CN1375357A - Amorphous alloy catalyst for hydrogenating cyclobufene sultone and its prepn. and application - Google Patents
Amorphous alloy catalyst for hydrogenating cyclobufene sultone and its prepn. and application Download PDFInfo
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- CN1375357A CN1375357A CN 02100292 CN02100292A CN1375357A CN 1375357 A CN1375357 A CN 1375357A CN 02100292 CN02100292 CN 02100292 CN 02100292 A CN02100292 A CN 02100292A CN 1375357 A CN1375357 A CN 1375357A
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Abstract
The present invention relates to a catalyst for cyclobutenesulfphone hydrogenation, its general formula is NixCoyBmPn, in which x=0-80, y=0.70, m=0-50 and n=0-50. It is an amorphous alloy, and possesses high low-temp. activity, and is easy to industrial production.
Description
Affiliated technical field:
The present invention relates to the catalyzer of hydrogenating cyclobufene sultone, specifically its amorphous alloy catalyst and preparation method and utilisation technology in the reaction of hydrogenating cyclobufene sultone system tetramethylene sulfone of forming by metal Ni or Co and B or P.
Background technology
Tetramethylene sulfone has another name called the tetramethylene sulfone, is a kind of solvent of important excellent property.Most of organic compound and polymkeric substance can be dissolved in tetramethylene sulfone or miscible with it.Tetramethylene sulfone generally is used as aromatic hydrocarbons extraction solvent, polymkeric substance spinning or moulding solvent; The purification of Sweet natural gas, synthetic gas and refinery gas, desulfurization solvent and plastics, rubber solvent; Can be used for weaving, printing and dyeing industry in addition as dyeing and printing auxiliary, can make in bright gay color light.
The suitability for industrialized production of tetramethylene sulfone comes from the Britain of early forties, is to be raw material with divinyl and sulfurous gas, generates cyclobufene sultone by Diels-Alder reaction, gets through the low-temperature catalyzed hydrogenation of nickel-containing catalyst again.Present domestic use tetramethylene sulfone depends on import mostly, and domestic have two families to produce tetramethylene sulfone, and industrial scale is all at 5000 tons/year, and catalyzer uses skeleton nickel.Because skeleton nickel exist to be used dangerous and environment had unfavorable factor such as pollution, thereby press for and develop a kind of efficient and eco-friendly new catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of amorphous alloy catalyst and preparation and application that is used for hydrogenating cyclobufene sultone, the present invention has very high low temperature active, and the preparation method is simple, is easy to industry's enlarging production, and environment is not polluted.
The present invention is that general formula is Ni
xCo
yB
mP
nAmorphous alloy, x=0-80 wherein, y=0-70, m=0-50, n=0-50.Median size is about 15-30nm.
Preparation of the present invention comprises the steps:
The Type B catalyzer is under 268K, nitrogen protection, with KBH
4Solution (2mol/l) and nickelous nitrate or the reaction of the mixing solutions of Xiao Suangu (0.1-0.7mol/l) or nickelous nitrate and Xiao Suangu, after the end, centrifugal, be washed to neutrality.Ethanol is medium-term and long-term to be preserved.The form of catalyzer is NiB, CoB or NiCoB.
P type catalyzer is that the aqueous solution with nickelous hypophosphite stirs KBH under 300K
4Solution causes the reaction of nickelous hypophosphite generation automatic oxidation reduction, and is after reaction finishes, centrifugal, be washed to neutrality.Ethanol is medium-term and long-term to be preserved.The form of catalyzer is NiP.
BP type catalyzer is under 300K, with KBH
4Solution (concentration 2mol/l) is added drop-wise in the nickelous hypophosphite solution.After reaction finishes, centrifugal, be washed to neutrality.Ethanol is medium-term and long-term to be preserved.The form of catalyzer is NiBP.
