CN1966151A - Zirconium dioxide loaded microsphere type silica gel superstrong acid catalyst - Google Patents
Zirconium dioxide loaded microsphere type silica gel superstrong acid catalyst Download PDFInfo
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- CN1966151A CN1966151A CN 200510110363 CN200510110363A CN1966151A CN 1966151 A CN1966151 A CN 1966151A CN 200510110363 CN200510110363 CN 200510110363 CN 200510110363 A CN200510110363 A CN 200510110363A CN 1966151 A CN1966151 A CN 1966151A
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Abstract
The invention relates to a ball silica gel solid corrosive acid catalyst which loads zirconia used in esterification and dehydration, wherein said silica gel solid corrosive acid has 1000 times protonation ability then dense sulfuric acid. And the ball silica gel solid corrosive acid uses porous ball silica gel as carrier, and absorbs zirconia and sulfuric acid in the inner hole of silica gel, with the properties of powder corrosive acid and the application in solid bed reactor, to process esterification at high pressure and temperature, to improve its transfer rate.
Description
Technical field
The present invention relates to the super acidic catalyst in the chemical reaction, relate in particular to a kind of Zirconium dioxide loaded microspheric form silica gel solid super acid catalyst that is used for carboxylic-reactive esterify hydroxy or hydroxyl dehydration.
Background technology
From M.H ino and K, Arat, J.C are successfully synthetic with ZrO in 1980
2And TiO
2Be carrier, and load H
2SO
4Solid super-strong acid after, solid super-strong acid as novel pollution less, free from corrosion acidic catalyst is widely used.Because it is Powdered that existing solid super-strong acid is, therefore can only be applied in ebullated bed and the tank reactor, and bring the trouble of separating catalyst.
Summary of the invention
The objective of the invention is at weak point of the prior art, is carrier with macroporous type microspheric form silica gel, has adsorbed zirconium dioxide and sulfuric acid and make microspheric form solid super strong catalyst in the endoporus of silica gel.It had both kept the characteristic of original super acids, had made coccoidly to be applicable to solid-bed reactor again, and the conversion ratio of esterification is improved greatly.
The preparation method's of catalyst of solid super strong acid in microspheric form of the present invention step comprises:
(1) does reaming and handle putting into the cushioning liquid of forming by C.P level glacial acetic acid and C.P ammonium acetate and pure water after the vacuum drying of macroporous type finished product silica gel bead, under the continuous bubbling of nitrogen, keep 43-47 ℃ of temperature, after 65-75 hour, leach the silica gel bead, vacuum drying;
(2) dried silica gel bead is put into zirconium chloride solution, under normal temperature, normal pressure, placed 65-75 hour, per hour stir once, leach bead;
(3) will leach the ammoniacal liquor that bead is put into the 1.0--1.2 weight percent concentration, add ice cube in the ammoniacal liquor, the volume ratio of ammonia spirit and bead is 8-12: 1, drip concentrated ammonia liquor again and equal 9 to PH, stirred at a slow speed at normal temperatures and pressures 65-75 hour, leach bead, it is dry to put into baking oven, baking temperature is 50--102 ℃, at 102 ℃ of constant temperature 65-75 hours, is cooled to room temperature;
(4) dried bead is immersed in the sulfuric acid solution, normal temperature and pressure was placed 65-75 hour down, per hour stirred once, leached bead;
(5) bead that leaches is put into oven drying, and baking temperature is 50--102 ℃, at 102 ℃ of constant temperature 65-75 hours, puts into the Muffle furnace roasting again, and sintering temperature is 550--650 ℃, and after constant temperature 3--4 hour, cooling promptly gets microspheric form solid super strong catalyst naturally.
In the step of the present invention (1) glacial acetic acid and and the pH value of the cushioning liquid formed of ammonium acetate and pure water equal 4.9-5.1, the volume ratio of reaming cushioning liquid and silica gel bead is 1.87-2.00: 1.
Zirconium chloride solution in the step of the present invention (2) is mixed by C.P level (chemical pure) concentrated hydrochloric acid and C.P level (chemical pure) zirconium chloride and forms, and the weight ratio of concentrated hydrochloric acid and zirconium chloride is 1.5-2.0: 1.
Sulfuric acid solution concentration in the step of the present invention (4) is 1.0-2.0N.
