CN100411735C - Solid super acidic catalyst and its preparing method - Google Patents
Solid super acidic catalyst and its preparing method Download PDFInfo
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- CN100411735C CN100411735C CNB2006101165914A CN200610116591A CN100411735C CN 100411735 C CN100411735 C CN 100411735C CN B2006101165914 A CNB2006101165914 A CN B2006101165914A CN 200610116591 A CN200610116591 A CN 200610116591A CN 100411735 C CN100411735 C CN 100411735C
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Abstract
The present invention discloses a solid super acidic catalyst and its preparation method. It is characterized by that the concentration of sulfuric acid radical ion in the solid super acid is 10-15 wt%, halide content of aluminium is 1-5 wt%, water content in the catalyst is less than 1 wt% and the rest is ZrO2 carrier, the mean pore size of said catalyst is 5-15nm. Its preparation method includes the following steps: adding water to dissolve zirconium oxychloride, using ammonia water to regulate pH value of solution to 9-10 and forming zirconium hydroxide precipitate; filtering and cleaning said precipitate until the pH value of filtrate is 6.9-7.1, having no Cl-, drying; mixing the precipitate with halide powder of aluminium, grinding to make grain size be less than 100 meshes, then using sulfuric acid solution whose concentration is 0.1-1.0 mol/L to soak the above-mentioned material, filtering, drying, roasting for 2-5 hr at 600-700deg.C so as to obtain the invented product solid super acidic catalyst.
Description
Technical field
The present invention relates to a kind of solid super acid catalyst and preparation method thereof, more particularly relate to a kind of modification ZrO that comprises sulfate ion
2Solid super acid catalyst of carrier and preparation method thereof.
Background technology
Solid super-strong acid is meant acid than the stronger solid acid of 100% sulfuric acid, represents the H of 100% sulfuric acid with the Hammett acidity function
0=-11.93, and the H of solid super-strong acid
0＜-11.93.Solid super-strong acid is compared with traditional catalyst has following characteristics: (1) catalytic efficiency height, and consumption is few, and side reaction is little, and accessory substance is few; (2) can at high temperature use, reusable, catalyst separates with product simply; (3) non-corrosiveness, free from environmental pollution; (4) preparation method is easy, available common metal salt preparation.Because above-mentioned advantage, the research of solid super-strong acid and application become the hot fields of seeking new green environment protection type catalyst, have great importance to promoting chemical industry to develop to the environmental protection direction.Synthesize SO first from people such as M.Hino in 1979
4 2-/ Fe
2O
3Since the solid super-strong acid, solid super-strong acid can be widely used in industries such as organic synthesis, fine chemistry industry, petrochemical industry because its high-specific surface area and special crystal structure make it become a kind of new catalytic agent material.SO
4 2-/ M
xO
yThe type solid super-strong acid owing to its catalytic activity height, Heat stability is good, selectivity is good, preparation is simple and do not have advantages such as three-waste pollution to cause people's extensive concern.The solid super-strong acid of having developed comprises SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2, SO
4 2-/ Fe
2O
3, SO
4 2-/ SnO
2Deng.SO wherein
4 2-/ ZrO
2Acid strength is higher, and various reactions such as alkane isomerization, esterification, acidylate, polymerization are all had catalytic action.
Fang Yongzheng, Yang Junhe, people such as Jin Minglin studies show that on " coal conversion " 26,4 (2003), high sintering temperature can improve the catalytic activity of solid super-strong acid.This can explain from two aspects: the one, and high sintering temperature can reduce the OH of solid super-strong acid
-Content; Because improving, sintering temperature can increase SO on the other hand
4 2-With the bonding of oxide surface, improved catalyst acid intensity.But high catalyst sintering temperature can cause the catalyst crystallization, reduces SO
4 2-The specific area that combines with catalyst.High sintering temperature also can cause SO
4 2-Decomposition, activity of such catalysts is descended.In addition, solid super-strong acid easily absorbs water, and the activity of suction back solid super-strong acid also can reduce.Therefore, development low water content, the solid super-strong acid of high activity and high sintering temperature are that the scientific research personnel attempts the difficult problem that solves always.
Summary of the invention
Technical problem to be solved by this invention provides a kind of low water content, the SO of high activity and high sintering temperature
4 2-/ ZrO
2Solid super-strong acid.Another technical problem to be solved by this invention provides a kind of method for preparing above-mentioned solid super-strong acid.
The technical scheme of product of the present invention: a kind of solid super acid catalyst, by the ZrO that contains sulfate ion
2The halide of carrier and aluminium is formed, and wherein the concentration of sulfate ion is 10～15wt%, and the halide of aluminium is selected from aluminum fluoride or aluminium chloride or the mixture of the two, and the halide content of aluminium is 1～5wt%, and moisture＜1wt ‰ in the catalyst, and surplus is ZrO
2Carrier, the average pore size of catalyst are 5～15nm.
