CN104888749A - Adjustable diatomite-based mineral solid acid material and preparation method thereof - Google Patents
Adjustable diatomite-based mineral solid acid material and preparation method thereof Download PDFInfo
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- CN104888749A CN104888749A CN201510221838.8A CN201510221838A CN104888749A CN 104888749 A CN104888749 A CN 104888749A CN 201510221838 A CN201510221838 A CN 201510221838A CN 104888749 A CN104888749 A CN 104888749A
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Abstract
The invention discloses an adjustable diatomite-based mineral solid acid material and a preparation method thereof. The preparation method comprises a, adding aluminum chloride into a strong base or strong alkali and weak acid salt solution with pH of 11-13 so that a mole ratio of Al<3+>/OH<-> in the solution of 1: 2-3, carrying out full stirring to obtain a uniform mixture, heating the mixture to a temperature of 50-70 DEG C, and keeping the temperature for 10-24h to obtain a polyhydroxyaluminum solution, b, according to a ratio of diatomite mass/polyhydroxyaluminum solution volume of 1g/20ml, adding diatomite into the polyhydroxyaluminum solution, carrying out full stirring, carrying out solid-liquid separation, drying the solids, and carrying out calcination at a temperature of 200-500 DEG C for 2h to obtain the adjustable diatomite-based mineral solid acid material. The diatomite-based mineral solid acid material has acid content and acid strength far higher than those of diatomite, has two acidic centers B and L and has heat adjustability.
Description
Technical field:
The invention belongs to mineral solids acid catalyst preparation field, being specifically related to one can modulation diatomite base mineral solids acid material and preparation method thereof.
Background technology:
Solid acid is a kind of new catalyst with high catalytic activity, pollution-free, less harmful.Replace the liquid acid with high environment potential hazard at present just gradually, become the catalyst that part industrial circle is important.It is applied is the important step realizing green industry.Diatomite is a kind of by the mineral resources formed after diatom organic remains (diatom shell) accumulation and sediment, and its primary chemical consists of amorphous silica.There is certain solid acid in its surface, is mainly derived from the silicone hydroxyl on surface.But diatomite surface solid acidity is more weak, acid amount is lower, only can be applicable in faintly acid catalyst system and catalyzing, therefore application is few.Up to now, only there is Chinese invention patent " a kind of diatomite prepares the method for porous charcoal and the white carbon " (patent No.: 201010245769.1), diatomite surface solid acid position is utilized to be catalyst, catalysis carbon source furfuryl alcohol etc. makes it polymerization, thus formation carbon precursor, and then go out to have the porous charcoal of diatomite pattern by template synthesis.Visible, the difficulty directly diatomite solid acid being used for Industrial Catalysis is larger.
On the other hand, utilize diatomite macropore pattern and comparatively single element composition and then preparation to become loaded solid-acid material then comparatively common, in Industrial Catalysis field, there is certain application.As, prepare the diatom soil matrix composite solid acid with high catalytic activity and intensity by load acid or metal oxide etc., comprise H
3pO
4/ diatomite, SnO
2/ diatomite, V
2o
5/ diatomite etc.Wherein, H
3pO
4/ diatomite supports acid and can be used for catalyzing propone polymerization and benzene-alkylation (Chen Yongfu, 1999); SnO
2/ composite diatomite solid acid can carry out catalytic esterification to n-butyric acie and isoamyl alcohol; And load has V
2o
5diatomite solid acid then can be used as catalyst (Yu Chien prepared by sulfuric acid, 1999).But there is following problem in above-mentioned composite solid acid material preparations and applicatio:
1) complicated process of preparation.With regard to the simplest H of processing step
3pO
4/ diatomite supports acid, first its synthesis needs polyphosphoric acid, diatomite and boric acid mixed-forming at a certain temperature by a certain percentage, then calcine high-temperature roasting at relatively high temperatures, also need subsequently can obtain (Zhu Zhirong, 1997) through steam treatment again.Oxide type diatomite supports acid and then needs first synthesis oxide, then through high-temperature calcination, needs high-temperature calcination together with the concentrated sulfuric acid (Chen Danyun, 2010) even again.
2) prepare material needed for and there is toxicity or latency environment harmfulness.As, SnO
2snO in/diatomite
2presoma SnCl
4there is certain toxicity; And V
2o
5for extremely toxic substance (Bi Xianjun, 2002), very big to harm.Above-mentionedly support liquid acid used in acid preparation process and then have certain potential hazard to environment, therefore, diatomite supports solid acid preparation process and does not possess environment friendly, to environment and harm all larger.
