CN104030315A - Method for synthesizing heteroatom aluminophosphate molecular sieve by utilizing natural ore - Google Patents

Method for synthesizing heteroatom aluminophosphate molecular sieve by utilizing natural ore Download PDF

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CN104030315A
CN104030315A CN201410291270.2A CN201410291270A CN104030315A CN 104030315 A CN104030315 A CN 104030315A CN 201410291270 A CN201410291270 A CN 201410291270A CN 104030315 A CN104030315 A CN 104030315A
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molecular sieve
aluminium
natural ore
mesapo
ore deposit
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CN104030315B (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 technical field of preparation of heteroatom aluminophosphate molecular sieves and in particular relates to a method for synthesizing a heteroatom aluminophosphate molecular sieve by utilizing natural ore. The method comprises the following steps: mixing natural ore subjected to smashing, purifying and activating treatment with an auxiliary aluminium source, a phosphorous source, fluorine ions, water and a structure directing agent to form slurry, and ageing the slurry; placing the aged slurry into a hydrothermal reaction kettle, and carrying out hydrothermal crystallization at certain temperature and time, so that molecular sieve raw power is obtained; and calcining the molecular sieve raw powder at a certain temperature to remove the structure directing agent, so that the heteroatom aluminophosphate molecular sieve can be obtained. Cheap natural ore is taken as a silicon source and part of aluminium source, so that production cost can be greatly reduced; a metal source in the natural ore is doped into the molecular sieve, so that acidity and oxidation property of the molecular sieve are enhanced.

Description

A kind of method of utilizing the synthetic heteroatoms phosphoric acid aluminum molecular screen of natural ore deposit soil
Technical field
The invention belongs to the preparing technical field of heteroatoms phosphoric acid aluminum molecular screen, be specifically related to a kind of method of utilizing the synthetic heteroatoms phosphoric acid aluminum molecular screen of natural ore deposit soil.
Background technology
Synthesizing mainly taking traditional Chemicals as raw material of the conventional zeolite molecular sieve of modern industry, although technical maturity, quality product is high, but the increase in demand with other industry to high reactivity raw material, prepare being becoming tight supply day of required siliceous, the aluminum-containing raw material of 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 have restricted the development of molecular sieve.In order to address this problem, people start to pay close attention to the natural ore deposit soil raw material that is rich in sial.With natural ore deposit soil synthetic zeolite, raw material sources are abundant, cheap, significantly reduced production cost.Make full use of natural ore deposit soil resource, opened up a new road for molecular sieve synthetic, there is vast potential for future development.
At present, there are Si-Al molecular sieve, aluminium silicophosphate molecular sieve and mesopore molecular sieve taking natural ore deposit soil as the synthetic molecular sieve main Types of raw material.And the natural ore deposit soil of mentioning in most patent and document is commercially available natural ore deposit soil, pass through the processing of deironing and other metallic elements etc.
In the time of patent or the natural ore deposit of document utilization soil synthesis of molecular sieve, the metallic ore material existing in natural mineral is mostly removed and is not utilized as impurity.In recent years, along with the rise of Green Chemical Engineering Process tide, use nontoxic raw material in chemical process, rationally utilizing starting material, adopting less energy-consumption, oligosaprobic chemical reaction process productive target product has been trend of the times.Make full use of natural ore deposit soil resource, can be used as the new direction in this field of soil synthesis of molecular sieve, the natural ore deposit of application.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of production cost lower, prepare the technique of heteroatoms phosphoric acid aluminum molecular screen (MeSAPO molecular sieve) by natural ore deposit soil, heteroatoms phosphoric acid aluminum molecular screen refers to: the aluminium phosphate molecular sieve of metallic ore material (Me) doping
Technique is: utilize natural ore deposit soil that the required silicon source of molecular sieve, aluminium source and doping type metallic ore material source are provided, prepare MeSAPO molecular sieve through hydrothermal crystallizing.
