CN103752336B - A kind of vanadium catalyst for nitrobenzene sulfonation and preparation method thereof - Google Patents
A kind of vanadium catalyst for nitrobenzene sulfonation and preparation method thereof Download PDFInfo
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- CN103752336B CN103752336B CN201410007546.XA CN201410007546A CN103752336B CN 103752336 B CN103752336 B CN 103752336B CN 201410007546 A CN201410007546 A CN 201410007546A CN 103752336 B CN103752336 B CN 103752336B
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- nitrobenzene
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Abstract
The invention discloses a kind of vanadium catalyst for nitrobenzene sulfonation, by V
2o
5, K
2sO
4, aluminium salt, calcium salt and silicon carrier composition, wherein, V
2o
5mass content be 20-30%, K
2sO
4mass content be 5.5-10%, aluminium salt is with Al
2o
3the mass content of metering is 1-2.5%, the calcium salt mass content of measuring with CaO is 5.5-10%, surplus is for silicon carrier.The vanadium catalyst of the nitrobenzene sulfonation of gained of the present invention, has that the burn into of resistance to oleum intensity is high, activity stabilized, active principle turnover rate is low, object products collection efficiency advantages of higher; Can apply mechanically more than 5 times, after applying mechanically 5 times, active component vanadic anhydride turnover rate is less than 10%, has saved production cost, decreases useless acid-treated difficulty, reduces the pollution to environment.
Description
Technical field
What the present invention relates to is a kind of vanadium catalyst for nitrobenzene sulfonation and preparation method thereof.
Background technology
In the middle of chemical industry, the sulfonating reaction of nitrobenzene is the very important chemical reaction of a class.Sulfonating agent used by traditional sulfonating reaction mainly oleum, catalyst is vanadium pentoxide powder.Because vanadic anhydride can react with oleum, therefore catalyst vanadic anhydride cannot recycle and reuse after the completion of reaction, and follow-up separating technology difficulty is large, and reacted spent acid is also difficult to process.The waste of fund can be caused on producing, and to environment.
Summary of the invention
The present invention seeks to be to provide a kind of vanadium catalyst for nitrobenzene sulfonation and preparation method thereof, efficiently solve sulfonating reaction and terminate the problem that rear vanadic anhydride can not reuse, and after recycling repeatedly, vanadic anhydride runs off very little.
To achieve these goals, the present invention realizes by the following technical solutions:
For a vanadium catalyst for nitrobenzene sulfonation, by V
2o
5, K
2sO
4, aluminium salt, calcium salt and silicon carrier composition, wherein, V
2o
5mass content be 20-30%, K
2sO
4mass content be 5.5-10%, aluminium salt is with Al
2o
3the mass content of metering is 1-2.5%, the calcium salt mass content of measuring with CaO is 5.5-10%, surplus is for silicon carrier.
Applicant finds after deliberation: in vanadium-potassium-Si catalyst system, add aluminium salt and the calcium salt structural promoter as carrier, add the interaction between vanadic anhydride and carrier, catalyst surface is made to form fine and close network structure, effectively active component vanadic anhydride is firmly bonded on silicon carrier, the object repeatedly used under reaching the environment that catalyst exists at liquid phase oleum, and catalytic efficiency is high.
The vanadium catalyst of the application's nitrobenzene sulfonation is coccoid, during reaction, is suspended in reactant, and after completion of the reaction, catalyst filtration, then cover is used for reaction next time.
In order to improve the resistance to sulfuric acid energy of catalyst, select silica-based carrier, selected silicon carrier is preferably the mixture of one or more any proportionings in SBA-15, MCM-41, ZSM-5 or Ludox.
In order to strengthen the interaction of vanadic anhydride and carrier, calcium salt is the mixture of one or more any proportionings in calcium nitrate, calcium oxide, calcium carbonate or calcium hydroxide.
In order to strengthen the interaction of vanadic anhydride and carrier further, aluminium salt is the mixture of one or more any proportionings in aluminum nitrate, calcium oxide, aluminium dihydrogen phosphate, aluminium hydroxide or aluminum sulfate.
The preparation method of the above-mentioned vanadium catalyst for nitrobenzene sulfonation, comprises the following steps that order connects:
A, by vanadic anhydride and potassium hydroxide water-soluble, and use H
2sO
4the obtained V of neutralization
2o
5-K
2sO
4colloidal liquid, wherein, V
2o
5concentration is 50g/L-300g/L;
B, the colloidal liquid of silicon carrier, steps A gained, aluminium salt and calcium salt mixed and rolls, drying, roasting, to sieve, to obtain final product.