The step that the present invention carries out the hydrogenating cyclobufene sultone reaction is: autoclave carries out the hydrogenating cyclobufene sultone reaction, reaction conditions: cyclobufene sultone and catalyzer (weight) were than 10: 1; Hydrogen pressure 3MPa; Temperature of reaction: 323K-333K; Stirring velocity: 250-450 rev/min; Reaction times is 2 hours.The gas chromatographic analysis product.
The present invention has very high low temperature active, and the preparation method is simple, is easy to industry's enlarging production, and environment is not polluted.
Substantive distinguishing features that the present invention gives prominence to and unusual effect can be embodied from following embodiment, but they are not that the present invention is imposed any restrictions.
Description of drawings
Fig. 1 is the XRD spectra of amorphous alloy catalyzer; Fig. 2 is the SEM photo of amorphous alloy; Fig. 3 is the TEM figure of amorphous alloy catalyzer.
Embodiment
Embodiment 1
Under 268K, the nitrogen protection, nickel nitrate solution (85ml, 0.4mol/l) is added drop-wise to KBH with the speed of 6ml/min
4(60ml) in the solution.After reaction finishes, centrifugal, be washed to neutrality after, place ethanol to protect.Occur the diffuse peaks of broadening in its x-ray diffraction pattern (Fig. 1) near 2 θ=45 °, this is the characteristic diffraction peak of NiB amorphous alloy, shows that the synthetic NiB of institute alloy really is non-crystalline state.Near the diffuse peaks that occurs broadening 2 θ=22 ° belongs to the characteristic peak of amorphous-type metal B.(Fig. 2 a) shows that the NiB Amorphous Alloy Grain is approximately spherical to sem photograph, and median size is about 15nm.The product atom is formed: Ni
69B
31
The present invention adopts the 250ml autoclave to carry out the hydrogenating cyclobufene sultone reaction.Reaction conditions: cyclobufene sultone compares 10-1 with catalyzer; Hydrogen pressure 3MPa; Temperature of reaction: 333K; Stirring velocity: 250 rev/mins; Reaction times is 2 hours.The gas chromatographic analysis product.The results are shown in Table 1.
Under the 300K 24 gram nickelous hypophosphites, 2 gram acetic acid are received, 4 gram Trisodium Citrates add in the 100ml distilled water, transfer pH value of solution value 7-8 with sodium hydroxide.Add several KBH in the stirring
4The solution initiation reaction is carried out.Product through centrifugal, be washed to neutrality after, place ethanol to protect.Occur the diffuse peaks of broadening in its x-ray diffraction pattern (Fig. 1) near 2 θ=45 °, this is the characteristic diffraction peak of NiP amorphous alloy, shows that the synthetic NiP of institute alloy really is non-crystalline state.(Fig. 3 a) shows the NiP Amorphous Alloy Grain for spherical to transmission electron microscope picture, the about 30nm of median size.The product atom is formed: Ni
65P
35
Reaction conditions is with embodiment 1.
Embodiment 3
Under the 300K with KBH
4Solution (26ml) splashes in the nickelous hypophosphite solution (50ml, 1mol/l) with the speed of 0.9ml/min.Product through centrifugal, be washed to neutrality after, place ethanol to protect.Occur the diffuse peaks of broadening in its x-ray diffraction pattern (Fig. 1) near 2 θ=45 °, this is the characteristic diffraction peak of NiPB amorphous alloy, shows that the synthetic NiPB of institute alloy really is non-crystalline state.Transmission electron microscope picture (Fig. 3 b) shows that the NiPB particle is irregularly shaped, and the about 20nm of median size is between NiP and NiB.The product atom is formed: Ni
69B
20P
11
Reaction conditions is with embodiment 1.
Comparative Examples 1
Cyclobufene sultone and catalyzer are than 7-1, and other reaction conditionss are with embodiment 1.
