CN1390643A - Application method of heteropoly acid type catalyst - Google Patents
Application method of heteropoly acid type catalyst Download PDFInfo
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- CN1390643A CN1390643A CN 02123293 CN02123293A CN1390643A CN 1390643 A CN1390643 A CN 1390643A CN 02123293 CN02123293 CN 02123293 CN 02123293 A CN02123293 A CN 02123293A CN 1390643 A CN1390643 A CN 1390643A
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Abstract
A process for improving the acid intensity stability of solid acid catalyst containing heteropoly acid or its salt (0.5-100 wt.%) features that said heteropoly acid or its salt has central atom (P or Si) and coordinating atom chosen from W, Mo and V, and there is water in reaction atmosphere.
Description
Technical field
The present invention relates to a kind of using method of heteropoly acid catalyst.
Background technology
Heteropoly acid and heteropolyacid salt with acidity, " accurate liquid phase " behavior of its uniqueness, and have advantages such as highly acid and strong oxidizing property as the novel catalysis material of a class simultaneously, are subjected to paying attention to widely in the catalyticing research field.
Chinese patent publication number 1185992 discloses a kind of ether-splitting that is used for and has separated the silicon dioxide carried phosphotungstic acid of preparing isobutene and the composite catalyst of magnesium nitrate, and the conversion ratio of methyl tertiary butyl ether(MTBE) and selective isobutene are all greater than 99%.
USP 5,750, and 457 disclose a kind of Cs that supports precious metals pd
2.5H
0.5PW
12O
40Catalyst is used for the normal butane isomerization reaction under hydro condition, can obtain the better result of n-butane conversion 33.6%, iso-butane selectivity 95.5%.
But a shortcoming when heteropoly acid or heteropolyacid salt are used as solid acid catalyst is that its acidity particularly its acid strength is unstable under common reaction condition.In the highly acid reaction system of needs, can make catalysqt deactivation because of its acid strength reduces gradually; In the more weak reaction system of the acid strength of needs, stronger acid site can cause disadvantageous side reactions such as polymerization, coking again.
Summary of the invention
The object of the present invention is to provide a kind of using method of heteropoly acid catalyst, make heteropoly acid catalyst keep certain acid strength.
For achieving the above object, the using method of heteropoly acid catalyst provided by the invention mainly contains:
(1) contain heteropoly acid or the heteropolyacid salt of weight ratio 0.5-100% in the catalyst, described heteropoly acid or heteropolyacid salt are that central atom is that P or Si, coordination atom are heteropoly acid or heteropolyacid salt or its mixture of at least a element among W, Mo, the V;
(2) have water to exist in the reaction atmosphere, the dividing potential drop of water is the 2-1000 millimetres of mercury;
Described heteropoly acid or heteropolyacid salt are phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid or its salt or their mixture.
Described heteropolyacid salt is normal salt or acid salt, and cation wherein is one or more the mixture in the transition metal ions such as hydrogen ion, ammonium ion, alkali metal ion, alkaline-earth metal ions and Cr, Mn, Fe, Co, Ni, Pt, Pd, Cu.
The heteropoly acid or the heteropolyacid salt that contain weight ratio 1-60% in the described heteropoly acid catalyst.
The heteropoly acid or the heteropolyacid salt that contain weight ratio 3-30% in the described heteropoly acid catalyst.
Contain one or more the mixture in the silica, aluminium oxide, titanium oxide, carborundum, alumina silicate, magnesium silicate, active carbon, ion exchange resin, carbide resin of weight ratio 0-99.5% in the described heteropoly acid catalyst.
In detail, the present invention can use pure heteropoly acid or heteropolyacid salt directly as heteropoly acid catalyst of the present invention, also can be with heteropoly acid or heteropolyacid salt and some inorganic oxide, as silica, aluminium oxide, titanium dioxide etc., with other inorganic matters, as one or more the mixture mixed-forming in carborundum, active carbon, alumina silicate, the magnesium silicate etc., be beneficial to catalyst and keep certain shape and intensity.
