CN105056976B - Preparation method of vulcanized zirconium dioxide serving as solid acid catalyst and having high specific surface area - Google Patents
Preparation method of vulcanized zirconium dioxide serving as solid acid catalyst and having high specific surface area Download PDFInfo
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Abstract
The invention provides a preparation method of vulcanized zirconium dioxide serving as a solid acid catalyst and having a high specific surface area and relates to a preparation method of the vulcanized zirconium dioxide serving as the solid acid catalyst. The preparation method solves the problems that an existing vulcanized zirconium dioxide preparation method is complicated, the preparation time is long, and the specific surface area of prepared vulcanized zirconium dioxide is small. The preparation method comprises steps as follows: (1), preparing hydroxide of zirconium; (2), preparing powdery solids; (3), performing calcination to obtain vulcanized zirconium dioxide which serves as a solid acid catalyst and has a high specific surface area. The method is used for preparing vulcanized zirconium dioxide serving as the solid acid catalyst and having the high specific surface area.
Description
Technical field
The present invention relates to solid acid catalyst vulcanizes the preparation method of zirconium dioxide.
Background technology
The organic reactions such as the isomerization reaction of hydro carbons have in the oil industry consequence, directly affect country Jing
The development of Ji.Generally these reactions only just can be carried out under strongly acidic conditions, but reaction liquid acid catalyst used can promote
Enter the corrosion of reaction member, be difficult to be separated with product, environment is polluted, while with certain danger.So using solid
Acid catalyst replaces liquid acid catalyst to have good development prospect, this is because solid acid catalyst can be solved well
The problems such as difficult separation, pollution environment, etching apparatus of liquid acid catalyst.Recently, existing lot of documents reports zeolite molecules
The preparation and application of the solid acid catalysts such as sieve, ion exchange resin, metal-oxide.
In solid acid catalyst, vulcanize zirconium dioxide (SO4 2-/ZrO2) extensive concern of researchers is caused, this is
Because sulfuration zirconium dioxide (SO4 2-/ZrO2) there is special surface acid property, it has in the important reaction of many industry
Good application prospect.On the other hand, the catalysis activity of catalyst is relevant with its specific surface area, and higher specific surface area can be with
More active site is provided.So the sulfuration zirconium dioxide (SO of the solid acid catalyst with high-specific surface area4 2-/
ZrO2) it is a kind of catalyst for having a good application prospect.
Although having lot of documents and document announcement sulfuration zirconium dioxide (SO4 2-/ZrO2) preparation method, that is, adopt
Sol-gel process, this preparation method is complicated and lasts longer, and required time is 72h～82h, and the sulfuration titanium dioxide for obtaining
Zirconium (SO4 2-/ZrO2) specific surface area it is less, i.e., specific surface area is generally 70m2/ g～100m2/g.So far there are no ratio can be increased
The document report of surface area and simplified preparation method.
The content of the invention
The invention solves the problems that the preparation method of existing sulfuration zirconium dioxide is complicated, preparation time is long, the sulfuration two prepared
The less problem of zirconium oxide specific surface area, and a kind of sulfuration of the solid acid catalyst with high-specific surface area zirconium dioxide is provided
Preparation method.
First, the hydroxide of zirconium is prepared：
At room temperature, by ZrOCl2·8H2O is mixed and stirred for dissolving with deionized water, obtains ZrOCl2Solution, by ammonia
Middle N element and ZrOCl2·8H2The mol ratio of Zr elements is 5.5 in O:1 ratio weighs ammonia, then in room temperature and stirring bar
Under part, the ammonia for weighing is added drop-wise to into ZrOCl2In solution, obtain mixture, at room temperature, stir the mixture for first 1h～
2h, is then aged 12h～24h, is precipitated liquid, and precipitated liquid is filtered, and is washed with deionized precipitate to nothing in cleaning mixture
Chloride ion, the precipitate after being washed finally is placed in the precipitate after washing in the baking oven that temperature is 80 DEG C～100 DEG C,
12h～24h is dried, that is, obtains the hydroxide of zirconium；
Described ZrOCl2·8H2The quality of O is 1g with the volume ratio of deionized water:7.7580mL；
2nd, pulverulent solids are prepared：
The hydroxide and solid ammonium sulfate of zirconium are weighed, at room temperature, by the hydroxide and solid sulphuric acid of the zirconium for weighing
Ammonium is placed in mortar, and mix homogeneously simultaneously grinds, and obtains white powdery solids；
The hydroxide of described zirconium and the mol ratio 1 of solid ammonium sulfate:(4～8)；
3rd, calcine：
White powdery solids are placed in Muffle furnace, with programming rate as 5 DEG C/min, Muffle furnace 600 DEG C is warming up to into
～750 DEG C, then under conditions of temperature is for 600 DEG C～750 DEG C, 5h is calcined, obtain solid acid catalyst SO4 2-/ZrO2, i.e.,
Solid acid catalyst with high-specific surface area sulfuration zirconium dioxide.
