CN103214336A - Method for producing cyclohexene through oxidative dehydrogenation of cyclohexane - Google Patents
Method for producing cyclohexene through oxidative dehydrogenation of cyclohexane Download PDFInfo
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- CN103214336A CN103214336A CN2013100074284A CN201310007428A CN103214336A CN 103214336 A CN103214336 A CN 103214336A CN 2013100074284 A CN2013100074284 A CN 2013100074284A CN 201310007428 A CN201310007428 A CN 201310007428A CN 103214336 A CN103214336 A CN 103214336A
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- catalyst
- cyclohexene
- oxidative dehydrogenation
- cyclonexane
- reaction
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Abstract
The invention discloses a method for producing cyclohexene through oxidative dehydrogenation of cyclohexane, wherein a used catalyst is a composite metal oxide catalyst adopting K, Mg and Mo as main active components and adopting V as an additive, and a catalyst carrier is gamma-alumina or titanium oxide. The method comprises that: cyclohexane is subjected to gasification in a gasification chamber under a 0-5 kPa pressure condition, wherein a gasification temperature is 160-240 DEG C; the gasified cyclohexane passes through a composite metal oxide catalyst bed layer, and reacts with air, wherein the gas phase cyclohexane is subjected to partial oxidation in a fixed bed reactor by the air, a gas phase reaction temperature is 400-600 DEG C, and a reaction time is 0.05-1 s; and the reaction product is subjected to processes such as cooling and separation to obtain the cyclohexene. The method has the following advantages that: with the composite metal oxide catalyst, activity and selectivity of the catalyst are increased, the method has characteristics of simple operation and mild reaction conditions, the cyclohexene selectivity can be up to 46.98%, and the by-product generation is less.
Description
Technical field
The present invention relates to a kind of preparation method of organic compound, specifically a kind of method of oxidative dehydrogenation of cyclonexane cyclohexene.
Background technology
Tetrahydrobenzene is a liquid colourless, that the specific stimulation smell is arranged, is a kind of important Organic Chemicals, is widely used in the production of medicine, food, agrochemicals, feed, poly-vinegar and other fine chemical products.As synthetic lysine, phenol, poly cyclene resin, chlorocyclohexane, rubber ingredients etc.Also can be used for catalyzer solvent and petroleum extn agent in addition, the stablizer of stop bracket gasoline.After tetrahydrobenzene direct oxidation synthesizing adipic acid was succeedd, tetrahydrobenzene was considered to the optimum feed stock of synthesizing cyclohexanone, hexalin and hexanodioic acid.
At present, the method for preparing tetrahydrobenzene mainly contains: (1) hexalin catalytic dehydration.Adopt the liquid-phase dehydration legal system of sulfuric acid or phosphoric acid catalyzed to be equipped with tetrahydrobenzene at present, this operational path is ripe, but product yield is not high, and corrodibility, and carbonization is serious, and side reaction and contaminate environment easily take place; Though phosphoric acid and polyphosphoric acid are good than sulfuric acid, productive rate is not high yet, and cost is higher simultaneously, and by product is many and be difficult to utilization, is not suitable for industrial production.(2) preparing cyclohexene from benzene added with hydrogen.The employed catalyzer of this method be with the Ru appendix on carriers such as silicon-dioxide, aluminum oxide, zeolite, mordenite, add certain auxiliary agent, be prepared from.CN 1597099A(applying date 2005-03-23 wherein) patent has been introduced Ru-M/ZrO
2(M is one or both among Zn, Fe, the La) makees catalyzer, reacts in high pressure reflection still, and temperature is controlled at 135 ℃, the cyclohexane conversion that obtains and the yield of tetrahydrobenzene are higher, but this method cost height, the easy poisoning and deactivation of catalyzer is to comprising S, Cl, NO
3 -, NH
4, Fe, As, elements such as Cu, Pb are very responsive, the element of denier just can cause catalyst deactivation, sulfide (except the vitriol) particularly has a strong impact on the selectivity of reaction.(3) hexanaphthene liquid phase reaction cyclohexene.With CuCl in the pyridine
2For catalyzer, tertbutyl peroxide are that oxygenant makes the dehydrogenation of hexanaphthene part prepare tetrahydrobenzene, when temperature was controlled at 28 ℃, cyclohexane conversion can reach 78%, but yield only is 16.7%.And produce more oxidized byproduct, have a strong impact on product cost.Therefore consider from the angle of green industry, need existing manufacturing technique is changed, realize the clean and effective production of tetrahydrobenzene preparation industry.