Advantageously make so-called carried heteropoly acid type catalyst.For example, can adopt infusion process, with the solution impregnation of heteropoly acid or heteropolyacid salt to carrier with certain pore structure, as silica, active carbon, aluminium oxide, titanium dioxide, carborundum, alumina silicate, ion exchange resin, carbide resin etc., afterwards can drying, roasting etc. handles the back as catalyst, also can directly be used as catalyst.
Carried heteropoly acid type catalyst can improve the intensity and the specific area of catalyst, reduces the consumption of heteropoly acid or heteropolyacid salt, reduces the catalyst cost, and the catalytic performance of catalyst is also had bigger change.The difference of the reaction system of using according to catalyst can adopt different carriers and heteropoly acid or heteropolyacid salt load capacity.Generally speaking, the weight content of heteropoly acid or heteropolyacid salt is between 1-60% in the catalyst, and preferred range is 3-30%.
The heteropoly acid of indication of the present invention or heteropolyacid salt are that central atom is a kind of element among P, the Si, heteropoly acid or the heteropolyacid salt that coordination atom is at least a element among W, Mo, the V.Wherein more easily preparation, stability better, price also lower be phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid or its salt of Keggin structure.These heteropoly acids or heteropolyacid salt can use as the active component of aforementioned heteropoly acid catalyst separately, also more than one heteropoly acid or heteropolyacid salt can be mixed use.
Characteristics of heteropoly acid catalyst are that its acid strength and its water content have direct relation.Foregoing heteropoly acid catalyst, in use, when particularly handling without high-temperature roasting, its acid strength gradually changes often.A kind ofly may be, with the prolongation in reaction time, the contained moisture content of heteropoly acid or heteropolyacid salt loses gradually in the catalyst, and acid strength improved before this thereupon, reduces gradually again afterwards, and this is very disadvantageous to catalytic reaction.
The using method of the heteropoly acid catalyst that the present invention proposes can make the acidity of heteropoly acid catalyst keep certain strength effectively, thereby obtains more stable catalytic performance.The method that is adopted is to add a certain amount of water and/or hydrogen in reaction atmosphere.
The existence of the water of certain dividing potential drop can suppress the dehydration of heteropoly acid or heteropolyacid salt under the uniform temperature, its water content is remained on the proper level, thereby keep certain acid strength.The dividing potential drop scope of suitable water is the 0.5-1000 millimetres of mercury, and in this scope, higher or lower water partial pressure makes heteropoly acid catalyst keep relatively low acid strength; Moderate water partial pressure then makes it keep higher relatively acid strength.Under different temperatures, it is different keeping the required water partial pressure of same acid strength; Generally speaking, temperature is high more, and required water partial pressure is also high more.
The specific embodiment
Be embodiments of the invention below, but the present invention is not limited to following examples.
Embodiment 1, preparation catalyst
With 100 gram SiO
2With watery hydrochloric acid washing, immersion 2 hours, be washed till neutrality with deionized water again, roasting is 4 hours in 350 ℃ of muffle furnaces.Take by weighing the SiO of 60 grams through above-mentioned processing
2, application of vacuum at room temperature 2 hours; Get 15 gram phosphotungstic acids and be dissolved in the 75 gram deionized waters, splash in the carrier under the vacuum condition, the sample behind the dipping continues to handle 1 hour under vacuum condition, and is dry in 120 ℃ of baking ovens then, makes catalyst A.
Embodiment 2, catalyst acid strength detection method
The acid strength of catalyst is measured and is used the Hammlett indicator method.Prepare a series of concentration and be 0.1% Hammett indicator solution.The catalyst sample that takes a morsel places small test tube, drips to go up indicator solution, observes it and whether becomes the acid type look by alkali type look.When heteropoly acid catalyst makes indicator show the acid type look, illustrate that the acidity function Ho of this catalyst is less than or equal to the pK of this indicator
aPress the pK of indicator
aAscending order sequentially determining makes indicator become the acid type look up to catalyst, then the pK of this indicator
aValue is the Ho value of this catalyst.The indicator that is adopted sees Table 1.