The invention has the beneficial effects as follows：1st, zirconium dioxide (SO is vulcanized4 2-/ZrO2) preparation by complicated sol-gel process
Solid-phase sequencing is reduced to, i.e., is participated in without solution in preparation process, preparation process can be simplified, preparation time is by original
72h～82h tapers to 50h-55h.
2nd, sulfuration zirconium dioxide (SO prepared by solid-phase sequencing4 2-/ZrO2) than the sulfuration dioxy of sol-gel process preparation
Change zirconium (SO4 2-/ZrO2) specific surface area it is big, surface area can reach 153m2/ g, and the standby sulfuration zirconium dioxide of traditional law system
(SO4 2-/ZrO2) specific surface area there was only 87m2/ g, larger specific surface area can provide more catalytic active sites for reaction
Point.
Description of the drawings
Fig. 1 is that calcining heat is identical, when mol ratio is different, the N of the sulfuration zirconium dioxide of preparation in 77K2Isothermal adsorption-de-
Attached curve；A is the standby sulfuration zirconium dioxide of example IV traditional law system, and b is sulfuration zirconium dioxide prepared by embodiment two；C is
Sulfuration zirconium dioxide prepared by embodiment one；D is sulfuration zirconium dioxide prepared by embodiment three；
Fig. 2 is that mol ratio is identical, when calcining heat is different, the N of the sulfuration zirconium dioxide of preparation in 77K2Isothermal adsorption-de-
Attached curve；E is sulfuration zirconium dioxide prepared by embodiment five；F is sulfuration zirconium dioxide prepared by embodiment six；G is embodiment
The one sulfuration zirconium dioxide for preparing；H is sulfuration zirconium dioxide prepared by embodiment seven；I is sulfuration dioxy prepared by embodiment eight
Change zirconium.
Specific embodiment
Specific embodiment one：A kind of sulfuration of the solid acid catalyst with high-specific surface area two described in present embodiment
Zirconic preparation method is completed according to the following steps：
First, the hydroxide of zirconium is prepared：
At room temperature, by ZrOCl2·8H2O is mixed and stirred for dissolving with deionized water, obtains ZrOCl2Solution, by ammonia
Middle N element and ZrOCl2·8H2The mol ratio of Zr elements is 5.5 in O:1 ratio weighs ammonia, then in room temperature and stirring bar
Under part, the ammonia for weighing is added drop-wise to into ZrOCl2In solution, obtain mixture, at room temperature, stir the mixture for first 1h～
2h, is then aged 12h～24h, is precipitated liquid, and precipitated liquid is filtered, and is washed with deionized precipitate to nothing in cleaning mixture
Chloride ion, the precipitate after being washed finally is placed in the precipitate after washing in the baking oven that temperature is 80 DEG C～100 DEG C,
12h～24h is dried, that is, obtains the hydroxide of zirconium；
Described ZrOCl2·8H2The quality of O is 1g with the volume ratio of deionized water:7.7580mL；
2nd, pulverulent solids are prepared：
The hydroxide and solid ammonium sulfate of zirconium are weighed, at room temperature, by the hydroxide and solid sulphuric acid of the zirconium for weighing
Ammonium is placed in mortar, and mix homogeneously simultaneously grinds, and obtains white powdery solids；
The hydroxide of described zirconium and the mol ratio 1 of solid ammonium sulfate:(4～8)；
3rd, calcine：
White powdery solids are placed in Muffle furnace, with programming rate as 5 DEG C/min, Muffle furnace 600 DEG C is warming up to into
～750 DEG C, then under conditions of temperature is for 600 DEG C～750 DEG C, 5h is calcined, obtain solid acid catalyst SO4 2-/ZrO2, i.e.,
Solid acid catalyst with high-specific surface area sulfuration zirconium dioxide.
Precipitate is washed with deionized in this specific embodiment step one, to using AgNO3In solution inspection cleaning mixture
Without chloride ion.
This specific embodiment step 3 can remove Nitrogen Impurities in product, moisture and other impurity.