The technical scheme of the inventive method: the preparation method of above-mentioned solid super acid catalyst comprises the following steps:
A. zirconium oxychloride is dissolved in water, the pH value of solution is adjusted to 9～10, generate the zirconium hydroxide precipitation with ammoniacal liquor;
B. above-mentioned zirconium hydroxide sedimentation and filtration is washed pH value to 6.9～7.1, and do not have Cl to filtrate
-, will precipitate dry then;
C. above-mentioned washed zirconium hydroxide precipitation is mixed with the halide powder of aluminium, the halid content of aluminium element is 1～5wt% in the mixture, mixture is ground to granularity＜100 orders,, and filters the back drying then with the sulfuric acid solution dipping of mixture with 0.1～1.0mol/L;
D. dried mixture obtains described solid super-strong acid 600～700 ℃ of following roastings 2～5 hours.
Beneficial effect of the present invention, the present invention is with the zirconium hydroxide precipitation and the halide of aluminium when baking mixed, halogen element can with OH
-Thereby reaction generates the hydrogen halides volatile matter has reached the purpose that dewaters, and makes moisture＜1wt ‰ in the catalyst, has improved the catalytic efficiency of catalyst.Simultaneously, because the introducing of aluminium element, improved the sintering temperature of catalyst and can not cause and the crystallization of catalyst increased SO in the catalyst
4 2-Content, also improved the acid strength of catalyst.
Description of drawings
Fig. 1 is differential weight-loss curve (DTG) figure of solid super-strong acid of the present invention.
The specific embodiment
Below by embodiment and accompanying drawing the present invention is described in further detail, a kind of solid super acid catalyst is by the ZrO that contains sulfate ion
2The halide of carrier and aluminium is formed, and wherein the concentration of sulfate ion is 10～15wt%, and the halide content of aluminium is 1～5wt%, and moisture＜1wt ‰ in the catalyst, and surplus is ZrO
2Carrier, the average pore size of catalyst are 5～15nm.The halide of described aluminium is selected from aluminum fluoride or aluminium chloride or the mixture of the two.The preparation method of this solid super acid catalyst comprises the following steps: that a. is dissolved in water zirconium oxychloride, with ammoniacal liquor the pH value of solution is adjusted to 9～10, generates the zirconium hydroxide precipitation; B. above-mentioned zirconium hydroxide sedimentation and filtration is washed pH value to 6.9～7.1, and do not have Cl to filtrate
-, will precipitate dry then; C. above-mentioned washed zirconium hydroxide precipitation is mixed with the halide powder of aluminium, the halid content of aluminium element is 1～5wt% in the mixture, mixture is ground to granularity＜100 orders,, and filters the back drying then with the sulfuric acid solution dipping of mixture with 0.1～1.0mol/L; D. dried mixture obtains described solid super-strong acid 600～700 ℃ of following roastings 2～5 hours.
In each Comparative Examples and embodiment, measure SO with the Emhorn block-regulations
4 2-/ ZrO
2The sulfur content of catalyst.Measure the acid strength of catalyst with the Hammett indicator method that flows.SO
4 2-Heat decomposition temperature ask for by the thermogravimetric curve of catalyst, see Fig. 1, the DTG curve of catalyst is analyzed Labsys in comprehensive heat
TMMeasure on the TG-DSC16.The crystallization temperature of catalyst is by the XRD test determination.The catalytic performance of solid acid is investigated with the naphthalene polycondensation reaction.The catalytic performance of solid acid is investigated with the naphthalene polycondensation reaction.In three-neck flask, naphthalene is mixed in 1: 0.85～1.25 ratio with solid super-strong acid, under design temperature, react certain hour.In reacted three-neck flask, pour toluene into.Filter, utilize fractionating device to steam toluene filtrate after, the naphthalene distillation with wherein obtains the naphthalene condensation polymer.Calculate the reactant yield with following formula: the quality of product yield=naphthalene condensation polymer quality/raw naphthalene material.