Concrete operations are:
(1) to the natural ore deposit soil after pulverizing, carry out acidifying purification or calcining and activating processing,
Natural ore deposit soil is one or more the mixture in kaolin, diatomite, wilkinite, alum clay and attapulgite,
Natural ore deposit soil after above-mentioned pulverizing refers to the powder of natural mineral, and particle diameter is less than 100 μ m, and preferably, at 1～50 μ m, particle diameter is unfavorable for too greatly crystallization,
What above-mentioned acidifying was purified is operating as: by after standing natural ore deposit soil (mass ratio of sulphuric acid soln and natural ore deposit soil is 8:1) in sulphuric acid solns 25 DEG C-60 DEG C, that solute massfraction is 8-10% or magnetic agitation 4h, after using distilled water to natural ore deposit soil washing extremely neutral (pH value is 6.0～7.0), at 105 DEG C, dry natural ore deposit soil
Above-mentioned calcining and activating processing refers to: natural ore deposit soil is calcined to 2h, naturally cooling at 700 DEG C-750 DEG C;
(2) acidifying in step (1) or the natural ore deposit soil that activate and auxiliary aluminum source (interpolation or do not add), phosphorus source, fluorion (interpolation or do not add), water and structure directing agent (representing with SDA below) are mixed with to slip; In slip, mole proportioning 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,
In the process of the synthetic slip of preparation, acidifying or the native elder generation in natural ore deposit that activate are mixed with phosphorus source, the crystallization of system is had to certain help,
Wherein, Me represents the doping type metallic ore material in natural mineral, and as the metal such as magnesium, iron, and metallic ore material in the natural mineral being entrained in itself provides by natural ore deposit soil, and concrete proportioning is determined according to contained metal content in the soil of natural ore deposit,
In the present invention, Zhong Gui source, molecular sieve structure unit is provided by natural ore deposit soil, aluminium source is provided aluminium source or whole aluminium source of part by natural ore deposit 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 the soil of natural ore deposit according to the molar ratio of sial in the soil of natural ore deposit si: n al=0～1, do not add auxiliary aluminum source; n si: n al=1～5, add auxiliary aluminum source,
Auxiliary aluminum source is for intending thin water aluminium, aluminium hydroxide, activated alumina, aluminum isopropylate or bauxitic clay, and the ratio (Si/Al) that ensures 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 the ratio (P/Al) that ensures the phosphorus aluminium mole number in slip is between 0.5～1.5, preferably between 0.8～1.2;
In step (2), the source of fluorion is that solute massfraction is the hydrofluoric acid solution of 20wt%, and selects add or do not add hydrofluoric acid solution according to the molar ratio of metallic ore material and aluminium in the soil of natural ore deposit: the mol ratio n of metallic ore material and aluminium in the soil of natural ore deposit me: n al=0～0.2, do not add fluorion; n me: n al>=0.2, add fluorion, and ensure that fluorine al mole ratio (F/Al) in 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 being prepared by step (2), be placed in hydrothermal reaction kettle, crystallization 2～100h at 120 DEG C～200 DEG C,
Slip is aging through stirring and for some time, is good for formation and the perfection of crystal of molecular sieve crystal,
In step (3), digestion time, between 6～24h, is selected concrete digestion time according to the consumption of fluorion in step (2): the mol ratio n of fluorion and aluminium f: n al=0～0.1 o'clock, digestion time was selected 12～24h; The mol ratio n of fluorion and aluminium f: n al=0.1～0.3 o'clock, digestion time was selected 6～12h,
In the time that metallic element is too much, metallic element is difficult for entering framework of molecular sieve, but at the metal oxide generating outside skeleton.And in fluorion system, the title complex that transition metal can generate fluorine is conducive to enter framework of molecular sieve; Meanwhile, F-affects process and the speed of crystallization as mineralizer and Synergist S-421 95, and in the time that F-is present in the reaction of Hydrothermal Synthesis molecular sieve, a small amount of nucleus forms fast, makes digestion time almost foreshorten to 1/3,
In step (3), crystallization temperature is between 120～200 DEG C, preferably between 160～200 DEG C; Crystallization time is preferably at 10～150h, and crystallization time is along with the setting of crystallization temperature is suitably selected, and crystallization temperature is higher, and crystallization time shortens thereupon;
(4) by the material after hydrothermal crystallizing in step (3) after filtration, washing, the dry molecular screen primary powder that obtains;
(5) molecular screen primary powder step (4) being obtained is calcined under 400～800 DEG C, 2～20h, removes structure directing agent, can obtain heteroatoms phosphoric acid aluminum molecular screen,
As preferably: the temperature that removes of structure directing agent is between 2～6h at 500～600 DEG C, time.
