aging 6 ~ 24h of slip step (2) prepared, hydrothermal reaction kettle is placed in, crystallization 2 ~ 100h at 120 DEG C ~ 200 DEG C,
Slip, through stirring and for some time aging, is good for the formation of molecular sieve crystal and perfection of crystal,
In step (3), digestion time, between 6 ~ 24h, selects concrete digestion time according to the consumption of fluorion in step (2): the mol ratio n of fluorion and aluminium f: n alwhen=0 ~ 0.1, digestion time selects 12 ~ 24h; The mol ratio n of fluorion and aluminium f: n alwhen=0.1 ~ 0.3, digestion time selects 6 ~ 12h,
When metallic element is too much, metallic element not easily enters framework of molecular sieve, but is generating the metal oxide outside skeleton.And in fluorion system, the title complex that transition metal can generate fluorine is conducive to entering framework of molecular sieve; Meanwhile, F-affects process and the speed of crystallization as mineralizer and Synergist S-421 95, and when F-is present in the reaction of Hydrothermal Synthesis molecular sieve, a small amount of nucleus is formed fast, makes digestion time almost foreshorten to 1/3,
In step (3), crystallization temperature between 120 ~ 200 DEG C, preferably between 160 ~ 200 DEG C; Crystallization time is preferably at 10 ~ 150h, and crystallization time is suitably selected along with the setting of crystallization temperature, and crystallization temperature is higher, and crystallization time then shortens thereupon;
(4) by the material after hydrothermal crystallizing in step (3) after filtration, washing, drying obtain molecular screen primary powder;
(5) molecular screen primary powder step (4) obtained in 400 ~ 800 DEG C, calcine under 2 ~ 20h, removing structure directing agent, can obtain heteroatoms aluminium phosphate molecular sieve,
As preferably: the removal temperature of structure directing agent 500 ~ 600 DEG C, the time is between 2 ~ 6h.
Beneficial effect of the present invention is: the present invention take natural ore soil as Material synthesis heteroatoms aluminium phosphate molecular sieve, compared with other prepare the industrial chemicals such as siliceous, aluminium needed for molecular sieve, and abundance, cheap, considerably reduce production cost.The more important thing is, to make use of in natural ore soil in the past that (the present invention does not then need to remove the process of metallic element by the source metal that removes as impurity, only through simple acidifying purification or calcining and activating process, save the metallic element in natural mineral), additionally source metal need not be added in slip, by the replacement of heteroatoms metal, strengthen acidity and the catalytic performance of aluminium phosphate molecular sieve;
Take full advantage of natural ore soil resource, the synthesis for heteroatoms aluminium phosphate molecular sieve opens a new road, has vast potential for future development.In addition, Silicified breccias in natural ore soil and source metal can effectively be built into heteroatoms aluminium phosphate molecular sieve at short notice, not only increase crystallization speed, and the silicone content in heteroatoms aluminium phosphate molecular sieve can be improved, increase stability and the acidity of molecular sieve.Heteroatoms aluminium phosphate molecular sieve through roasting removing structure directing agent can be used as ion-exchange material, adsorption and separation material and the catalytic material etc. in oil, refining of petroleum and fine chemistry industry.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of synthesizing MeSAPO-5 molecular sieve in example 1 of the present invention.
Fig. 2 is the XRD figure spectrum of synthesizing MeSAPO-11 molecular sieve in example 6 of the present invention.
Embodiment
Embodiment 1
The main component of employing attapulgite is: SiO 2content is 60.5%; Al 2o 3content is 10.1%; Content of MgO is 11.0%; Fe 2o 3content be 5.7%.
Above-mentioned attapulgite is ground to 40 ~ 50 μm, purification activation treatment is carried out with the sulphuric acid soln that massfraction is 10%, the mass ratio of sulphuric acid soln and attapulgite is 8:1, at 25 DEG C, attapulgite is in sulphuric acid soln after magnetic agitation 4h, use distilled water repeatedly to wash to neutrality, dry at 105 DEG C.