3) catalytic applications narrow range, universality is poor.Above-mentionedly support acid only there is a kind of solid acid:
(B) or Lewis (L) acid, range of application is narrower.H
3pO
4it is acid that/diatomite supports acid main display B, and V
2o
5/ diatomite supports acid and then there is L acidity.And above-mentioned solid acid acidity can not modulation, therefore, only can play remarkable catalytic action for certain catalytic reaction specific, not possess catalysis universality.In addition, above-mentioned catalyst also exists that catalytic active center load is uneven, and acid site is easily separated with diatomite support, cause catalytic effect to be difficult to ensure, and preparation cost is high, is unfavorable for the problems such as practical application.
Therefore, preparation has that technique is simple, the low cost diatomite based solid acid catalyst of environmental protection and universality strong (polyacid, acidity can modulation) is the key solved the problem.
Summary of the invention:
The object of the invention is to overcome that diatomite solid acid in prior art directly utilizes difficulty, supports sour complicated process of preparation, environmental hazard is large, catalytic applications narrow range and catalytic effect be difficult to the shortcomings such as guarantee, there is provided a kind of polyacid and acidity can modulation, what all have good catalytic activity before and after modulation can modulation diatomite base mineral solids acid material and preparation method thereof.It is simple that this preparation method has technique, mild condition, and energy consumption is low, and latency environment harm is lower, the advantages such as low cost.
Of the present invention can modulation diatomite base mineral solids acid material prepare by the following method, the method comprises the following steps:
In a, highly basic aluminium chloride being joined pH 11 ~ 13 or strong base weak acid salting liquid, make the Al in solution
3+/ OH
-the ratio of amount of substance is 1:2 ~ 3, is warming up to 50 ~ 70 DEG C after fully stirring and evenly mixing, and constant temperature, after 10 ~ 24 hours, obtains polyhydroxy aluminum solutions;
B, according to diatomite quality/polyhydroxy aluminum solutions volume ratio 1g/20ml, diatomite is joined in polyhydroxy aluminum solutions, Separation of Solid and Liquid after abundant stirring, by gained solid after drying at 200 ~ 500 DEG C of calcining 1-3 hour, obtaining can modulation diatomite base mineral solids acid material.
Highly basic in described step a is NaOH or potassium hydroxide, and described strong base-weak acid salt is sodium acid carbonate, sodium carbonate, saleratus or potash etc.
In described step b, diatomite refers to the diatomite that in raw ore, diatom shell mass percentage content is greater than 60%.
Advantage of the present invention and good effect embody a concentrated reflection of in following some:
1. shortcoming, the obtained strong acid center containing Al-, Si-OH-Al or Si-O-Al-OH, the low cost diatom soil matrix mineral solids acid material such as instant invention overcomes that existing diatomite catalyst solid acidity is weak, the low and diatomite of acid amount supports acid preparation process complexity, environment potential hazard is large and cost is higher.In addition, preparation method of the present invention and end product, all do not produce radioactive substance environment to threat.Therefore, its chemical production processes should belong to " Green Chemistry " with environmental protection and energy saving feature.
2. instant invention overcomes diatomite and diatomite and support the deficiency that the solid-acid material such as acid only possess a kind of acid site.Gained diatomite based solid acid possesses two kinds of acid sites simultaneously, and its acidity carries out modulation by heat treatment.As, there are close B and the L two kinds of sour positions of sour amount in 200 DEG C of heat treatment gained diatomite based solid acid surfaces, and after further heat treatment (500 DEG C), its solid acid is based on L acid simultaneously, only sour containing minute quantity B.
3. the present invention carries out the method for condensation by the hydroxyl in diatomite surface hydroxyl and polyhydroxy aluminium, improves diatomite surface solid acid.The solid acid position formed is diatomite-polyhydroxy aluminium complex inherent structure, but not similar support sour solid acid position be only loaded article own, it has high stability.Avoiding problems loaded solid acid acidity and be subject to acid centre load characteristic, as load capacity, Load Balanced degree etc. and load acid site are easy to the impact that to be come off etc. by diatomite surface.
The silicone hydroxyl that the present invention utilizes diatomite surface abundant, polyhydroxy aluminium is adopted to be presoma, make it condensation reaction occurs under the condition of Low Temperature Heat Treatment, by aluminium " grafting " in diatomite surface, form B acid site (Si-OH-Al or Si-O-Al-OH) and L acid site (Al-) with strong solid acidity simultaneously, thus form the composite solid acid with two solid acid activated centre.The diatomite based solid acid material acid amount utilizing the present invention to obtain and acid strength are not only far above diatomite, and it possesses B and L two kinds of acid centres simultaneously, and the adjustable sex change of tool heat.In addition, this compound solid-acid stability of material is far above loaded diatomite solid acid.Meanwhile, the preparation method of diatomite based solid acid material provided by the invention has technique simply, and mild condition, pollutes low, the feature that energy consumption is low, and prospects for commercial application is wide.