Beneficial effect of the present invention is: the present invention is synthetic heteroatoms phosphoric acid aluminum molecular screen taking natural ore deposit soil as raw material, prepares compared with the industrial chemicals such as required siliceous, the aluminium of molecular sieve with other, and source is abundant, cheap, has significantly reduced production cost.The more important thing is, utilize and in the soil of natural ore deposit, be used as the source metal that impurity removes in the past (the present invention does not need to remove the processing of metallic element, only through simple acidifying purification or calcining and activating processing, preserve the metallic element in natural mineral), in slip, need not additionally add source metal, by the replacement of heteroatoms metal, strengthen acidity and the catalytic performance of aluminium phosphate molecular sieve;
Take full advantage of natural ore deposit soil resource, opened up a new road for heteroatoms phosphoric acid aluminum molecular screen synthetic, there is vast potential for future development.In addition, silicon in the soil of natural ore deposit and aluminium and source metal can effectively be built into heteroatoms phosphoric acid aluminum molecular screen at short notice, not only improve crystallization speed, and can improve the silicone content in heteroatoms phosphoric acid aluminum molecular screen, increased stability and the acidity of molecular sieve.The heteroatoms phosphoric acid aluminum molecular screen of removing structure directing agent through roasting can be used as ion-exchange material, adsorption and separation material and the catalytic material in oil, refining of petroleum and fine chemistry industry etc.
Brief description of the drawings
Fig. 1 is the XRD figure spectrum of synthetic MeSAPO-5 molecular sieve in example 1 of the present invention.
Fig. 2 is the XRD figure spectrum of synthetic MeSAPO-11 molecular sieve in example 6 of the present invention.
Embodiment
Embodiment 1
Adopt the main component of attapulgite to be: SiO 2content is 60.5%; Al 2o 3content is 10.1%; MgO content is 11.0%; Fe 2o 3content be 5.7%.
Above-mentioned attapulgite is ground to 40～50 μ m, by the sulphuric acid soln that massfraction is 10% activation treatment of purifying, 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, at 105 DEG C, dry.
By the attapulgite of the above-mentioned processing of 10.0g, 13.0gAl 2o 3content is 71% the thin water aluminium of plan and 270g water mix and blend 14h, then adds 85% phosphoric acid solution 23.1g, continues to stir after 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.
The above-mentioned slip for the treatment of crystallization is transferred in 500mL hydrothermal reaction kettle to crystallization 24h at 180 DEG C.Reaction finish 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 to 6h at 550 DEG C, can remove structure directing agent, obtain target product MeSAPO-5 molecular sieve.The XRD figure of the MeSAPO-5 molecular sieve of gained is composed as shown in Figure 1.
Embodiment 2
Adopt the composition of alum clay to be: 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 μ m, at 700 DEG C, calcines 2h and activate.
By the alum clay of the above-mentioned processing of 16.2g and 180g water mix and blend 14h, add again 85% phosphoric acid solution 23.1g, continue to stir after 2h, add the hydrofluoric acid of 0.500g20wt% to stir the triethylamine that adds 10.1g after 1h, at room temperature the aging 6h of mix and blend forms the slip for the treatment of crystallization.Me/Al mol ratio in slip is 0.3.
The above-mentioned slip for the treatment of crystallization is transferred in 500mL hydrothermal reaction kettle to crystallization 24h at 180 DEG C.Question response finishes rear material and goes out reactor, and naturally cools to after room temperature, and mix products, through filtering, washing, is dried at 80 DEG C, can obtain the MeSAPO-5 molecular screen primary powder that contains structure directing agent.
MeSAPO-5 molecular screen primary powder is calcined to 5.5h at 550 DEG C, remove structure directing agent, obtain target product MeSAPO-5 molecular sieve.
Embodiment 3
Adopt the composition of attapulgite to be: SiO 2content is 60.5%; Al 2o 3content is 10.1%; MgO content is 11.0%; Fe 2o 3content be 5.7%.
Above-mentioned attapulgite is ground to 20～30 μ m, by the sulphuric acid soln that massfraction is 10% activation treatment of purifying: the mass ratio of sulphuric acid soln and attapulgite is 8: 1, attapulgite magnetic agitation 4h in sulphuric acid soln at 25 DEG C, then use distilled water repeatedly to wash, until pH value is to stop washing at 6.0～7.0 o'clock, then dry at 105 DEG C.
By the attapulgite of the above-mentioned processing of 10.0g, 13.0gAl 2o 3content is 71% the thin water aluminium of plan and 270g water mix and blend 14h, add again 85% phosphoric acid solution 23.1g, continue to stir after 2h, add the diethanolamine of 10.5g, at room temperature the aging 12h of mix and blend forms the slip for the treatment of crystallization, and the Me/Al mol ratio in slip is 0.09.
The above-mentioned slip for the treatment of crystallization is transferred in 500mL hydrothermal reaction kettle to crystallization 36h at 200 DEG C.Question response finishes rear removal reactor and naturally cools to after room temperature, and mix products, through filtering, washing, is dried at 80 DEG C, can obtain the MeSAPO-5 molecular screen primary powder that contains structure directing agent.