CN 101289365(applying date 2008-10-22) patent has been introduced the method for low-temperature catalytic benzene hydrogenation, this method has realized benzene hydrogenation under low temperature even room temperature condition, but the selectivity of still inevitable sulfide (except the vitriol) the influence reaction that generates.
At present, the industrial production main method of tetrahydrobenzene still is a benzene catalysed partial hydrogenation, obtain tetrahydrobenzene through charging, reaction, cooling, gas-liquid separation and collecting processes successively, the benzene transformation efficiency is 40%, the tetrahydrobenzene selectivity is 80%, but this process need carries out under condition of high voltage, and complex disposal process.Therefore need to explore new operational path, make operational condition simple, reduce the generation of by product, improve the productive rate of tetrahydrobenzene.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, and improving one's methods of a kind of hexamethylene alcoxyl dehydrogenation cyclohexene is provided.
The object of the invention can realize by following measure: the method for oxidative dehydrogenation of cyclonexane cyclohexene, it is characterized in that: this method is that hexanaphthene is under the 0-5kPa pressure condition, in vaporizer, gasify, gasification temperature is 160-240 ℃, the hexanaphthene of gasification is by the O composite metallic oxide catalyst bed, with air reaction, the gas phase hexanaphthene is by air partial oxidation in fixed-bed reactor, temperature of reaction is 400-600 ℃, reaction times is 0.1s-5s, and reaction product obtains tetrahydrobenzene through cooling, sepn process then.。
Wherein, the cyclohexane feed flow is 0.2-2mL/min, preferred 0.5-1.2mL/min, and air flow quantity is 100-200 mL/min, preferred 120-160 mL/min.
Described O composite metallic oxide catalyst is alkali metal, alkali earth metal, transition metal or its mixture, the content of single alkali element, alkaline earth element and transition element is the 1-50 weight % of total catalyst weight benchmark meter in the catalyzer, and support of the catalyst is gama-alumina or titanium oxide.
Preferably, described O composite metallic oxide catalyst is vanadium and alkali metal, vanadium and alkali earth metal or vanadium and transition metal, the content of alkali metal, alkali earth metal and transition metal is the 1-50 weight % of total catalyst weight benchmark meter in the catalyzer, and support of the catalyst is gama-alumina or titanium oxide.
Further preferred, transition metal is a vanadium in the O composite metallic oxide catalyst; Alkali metal is potassium, lithium, sodium and caesium in the O composite metallic oxide catalyst; Alkali earth metal is magnesium, calcium, strontium and barium in the O composite metallic oxide catalyst; Transition metal Shi Molybdenum, iron, cobalt and nickel in the O composite metallic oxide catalyst.Further preferred, O composite metallic oxide catalyst is V-K-γ-Al
2O
3, V-Mg-γ-Al
2O
3, V-Mo-γ-Al
2O
3Or V-K-TiO2.
The present invention compared with prior art, has following advantage: the O composite metallic oxide catalyst that the present invention is used, activity of such catalysts and selectivity have been improved, and with low cost, the suitability for industrialized large-scale application, this method is simple to operate simultaneously, the reaction conditions gentleness, the tetrahydrobenzene selectivity reaches as high as 47.00%, and by product generates few, and environmental pollution is little.
