CN102658191A - Catalyst for preparing caprolactam from cyclohexanone-oxime by liquid-phase Beckmann rearrangement - Google Patents
Catalyst for preparing caprolactam from cyclohexanone-oxime by liquid-phase Beckmann rearrangement Download PDFInfo
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- CN102658191A CN102658191A CN2012101517302A CN201210151730A CN102658191A CN 102658191 A CN102658191 A CN 102658191A CN 2012101517302 A CN2012101517302 A CN 2012101517302A CN 201210151730 A CN201210151730 A CN 201210151730A CN 102658191 A CN102658191 A CN 102658191A
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- cyclohexanone oxime
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a catalyst for preparing caprolactam from cyclohexanone-oxime by liquid-phase Beckmann rearrangement, which is a supported solid acid catalyst using heteropoly acid as an active component and mesoporous molecular sieve (HMS) as a support, wherein the support capacity of the heteropoly acid is 10-70 wt%. The heteropoly acid is heteropolyphosphatotungstate (HPW). Compared with the existing catalyst, the invention has the following advantages: (1) the catalyst adopts heterogeneous catalysis, and can be recycled in a vacuum filtration mode; (2) the heteropoly acid is used as the catalyst, and thus, the invention is environment-friendly, can not generate low-value byproduct ammonium sulfate, and does not corrode the equipment; (3) the reaction is carried out under ordinary pressure, the reaction temperature is not high, the requirements for reaction equipment are not high, and the operation is convenient; and (4) the yield and selectivity of caprolactam are high, respectively reaching 82.5% and 87.1%.
Description
Technical field
The present invention relates to the preparation of caprolactam, be specially a kind of catalyst that caprolactam is produced in the Beckmann rearrangement of cyclohexanone oxime liquid phase that is used for.
Background technology
Epsilon-caprolactams is a kind of important Organic Chemicals, and outward appearance is white crystal or crystalline powder, soluble in water, ethanol, ether, chloroform and benzene etc.Mainly as producing polyamide-6 fiber and polyamide-6 engineering plastics, caprolactam also can be used for producing antiplatelet drug 6-aminocaprolc acid, resin and film to caprolactam in addition.
Cyclohexanone oxime Beckmann rearrangement equation is following:
The cyclohexanone oxime Beckmann rearrangement is an acid catalyzed reaction, and the current industrial production caprolactam is to make catalyst with the oleum or the concentrated sulfuric acid, earlier cyclohexanone oxime is changed into caprolactam sulfate, makes with the ammoniacal liquor neutralization again.Though use the concentrated sulfuric acid as catalyst, the selectivity of caprolactam is very high, also has many shortcomings: the ammoniacal liquor neutralization is used in (1), inevitably produces a large amount of low value producing ammonium sulfate byproducts; (2) concentrated sulfuric acid severe corrosion equipment; (3) produce a large amount of sewage; (4) in the course of reaction owing to use the concentrated sulfuric acid, heat release is violent, causes danger easily.In order to address the above problem, the new catalyst that the Beckmann rearrangement of exploitation cyclohexanone oxime prepares caprolactam becomes the focus of various countries production firm.The someone studies vapor phase beckmann rearrangement reaction under the solid acid effect in early days, and the catalyst of studying mainly contains oxide, molecular sieve etc.Original research be single oxide, like Al
2O
3, SiO
2, B
2O
3But catalytic activity is very low.So the chemist just turns to the multi-component oxide catalyst system and catalyzing with the emphasis of research, particularly with B
2O
3Be carried on other oxide carrier, like B
2O
3/ Al
2O
3, B
2O
3/ SiO
2, B
2O
3/ ZrO
2Deng.B
2O
3/ ZrO
2Carry out Beckmann rearrangement on the catalyst, the selectivity of caprolactam is up to 98% (Yin Shuanfeng, Xu Baiqing, catalysis journal, 2002,23 (6): 507-512).But vapor phase beckmann rearrangement reaction needs hot conditions, and accessory substance is more, and the easy inactivation of catalyst.For head it off, part scholar begins to be devoted to the research of cyclohexanone oxime liquid phase Beckmann rearrangement, a collection of solid acid occurred and has replaced the Beckmann rearrangement of sulphuric acid catalysis cyclohexanone oxime liquid phase to produce the technology of caprolactam.Room-temperature ion liquid 1-butyl-3-methylimidazole trifluoroacetate (BMImTFA), 1-butyl-3-methylimidazole borofluoride (BMImBF
4) and normal-butyl pyridine borofluoride (BPyBF
4) wait the catalyst system and catalyzing of forming with phosphorus-containing compound, can not use other organic solvent, reaction condition is gentle.But ion liquid preparation process is more, complex operation (Peng Jiajian, Deng Youquan, petrochemical industry, 2001,30 (2): 91-92).To comprise Cs
+Phospho heteropoly tungstate be used for Beckmann rearrangement, catalytic effect is fine, but its particle diameter smaller (about 10nm), the preparation difficulty.(N.R.?Shiju,?H.M.?Williams,?D.R.?Brown,?Applied?Catalysis?B:Environmental,2009,90(3-4):451–457)。
To sum up; Use the shortcoming of liquid acid catalyst a lot of in traditional cyclohexanone oxime liquid phase Beckmann rearrangement; And the complicated process of preparation of existing solid acid catalyst, catalyst is difficult for reclaiming, so develop the key point that the heterogeneous catalyst of this technology is a caprolactam production.