MeSAPO-5 molecular screen primary powder is calcined to 5.5h at 550 DEG C, can remove structure directing agent, obtain target product MeSAPO-5 molecular sieve.
Embodiment 4
Adopt kaolinic composition to be: SiO 2content is 10.7%; Al 2o 3content is 58.2%;
Adopt the composition of recessed soil rod soil to be: SiO 2content is 60.5%; Al 2o 3content is 10.1%; MgO content is 11.0%; Fe 2o 3content be 5.7%.
Above-mentioned kaolin and attapulgite are ground to 60～80 μ m.Kaolin is calcined 2h and is carried out activation treatment at 750 DEG C.The sulphuric acid soln that massfraction is 10% activation treatment of purifying for attapulgite: 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 use distilled water repeatedly to wash, until pH value is to stop washing at 6.0～7.0 o'clock, then dry at 105 DEG C.
By the kaolin of the above-mentioned processing of 10.3g, 5.0g attapulgite and 180g water mix and blend 14h, add again 85% phosphoric acid solution 23.1g, continue to stir after 2h, add the triethylamine of 10.1g, the aging 6h of mix and blend under room temperature again, the slip of crystallization is treated in formation, and the Me/Al mol ratio in slip is 0.05.
The above-mentioned slip for the treatment of crystallization is transferred in 500mL hydrothermal reaction kettle to crystallization 24h at 180 DEG C.Question response finishes rear removal reactor and naturally cools to after room temperature, and mix products, through filtering, washing, is dried at 80 DEG C, can obtain the MeSAPO-5 molecular screen primary powder that contains structure directing agent.
MeSAPO-5 molecular screen primary powder is calcined to 5.5h at 550 DEG C, can remove structure directing agent, obtain target MeSAPO-5 molecular sieve.
Embodiment 5
Adopt the composition of alum clay to be: 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 μ m, at 700 DEG C, calcines 2h and activate.
By the alum clay of the above-mentioned processing of 16.2g and 180g water mix and blend 14h, add again 85% phosphoric acid solution 23.1g, continue to stir after 2h, add the di-n-propylamine of 10.1g, at room temperature the aging 6h of mix and blend forms the slip for the treatment of crystallization, and the Me/Al mol ratio in slip is 0.3.
The above-mentioned slip for the treatment of crystallization is transferred in 500mL hydrothermal reaction kettle to crystallization 36h at 180 DEG C.Question response finishes rear removal reactor and naturally cools to after room temperature, and mix products, through filtering, washing, is dried at 80 DEG C, can obtain the MeSAPO-11 molecular screen primary powder that contains structure directing agent.
MeSAPO-11 molecular screen primary powder is calcined to 5.5h at 550 DEG C, can remove structure directing agent completely, obtain target MeSAPO-11 molecular sieve.
Embodiment 6
Adopt the composition of attapulgite to be: SiO 2content is 60.5%; Al 2o 3content is 10.1%; MgO content is 11.0%; Fe 2o 3content be 5.7%.
Above-mentioned attapulgite is ground to 40～50 μ m, by the sulphuric acid soln that massfraction is 8% activation treatment of purifying: 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 use distilled water repeatedly to wash, until pH value is to stop washing at 6.0～7.0 o'clock, then dry at 105 DEG C.
By the attapulgite of the above-mentioned processing of 10.0g, 13.0gAl 2o 3content is 71% the thin water aluminium of plan and 270g water mix and blend 14h, add again 85% phosphoric acid solution 23.1g, continue to stir after 2h, add the HF solution of 1.0g20wt%, after stirring 1h, add the Diisopropylamine of 12.1g, under room temperature, the aging 6h of mix and blend forms the slip for the treatment of crystallization again, and the Fe/Al in slip is 0.03.
The above-mentioned slip for the treatment of crystallization is transferred in 500mL hydrothermal reaction kettle to crystallization 24h at 180 DEG C.Question response finishes rear removal reactor and naturally cools to after room temperature, and mix products, through filtering, washing, is dried at 80 DEG C, can obtain the MeSAPO-11 molecular screen primary powder that contains structure directing agent.
MeSAPO-11 molecular screen primary powder is calcined to 5.5h at 550 DEG C, can remove structure directing agent completely, obtain target MeSAPO-11 molecular sieve.The XRD figure of the MeSAPO-11 molecular sieve of gained is composed as shown in Figure 2.

Claims (8)

1. a synthetic method for heteroatoms phosphoric acid aluminium MeSAPO molecular sieve, is characterized in that: described synthetic method is, utilizes natural ore deposit soil that the required silicon source of molecular sieve, aluminium source and doping type metallic ore material source are provided, and prepares MeSAPO molecular sieve through hydrothermal crystallizing.
