CN103910598B - A kind of chlorination aromatic hydrocarbon dechlorination Hydrogenation is for the method for cyclohexane - Google Patents
A kind of chlorination aromatic hydrocarbon dechlorination Hydrogenation is for the method for cyclohexane Download PDFInfo
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- CN103910598B CN103910598B CN201410099568.3A CN201410099568A CN103910598B CN 103910598 B CN103910598 B CN 103910598B CN 201410099568 A CN201410099568 A CN 201410099568A CN 103910598 B CN103910598 B CN 103910598B
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Abstract
The present invention relates to the method for a kind of chlorination aromatic hydrocarbon dechlorination Hydrogenation for cyclohexane, under catalyst action, hydrogen and chlorination aromatic hydrocarbon are carried out to catalysis dechlorination hydrogenation reaction one step and make cyclohexane, described reaction temperature is 150～350 DEG C, and hydrogen gas space velocity is 5～50h-1, the air speed of chlorination aromatic hydrocarbon is 0.4～8h-·, the present invention has the advantages such as technique is simple, reaction condition is gentle, catalyst activity and selectivity is high, long service life.
Description
Technical field
The present invention relates to the preparation method of cyclohexane, particularly a kind of chlorination aromatic hydrocarbon dechlorination Hydrogenation is for the side of cyclohexaneMethod.
Background technology
Chlorination aromatic hydrocarbon is important industrial chemicals, organic synthesis intermediate and organic solvent, be widely used in chemical industry,The industries such as medicine, agricultural chemicals, dyestuff, electronics. But, also strong to the mankind when the extensive use of chlorination aromatic hydrocarbon compoundThe threat that health and environment structure are day by day serious. For example, a lot of organo-chlorine pesticides (lindane, drinox and dieldrite etc.) withAnd chlorobenzene class, chloro phenol compound have toxicity and " three cause effect " (carcinogenic, teratogenesis, mutagenesis); Polychlorinated biphenylsExtensive use, existence and the enrichment in food chain even more serious to the harm of human body. UNEP (United Nations Environment Program) is " about lastinglyThe Convention of Stockholm of property organic pollution (PoPs) " 12 kinds of controlled chemistry materials of 3 class of first announcement areChloro organic cpd. Therefore pollution, how effectively to eliminate the harm of chloro debirs to human health and environmentThrough extremely urgent.
At present, the method that chlorination aromatic hydrocarbon pollutant is eliminated mainly comprises biodegradation, photocatalytic degradation, burning, wet methodCatalytic oxidation, catalysis dechlorination hydrogenation etc. In high concentration cl organic degradation process of generation, light degradation and biodegradation effectRate is lower, degrades thorough not; High temperature incineration and wet method catalyzing oxidizing degrading condition are comparatively harsh, and chloro organisesThe incomplete burning of compound easily generates the higher bioxin of toxicity, also can discharge NOx and greenhouse gases CO simultaneously2，Thereby cause the secondary pollution to environment. Catalysis dechlorination hydrogenation process reaction condition is relatively gentle, the chlorine atom in reactantWhen being eliminated, generate the organic compound that can recycle, and without CO2Discharge. Therefore, catalysis dechlorination addsHydrogen has the feature of low waste discharge, is the green catalysis process that Atom economy is high, is considered to eliminate chlorination aromatic hydrocarbonEnvironmental pollution a kind of simple, effectively and have a treatment technology of prospect.
At present, the dechlorination hydrogenation process of bibliographical information mainly adopts nickel-containing catalyst or monometallic or two gold containing noble metalMetal catalyst, wherein noble metal catalyst dechlorination hydrogenation activity is better than nickel-base catalyst, these catalyst all exist due toThe reasons such as HCl is poisoning, carbon distribution or sintering cause the problem such as short, the easy inactivation of catalyst life, regeneration difficulty, are difficult to realizeRecycling of catalyst, especially in gas phase dechlorination hydrogenation process, deactivation phenomenom is more obvious.
Chinese invention patent publication number CN101007280A, denomination of invention: a kind of novel hydrogenation and dechlorination catalyst of preparingMethod. This disclosure of the invention a kind of method of preparing novel hydrogenation and dechlorination catalyst, at nanometer NiB amorphous alloy or receiveThe Pd cluster of load high dispersive on rice nickel by powder, through crystallization, processing prepares novel surperficial NiPd alloy as catalystAgent. Use above-mentioned catalyst in compressive reaction still, 70 DEG C of reaction temperatures, react under pressure 1.0MPa, and chlorobenzene is urgedChange dechlorination and make benzene. Although the method reaction temperature is low, have that reaction pressure is high, the easy loss of catalyst can not circulateThe shortcomings such as use.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provide that a kind of technique is simple, reaction condition is gentle, yield is highChlorination aromatic hydrocarbon dechlorination Hydrogenation for the method for cyclohexane.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: a kind of chlorination aromatic hydrocarbon dechlorinationHydrogenation, for the method for cyclohexane, under catalyst action, carries out catalysis dechlorination hydrogenation reaction by hydrogen and chlorination aromatic hydrocarbonOne step makes cyclohexane, and described reaction temperature is 150～350 DEG C, and hydrogen gas space velocity is 5～50h-1, the sky of chlorination aromatic hydrocarbonSpeed is 0.4～8h-1. Described catalyst is palladium/Ni type bimetallic catalyst.