The physical and chemical index of resulting microspheric form solid super strong catalyst is in the step of the present invention (5):
A, acid strength
Hami several Hommett Pka values of writing :-15.05
B, physical constant
Specific area: 160-190m
2/ g,
Pore volume: 0.546-0.560cm
3/ g,
But machine aperture D:112.5-118.5 ,
Particle diameter: 4.5-5.8mm,
Internal pressure strength: mean value 〉=6kg/.
Select the carrier of macroporous type finished product silica gel among the present invention for use as catalyst and since macroporous type finished product silica gel load ZrO
2After, its pore volume, aperture all will diminish, and be unfavorable for interior diffusion.Therefore, need do reaming earlier before as carrier handles.
The zirconium chloride solution of overrich can make macroporous type silica gel excessively adsorb zirconium chloride, thereby causes excessive loads ZrO
2, be unfavorable for the interior diffusion of sulfuric acid solution.Therefore add concentrated hydrochloric acid (C.P) in zirconium chloride (C.P), zirconium chloride is carried out dilution process.
The silica gel bead of load zirconium chloride solution is put into ammoniacal liquor ammonia separate, make ZrCl
4Solution changes Zr (OH) into
4, be deposited on the macroporous type silica gel bead.
Be placed in the baking oven dryly after silica gel bead after ammonia separated leaches, make the Zr (OH) that is adsorbed on the silica gel bead
4Change ZrO into
2
Solid super-strong acid has the protonated ability higher 1000 times than concentrated acid, and the spent acid amount is big when having overcome the usefulness concentrated sulfuric acid as catalyst again, equipment corrosion serious, the shortcoming of poor selectivity, therefore has bigger economic benefit and environmental benefit.
But pulverous superpower solid acid can only be used in ebullated bed and the tank reactor, and separating catalyst is cumbersome.Zirconium dioxide loaded microspheric form silica gel solid super acid catalyst of the present invention can be used in fixed bed reactors, in esterification, can carry out under elevated pressures; improved reaction temperature; the conversion ratio of esterification is improved greatly, do not have the spent acid discharging, protected environment.
Description of drawings
Accompanying drawing is a fixed bed reactors synthesizing ethyl acetate schematic representation of apparatus.
Number in the figure is represented the 1-constant displacement pump, 2-fixed bed reactors, 3-point for measuring temperature, 4-condenser, A-material inlet, B-fixed bed reactors bottom, C-fixed bed reactors top, the outlet of D-ethyl acetate.
The specific embodiment
With embodiment content of the present invention is described further below.
Embodiment 1
The cushioning liquid of putting into C.P level glacial acetic acid and C.P level ammonium acetate and pure water composition after the vacuum drying of macroporous type finished product silica gel bead is done reaming handle, the pH value of cushioning liquid equals 4.9-5.1, and the volume ratio of cushioning liquid and silica gel bead is 2: 1.Under nitrogen bubble, be incubated 45 ℃, after 72 hours, leach the silica gel bead, vacuum drying.(2) dried silica gel bead is put into zirconium chloride solution.This solution is mixed by C.P level concentrated hydrochloric acid and C.P level zirconium chloride and forms, and their weight ratio is 2.0: 1.Placed at normal temperatures and pressures 70 hours, and per hour stirred once, leach bead.(3) bead that leaches is put into the ammoniacal liquor of 1.0-2.0 concentration expressed in percentage by weight, it is fast to add ice in the ammoniacal liquor, and the volume ratio of ammoniacal liquor and bead is 10: 1.Drip concentrated ammonia liquor again and equal 9 to PH, stir 72 hours at a slow speed under normal temperature, the normal pressure after, leach bead, it is dry to put into baking oven, baking temperature is 50--102 ℃, is cooled to room temperature at 102 ℃ of constant temperature after 72 hours.(4) dried bead is put into the sulfuric acid solution of 1.0N, normal temperature, normal pressure were placed 72 hours down, per hour stirred once.(5) leach bead, put into oven drying, baking temperature 50--102 ℃,, put into the Muffle furnace roasting 102 ℃ of constant temperature 72 hours, 550 ℃ of sintering temperatures, behind the constant temperature 4 hours, cooling naturally gets Zirconium dioxide loaded microspheric form silica gel solid super strong catalyst, its physical and chemical index is: acid strength Hami several Pka values of writing equal-15.05, specific area 160-190m
2/ g, pore volume 0.548cm
3/ g, but machine aperture D equals 115.3 , particle diameter 4.5-5.8mm, internal pressure strength (mean value) 〉=6kg/.