Embodiment 4
Change the nickel nitrate aqueous solution among the embodiment 1 into cobalt nitrate solution, strength of solution is 0.1mol/l; Other are with embodiment 1.Occur the diffuse peaks of broadening in its x-ray diffraction pattern (Fig. 1) near 2 θ=45 °, this is the characteristic diffraction peak of CoB amorphous alloy, shows that the synthetic CoB of institute alloy really is non-crystalline state.Sem photograph (Fig. 2 b) shows that the CoB non-crystaline amorphous metal is similar to a kind of reticulated structure, and particle is tiny of can not differentiating its size.The hydrogenating cyclobufene sultone temperature of reaction is 328K, and other reaction conditionss are with embodiment 1.The product atom is formed: Co
65B
35
Comparative Examples 2
Cyclobufene sultone and catalyzer are than 7-1, and other reaction conditionss are with embodiment 4.
Embodiment 5
Under the 268K, the mixing solutions (50ml, 0.7mol/l) of nickelous nitrate and Xiao Suangu is added drop-wise to KBH with the speed of 1.5ml/min
4In the solution (43ml).After reaction finishes, centrifugal, be washed to neutrality.Ethanol is medium-term and long-term to be preserved.Occur the diffuse peaks of broadening in its x-ray diffraction pattern (Fig. 1) near 2 θ=45 °, this is the characteristic diffraction peak of NiCoB amorphous alloy, shows that the synthetic NiCoB of institute alloy really is non-crystalline state.Sem photograph (Fig. 2 c) shows that the NiCoB non-crystaline amorphous metal has formed the aggregate that is similar to skeleton structure.
The hydrogenating cyclobufene sultone temperature of reaction is 330K, and other reaction conditionss are with embodiment 1.
Embodiment 6
With the 43mlKBH among the embodiment 5
4Solution changes 85mlKBH into
4Solution, other conditions are with embodiment 5.
Comparative Examples 3
Cyclobufene sultone and catalyzer are than 7-1, and other reaction conditionss are with embodiment 5.
Embodiment 7
With the 43mlKBH among the embodiment 5
4Solution changes 60mlKBH into
4Solution; With KBH
4Drips of solution is added in the mixing solutions of nickelous nitrate and Xiao Suangu; The hydrogenating cyclobufene sultone temperature of reaction is 323K, and stirring velocity changes 420 rev/mins into, and other conditions together
Embodiment 5.
Embodiment 8
With KBH among the embodiment 7
4The mixing solutions of solution and nickelous nitrate and Xiao Suangu is used the preparation of second distillation water dissolution instead, and other conditions are with embodiment 7.
Embodiment 9
The mixing solutions of nickelous nitrate and Xiao Suangu is added drop-wise to KBH
4In the solution, other are with embodiment 8.
Comparative Examples 4
Cyclobufene sultone and catalyzer are than 7-1, and other reaction conditionss are with embodiment 7.
Table 1 different catalysts under the differential responses condition to hydrogenating cyclobufene sultone reactivity catalyst reaction temperatures (K) mixing speed (rev/min) sulfolane yield (%) embodiment 1 338 250 68.6 embodiment 2 338 250 20.0 embodiment 3 338 250 36.3 Comparative Examples 1 338 250 67.4 embodiment 4 328 250 49.9 Comparative Examples 2 328 250 85.5 embodiment 5 330 250 98.1 embodiment 6 330 250 97.1 Comparative Examples 3 330 250 92.4 embodiment 7 323 420＞99.9 embodiment 8 323 420 98.6 embodiment 9 323 420 97.5 Comparative Examples 4 323 400 99.0
Claims (4)
1, a kind of amorphous alloy catalyst that is used for hydrogenating cyclobufene sultone is characterized in that it is that general formula is
Ni
xCo
yB
mP
nAmorphous alloy, x=0-80 wherein, y=0-70, m=0-50, n=0-50.
2,, it is characterized in that described amorphous alloy median size is about 15-30nm according to the described amorphous alloy catalyst that is used for hydrogenating cyclobufene sultone of claim 1.