In order to increase vanadium catalyst dispersion effect in the solution and access times, in step C, after sieving, the particle diameter of vanadium catalyst is 2-5mm, and shape is sphere.
The not specified technology of the present invention is prior art.
The vanadium catalyst of the nitrobenzene sulfonation of gained of the present invention, has that the burn into of resistance to oleum intensity is high, activity stabilized, active principle turnover rate is low, object products collection efficiency advantages of higher; Can reuse more than 5 times, after reusing 5 times, active component vanadic anhydride turnover rate is less than 10%, has saved production cost, be beneficial to the separation and purification of final sulfonated product, and add the utilization rate of resource, decrease useless acid-treated difficulty, reduce the pollution to environment.
Accompanying drawing explanation
Fig. 1 is the content that in embodiment 3, gained vanadium catalyst reuses rear vanadic anhydride.
Detailed description of the invention
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Nitrobenzene sulfonation reaction experiment method:
In the round-bottomed flask that agitator, rupture pressure disc and thermometer are housed, add 17g nitrobenzene and 0.5-2.5g catalyst, material is stirred fully; Then at room temperature drip the oleum of 32.2g110%, control feed temperature <90oC simultaneously, dropwise in 2 hours; Subsequently material is slowly heated to 105oC, stirring reaction 5 hours, reaction terminates.Take a morsel product, detects analyze (internal standard method) nitrobenzene conversion rate and m-nitrobenzene sulfonic acid yield through liquid chromatograph.
Catalyst after filtration, dry and reclaim after, apply mechanically 5 times continuously, investigate service life of catalyst.
Embodiment 1
Vanadium catalyst is made up of following component: V
2o
520%, K
2sO
410%, Al
2o
32.5%, CaO10.0%, surplus is SBA-15.
Prepared by vanadium catalyst: be dissolved in by 6.4gKOH in 200ml deionized water, slowly add 20gV while stirring
2o
5powder, obtained mixed solution.And then slowly add the concentrated sulfuric acid and neutralize, regulate pH to 7.0, obtained V
2o
5-K
2sO
4jelly.Accurately take aluminium oxide 2.5g, calcium oxide 15.0g, SBA-1552.5g, above-mentioned material is poured in puddle mixer, roll 1 hour, granulation (2-5mm), 120 degree of oven dry, 550 degree of roastings, obtained 100g catalyst.Get obtained catalyst 2.5g, carry out nitrobenzene sulfonation reaction experiment, detect through liquid chromatograph and analyze (internal standard method), nitrobenzene conversion rate 99.7%, m-nitrobenzene sulfonic acid yield 92.3%.
Embodiment 2
Vanadium catalyst is made up of following component: V
2o
520%, K
2sO
410%, Al
2o
32.5%, CaO10%, surplus is MCM-41.Adopt embodiment 1 production technology, the aluminium salt selected and calcium salt are aluminum sulfate, calcium hydroxide respectively.Get obtained vanadium catalyst 2.5g, carry out nitrobenzene sulfonation reaction experiment, detect through liquid chromatograph and analyze (internal standard method), nitrobenzene conversion rate 99.0%, m-nitrobenzene sulfonic acid yield 91.2%.
Embodiment 3
Vanadium catalyst is made up of following component: V
2o
525%, K
2sO
47%, Al
2o
32.0%, CaO10.0%, surplus is ZSM-5.Adopt embodiment 1 production technology, the aluminium salt selected and calcium salt are aluminum sulfate, calcium sulfate respectively.Get obtained catalyst 2.0g, carry out nitrobenzene sulfonation reaction experiment, detect through liquid chromatograph and analyze (internal standard method), nitrobenzene conversion rate 99.9%, m-nitrobenzene sulfonic acid yield 93.5%.
Embodiment 4
Vanadium catalyst is made up of following component: V
2o
520%, K
2sO
410%, Al
2o
32.0%, CaO5.0%, surplus is Ludox.Adopt embodiment 1 production technology, the aluminium salt selected and calcium salt are aluminum nitrate, calcium bicarbonate respectively.Get obtained catalyst 2.5g, carry out nitrobenzene sulfonation reaction experiment, detect through liquid chromatograph and analyze (internal standard method), nitrobenzene conversion rate 99.9%, m-nitrobenzene sulfonic acid yield 90.5%.
Comparative example 1
Get the catalyst that Powdered vanadic anhydride (content 99%) reacts as nitrobenzene sulfonation.(0.5g) is consistent in active component vanadic anhydride consumption and embodiment.Get product, detect through liquid chromatograph and analyze (internal standard method), nitrobenzene conversion rate 99.9%, m-nitrobenzene sulfonic acid yield 87.5%.