The load metal oxide Preparation of catalysts adopts the method for dipping, co-precipitation, ion-exchange among the present invention, all is to well known to a person skilled in the art technology.
Preferably reaction conditions be hexanaphthene, oxygen and V/K-γ-Al2O3 catalyzer at 400-600 ℃, or 450-550 ℃ of down contact, the reaction times is that flow velocity is 720-36000 hour preferably
-1Total gas hourly space velocity.
Embodiment
Enumerate Preparation of Catalyst embodiment below, the present invention is further specified, but the present invention is not limited only to these embodiment.
Embodiment 1 vanadium-potassium is with γ-Al
2O
3Preparation of catalysts for carrier:
Accurately take by weighing 0.77g ammonium meta-vanadate and 1.1g oxalic acid and be dissolved in the 20mL distilled water, fully stirring is all dissolved ammonium meta-vanadate at ambient temperature, then with 20g γ-Al
2O
3Put into solution and stir 4h, standing over night, gained solution revolves steaming to remove redundant moisture under 70 ℃ of conditions, will revolve to steam the catalyzer dry 12h in 120 ℃ loft drier that obtains.After drying finishes, put it in 650 ℃ the retort furnace and calcine 7h.
Appendix potassium in the above-mentioned catalyzer that makes takes by weighing 1.33g saltpetre and is dissolved in the 20mL distilled water, fully stirs and makes its whole dissolvings.Above-mentioned catalyzer is put into this solution stir 4h, standing over night, gained solution revolves steaming to remove redundant moisture under 70 ℃ of conditions, will revolve to steam the catalyzer dry 12h in 120 ℃ loft drier that obtains.After drying finishes, put it in 650 ℃ the retort furnace and calcine 7h.Thereby make V/K-γ-Al
2O
3Catalyzer, its content of vanadium are 1.7 weight %, and potassium content is 2.4 weight %.
Above-mentioned catalyzer is put into fixed-bed reactor, 500 ℃ of the temperature of controlling reactor, atmospheric pressure state; Air enters reactor with 150ml/min, and hexanaphthene enters 180 ℃ of vaporizers by constant-flux pump with the 0.5ml/min flow, makes its gasification.Thereby hexanaphthene is mixed at vaporizer with air, react in reactor, the product that obtains carries out gas chromatographic analysis, so calculate conversion of cyclohexane be 18.0% and the selectivity of tetrahydrobenzene be 32.5%.
Embodiment 2 vanadium-magnesium is with γ-Al
2O
3Preparation of catalysts for carrier:
The preparation method is the same, and the amount of wherein used ammonium meta-vanadate and magnesium nitrate is respectively 0.77g, 3.38g.Thereby make V/Mg-γ-Al
2O
3Catalyzer, its content of vanadium are 1.5 weight %, and Mg content is 1.5 weight %.
Above-mentioned catalyzer is put into fixed-bed reactor, 500 ℃ of the temperature of controlling reactor, atmospheric pressure state; Air enters reactor with 150ml/min, and hexanaphthene enters 180 ℃ of vaporizers by constant-flux pump with the 0.5ml/min flow, makes its gasification.Thereby hexanaphthene is mixed at vaporizer with air, react in reactor, the product that obtains carries out gas chromatographic analysis, so calculate conversion of cyclohexane be 16.4% and the selectivity of tetrahydrobenzene be 19.6%.
Embodiment 3 vanadium-molybdenum is with γ-Al
2O
3Preparation of catalysts for carrier:
The preparation method is the same, and the amount of wherein used ammonium meta-vanadate and ammonium molybdate is respectively 0.77g, 2.33g.Thereby make V/Mo-γ-Al
2O
3Catalyzer, its content of vanadium are that 1.6 weight % ， Molybdenum content are 5.5 weight %.
Evaluation method is with example 1.Its reaction conditions and reaction result are as shown in table 1.