Summary of the invention
The shortcoming and the problems such as solid catalyst complicated process of preparation, recovery difficulty that prepare the liquid catalyst that exists in the caprolactam reaction to existing cyclohexanone oxime liquid phase Beckmann rearrangement; The invention provides the Beckmann rearrangement of a kind of cyclohexanone oxime liquid phase and produce the Catalysts and its preparation method of caprolactam, can simplify obviously that catalyst preparation process, catalyst are prone to reclaim, process conditions are simple.
Technical scheme among the present invention is:
A kind ofly be used for the catalyst that caprolactam is produced in the Beckmann rearrangement of cyclohexanone oxime liquid phase; This catalyst is to be active constituent with the heteropoly acid; With mesopore molecular sieve (HMS) is the load-type solid acid catalyst of carrier, and wherein, the load capacity of heteropoly acid is mass percent 10-70%.
Described heteropoly acid is phosphorus heteropoly tungstic acid HPW (H
3PW
12O
40XH
2O).
Describedly be used for the Preparation of catalysts method that caprolactam is produced in the Beckmann rearrangement of cyclohexanone oxime liquid phase, it is characterized by and comprise the steps:
Equi-volume impregnating: according to the load capacity (10-70wt.%) of the last heteropoly acid of HMS, the heteropoly acid of weighing respective quality respectively is dissolved in the deionized water, gets settled solution; Then with the HMS carrier impregnation in above-mentioned solution, leave standstill 24h under the room temperature, 30-60 ℃ revolve steam the white solid powder, at 100 ~ 500 ℃ of roasting temperature 4-10h, obtain the carried heteropoly acid that load capacity is 10-70wt.%.
Saidly be used for the Application of Catalyst that caprolactam is produced in the Beckmann rearrangement of cyclohexanone oxime liquid phase; Its characteristic comprises the steps: carried heteropoly acid catalyst HPW/HMS, cyclohexanone oxime and solvent are placed reactor; Making cyclohexanone oxime concentration is 0.001 ~ 0.04g cyclohexanone oxime/mL solvent, and its material proportion mass ratio is: catalyst (in the active constituent heteropoly acid): cyclohexanone oxime=0.1 ~ 100
:1.Under normal pressure, 100 ~ 180 ℃ of reaction temperatures, constant temperature stirring reaction 1 ~ 10 h isolates organic facies, promptly gets the product caprolactam.
Described solvent is specially dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF) or acetonitrile.
In the described catalyst applications, the material proportion mass ratio is preferably: catalyst (in the active constituent heteropoly acid): cyclohexanone oxime=0.3 ~ 1.5
:1.
Beneficial effect of the present invention is embodied in:
Compare with existing catalyst, hexanolactam catalyst is produced in cyclohexanone oxime liquid phase of the present invention Beckmann rearrangement, has:
(1) heterogeneous catalysis, catalyst just can reclaim through the suction filtration mode.
(2) use heteropoly acid as catalyst, environmental friendliness does not produce the low value producing ammonium sulfate byproduct, and equipment is not had corrosion.
(3) be reflected under the normal pressure and carry out, reaction temperature is not high, and is not high, easy to operate to the requirement of consersion unit yet.
(4) yield of caprolactam and selectivity are higher, can be respectively up to 82.5% and 87.1%.