Table 1: acid strength is measured used indicator
Indicator alkali type color acid type look pK
a
The benzeneazo-naphthylamine Huang is red+and 4.0
The dimethyl yellow Huang is red+and 3.3
Two Chinese cassia tree acetone Huangs red-3.0
Benzylidene ethyl ketone colourless Huang-5.6
Anthraquinone colourless Huang-8.2
Para-nitrotoluene colourless Huang-11.35
Parachloronitrobenzene colourless Huang-12.70
2,4-dinitrotoluene (DNT) colourless Huang-13.75
Embodiment 3, water partial pressure are measured catalyst down
Get 10 gram catalyst A, the glass reaction tube of packing into is placed in the tubular heater, make flow be the nitrogen of 40ml/min in the water of uniform temperature bubbling by after flow through reaction tube.Regulating water temperature, to make the dividing potential drop of steam be 12.8 millimetress of mercury, be warming up to 300 ℃ after constant temperature, take out little amount of catalyst at regular intervals, with its acid strength of Hammett indicator method rapid test.Measurement result sees Table 2.
The acid strength of catalyst A changes under the table 2 12.8 millimetres of mercury water partial pressures
300 ℃ of constant temperature time/h Ho
0 -11.35≤Ho≤-8.20
1 -13.75≤Ho≤-12.70
2 Ho≤-13.75
4 Ho≤-13.75
6 Ho≤-13.75
8 Ho≤-13.75
19 Ho≤-13.75
21 Ho≤-13.75
23 Ho≤-13.75
25 Ho≤-13.75
27 -13.75≤Ho≤-12.70
29 -13.75≤Ho≤-12.70
31 -13.75≤Ho≤-12.70
33 -13.75≤Ho≤-12.70
35 -13.75≤Ho≤-12.70
42 -13.75≤Ho≤-12.70
46 -13.75≤Ho≤-12.70
49 -13.75≤Ho≤-12.70
51 -13.75≤Ho≤-12.70
53 -13.75≤Ho≤-12.70
56 -13.75≤Ho≤-12.70
Embodiment 4, water partial pressure are measured catalyst down
Get 10 gram catalyst A, the glass reaction tube of packing into is placed in the tubular heater, make flow be the nitrogen of 40ml/min in the water of uniform temperature bubbling by after flow through reaction tube.Regulating water temperature, to make the dividing potential drop of steam be 31.8 millimetress of mercury, be warming up to 300 ℃ after constant temperature, take out little amount of catalyst at regular intervals, with its acid strength of Hammett indicator method rapid test.Measurement result sees Table 3.
The acid strength of catalyst A changes under the table 3 31.8 millimetres of mercury water partial pressures
300 ℃ of constant temperature time/h Ho
0 -11.35≤Ho≤-8.20
1 -11.35≤Ho≤-8.20
2 -11.35≤Ho≤-8.20
4 -11.35≤Ho≤-8.20
6 -11.35≤Ho≤-8.20
8 -11.35≤Ho≤-8.20
19 -11.35≤Ho≤-8.20
21 -11.35≤Ho≤-8.20
23 -11.35≤Ho≤-8.20
25 -11.35≤Ho≤-8.20
27 -11.35≤Ho≤-8.20
29 -11.35≤Ho≤-8.20
31 -11.35≤Ho≤-8.20
33 -11.35≤Ho≤-8.20
35 -11.35≤Ho≤-8.20
42 -11.35≤Ho≤-8.20
46 -11.35≤Ho≤-8.20
49 -11.35≤Ho≤-8.20
51 -11.35≤Ho≤-8.20
53 -11.35≤Ho≤-8.20
56 -11.35≤Ho≤-8.20
Comparative Examples 1
Get 10 gram catalyst A, the glass reaction tube of packing into is placed in the tubular heater, is constant temperature after being warming up to 300 ℃ under the nitrogen atmosphere of 40ml/min at flow, takes out little amount of catalyst at regular intervals, with its acid strength of Hammett indicator method rapid test.Measurement result sees Table 4.