Accompanying drawing illustrates:
Fig. 1 be diatomite original soil and gained of the present invention can the X-ray diffractogram of modulation diatomite base mineral solids acid material.As we can see from the figure, though through the load of polyhydroxy aluminium and through different temperatures calcining, it can modulation diatomite base mineral solids acid material be still unformed phase that institute obtains.Prove that this can not form new mineral or oxide crystal phase by modulation diatomite base mineral solids acid material.
Fig. 2 is that diatomite original soil and gained of the present invention can the infrared spectrograms of modulation diatomite base mineral solids acid material.Contrast diatomite original soil and gained can the infrared spectrum of modulation diatomite base mineral solids acid material known, diatomite is through the load of polyhydroxy aluminium and after heat-treating, occurred Si-O-Al key (745cm
-1), this shows, can be formed by surface hydroxyl and the generation condensation reaction of polyhydroxy aluminium hydroxyl by diatomite by modulation diatomite base mineral solids acid material.
Fig. 3 is that diatomite original soil and gained of the present invention can the ammonia absorption infrared spectrograms of modulation diatomite base mineral solids acid material.By ammonia from can the product that reacts of modulation diatomite base mineral solids acid material different acid centre different, can obtain can the acids type of modulation diatomite base mineral solids acid material and relative amount.As seen from the figure, after load also 200 and 350 DEG C of calcinings, can all there is significant 1640 and 1405cm by modulation diatomite base mineral solids acid material in gained
-1l and the B acid position of wave number, in conjunction with the characteristic peak of ammonia, show it all containing L and B acid position, and after 200 DEG C of calcinings, itself L with B acid amount is substantially identical.But can its L acid of modulation diatomite base mineral solids acid material measure far above B acid amount through 500 DEG C of calcining gained, this shows, high-temperature heat treatment can carry out modulation to B and L acid site quantity.
Detailed description of the invention:
Following examples further illustrate of the present invention, instead of limitation of the present invention.
Embodiment 1:
1) preparation of polyhydroxy aluminium: joined by aluminium chloride in the sodium hydroxide solution of pH 11, makes the Al in solution
3+/ OH
-the ratio of amount of substance is 1:2, is warming up to 50 DEG C after fully stirring and evenly mixing, and constant temperature, after 10 hours, can obtain polyhydroxy aluminum solutions.
2) can modulation diatomite base mineral solids acid material preparation: according to the diatomite (diatomite that in raw ore, diatom shell mass percentage content is greater than 60%, down together) diatomite joins in above-mentioned polyhydroxy aluminum solutions by the ratio of quality/polyhydroxy aluminum solutions volume ratio 1g/20mL (namely adding the diatomite of 1g in every 20ml polyhydroxy aluminum solutions), abundant stirring carries out Separation of Solid and Liquid by filtration afterwards, by gained solid after drying 200 DEG C of calcinings 3 hours, obtaining can modulation diatomite base mineral solids acid material.
Obtained can modulation diatomite base mineral solids acid material its still retain diatomite undefined structure (solid acid in Fig. 1, Fig. 1 200 DEG C is fired), there is not new mineral diffractive features peak or oxide crystal characteristic peak.Si-O-Al (745cm is there is in infrared spectrum
-1) infrared signature peak (Fig. 2, solid acid in Fig. 2 200 DEG C is fired), this peak derives from Si-O-Al-OH or Si-OH-Al, and this shows to be formed by surface hydroxyl and the generation condensation reaction of polyhydroxy aluminium hydroxyl by diatomite by modulation diatomite base mineral solids acid material.After ammonia and diatomite based solid acid material acid site react, infrared spectrum occurs obvious 1640 and 1405cm
-1l and B acid position in conjunction with the characteristic peak (solid acid in Fig. 3, Fig. 3 200 DEG C is fired) of ammonia, show it simultaneously containing L and B acid site.And above-mentioned two peak relative integral area difference are less, show that the acid amount in two kinds of acid sites is close to identical.
Embodiment 2:
1) preparation of polyhydroxy aluminium: joined by aluminium chloride in the sodium hydroxide solution of pH 12, makes the Al in solution
3+/ OH
-the ratio of amount of substance is 1:3, is warming up to 70 DEG C after fully stirring and evenly mixing, and constant temperature, after 24 hours, can obtain polyhydroxy aluminum solutions.
2) can modulation diatomite base mineral solids acid material preparation: according to diatomite quality/polyhydroxy aluminum solutions volume ratio 1g/20mL, diatomite is joined in above-mentioned polyhydroxy aluminum solutions, abundant stirring carries out Separation of Solid and Liquid by filtration afterwards, by gained solid after drying 350 DEG C of calcinings 2 hours, obtaining can modulation diatomite base mineral solids acid material.