Comparative Examples 1
Zirconium oxychloride is dissolved in water, uses ammoniacal liquor the solution pH value to be adjusted in 9～10 the scope, generate the zirconium hydroxide precipitation.Sedimentation and filtration washed to filtrate PH be 7 and do not have a Cl
-, will precipitate dry then.Precipitation is ground to＜100 orders, with the sulfuric acid solution dipping of 0.5mol/L, filters the back drying then.Dry back mixture carries out roasting 5 hours under 600 ℃.The character and the product yield of gained catalyst are as shown in table 1.Table 1
Zirconium oxychloride is dissolved in water, uses ammoniacal liquor the solution pH value to be adjusted in 9 the scope, generate the zirconium hydroxide precipitation.Sedimentation and filtration washed to filtrate PH be 7 and do not have a Cl
-, will precipitate dry then.To precipitate and AlF
3Mixture of powders is ground to＜100 orders (AlF in the mixture
3The content of powder is 1wt%), with the sulfuric acid solution dipping of 0.5mol/L, filter the back drying then.Dry back mixture carries out roasting 5 hours under 600 ℃.The character and the product yield of gained catalyst are as shown in table 2.Table 2
Embodiment 2
Method by embodiment 1 prepares catalyst, and that different is AlF in the mixture
3Content is 3wt%, and the character and the product yield of gained catalyst are as shown in table 3.Table 3
Embodiment 3
Method by embodiment 1 prepares catalyst, and that different is AlF in the mixture
3Content is 5wt%, and the character and the product yield of gained catalyst are as shown in table 4.Table 4
Embodiment 4
Method by embodiment 1 prepares catalyst, and that different is AlF in the mixture
3Content is 3wt%, and the sintering temperature of dry back mixture is 700 ℃, and the character and the product yield of gained catalyst are as shown in table 5.Table 5
Embodiment 5
Method by embodiment 1 prepares catalyst, and different is to use AlCl in the mixture
3Replace AlF
3AlCl
3Content is 3wt%, and the sintering temperature of dry back mixture is 700 ℃, and the character and the product yield of gained catalyst are as shown in table 6.Table 6
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (2)
1. solid super acid catalyst is by the ZrO that contains sulfate ion
2The halide of carrier and aluminium is formed, and wherein the concentration of sulfate ion is 10～15wt%, and the halide of aluminium is selected from aluminum fluoride or aluminium chloride or the mixture of the two, and the halide content of aluminium is 1～5wt%, and moisture＜1wt ‰ in the catalyst, and surplus is ZrO
2Carrier, the average pore size of catalyst are 5～15nm.
2. the preparation method of the described solid super acid catalyst of claim 1 comprises the following steps:
A. zirconium oxychloride is dissolved in water, the pH value of solution is adjusted to 9～10, generate the zirconium hydroxide precipitation with ammoniacal liquor;
B. above-mentioned zirconium hydroxide sedimentation and filtration is washed pH value to 6.9～7.1, and do not have Cl to filtrate
-, will precipitate dry then;
C. above-mentioned washed zirconium hydroxide precipitation is mixed with the halide powder of aluminium, the halid content of aluminium element is 1～5wt% in the mixture, mixture is ground to granularity＜100 orders,, and filters the back drying then with the sulfuric acid solution dipping of mixture with 0.1～1.0mol/L;
D. dried mixture obtains described solid super-strong acid 600～700 ℃ of following roastings 2～5 hours.
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| CN102962081B (en) * | 2012-11-21 | 2014-05-28 | 武汉工程大学 | Solid super acid and method for catalyzing and preparing chloracetate by using same |
| CN111097453A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of zirconium oxide sulfate |
| CN112705229B (en) * | 2019-10-24 | 2023-07-04 | 中国石油化工股份有限公司 | Sulfated zirconia catalyst, and preparation method and application thereof |
| CN114588928B (en) * | 2022-05-09 | 2022-08-23 | 浙江晟格生物科技有限公司 | Regeneration method of carbon-based sulfate catalyst in galactose waste liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62278126A (en) * | 1986-05-28 | 1987-12-03 | Res Assoc Util Of Light Oil | Solid acid substance, production thereof and method for decomposing hydrocarbon using said solid acid substance |
| CN1067393A (en) * | 1991-06-06 | 1992-12-30 | 北京师范大学 | Presence of compound solid superacid catalyst agent and manufacture method thereof |
| CN1425500A (en) * | 2002-12-31 | 2003-06-25 | 曲阜师范大学 | Granular solid super strong acid catalyst and its preparing method |
| CN1428196A (en) * | 2001-12-25 | 2003-07-09 | 中国石油化工股份有限公司 | Solid super acidic catalyst and its preparation method |
| WO2005073348A1 (en) * | 2004-02-02 | 2005-08-11 | Japan Energy Corporation | Method of desulfurizing hydrocarbon oil |
-
2006
- 2006-09-27 CN CNB2006101165914A patent/CN100411735C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62278126A (en) * | 1986-05-28 | 1987-12-03 | Res Assoc Util Of Light Oil | Solid acid substance, production thereof and method for decomposing hydrocarbon using said solid acid substance |
| CN1067393A (en) * | 1991-06-06 | 1992-12-30 | 北京师范大学 | Presence of compound solid superacid catalyst agent and manufacture method thereof |
| CN1428196A (en) * | 2001-12-25 | 2003-07-09 | 中国石油化工股份有限公司 | Solid super acidic catalyst and its preparation method |
| CN1425500A (en) * | 2002-12-31 | 2003-06-25 | 曲阜师范大学 | Granular solid super strong acid catalyst and its preparing method |
| WO2005073348A1 (en) * | 2004-02-02 | 2005-08-11 | Japan Energy Corporation | Method of desulfurizing hydrocarbon oil |
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Effective date of registration: 20090320 Address after: New Gang Town, Dexing, Jiangxi Patentee after: Jiangxi Dexing PARCHN Sodium VC Co., Ltd. Address before: No. 120, Caobao Road, Shanghai, Xuhui District Patentee before: Shanghai Institute of Technology |
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Owner name: JIANGXI PROVINCE DEXING CITY BAIQIN ISO-ASCORBYL S Free format text: FORMER OWNER: SHANGHAI COLLEGE OF APPLIED TECHNOLOGY Effective date: 20090320 |