Principle：The standby sulfuration zirconium dioxide (SO of polishing and traditional law system4 2-/ZrO2), sulfate radical with double coordination modes with
The zirconium effect of zirconium surface, and the double Coordination Adsorptions formed on this surface are sulfuration zirconium dioxide (SO4 2-/ZrO2) provide
Solid acid acid site, and the hydroxide of zirconium is different from the model of action of sulfate radical, can make the sulfuration zirconium dioxide of preparation
(SO4 2-/ZrO2) in it is different with the amount of the sulfate radical of double Coordination Adsorptions, so as to form the acid intensity in acid site and the ratio of particle
Surface area is also not quite similar.So the particle size and specific surface area that vulcanize zirconium dioxide that different preparation methoies is prepared are not
Together.Meanwhile, the change of calcining heat can change sulfuration zirconium dioxide (SO4 2-/ZrO2) in the sulfate radical of double Coordination Adsorptions
Amount, so the specific surface area of the acid intensity of the sulfuration zirconium dioxide after different calcining heats is processed and particle is also different.
The beneficial effect of present embodiment is：1st, zirconium dioxide (SO is vulcanized4 2-/ZrO2) preparation by complicated colloidal sol-solidifying
Glue method is reduced to solid-phase sequencing, i.e., participate in without solution in preparation process, can simplify preparation process, and preparation time is by original
72h～the 82h for coming tapers to 50h-55h.
2nd, sulfuration zirconium dioxide (SO prepared by solid-phase sequencing4 2-/ZrO2) than the sulfuration dioxy of sol-gel process preparation
Change zirconium (SO4 2-/ZrO2) specific surface area it is big, surface area can reach 153m2/ g, and the standby sulfuration zirconium dioxide of traditional law system
(SO4 2-/ZrO2) specific surface area there was only 87m2/ g, larger specific surface area can provide more catalytic active sites for reaction
Point.
Specific embodiment two：Present embodiment from unlike specific embodiment one：In step one at room temperature, it is first
1h is first stirred the mixture for, 24h is then aged, liquid is precipitated.Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment from unlike specific embodiment one or one of two：In step one most
The precipitate after washing is placed in the baking oven that temperature is 100 DEG C afterwards, is dried 24h, that is, obtain the hydroxide of zirconium.Other and tool
Body embodiment one or two is identical.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Institute in step 2
The hydroxide of the zirconium stated and the mol ratio 1 of solid ammonium sulfate:4.Other are identical with specific embodiment one to three.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：Institute in step 2
The hydroxide of the zirconium stated and the mol ratio 1 of solid ammonium sulfate:6.Other are identical with specific embodiment one to four.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：Institute in step 2
The hydroxide of the zirconium stated and the mol ratio 1 of solid ammonium sulfate:8.Other are identical with specific embodiment one to five.
Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：Will in step 3
White powdery solids are placed in Muffle furnace, with programming rate as 5 DEG C/min, Muffle furnace are warming up to into 600 DEG C.Other with it is concrete
Embodiment one to six is identical.
Specific embodiment eight：Unlike one of present embodiment and specific embodiment one to seven：In step 3 so
Afterwards under conditions of temperature is for 600 DEG C, 5h is calcined.Other are identical with specific embodiment one to seven.
Specific embodiment nine：Unlike one of present embodiment and specific embodiment one to eight：Will in step 3
White powdery solids are placed in Muffle furnace, with programming rate as 5 DEG C/min, Muffle furnace are warming up to into 650 DEG C.Other with it is concrete
Embodiment one to eight is identical.
Specific embodiment ten：Unlike one of present embodiment and specific embodiment one to nine：In step 3 so
Afterwards under conditions of temperature is for 650 DEG C, 5h is calcined.Other are identical with specific embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：
A kind of solid acid catalyst with high-specific surface area described in the present embodiment vulcanizes the preparation method of zirconium dioxide
Complete according to the following steps：
First, the hydroxide of zirconium is prepared：
At room temperature, by 6.445g ZrOCl2·8H2O is mixed and stirred for dissolving with 50mL deionized waters, obtains ZrOCl2
Solution, by N element in ammonia and ZrOCl2·8H2The mol ratio of Zr elements is 5.5 in O:1 ratio weighs 7.205g mass hundred
Fraction is 26% ammonia, then under room temperature and stirring condition, the ammonia for weighing is added drop-wise to into ZrOCl2In solution, mixed
Compound, at room temperature, stirs the mixture for first 1h, is then aged 24h, is precipitated liquid, and precipitated liquid is filtered, and uses deionization
Precipitate after washing, without chloride ion, the precipitate after being washed, is finally placed in temperature by water washing precipitate into cleaning mixture
Spend in the baking oven for 100 DEG C, be dried 24h, that is, obtain the hydroxide of zirconium；
2nd, pulverulent solids are prepared：
The hydroxide and 3.6113g solid ammonium sulfates of 0.725g zirconiums are weighed, at room temperature, by the hydroxide of the zirconium for weighing
Thing and solid ammonium sulfate are placed in mortar, and mix homogeneously simultaneously grinds, and grind 30min, obtain white powdery solids；
3rd, calcine：
White powdery solids are placed in Muffle furnace, with programming rate as 5 DEG C/min, Muffle furnace 600 DEG C is warming up to into,
Then under conditions of temperature is for 600 DEG C, 5h is calcined, obtains solid acid catalyst SO4 2-/ZrO2, i.e., with high-specific surface area
Solid acid catalyst vulcanizes zirconium dioxide.