2. the synthetic method of heteroatoms phosphoric acid aluminium MeSAPO molecular sieve as claimed in claim 1, is characterized in that: the concrete steps of described method are,
(1) to the natural ore deposit soil after pulverizing, carry out acidifying purification or calcining and activating processing;
(2) acidifying in step (1) or the natural ore deposit soil that activated are mixed with to slip, in slip, mole proportioning 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;
(3), after the aging 6～24h of slip being prepared by step (2), be placed in hydrothermal reaction kettle, crystallization 2～100h at 120 DEG C～200 DEG C;
(4) by the material after hydrothermal crystallizing in step (3) after filtration, washing, the dry molecular screen primary powder that obtains;
(5) molecular screen primary powder step (4) being obtained is calcined under 400～800 DEG C, 2～20h, removes structure directing agent SDA, can obtain heteroatoms phosphoric acid aluminum molecular screen.
3. the synthetic method of heteroatoms phosphoric acid aluminium MeSAPO molecular sieve as claimed in claim 2, it is characterized in that: in step (1), described natural ore deposit soil is one or more the mixture in kaolin, diatomite, wilkinite, alum clay and attapulgite, natural ore deposit soil after pulverizing, grain diameter is 0.1～100 μ m.
4. the synthetic method of heteroatoms phosphoric acid aluminium MeSAPO molecular sieve as claimed in claim 2, 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 the soil of natural ore deposit according to the molar ratio of sial in the soil of natural ore deposit si: n al=0～1, do not add auxiliary aluminum source; n si: n al=1～5, add auxiliary aluminum source.
5. the synthetic method of heteroatoms phosphoric acid aluminium MeSAPO molecular sieve as claimed in claim 4, is characterized in that: described auxiliary aluminum source is for intending thin water aluminium, aluminium hydroxide, activated alumina, aluminum isopropylate or bauxitic clay.
6. the synthetic method of heteroatoms phosphoric acid aluminium MeSAPO molecular sieve as claimed in claim 2, it is characterized in that: in step (2), the source of fluorine is that solute massfraction is the hydrofluoric acid solution of 20wt%, and selects add or do not add hydrofluoric acid solution according to the molar ratio of metallic ore material and aluminium in the soil of natural ore deposit: the mol ratio n of metallic ore material and aluminium in the soil of natural ore deposit me: n al=0～0.2, do not add fluorion; n me: n al>=0.2, add fluorion.
7. the synthetic method of heteroatoms phosphoric acid aluminium MeSAPO molecular sieve as claimed in claim 2, 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.
8. the synthetic method of heteroatoms phosphoric acid aluminium MeSAPO molecular sieve as claimed in claim 2, is characterized in that: in step (3), select concrete digestion time, the mol ratio n of fluorine and aluminium according to the consumption of fluorine in step (2) f: n al=0～0.1 o'clock, digestion time was selected 12～24h; The mol ratio n of fluorine and aluminium f: n al=0.1～0.3 o'clock, digestion time was selected 6～12h.
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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CN107777702A (en) * 2017-11-09 2018-03-09 常州大学 A kind of preparation method of multi-stage porous hetero atom aluminium phosphate molecular sieve for oxidation sweetening
CN110040744A (en) * 2019-04-08 2019-07-23 福建师范大学 A kind of MeAPSO-34 molecular sieve and preparation method thereof
CN110372005A (en) * 2019-07-03 2019-10-25 常州大学 A method of multi-stage porous aluminium phosphate molecular sieve is synthesized using fluorine ion
CN110394151A (en) * 2019-08-06 2019-11-01 营口理工学院 A kind of high-grade diatomite and preparation method thereof with molecular sieve structure

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN107777702A (en) * 2017-11-09 2018-03-09 常州大学 A kind of preparation method of multi-stage porous hetero atom aluminium phosphate molecular sieve for oxidation sweetening
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
CN110040744A (en) * 2019-04-08 2019-07-23 福建师范大学 A kind of MeAPSO-34 molecular sieve and preparation method thereof
CN110040744B (en) * 2019-04-08 2022-07-01 福建师范大学 MeAPSO-34 molecular sieve and preparation method thereof
CN110372005A (en) * 2019-07-03 2019-10-25 常州大学 A method of multi-stage porous aluminium phosphate molecular sieve is synthesized using fluorine ion
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
CN110394151A (en) * 2019-08-06 2019-11-01 营口理工学院 A kind of high-grade diatomite and preparation method thereof with molecular sieve structure
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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