Embodiment 2
Except the volume ratio of cushioning liquid in the step (1) and silica gel bead is 1.87: 1, the weight ratio of C.P level concentrated hydrochloric acid and C.P level zirconium chloride is 1.5: 1 in the step (2), sulfuric acid solution concentration is outside the 1.5N in the step (4), and remaining reaction step and reaction condition are all with embodiment 1.The result gets catalyst of solid super strong acid in microspheric form, and its physical and chemical index is: acid strength Hami several Pka values of writing are-15.05, specific area 160--190m
2/ g, pore volume are 0.546cm
3/ g, but machine aperture D equals 112.5 , particle diameter 4.5-5.8mm, internal pressure strength (mean value) 〉=6kg/.
Embodiment 3
Except the volume ratio of cushioning liquid in the step (1) and silica gel bead is 1.95: 1, the weight ratio of C.P level concentrated hydrochloric acid and C.P level zirconium chloride is 1.8: 1 in the step (2), sulfuric acid solution concentration is outside the 1.5N in the step (4), and remaining reaction step and reaction condition are all with embodiment 1.The result gets catalyst of solid super strong acid in microspheric form, and its physical and chemical index is: acid strength Hami several Pka values of writing are-15.05, specific area 160--190m
2/ g, pore volume are 0.560cm
3/ g, but machine aperture D equals 118.5 , particle diameter 4.5-5.8mm, internal pressure strength (mean value) 〉=6kg/.
Embodiment 4
The fixed bed reactors synthesizing ethyl acetate.Install as shown in Figure 1, fixed bed reactors are by Φ 32mm, and length is 750mm, and wall thickness is that the stainless steel tube (1Cr18Ni9Ti) of 3mm is formed, and adopts the pipe external heating mode.After the microspheric form solid super-strong acid for preparing filled, can use.(design pressure is 1.6MPa)
With glacial acetic acid and ethanol with 1: 1 ratio of mol ratio after fully mixing, hold through constant displacement pump injecting reactor bottom B by the A end, carry out esterification by tube wall heating back under the catalysis of solid super-strong acid, the ethyl acetate of generation is overflowed by reactor napex C end, collects at the D end after the condensation cooling.Product after will collecting is again isolated ethyl acetate after dehydration, unreacted ethanol and acetate are recycled to the A end again and reuse.Reaction condition and result are as showing:
| Constant displacement pump flow velocity (ml/min) | The reactor center temperature (℃) | Reactor pressure (MPa) | Conversion per pass (%) | Selectivity (%) |
| 8--12 | 100--120 | 0.9-1.3 | 60--75 | 92--95 |
The catalytic performance of catalyst of solid super strong acid in microspheric form of the present invention and pulverulent solids super acids and sulfuric acid catalyst is compared as follows table and says and show:
| Catalyst | Reactor | Reaction temperature (℃) | Reaction pressure (℃) | One way rate of rotation (%) | Selectivity (%) | The corrosivity and the three wastes |
| Sulfuric acid | The still formula intermittently | 100-110 | 0-0.05 | 85 | 85 | Greatly |
| The pulverulent solids super acids | The still formula intermittently | 80 | 0.3-0.45 | 12 | 98 | Little |
| Microspheric form solid super-strong acid of the present invention | The fixed bed tubular type connects | 100--120 | 0.9-1.3 | 60--75 | 92--95 | Little |
Claims (4)
1, a kind of preparation method of Zirconium dioxide loaded microsphere type silica gel superstrong acid catalyst is characterized in that its step comprises:
(1) does reaming and handle putting into the cushioning liquid of forming by C.P level glacial acetic acid and C.P level ammonium acetate and pure water after the vacuum drying of macroporous type finished product silica gel bead, under the continuous bubbling of nitrogen, keep 43-47 ℃ of temperature, after 65-75 hour, leach the silica gel bead, vacuum drying;
(2) dried silica gel bead is put into zirconium chloride solution, under normal temperature, normal pressure, placed 65-75 hour, per hour stir once, leach bead;
(3) put into the ammoniacal liquor that the 1.0-1.2 weight percent concentration is added ice cube with leaching bead, the volume ratio of ammonia spirit and bead is 8-12: 1, drip concentrated ammonia liquor again and equal 9 to PH, stirred at a slow speed at normal temperatures and pressures 65-75 hour, leach bead, it is dry to put into baking oven, and baking temperature is 50--102 ℃, at 102 ℃ of constant temperature 65-75 hours, be cooled to room temperature;
(4) dried bead is immersed in the sulfuric acid solution, normal temperature and pressure was placed 65-75 hour down, per hour stirred once, leached bead;
(5) bead that leaches is put into oven drying, and baking temperature is 50--102 ℃, at 102 ℃ of constant temperature 65-75 hours, puts into the Muffle furnace roasting again, and sintering temperature is 550--650 ℃, and after constant temperature 3--4 hour, cooling promptly gets microspheric form solid super strong catalyst naturally.