The acid strength of catalyst A changes under table 4 nitrogen atmosphere
300 ℃ of constant temperature time/h Ho
0 -11.35≤Ho≤-8.20
1 -13.75≤Ho≤-12.70
2 Ho≤-13.75
4 Ho≤-13.75
5 -13.75≤Ho≤-12.70
6 -13.75≤Ho≤-12.70
7 -12.70≤Ho≤-11.35
8 -12.70≤Ho≤-11.35
19 -12.70≤Ho≤-11.35
21 -12.70≤Ho≤-11.35
23 -12.70≤Ho≤-11.35
25 -12.70≤Ho≤-11.35
27 -12.70≤Ho≤-11.35
29 -12.70≤Ho≤-11.35
31 -12.70≤Ho≤-11.35
33 -12.70≤Ho≤-11.35
35 -12.70≤Ho≤-11.35
42 -12.70≤Ho≤-11.35
46 -12.70≤Ho≤-11.35
47 -11.35≤Ho≤-8.20
49 -11.35≤Ho≤-8.20
51 -11.35≤Ho≤-8.20
53 -11.35≤Ho≤-8.20
56 -11.35≤Ho≤-8.20
The result of Comparative Examples shows that under the condition that does not have water or hydrogen to exist, the stability of the acid strength of heteropolyacid catalyst A under 300 ℃ is obviously relatively poor.
Claims (6)
1, a kind of using method of heteropoly acid catalyst is characterized in that:
(1) contain heteropoly acid or the heteropolyacid salt of weight ratio 0.5-100% in the catalyst, described heteropoly acid or heteropolyacid salt are that central atom is that P or Si, coordination atom are heteropoly acid or heteropolyacid salt or its mixture of at least a element among W, Mo, the V;
(2) have water to exist in the reaction atmosphere, the dividing potential drop of water is the 2-1000 millimetres of mercury;
2, in accordance with the method for claim 1, it is characterized in that described heteropoly acid or heteropolyacid salt are phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid or its salt or their mixture.
3, in accordance with the method for claim 1, it is characterized in that, described heteropolyacid salt is normal salt or acid salt, and cation wherein is one or more the mixture in the transition metal ions such as hydrogen ion, ammonium ion, alkali metal ion, alkaline-earth metal ions and Cr, Mn, Fe, Co, Ni, Pt, Pd, Cu.
4, in accordance with the method for claim 1, it is characterized in that, contain heteropoly acid or the heteropolyacid salt of weight ratio 1-60% in the described heteropoly acid catalyst.
5, in accordance with the method for claim 1, it is characterized in that, contain heteropoly acid or the heteropolyacid salt of weight ratio 3-30% in the described heteropoly acid catalyst.
6, in accordance with the method for claim 1, it is characterized in that, contain one or more the mixture in the silica, aluminium oxide, titanium oxide, carborundum, alumina silicate, magnesium silicate, active carbon, ion exchange resin, carbide resin of weight ratio 0-99.5% in the described heteropoly acid catalyst.
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| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
| CN103566969A (en) * | 2012-07-31 | 2014-02-12 | 中国科学院大连化学物理研究所 | Preparation method of vanadium-base catalytic material for catalyzing benzene hydroxylation to prepare phenol |
| CN103691484A (en) * | 2013-12-17 | 2014-04-02 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compounds |
| CN104874426A (en) * | 2015-05-13 | 2015-09-02 | 安徽金邦医药化工有限公司 | Modified crushed-gravel-based compound solid acid catalyst and preparation method thereof |
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2002
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| CN103691484A (en) * | 2013-12-17 | 2014-04-02 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compounds |
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| CN105797769A (en) * | 2016-04-06 | 2016-07-27 | 上海应用技术学院 | (R)-1-(2-hydroxy-1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as preparation method and application thereof |
| CN105833909A (en) * | 2016-04-06 | 2016-08-10 | 上海应用技术学院 | (S)-1-(2-hydrox-1-phenethyl)thiourea modified Cr-Anderson heteropolyacid catalyst, and preparation method and application thereof |
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