The hydroxide of the zirconium i.e. described in the present embodiment step 2 and the mol ratio 1 of solid ammonium sulfate:6.
Embodiment two：The present embodiment from unlike embodiment one：Weigh in step 2 0.725g zirconiums hydroxide and
2.4075g solid ammonium sulfate.Other are identical with embodiment one.
The hydroxide of the zirconium i.e. described in the present embodiment step 2 and the mol ratio 1 of solid ammonium sulfate:4.
Embodiment three：The present embodiment from unlike embodiment one：Weigh in step 2 0.725g zirconiums hydroxide and
4.8151g solid ammonium sulfate.Other are identical with embodiment one.
The hydroxide of the zirconium i.e. described in the present embodiment step 2 and the mol ratio 1 of solid ammonium sulfate:8.
Example IV：The contrast experiment of embodiment one to three, is specifically carried out according to the following steps：By 0.99g solid sulfurs
Sour ammonium is dissolved in deionized water, obtains the ammonium sulfate that 15mL concentration is 0.5mol/L, then adds in the hydroxide of 1g zirconiums
Enter in the ammonium sulfate that concentration is 0.5mol/L, 2h is stirred at room temperature, filter, solid product is obtained, by solid product
In being placed in the baking oven that temperature is 100 DEG C, 12h is dried, obtains dried product, dried product is placed in Muffle furnace,
With programming rate as 5 DEG C/min, Muffle furnace is warming up to into 600 DEG C, then under conditions of temperature is for 600 DEG C, calcines 5h, obtained
The standby solid acid catalyst SO of traditional law system4 2-/ZrO2。
Embodiment five：For contrast experiment, the present embodiment from unlike embodiment one：With programming rate as 5 in step 3
DEG C/min, and Muffle furnace is warming up to into 450 DEG C, then under conditions of temperature is for 450 DEG C, calcine 5h.Other and the phase of embodiment one
Together.
Embodiment six：For contrast experiment, the present embodiment from unlike embodiment one：With programming rate as 5 in step 3
DEG C/min, and Muffle furnace is warming up to into 550 DEG C, then under conditions of temperature is for 550 DEG C, calcine 5h.Other and the phase of embodiment one
Together.
Embodiment seven：The present embodiment from unlike embodiment one：With programming rate as 5 DEG C/min in step 3, by horse
Not stove is warming up to 650 DEG C, then under conditions of temperature is for 650 DEG C, calcines 5h.Other are identical with embodiment one.
Embodiment eight：The present embodiment from unlike embodiment one：With programming rate as 5 DEG C/min in step 3, by horse
Not stove is warming up to 750 DEG C, then under conditions of temperature is for 750 DEG C, calcines 5h.Other are identical with embodiment one.
SO obtained in the distinct methods of table 14 2-/ZrO2Specific surface area and pore volume
As shown in Table 1, when calcining heat is 600 DEG C, with the increase of ammonium sulfate solids amount, zirconium dioxide is vulcanized
(SO4 2-/ZrO2) specific surface area first increases and then decreases.When the hydroxide of the zirconium of solid and the mol ratio of solid ammonium sulfate are
1:When 6, the sulfuration zirconium dioxide (SO of preparation4 2-/ZrO2) specific surface area be 124m2/ g, and sulfuration two prepared by traditional method
Zirconium oxide (SO4 2-/ZrO2) specific surface area be 87m2/ g, so, when calcining heat is 600 DEG C, the hydrogen of the zirconium of abrasive solid
The mol ratio of oxide and solid ammonium sulfate is 1:Sulfuration zirconium dioxide (the SO that 6 mixture is prepared4 2-/ZrO2) than passing
Sulfuration zirconium dioxide (SO prepared by system method4 2-/ZrO2) specific surface area it is big.Polishing selects the hydroxide of the zirconium of solid
It is 1 with the mol ratio of solid ammonium sulfate:6.