Description of drawings
Fig. 1 is the XRD spectra of HPW among the embodiment 1.
Fig. 2 is HMS and the XRD spectra of 10wt.% HPW/HMS among the embodiment 1.
Fig. 3 is HMS and the XRD spectra of 40wt.% HPW/HMS among the embodiment 4.
The specific embodiment
Substantive features of the present invention and remarkable result can be able to from following embodiment embody, but they do not do any restriction to the present invention.
Its specific surface of mesopore molecular sieve HMS that the present invention uses is 730m
2/ g, average pore size is 3nm, but is not limited thereto kind of a HMS.
Through the specific embodiment the present invention is further described below.
Embodiment 1
Adopt equi-volume impregnating to prepare phosphorus heteropoly tungstic acid HPW (HPW/HMS) catalyst of mesopore molecular sieve HMS load: to take by weighing 0.2 g phosphorus heteropoly tungstic acid (H
3PW
12O
40XH
2O) be dissolved in the 10 ml deionized waters, obtain settled solution.Get 2.0 g HMS and place above-mentioned clarified solution liquid, leave standstill dipping 24 h under the room temperature.60 ℃ revolve steam the white solid powder, 180 ℃ of roasting temperature 9 h, the load capacity that obtains HPW is the HPW/HMS of 10wt.%.
In accompanying drawing 1, HPW in 2 θ=10.3 ° and 25.4 ° two obvious characteristics diffraction maximums are arranged, show that used HPW has the Keggin structure in the experimentation; And the diffracted intensity of these two characteristic peaks is very strong; The peak type is more sharp-pointed, explains that the degree of crystallinity of HPW is very high, and crystal formation is relatively more perfect.
In accompanying drawing 2, when the load capacity of HPW was 10wt.%, the XRD spectra of support type HPW/HMS and HMS was not observed the characteristic diffraction peak of HPW much at one, explained that HPW is the high degree of dispersion state on carrier HMS, do not form the HPW crystal; Simultaneously can explain that also HMS has enough big specific surface HPW is disperseed on its surface well, reduce the possibility that HPW assembles.
In the infrared spectrum of HPW, 1080,983,899 and 806cm
-1There are four obvious characteristics absworption peaks at the place, and this is to be caused by special Keggin structure, divides according to anion structure, and HPW belongs to the Keggin type.1080cm wherein
-1The absworption peak at place is PO
4The symmetrical stretching vibration peak of P – O in the tetrahedron; 983cm
-1The absworption peak at place is W=O
tStretching vibration peak; 899cm
-1And 806cm
-1The absworption peak at place is the stretching vibration peak of W – O – W, 899cm
-1The absworption peak at place is W – O
cThe stretching vibration peak of – W (inter-bridges between corner-sharing octahedra), 806cm
-1The absworption peak at place is W – O
eThe stretching vibration peak of – W (intra-bridges between edge-sharing octahedra).
In three mouthfuls of round-bottomed flasks of 100ml, add cyclohexanone oxime 0.3 g, solvent DMSO10 ml and 10wt.% HPW/HMS 1.0 g successively, N
2Protection, magnetic agitation, reflux condensation mode, oil bath temperature control.When treating that temperature reaches 150 ℃, pick up counting, behind the synthesis under normal pressure 6h, be cooled to room temperature, suction filtration is isolated catalyst.In gas-chromatography, analyze fid detector through the PEG-2M capillary column.Analysis condition is: 250 ℃ of detector temperatures, and 250 ℃ of temperature of vaporization chamber, 10 ℃/min of heating rate, column temperature keeps 3 min for 80 ℃, is warming up to 250 ℃, sample size 0.2 μ l.Adopt area normalization method to carry out quantitative analysis.Experimental result is as shown in table 1.
Embodiment 2 ~ 5
Load capacity be the preparation of HPW/HMS of 20wt.%, 30wt.%, 40wt.% and 50wt.% with embodiment 1, phosphorus heteropoly tungstic acid (H just
3PW
12O
40XH
2O) quality is respectively 0.4 g, 0.6 g, 0.8 g and 1.0g.
In accompanying drawing 3, when the load capacity of HPW is 40wt.%, in 2 θ=10 ° and many places such as 25 ° the characteristic diffraction peak of HPW has all appearred; And the peak type of these characteristic diffraction peaks is sharp-pointed; Peak intensity is stronger, and the XRD technological means detects the existence of HPW crystal, explains when the load capacity of HPW increases to 40wt.%; Beginning is assembled on the surface of HMS, forms the HPW crystal.