By attapulgite, the 13.0gAl of above-mentioned for 10.0g process 2o 3content is the thin water aluminium of plan and the 270g water mix and blend 14h of 71%, then adds the phosphoric acid solution 23.1g of 85%, after continuing to stir 2h, adds the triethylamine of 10.1g, and at room temperature the aging 12h of mix and blend forms slip, and the Me/Al mol ratio in slip is 0.09.
Treat that the slip of crystallization is transferred in 500mL hydrothermal reaction kettle, crystallization 24h at 180 DEG C by above-mentioned.Reaction terminate after, reactor naturally cools to room temperature, mix products after filtration, washing, at 80 DEG C dry, can obtain containing MeSAPO-5 molecular screen primary powder.
MeSAPO-5 molecular screen primary powder is calcined 6h at 550 DEG C, can structure directing agent be removed, obtain target product MeSAPO-5 molecular sieve.The XRD figure spectrum of the MeSAPO-5 molecular sieve of gained as shown in Figure 1.
Embodiment 2
The composition of employing alum clay is: SiO 2content is 8.3%; Al 2o 3content is 48.0%; Fe 2o 3content be 10.1%.
Above-mentioned alum clay is ground to 80 ~ 100 μm, at 700 DEG C, calcines 2h activate.
By the alum clay of above-mentioned for 16.2g process and 180g water mix and blend 14h, add the phosphoric acid solution 23.1g of 85% again, after continuing to stir 2h, add the triethylamine of 10.1g after adding the hydrofluoric acid stirring 1h of 0.500g20wt%, at room temperature the aging 6h of mix and blend forms the slip treating crystallization.Me/Al mol ratio in slip is 0.3.
Treat that the slip of crystallization is transferred in 500mL hydrothermal reaction kettle, crystallization 24h at 180 DEG C by above-mentioned.Question response terminates rear material and goes out reactor, and after naturally cooling to room temperature, mix products, through filtering, washing, is dried, can be obtained the MeSAPO-5 molecular screen primary powder containing structure directing agent at 80 DEG C.
MeSAPO-5 molecular screen primary powder is calcined 5.5h at 550 DEG C, removes structure directing agent, obtain target product MeSAPO-5 molecular sieve.
Embodiment 3
The composition of employing attapulgite is: SiO 2content is 60.5%; Al 2o 3content is 10.1%; Content of MgO is 11.0%; Fe 2o 3content be 5.7%.
Above-mentioned attapulgite is ground to 20 ~ 30 μm, purification activation treatment is carried out: the mass ratio of sulphuric acid soln and attapulgite is 8: 1 with the sulphuric acid soln that massfraction is 10%, attapulgite magnetic agitation 4h in sulphuric acid soln at 25 DEG C, then distilled water is used repeatedly to wash, until stop washing when pH value is 6.0 ~ 7.0, then dry at 105 DEG C.
By attapulgite, the 13.0gAl of above-mentioned for 10.0g process 2o 3content is the thin water aluminium of plan and the 270g water mix and blend 14h of 71%, add the phosphoric acid solution 23.1g of 85% again, after continuing to stir 2h, add the diethanolamine of 10.5g, at room temperature the aging 12h of mix and blend forms the slip treating crystallization, and the Me/Al mol ratio in slip is 0.09.
Treat that the slip of crystallization is transferred in 500mL hydrothermal reaction kettle, crystallization 36h at 200 DEG C by above-mentioned.Question response terminates after rear removal reactor naturally cools to room temperature, mix products through filtering, washing, dry at 80 DEG C, the MeSAPO-5 molecular screen primary powder containing structure directing agent can be obtained.
MeSAPO-5 molecular screen primary powder is calcined 5.5h at 550 DEG C, can structure directing agent be removed, obtain target product MeSAPO-5 molecular sieve.
Embodiment 4
Kaolinic composition is adopted to be: SiO 2content is 10.7%; Al 2o 3content is 58.2%;
Adopt recessed soil rod soil composition be: SiO 2content is 60.5%; Al 2o 3content is 10.1%; Content of MgO is 11.0%; Fe 2o 3content be 5.7%.