The SO that in the polishing of table 2 prepared by different calcining heats4 2-/ZrO2Specific surface area and pore volume
As shown in Table 2, when the hydroxide of zirconium and the mol ratio of solid ammonium sulfate of solid are 1:When 6, with calcining temperature
The rising of degree, vulcanizes zirconium dioxide (SO4 2-/ZrO2) specific surface area first increases and then decreases.When calcining heat is 650 DEG C, system
Standby sulfuration zirconium dioxide (SO4 2-/ZrO2) specific surface area it is maximum, so the calcining heat that polishing is selected is 650 DEG C.
Fig. 1 is that calcining heat is identical, when mol ratio is different, the N of the sulfuration zirconium dioxide of preparation in 77K2Isothermal adsorption-de-
Attached curve；A is the standby sulfuration zirconium dioxide of example IV traditional law system, and b is sulfuration zirconium dioxide prepared by embodiment two；C is
Sulfuration zirconium dioxide prepared by embodiment one；D is sulfuration zirconium dioxide prepared by embodiment three.Can show that solid phase is ground by Fig. 1
Sulfuration zirconium dioxide (SO prepared by mill method4 2-/ZrO2Although) material molar ratio difference, in the N of 77K2Adsorption-desorption isothermal is bent
Line has obvious hysteresis loop, is III type adsorption-desorption curve.
Fig. 2 is that mol ratio is identical, when calcining heat is different, the N of the sulfuration zirconium dioxide of preparation in 77K2Isothermal adsorption-de-
Attached curve；E is sulfuration zirconium dioxide prepared by embodiment five；F is sulfuration zirconium dioxide prepared by embodiment six；G is embodiment
The one sulfuration zirconium dioxide for preparing；H is sulfuration zirconium dioxide prepared by embodiment seven；I is sulfuration dioxy prepared by embodiment eight
Change zirconium.Can be drawn by Fig. 2, sulfuration zirconium dioxide (SO prepared by solid-phase sequencing4 2-/ZrO2Although) calcining heat difference,
In the N of 77K2Adsorption-desorption isothermal curve has obvious hysteresis loop, is III type adsorption-desorption curve.
Claims (2)
1. a kind of solid acid catalyst with high-specific surface area vulcanizes the preparation method of zirconium dioxide, it is characterised in that one kind tool
The preparation method for having the solid acid catalyst sulfuration zirconium dioxide of high-specific surface area is completed according to the following steps：
First, the hydroxide of zirconium is prepared：
At room temperature, by ZrOCl2·8H2O is mixed and stirred for dissolving with deionized water, obtains ZrOCl2Solution, it is first by N in ammonia
Element and ZrOCl2·8H2The mol ratio of Zr elements is 5.5 in O:1 ratio weighs ammonia, then under room temperature and stirring condition,
The ammonia for weighing is added drop-wise to into ZrOCl2In solution, mixture is obtained, at room temperature, 1h～2h is stirred the mixture for first, so
Afterwards be aged 12h～24h, be precipitated liquid, precipitated liquid is filtered, be washed with deionized precipitate into cleaning mixture without chlorine from
Son, the precipitate after being washed finally is placed in the precipitate after washing in the baking oven that temperature is 80 DEG C～100 DEG C, is dried
12h～24h, that is, obtain the hydroxide of zirconium；
Described ZrOCl2·8H2The quality of O is 1g with the volume ratio of deionized water:7.7580mL；
2nd, pulverulent solids are prepared：
The hydroxide and solid ammonium sulfate of zirconium are weighed, at room temperature, the hydroxide and solid ammonium sulfate of the zirconium for weighing is put
In mortar, mix homogeneously simultaneously grinds, and obtains white powdery solids；
The hydroxide of described zirconium and the mol ratio 1 of solid ammonium sulfate:6；
3rd, calcine：
White powdery solids are placed in Muffle furnace, with programming rate as 5 DEG C/min, Muffle furnace 600 DEG C is warming up to into, then
Under conditions of temperature is for 600 DEG C, 5h is calcined, obtain solid acid catalyst SO4 2-/ZrO2, i.e. the solid with high-specific surface area
Acid catalyst vulcanizes zirconium dioxide.
2. a kind of solid acid catalyst with high-specific surface area according to claim 1 vulcanizes the preparation side of zirconium dioxide
Method, it is characterised in that finally the precipitate after washing is placed in the baking oven that temperature is 100 DEG C in step one, is dried 24h, obtained final product
To the hydroxide of zirconium.
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