Obtained can modulation diatomite base mineral solids acid material its still retain diatomite undefined structure (solid acid in Fig. 1, Fig. 1 350 DEG C is fired).Also there is Si-O-Al infrared signature peak (solid acid in Fig. 2, Fig. 2 350 DEG C is fired) in infrared spectrum, shown that this solid acid architectural source is in the condensation reaction of diatomite and polyhydroxy aluminium.Ammonia with can there is 1640 and 1405cm in the infrared spectrum that reacts of modulation diatomite base mineral solids acid material
-1l and B acid position in conjunction with the characteristic peak (solid acid in Fig. 3, Fig. 3 350 DEG C is fired) of ammonia, show it simultaneously containing L and B acid site.Can according to above-mentioned two peak relative integral areas, what obtain under distinguishing this temperature (350 DEG C) can modulation diatomite base mineral solids acid material L acid amount measure slightly larger than B acid.
Embodiment 3:
1) preparation of polyhydroxy aluminium: joined by aluminium chloride in the sodium hydroxide solution of pH 13, makes the Al in solution
3+/ OH
-the ratio of amount of substance is 1:2.4, is warming up to 60 DEG C after fully stirring and evenly mixing, and constant temperature, after 12 hours, can obtain polyhydroxy aluminum solutions.
2) preparation of diatomite based solid acid material: diatomite is joined in above-mentioned polyhydroxy aluminum solutions according to diatomite quality/polyhydroxy aluminum solutions volume ratio 1g/20mL, Separation of Solid and Liquid is carried out by centrifugal after abundant stirring, by gained solid after drying 500 DEG C of calcinings 1 hour, obtaining can modulation diatomite base mineral solids acid material.
Obtained can modulation diatomite base mineral solids acid material its still retain diatomite undefined structure (solid acid in Fig. 1, Fig. 1 500 DEG C is fired).Also there is Si-O-Al infrared signature peak (solid acid in Fig. 2, Fig. 2 500 DEG C is fired) in infrared spectrum, shown that this solid acid architectural source is in the condensation reaction of diatomite and polyhydroxy aluminium.Ammonia with can there is strong 1640cm in the infrared spectrum that reacts of modulation diatomite base mineral solids acid material
-1the characteristic peak of ammonia and L acid position product and weak 1405cm
-1ammonia and B acid position product characteristic peak (solid acid in Fig. 3, Fig. 3 500 DEG C is fired), show it simultaneously containing L and B acid site, but its B acid position content is considerably less, L acid site quantity is far above B acid site quantity.Show, this solid-acid material is acid based on L.
Claims (3)
1. can modulation diatomite base mineral solids acid material a preparation method, it is characterized in that, comprise the following steps:
In a, highly basic aluminium chloride being joined pH 11 ~ 13 or strong base weak acid salting liquid, make the Al in solution
3+/ OH
-the ratio of amount of substance is 1:2 ~ 3, is warming up to 50 ~ 70 DEG C after fully stirring and evenly mixing, and constant temperature, after 10 ~ 24 hours, obtains polyhydroxy aluminum solutions;
B, according to diatomite quality/polyhydroxy aluminum solutions volume ratio 1g/20ml, diatomite is joined in polyhydroxy aluminum solutions, Separation of Solid and Liquid after abundant stirring, by gained solid after drying at 200 ~ 500 DEG C of calcining 1-3 hour, obtaining can modulation diatomite base mineral solids acid material.
2. preparation method according to claim 1, is characterized in that, the highly basic in described step a is NaOH or potassium hydroxide, and described strong base-weak acid salt is sodium acid carbonate, sodium carbonate, saleratus or potash.
3. one kind according to preparation method according to claim 1 prepare can modulation diatomite base mineral solids acid material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614453A (en) * | 1991-09-11 | 1997-03-25 | Uop | Catalyst containing zeolite beta and a pillared clay |
| CN102698711A (en) * | 2012-06-08 | 2012-10-03 | 中南林业科技大学 | Pillared modified kieselguhr for adsorbing Pb<2+> and/or Cd<2+> and preparation method and application of pillared modified kieselguhr |
-
2015
- 2015-04-30 CN CN201510221838.8A patent/CN104888749A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614453A (en) * | 1991-09-11 | 1997-03-25 | Uop | Catalyst containing zeolite beta and a pillared clay |
| CN102698711A (en) * | 2012-06-08 | 2012-10-03 | 中南林业科技大学 | Pillared modified kieselguhr for adsorbing Pb<2+> and/or Cd<2+> and preparation method and application of pillared modified kieselguhr |
Non-Patent Citations (1)
| Title |
|---|
| 温勇等: "柱撑粘土合成柱化机理及应用研究进展", 《南京工业大学学报》 * |
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Application publication date: 20150909 |
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