2, preparation method according to claim 1 is characterized in that: the pH value of the cushioning liquid that glacial acetic acid and ammonium acetate are formed in the step (1) equals 4.9-5.1, and the volume ratio of reaming cushioning liquid and silica gel bead is 1.87-2.00: 1.
3, preparation method according to claim 1 is characterized in that: the zirconium chloride solution in the step (2) is mixed by C.P level concentrated hydrochloric acid and C.P level zirconium chloride and forms, and the weight ratio of concentrated hydrochloric acid and zirconium chloride is 1.5-2.0: 1.
4, preparation method according to claim 1 is characterized in that: the physical and chemical index of the resulting microspheric form solid super strong of step (5) catalyst is:
A, acid strength
Hami several Hommett Pka values of writing :-15.05
B, physical constant
Specific area: 160-190m
2/ g,
Pore volume: 0.546-0.560cm
3/ g,
But machine aperture D:112.5-118.5A,
Particle diameter: 4.5-5.8mm,
Internal pressure strength: mean value 〉=6kg/.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101103631A CN100441299C (en) | 2005-11-15 | 2005-11-15 | Zirconium dioxide loaded microsphere type silica gel superstrong acid catalyst |
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|---|---|---|---|
| CNB2005101103631A CN100441299C (en) | 2005-11-15 | 2005-11-15 | Zirconium dioxide loaded microsphere type silica gel superstrong acid catalyst |
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| CN1966151A true CN1966151A (en) | 2007-05-23 |
| CN100441299C CN100441299C (en) | 2008-12-10 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452933A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of carboxylic ester |
| CN103785385A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Alkane dehydrogenation catalyst and preparation method thereof |
| CN103785388A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Propane dehydrogenation catalyst containing V and preparation method thereof |
| CN106861566A (en) * | 2015-12-11 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of Zirconium oxide nano grain modifies the preparation method of Bio-sil microballoon |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0649568B2 (en) * | 1986-03-22 | 1994-06-29 | 軽質留分新用途開発技術研究組合 | Solid acid substance, method for producing the same, and method for decomposing hydrocarbon using the solid acid substance |
| CN1040846C (en) * | 1993-05-11 | 1998-11-25 | 中国石油化工总公司 | Method for preparation of superstrong acid of carried oxide system |
| JP2001220439A (en) * | 1999-11-29 | 2001-08-14 | Mitsubishi Chemicals Corp | Method for continuously producing polyalkylene ether glycol diester |
| CN1111084C (en) * | 2001-05-18 | 2003-06-11 | 吉林大学 | Process for preparing sulfated ultrahigh-acidic binary (ZrO/MxOy) composite nm catalyst |
| CN1142017C (en) * | 2001-11-29 | 2004-03-17 | 中国石油化工股份有限公司 | Prepn process of solid super acidic catalyst |
| CN100374201C (en) * | 2003-09-05 | 2008-03-12 | 中国石化集团天津石油化工公司 | Solid ultra strong acid type catalyst |
-
2005
- 2005-11-15 CN CNB2005101103631A patent/CN100441299C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452933A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of carboxylic ester |
| CN103785385A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Alkane dehydrogenation catalyst and preparation method thereof |
| CN103785388A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Propane dehydrogenation catalyst containing V and preparation method thereof |
| CN103785388B (en) * | 2012-11-01 | 2015-12-16 | 中国石油化工股份有限公司 | A kind of containing V propane dehydrogenation catalyst and preparation method thereof |
| CN103785385B (en) * | 2012-11-01 | 2016-04-13 | 中国石油化工股份有限公司 | A kind of alkane dehydrogenating catalyst and preparation method thereof |
| CN106861566A (en) * | 2015-12-11 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of Zirconium oxide nano grain modifies the preparation method of Bio-sil microballoon |
| CN106861566B (en) * | 2015-12-11 | 2019-07-19 | 中国科学院大连化学物理研究所 | A kind of preparation method of Zirconium oxide nano grain modification Bio-sil microballoon |
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| CN100441299C (en) | 2008-12-10 |
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