Activity of such catalysts test operating procedure and reaction condition are with embodiment 1.Experimental result is as shown in table 1.
Table 1 HPW load capacity is to the influence of cyclohexanone oxime Beckmann rearrangement
| Embodiment | The load capacity of HPW (%) | The yield of caprolactam (%) | The selectivity of caprolactam (%) |
| 1 | 10 | 30.3 | 70.2 |
| 2 | 20 | 44.2 | 82.3 |
| 3 | 30 | 37.3 | 75.6 |
| 4 | 40 | 36.8 | 82.1 |
| 5 | 50 | 34.3 | 76.5 |
Embodiment 6～7
Identical with Preparation of catalysts operating procedure and the reaction condition of embodiment 2, just the sintering temperature of loaded catalyst HPW/HMS is respectively 240 ℃, 300 ℃.Experimental result is as shown in table 2.
Table 2 HPW/HMS sintering temperature is to the influence of cyclohexanone oxime Beckmann rearrangement
| Embodiment | Sintering temperature (℃) | The yield of caprolactam (%) | The selectivity of caprolactam (%) |
| 2 | 180 | 44.2 | 82.3 |
| 6 | 240 | 55.2 | 84.1 |
| 7 | 300 | 55.5 | 78.0 |
Embodiment 8～10
Identical with Preparation of catalysts operating procedure and the reaction condition of embodiment 6, just liquid phase Beckmann rearrangement temperature is respectively 110 ℃, and 130 ℃, 160 ℃.Experimental result is as shown in table 3.
Table 3 reaction temperature is to the influence of cyclohexanone oxime Beckmann rearrangement
| Embodiment | Reaction temperature (℃) | The yield of caprolactam (%) | The selectivity of caprolactam (%) |
| 8 | 110 | 5.4 | 53.4 |
| 9 | 130 | 7.0 | 61.0 |
| 6 | 150 | 55.2 | 84.1 |
| 10 | 160 | 70.5 | 78.3 |
Embodiment 11～14
Identical with Preparation of Catalyst operating procedure and the reaction condition of embodiment 6, just the liquid phase Beckmann rearrangement time is respectively 4h, 5h, 7h, 8h.Experimental result is as shown in table 4.
Table 4 reaction time is to the influence of cyclohexanone oxime Beckmann rearrangement
| Embodiment | Reaction time (h) | The yield of caprolactam (%) | The selectivity of caprolactam (%) |
| 11 | 4 | 7.3 | 38.5 |
| 12 | 5 | 9.4 | 47.2 |
| 6 | 6 | 55.2 | 84.1 |
| 13 | 7 | 46.8 | 74.3 |
| 14 | 8 | 35.6 | 59.4 |
Identical with Preparation of Catalyst operating procedure and the reaction condition of embodiment 6, just m (HPW)/m (oxime) is respectively 0.3,0.9,1.2,1.5.Experimental result is as shown in table 5.
Table 5 catalyst amount is to the influence of cyclohexanone oxime Beckmann rearrangement
| Embodiment | M (HPW)/m (oxime) | The yield of caprolactam (%) | The selectivity of caprolactam (%) |
| 15 | 0.3 | 12.2 | 60.0 |
| 6 | 0.6 | 55.2 | 84.1 |
| 16 | 0.9 | 61.2 | 86.6 |
| 17 | 1.2 | 82.5 | 87.1 |
| 18 | 1.5 | 83.2 | 85.4 |
Carried phospho-tungstic acid catalyst of the present invention, preparation flow is simple, and is environmentally friendly, easy recovery; In liquid phase cyclohexanone oxime Beckmann rearrangement, show good catalytic performance, load capacity be the HPW/HMS of 20wt.% under appropriate reaction conditions, the yield of caprolactam and selectivity can reach 82.5% and 87.1%.
Unaccomplished matter of the present invention belongs to known technology.
Claims (5)
1. one kind is used for the catalyst that caprolactam is produced in the Beckmann rearrangement of cyclohexanone oxime liquid phase; It is characterized by this catalyst is to be active constituent with the heteropoly acid; With mesopore molecular sieve (HMS) is the load-type solid acid catalyst of carrier, and wherein, the load capacity of heteropoly acid is mass percent 10-70%; Described heteropoly acid is phosphorus heteropoly tungstic acid (HPW).