Embodiment 4 vanadium-potassium is the Preparation of catalysts of carrier with the titanium oxide:
Same vanadium-the potassium of preparation method is with γ-Al
2O
3Be the Preparation of catalysts of carrier, wherein with γ-Al
2O
3Be changed to titanium oxide.
Evaluation method is with example 5.Its reaction conditions and reaction result are shown in table 1-5
The method that is prepared tetrahydrobenzene by oxidative dehydrogenation of cyclonexane is:
Embodiment 5
Feed rate be the hexanaphthene of 0.5 mL/min under condition of normal pressure, in vaporizer, gasify, gasification temperature is 180 ℃, the hexanaphthene of gasification is by V/K-γ-Al
2O
3Beds, with flow be the air reaction of 150 mL/min, the gas phase hexanaphthene is by air partial oxidation in fixed-bed reactor, the gas-phase reaction temperature is 500 ℃, reaction times is 0.05s-1s, and reaction product obtains tetrahydrobenzene through cooling, sepn process then.After testing, cyclohexane conversion 18.0%, tetrahydrobenzene selectivity 32.5%.
Table 1 hexanaphthene partial oxidation reaction condition and reaction result
Table 2 hexanaphthene partial oxidation reaction condition and reaction result
Table 3 hexanaphthene partial oxidation reaction condition and reaction result
Table 4 hexanaphthene partial oxidation reaction condition and reaction result
Table 5 hexanaphthene partial oxidation reaction condition and reaction result
Claims (8)
1. the method for oxidative dehydrogenation of cyclonexane cyclohexene, it is characterized in that: this method is that hexanaphthene is under the 0-5kPa pressure condition, in vaporizer, gasify, gasification temperature is 160-240 ℃, and the hexanaphthene of gasification is by the O composite metallic oxide catalyst bed, with air reaction, the gas phase hexanaphthene is by air partial oxidation in fixed-bed reactor, temperature of reaction is 400-600 ℃, and the reaction times is 0.1s-5s, and reaction product obtains tetrahydrobenzene through cooling, sepn process then.
2. the method for oxidative dehydrogenation of cyclonexane cyclohexene according to claim 1 is characterized in that: described cyclohexane feed flow is 0.2-2mL/min, and air flow quantity is 100-200 mL/min.
3. the method for oxidative dehydrogenation of cyclonexane cyclohexene according to claim 1 is characterized in that: described cyclohexane feed flow is 0.5-1.2mL/min, and air flow quantity is 120-160 mL/min.
4. according to the method for arbitrary described oxidative dehydrogenation of cyclonexane cyclohexene among the claim 1-3, it is characterized in that: described O composite metallic oxide catalyst is alkali metal, alkali earth metal, transition metal or its mixture, the content of alkali metal, alkali earth metal and transition metal is the 1-50 weight % of total catalyst weight benchmark meter in the catalyzer, and support of the catalyst is gama-alumina or titanium oxide.
5. the method for oxidative dehydrogenation of cyclonexane cyclohexene according to claim 1, it is characterized in that: described O composite metallic oxide catalyst is vanadium and alkali metal, vanadium and alkali earth metal or vanadium and transition metal, the content of alkali metal, alkali earth metal and transition metal is the 1-50 weight % of total catalyst weight benchmark meter in the catalyzer, and support of the catalyst is gama-alumina or titanium oxide.
6. the method for oxidative dehydrogenation of cyclonexane cyclohexene according to claim 5 is characterized in that: alkali metal is potassium, lithium, sodium and caesium in the described O composite metallic oxide catalyst.
7. the method for oxidative dehydrogenation of cyclonexane cyclohexene according to claim 5 is characterized in that: alkali earth metal is magnesium, calcium, strontium and barium in the described O composite metallic oxide catalyst.