Above-mentioned kaolin and attapulgite are ground to 60 ~ 80 μm.Kaolin is calcined 2h and is carried out activation treatment at 750 DEG C.Attapulgite massfraction be 10% sulphuric acid soln carry out purification activation treatment: the mass ratio of sulphuric acid soln and attapulgite is 8: 1, at 60 DEG C, attapulgite stirs and soaks 4h in sulphuric acid soln, then distilled water is used repeatedly to wash, until stop washing when pH value is 6.0 ~ 7.0, then dry at 105 DEG C.
By the kaolin of above-mentioned for 10.3g process, 5.0g attapulgite and 180g water mix and blend 14h, add the phosphoric acid solution 23.1g of 85% again, after continuing to stir 2h, add the triethylamine of 10.1g, the aging 6h of mix and blend under room temperature again, form the slip treating crystallization, the Me/Al mol ratio in slip is 0.05.
Treat that the slip of crystallization is transferred in 500mL hydrothermal reaction kettle, crystallization 24h at 180 DEG C by above-mentioned.Question response terminates after rear removal reactor naturally cools to room temperature, mix products through filtering, washing, dry at 80 DEG C, the MeSAPO-5 molecular screen primary powder containing structure directing agent can be obtained.
MeSAPO-5 molecular screen primary powder is calcined 5.5h at 550 DEG C, can structure directing agent be removed, obtain target MeSAPO-5 molecular sieve.
Embodiment 5
The composition of employing alum clay is: SiO 2content is 8.3%; Al 2o 3content is 48.0%; Fe 2o 3content be 10.1%.
Above-mentioned alum clay is ground to 50 ~ 70 μm, at 700 DEG C, calcines 2h activate.
By the alum clay of above-mentioned for 16.2g process and 180g water mix and blend 14h, add the phosphoric acid solution 23.1g of 85% again, after continuing to stir 2h, add the di-n-propylamine of 10.1g, at room temperature the aging 6h of mix and blend forms the slip treating crystallization, and the Me/Al mol ratio in slip is 0.3.
Treat that the slip of crystallization is transferred in 500mL hydrothermal reaction kettle, crystallization 36h at 180 DEG C by above-mentioned.Question response terminates after rear removal reactor naturally cools to room temperature, mix products through filtering, washing, dry at 80 DEG C, the MeSAPO-11 molecular screen primary powder containing structure directing agent can be obtained.
MeSAPO-11 molecular screen primary powder is calcined 5.5h at 550 DEG C, structure directing agent can be removed completely, obtain target MeSAPO-11 molecular sieve.
Embodiment 6
The composition of employing attapulgite is: SiO 2content is 60.5%; Al 2o 3content is 10.1%; Content of MgO is 11.0%; Fe 2o 3content be 5.7%.
Above-mentioned attapulgite is ground to 40 ~ 50 μm, purification activation treatment is carried out: the mass ratio of sulphuric acid soln and attapulgite is 8: 1 with the sulphuric acid soln that massfraction is 8%, at 60 DEG C, attapulgite stirs and soaks 4h in sulphuric acid soln, then distilled water is used repeatedly to wash, until stop washing when pH value is 6.0 ~ 7.0, then dry at 105 DEG C.
By attapulgite, the 13.0gAl of above-mentioned for 10.0g process 2o 3content is the thin water aluminium of plan and the 270g water mix and blend 14h of 71%, add the phosphoric acid solution 23.1g of 85% again, after continuing to stir 2h, add the HF solution of 1.0g20wt%, the Diisopropylamine of 12.1g is added after stirring 1h, under room temperature, the aging 6h of mix and blend forms the slip treating crystallization again, and the Fe/Al in slip is 0.03.
Treat that the slip of crystallization is transferred in 500mL hydrothermal reaction kettle, crystallization 24h at 180 DEG C by above-mentioned.Question response terminates after rear removal reactor naturally cools to room temperature, mix products through filtering, washing, dry at 80 DEG C, the MeSAPO-11 molecular screen primary powder containing structure directing agent can be obtained.
MeSAPO-11 molecular screen primary powder is calcined 5.5h at 550 DEG C, structure directing agent can be removed completely, obtain target MeSAPO-11 molecular sieve.The XRD figure spectrum of the MeSAPO-11 molecular sieve of gained as shown in Figure 2.