The service life of catalyst is investigated
Catalyst vanadium pentoxide powder in comparative example 1 cannot be recycled, and the solid vanadium catalyst adopting example of the present invention to prepare, not only the productive rate of nitrobenzene-sulfonic acid can reach more than 90%, and solid vanadium catalyst after filtration, dry after, can recycle.
Vanadium catalyst repeats to apply mechanically experimental result and shows, when the catalyst described in the embodiment of the present invention 3 has been reused after five times, active component pentoxide content (method of testing is with reference to HG/T2516-93) in solid vanadium catalyst still can retain more than 90%, as shown in Figure 1, this catalyst activity is substantially constant simultaneously, in 5th experiment, nitrobenzene conversion rate is 99.8%, and the yield of m-nitrobenzene sulfonic acid still can remain on 90.0%.
Claims (6)
1. for a vanadium catalyst for nitrobenzene sulfonation, it is characterized in that: by V
2o
5, K
2sO
4, aluminium salt, calcium salt and silicon carrier composition, wherein, V
2o
5mass content be 20-30%, K
2sO
4mass content be 5.5-10%, aluminium salt is with Al
2o
3the mass content of metering is 1-2.5%, the calcium salt mass content of measuring with CaO is 5.5-10%, surplus is for silicon carrier.
2. as claimed in claim 1 for the vanadium catalyst of nitrobenzene sulfonation, it is characterized in that: silicon carrier is the mixture of one or more any proportionings in SBA-15, MCM-41, ZSM-5 or Ludox.
3., as claimed in claim 1 or 2 for the vanadium catalyst of nitrobenzene sulfonation, it is characterized in that: calcium salt is the mixture of calcium nitrate or calcium carbonate or both any proportionings.
4., as claimed in claim 1 or 2 for the vanadium catalyst of nitrobenzene sulfonation, it is characterized in that: aluminium salt is the mixture of one or more any proportionings in aluminum nitrate, aluminium dihydrogen phosphate or aluminum sulfate.
5. the preparation method of the vanadium catalyst for nitrobenzene sulfonation described in claim 1-4 any one, is characterized in that: comprise the following steps that order connects:
A, by vanadic anhydride and potassium hydroxide water-soluble, and use H
2sO
4the obtained V of neutralization
2o
5-K
2sO
4colloidal liquid, wherein, V
2o
5concentration is 50g/L-300g/L;
B, the colloidal liquid of silicon carrier, steps A gained, aluminium salt and calcium salt mixed and rolls, shaping, dry, roasting, to sieve, to obtain final product.
6. method as claimed in claim 5, it is characterized in that: in step B, after sieving, the particle diameter of vanadium catalyst is 2-5mm, and shape is sphere.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785241A (en) * | 2015-04-21 | 2015-07-22 | 桂林理工大学 | Visible light responsible photocatalyst CaSiV2O8 and preparation method thereof |
| CN106674062B (en) * | 2016-12-27 | 2018-09-04 | 沈阳化工研究院有限公司 | A method of catalysis sulfonation prepares m-nitrobenzene sodium sulfonate |
| CN109174164B (en) * | 2018-08-14 | 2022-02-15 | 江苏大学 | Vanadium phosphorus oxide/MCM-41 catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0516001A1 (en) * | 1991-05-24 | 1992-12-02 | Haldor Topsoe A/S | Process for the regeneration of spent sulphuric acid |
| CN101088607A (en) * | 2006-06-13 | 2007-12-19 | 攀枝花学院 | Technological process of preparing high efficient vanadium catalyst with nanometer vanadium material |
| CN101648138A (en) * | 2008-08-12 | 2010-02-17 | 襄樊市精信催化剂有限责任公司 | Arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide and preparation method thereof |
| CN102188942A (en) * | 2011-04-01 | 2011-09-21 | 沈阳化工大学 | Production method for preparing m-nitrobenzenesulfonic acid by tubular sulfonation reactor |
-
2014
- 2014-01-07 CN CN201410007546.XA patent/CN103752336B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0516001A1 (en) * | 1991-05-24 | 1992-12-02 | Haldor Topsoe A/S | Process for the regeneration of spent sulphuric acid |
| CN101088607A (en) * | 2006-06-13 | 2007-12-19 | 攀枝花学院 | Technological process of preparing high efficient vanadium catalyst with nanometer vanadium material |
| CN101648138A (en) * | 2008-08-12 | 2010-02-17 | 襄樊市精信催化剂有限责任公司 | Arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide and preparation method thereof |
| CN102188942A (en) * | 2011-04-01 | 2011-09-21 | 沈阳化工大学 | Production method for preparing m-nitrobenzenesulfonic acid by tubular sulfonation reactor |
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