8. the method for oxidative dehydrogenation of cyclonexane cyclohexene according to claim 5 is characterized in that: transition metal Shi Molybdenum, iron, cobalt and nickel in the described O composite metallic oxide catalyst.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785256A (en) * | 2015-03-30 | 2015-07-22 | 湘潭大学 | Preparation method and application of catalyst for preparing cyclohexene through cyclohexane dehydrogenation |
| CN105820030A (en) * | 2016-04-26 | 2016-08-03 | 康瑞琴 | Production technology of chlorocyclohexane |
| WO2016158437A1 (en) * | 2015-03-27 | 2016-10-06 | Ｊｘエネルギー株式会社 | Dehydrogenation catalyst for hydrocarbons, hydrogen production system, and hydrogen production method |
| CN106238034A (en) * | 2016-06-28 | 2016-12-21 | 内蒙古工业大学 | The preparation of metal aluminum alloy cyclohexane oxidation catalyst and application |
| CN106268757A (en) * | 2015-05-20 | 2017-01-04 | 中国科学院兰州化学物理研究所苏州研究院 | Vanadio diisobutylene xylol catalyst, its preparation method and application |
| CN109806863A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | The preparation of Au catalyst and its application in oxidative dehydrogenation of cyclonexane reaction |
| CN112717919A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing isobutene by dehydrogenating isobutane |
| CN112912174A (en) * | 2018-09-05 | 2021-06-04 | 沙特基础全球技术有限公司 | Vanadium oxide supported catalysts for alkane dehydrogenation |
| CN114075096A (en) * | 2020-08-18 | 2022-02-22 | 中石化南京化工研究院有限公司 | Cyclohexene synthesis process |
| CN115254105A (en) * | 2022-08-10 | 2022-11-01 | 郑州大学 | Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method and use method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016158437A1 (en) * | 2015-03-27 | 2016-10-06 | Ｊｘエネルギー株式会社 | Dehydrogenation catalyst for hydrocarbons, hydrogen production system, and hydrogen production method |
| JPWO2016158437A1 (en) * | 2015-03-27 | 2018-01-18 | Ｊｘｔｇエネルギー株式会社 | Dehydrogenation catalyst for hydrocarbon, hydrogen production system, and hydrogen production method |
| CN104785256A (en) * | 2015-03-30 | 2015-07-22 | 湘潭大学 | Preparation method and application of catalyst for preparing cyclohexene through cyclohexane dehydrogenation |
| CN104785256B (en) * | 2015-03-30 | 2017-06-30 | 湘潭大学 | A kind of preparation method and application of cyclohexane dehydrogenation cyclohexene catalyst |
| CN106268757B (en) * | 2015-05-20 | 2019-03-29 | 中国科学院兰州化学物理研究所苏州研究院 | Vanadium base diisobutylene paraxylene catalyst, preparation method and application |
| CN106268757A (en) * | 2015-05-20 | 2017-01-04 | 中国科学院兰州化学物理研究所苏州研究院 | Vanadio diisobutylene xylol catalyst, its preparation method and application |
| CN105820030A (en) * | 2016-04-26 | 2016-08-03 | 康瑞琴 | Production technology of chlorocyclohexane |
| CN106238034A (en) * | 2016-06-28 | 2016-12-21 | 内蒙古工业大学 | The preparation of metal aluminum alloy cyclohexane oxidation catalyst and application |
| CN109806863A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | The preparation of Au catalyst and its application in oxidative dehydrogenation of cyclonexane reaction |
| CN112912174A (en) * | 2018-09-05 | 2021-06-04 | 沙特基础全球技术有限公司 | Vanadium oxide supported catalysts for alkane dehydrogenation |
| CN112717919A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing isobutene by dehydrogenating isobutane |
| CN114075096A (en) * | 2020-08-18 | 2022-02-22 | 中石化南京化工研究院有限公司 | Cyclohexene synthesis process |
| CN114075096B (en) * | 2020-08-18 | 2023-12-12 | 中石化南京化工研究院有限公司 | Cyclohexene synthesis process |
| CN115254105A (en) * | 2022-08-10 | 2022-11-01 | 郑州大学 | Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method and use method thereof |
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