Claims (5)

1. a synthetic method for heteroatoms aluminum phosphate MeSAPO molecular sieve, is characterized in that:
Described synthetic method is, utilizes natural ore soil to provide silicon source needed for molecular sieve, aluminium source and doping type metallic ore substance source, prepares MeSAPO molecular sieve through hydrothermal crystallizing;
The concrete steps of described method are,
(1) to the natural ore soil after pulverizing, acidifying purification or calcining and activating process is carried out;
(2) acidifying in step (1) or the natural ore soil that activated are mixed with slip, in slip, the mol ratio of each composition and water is n si: n al: n p: n f: n me: n h2O=0.05 ~ 0.5:0.5 ~ 1.5:0.5 ~ 1.5:0 ~ 0.5:0.003 ~ 0.2:25 ~ 100, and add structure directing agent SDA, the mol ratio of structure directing agent SDA and silicon, phosphorus, aluminium element sum is n sDA: (n si+ n al+ n p)=0.2 ~ 1.0,
Wherein, n me: n althe hydrofluoric acid solution of>=0.2, and add fluorion, to be Solute mass fraction be in the source of fluorine 20wt%, the mol ratio n of fluorine and aluminium f: n al=0.1 ~ 0.3;
(3), after the aging 6h of slip step (2) prepared, hydrothermal reaction kettle is placed in, crystallization 24h at 180 DEG C;
(4) by the material after hydrothermal crystallizing in step (3) after filtration, washing, drying obtain molecular screen primary powder;
(5) molecular screen primary powder step (4) obtained in 400 ~ 800 DEG C, calcine under 2 ~ 20h, removing structure directing agent SDA, can obtain heteroatoms aluminium phosphate molecular sieve.
2. the synthetic method of heteroatoms aluminum phosphate MeSAPO molecular sieve as claimed in claim 1, it is characterized in that: in step (1), described natural ore soil is one or more the mixture in kaolin, diatomite, wilkinite, alum clay and attapulgite, natural ore soil after pulverizing, grain diameter is 0.1 ~ 100 μm.
3. the synthetic method of heteroatoms aluminum phosphate MeSAPO molecular sieve as claimed in claim 1, it is characterized in that: in step (2), need to select add or do not add auxiliary aluminum source, the mol ratio n of sial in natural ore soil according to the molar ratio of sial in natural ore soil si: n al=0 ~ 1, do not add auxiliary aluminum source; n si: n al=1 ~ 5, add auxiliary aluminum source.
4. the synthetic method of heteroatoms aluminum phosphate MeSAPO molecular sieve as claimed in claim 3, is characterized in that: described auxiliary aluminum source is for intending thin water aluminium, aluminium hydroxide, activated alumina, aluminum isopropylate or bauxitic clay.
5. the synthetic method of heteroatoms aluminum phosphate MeSAPO molecular sieve as claimed in claim 1, it is characterized in that: in step (2), structure directing agent SDA is one or more the mixture in triethylamine, Diisopropylamine, di-n-propylamine, tripropyl amine, diethanolamine, tetraethyl ammonium hydroxide, TPAOH, TBAH.
CN201410291270.2A 2014-06-25 2014-06-25 A kind of method utilizing natural ore soil to synthesize heteroatoms aluminium phosphate molecular sieve Expired - Fee Related CN104030315B (en)

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CN107777702B (en) * 2017-11-09 2020-05-26 常州大学 Preparation method of hierarchical-pore heteroatom aluminum phosphate molecular sieve for oxidative desulfurization
CN110040744B (en) * 2019-04-08 2022-07-01 福建师范大学 MeAPSO-34 molecular sieve and preparation method thereof
CN110372005B (en) * 2019-07-03 2022-10-28 常州大学 Method for synthesizing hierarchical pore aluminum phosphate molecular sieve by using fluorine ions
CN110394151B (en) * 2019-08-06 2022-03-08 营口理工学院 High-grade diatomite with molecular sieve structure and preparation method thereof

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CN103801391A (en) * 2014-02-19 2014-05-21 山西大学 Preparation method for titanium-silicon-aluminum phosphate molecular sieve catalyst

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