3, the described preparation method who is used for the amorphous alloy catalyst of hydrogenating cyclobufene sultone of claim 1 is characterized in that it is to comprise the steps:
1) the Type B catalyzer is under 268K, nitrogen protection, with 2mol/l KBH
4The reaction of the mixing solutions of solution and 0.1-0.7mol/l nickelous nitrate or Xiao Suangu or nickelous nitrate and Xiao Suangu, centrifugal, be washed to neutrality, ethanol is medium-term and long-term to be preserved;
2) P type catalyzer is that the aqueous solution with nickelous hypophosphite stirs KBH under 300K
4Solution causes the reaction of nickelous hypophosphite generation automatic oxidation reduction, and centrifugal, be washed to neutrality after reaction finishes, ethanol is medium-term and long-term to be preserved;
3) BP type catalyzer is under 300K, with 2mol/l KBH
4Drips of solution is added in the nickelous hypophosphite solution, and centrifugal, be washed to neutrality after reaction finishes, ethanol is medium-term and long-term to be preserved.
4, the described using method that is used for the amorphous alloy catalyst of hydrogenating cyclobufene sultone of claim 1 is characterized in that it comprises the steps:
Autoclave carries out hydrogenating cyclobufene sultone reaction, reaction conditions: the weight ratio of cyclobufene sultone and catalyzer 10: 1; Hydrogen pressure 3MPa; Temperature of reaction: 323K-333K; Stirring velocity: 250-450 rev/min; Reaction times is 2 hours, the gas chromatographic analysis product.
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| CN 02100292 CN1128015C (en) | 2002-01-18 | 2002-01-18 | Amorphous alloy catalyst for hydrogenating cyclobufene sultone and its prepn. and application |
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| CN 02100292 CN1128015C (en) | 2002-01-18 | 2002-01-18 | Amorphous alloy catalyst for hydrogenating cyclobufene sultone and its prepn. and application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100594059C (en) * | 2006-01-12 | 2010-03-17 | 南开大学 | Method for preparing NiB non-crystalline alloy catalyst with the aid of microwave |
| CN101898135A (en) * | 2010-07-16 | 2010-12-01 | 武汉凯马仕精细化工有限公司 | Amorphous catalyst for catalytic hydrogenation of 2-cyan-4-nitroaniline and preparation method of 2,5-diamincyanophenyl |
| CN104549384A (en) * | 2014-12-23 | 2015-04-29 | 桂林电子科技大学 | Preparation method of Ni-P-B nano-spherical alloy catalyst as well as application of catalyst |
-
2002
- 2002-01-18 CN CN 02100292 patent/CN1128015C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100594059C (en) * | 2006-01-12 | 2010-03-17 | 南开大学 | Method for preparing NiB non-crystalline alloy catalyst with the aid of microwave |
| CN101898135A (en) * | 2010-07-16 | 2010-12-01 | 武汉凯马仕精细化工有限公司 | Amorphous catalyst for catalytic hydrogenation of 2-cyan-4-nitroaniline and preparation method of 2,5-diamincyanophenyl |
| CN101898135B (en) * | 2010-07-16 | 2012-10-03 | 武汉凯马仕精细化工有限公司 | Amorphous catalyst for catalytic hydrogenation of 2-cyan-4-nitroaniline and preparation method of 2,5-diamincyanophenyl |
| CN104549384A (en) * | 2014-12-23 | 2015-04-29 | 桂林电子科技大学 | Preparation method of Ni-P-B nano-spherical alloy catalyst as well as application of catalyst |
| CN104549384B (en) * | 2014-12-23 | 2020-03-10 | 桂林电子科技大学 | Preparation method and application of Ni-P-B nanosphere alloy catalyst |
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| Publication number | Publication date |
|---|---|
| CN1128015C (en) | 2003-11-19 |
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