2. as claimed in claim 1ly be used for the Preparation of catalysts method that caprolactam is produced in the Beckmann rearrangement of cyclohexanone oxime liquid phase, it is characterized by and comprise the steps:
Equi-volume impregnating: according to the load capacity (10-70wt.%) of the last heteropoly acid of HMS, the heteropoly acid of weighing respective quality respectively is dissolved in the deionized water, gets settled solution; Then with the HMS carrier impregnation in above-mentioned solution, leave standstill 24h under the room temperature, 30-60 ℃ revolve steam the white solid powder, at 100 ~ 500 ℃ of roasting temperature 4-10h, obtain the carried heteropoly acid that load capacity is 10-70wt.%.
3. be used for the Beckmann rearrangement of cyclohexanone oxime liquid phase according to claim 1 and produce the Application of Catalyst of caprolactam; It is characterized by and comprise the steps: carried heteropoly acid catalyst HPW/HMS, cyclohexanone oxime and solvent are placed reactor; Making cyclohexanone oxime concentration is 0.001 ~ 0.04g cyclohexanone oxime/mL solvent, and its material proportion mass ratio is: catalyst (in the active constituent heteropoly acid): cyclohexanone oxime=0.1 ~ 100
:1; Under normal pressure, 100 ~ 180 ℃ of reaction temperatures, constant temperature stirring reaction 1 ~ 10 h isolates organic facies, promptly gets the product caprolactam.
4. be used for the Application of Catalyst that caprolactam is produced in the Beckmann rearrangement of cyclohexanone oxime liquid phase as claim 3 is said, it is characterized by described solvent and be specially dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF) or acetonitrile.
5. be used for the Application of Catalyst that caprolactam is produced in the Beckmann rearrangement of cyclohexanone oxime liquid phase as claim 3 is said; It is characterized by in the described catalyst applications, the material proportion mass ratio is preferably: catalyst (in the active constituent heteropoly acid): cyclohexanone oxime=0.3 ~ 1.5
:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017153A (en) * | 2014-04-24 | 2015-11-04 | 中国石油化工股份有限公司 | Method for refining caprolactam |
| CN109503483A (en) * | 2018-12-27 | 2019-03-22 | 中国天辰工程有限公司 | A kind of liquid phase Beckmann rearrangement prepares catalyst of caprolactam and preparation method thereof |
Citations (1)
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| CN1768937A (en) * | 2004-11-05 | 2006-05-10 | 中国石油化工股份有限公司 | Microcellular structured heteropoly acid/ silicon dioxide catalyst |
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2012
- 2012-05-16 CN CN201210151730.2A patent/CN102658191B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1768937A (en) * | 2004-11-05 | 2006-05-10 | 中国石油化工股份有限公司 | Microcellular structured heteropoly acid/ silicon dioxide catalyst |
Non-Patent Citations (3)
| Title |
|---|
| N.R. SHIJU, ET AL.: "Cs exchanged phosphotungstic acid as an efficient catalyst for liquid-phase Beckmann rearrangement of oximes", 《APPLIED CATALYSIS B: ENVIRONMENTAL》, vol. 90, 17 April 2009 (2009-04-17), pages 451 - 457, XP026195151, DOI: doi:10.1016/j.apcatb.2009.04.016 * |
| R. MAHESWARI, ET AL.: "Beckmann rearrangement over phosphotungstic acid/SiMCM-41 cyclohexanone oxime to epsilon-caprolactam", 《APPLIED CATALYSIS A: GENERAL》, vol. 248, 31 December 2003 (2003-12-31), pages 291 - 301, XP004443507, DOI: doi:10.1016/S0926-860X(03)00182-0 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017153A (en) * | 2014-04-24 | 2015-11-04 | 中国石油化工股份有限公司 | Method for refining caprolactam |
| CN109503483A (en) * | 2018-12-27 | 2019-03-22 | 中国天辰工程有限公司 | A kind of liquid phase Beckmann rearrangement prepares catalyst of caprolactam and preparation method thereof |
| CN109503483B (en) * | 2018-12-27 | 2021-12-14 | 中国天辰工程有限公司 | Catalyst for preparing caprolactam through liquid phase Beckmann rearrangement and preparation method thereof |
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