Described palladium/Ni type bimetallic catalyst is preferably taking coconut husk charcoal as carrier, the mass percent of nickel in active componentContent is preferably 5～25%, the mass percentage content of palladium is preferably 0.1～5%.
Described chlorination aromatic hydrocarbon is preferably chlorobenzene, paracide, o-dichlorohenzene, m-dichlorobenzene, 1,2,3-trichloro-benzenes,1,2,4-trichloro-benzenes, 1,3,5-trichloro-benzenes, 1,2,3, the one in 4-tetrachlorobenzene and 1,2,3,5-tetrachlorobenzene, pentachlorobenzene, hexachloro-benzeneOr multiple mixture.
Described reaction temperature is preferably 200～300 DEG C, and hydrogen gas space velocity is preferably 7～40h-1, the air speed of chlorination aromatic hydrocarbonBe preferably 0.4～5h-1。
Chlorination aromatic hydrocarbon dechlorination Hydrogenation of the present invention, for the method for cyclohexane, adopts the palladium/Ni of high activity and stabilityType bimetallic catalyst, thus make chlorination aromatic hydrocarbon compound for catalysis dechlorination hydrogenation make cyclohexane.
Method of the present invention has that technique is simple, reaction condition is gentle, catalyst activity and selectivity is high, long service lifeEtc. advantage, can make chlorination aromatic hydrocarbon catalysis dechlorination hydrogenation after a step make cyclohexane, realize continuous operation, and nothingIncrease the three wastes newly, have a extensive future. Chlorination aromatic hydrocarbon catalysis dechlorination hydrogenation is obtained cyclohexane by the present invention can destroy chloroAromatic hydrocarbon, does not harm environment, produces again good economic benefit. The present invention can adopt reactor conventional in Chemical ManufactureAs fixed bed reactors react, thereby realize continuous operation, have a extensive future.
Compared with prior art, the present invention has the following advantages:
1, technique is simple, reaction condition is gentle, can make chlorination aromatic hydrocarbon catalysis dechlorination hydrogenation after a step make cyclohexane,And realize continuous operation, be easy to industrialization;
2, high, the long service life of catalyst activity, cyclohexane selectively can reach more than 98.2%, reaches as high as 99.2%;Continuously operation 1000 hours, its conversion ratio and selectively still more than 98%;
3, society and remarkable in economical benefits, obtains cyclohexane by chlorination aromatic hydrocarbon catalysis dechlorination hydrogenation and can destroy chloro virtueFragrant hydrocarbon, does not harm environment, produces again good economic benefit.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not limited only to following enforcementExample.
Embodiment 1
By the palladium/Ni type bimetallic catalyst after reduction activation (taking coconut husk charcoal as carrier, the wherein mass percent of nickelContent is 5%, the mass percentage content of palladium is 5%) 100 grams fill in fixed bed reactors, temperature programming and withAir speed 20h-1Pass into hydrogen to 200 DEG C of reaction temperatures, then improve hydrogen gas space velocity to 40h-1, by after chlorobenzene heating vaporizationTaking air speed as 5h-1Speed pass into fixed bed reactors reactions, after product water absorbs, adopt gas chromatographic analysis gas to produceThing content, result is as table 1.
Embodiment 2
By the palladium/Ni type bimetallic catalyst after reduction activation (taking coconut husk charcoal as carrier, the wherein mass percent of nickelContent is 10%, the mass percentage content of palladium is 0.5%) 100 grams fill in fixed bed reactors, temperature programming is alsoWith air speed 20h-1Pass into hydrogen to 300 DEG C of reaction temperatures, then reduce hydrogen gas space velocity to 7h-1, by hexachloro-benzene heating vaporizationAfter taking air speed as 0.4h-1Speed pass into fixed bed reactors reactions, after product water absorbs, adopt gas chromatographic analysis gasBody product content, result is as table 1.
Embodiment 3
By the palladium/Ni type bimetallic catalyst after reduction activation (taking coconut husk charcoal as carrier, the wherein mass percent of nickelContent is 15%, the mass percentage content of palladium is 1%) 100 grams fill in fixed bed reactors, temperature programming is alsoWith air speed 20h-1Pass into hydrogen to 150 DEG C of reaction temperatures, then reduce hydrogen gas space velocity to 5h-1, then by 1,2,3,4-tetrachloroAfter the mixture heating vaporization of benzene and 1,2,3,5-tetrachlorobenzene taking air speed as 0.4h-1Speed pass into fixed bed reactors reactions,After product water absorbs, adopt gas chromatographic analysis gaseous product content, result is as table 1.
Embodiment 4
By the palladium/Ni type bimetallic catalyst after reduction activation (taking coconut husk charcoal as carrier, the wherein mass percent of nickelContent is 20%, the mass percentage content of palladium is 2%) 100 grams fill in fixed bed reactors, temperature programming is alsoWith air speed 20h-1Pass into hydrogen to 250 DEG C of reaction temperatures, then improve hydrogen gas space velocity to 21h-1, by chlorobenzene, to dichloroAfter the mixture heating vaporization of benzene and 1,3,5-trichloro-benzenes taking air speed as 2h-1Speed pass into fixed bed reactors reactions, produceAfter thing water absorbs, adopt gas chromatographic analysis gaseous product content, result is as table 1.
Embodiment 5
By the palladium/Ni type bimetallic catalyst after reduction activation (taking coconut husk charcoal as carrier, the wherein mass percent of nickelContent is 25%, the mass percentage content of palladium is 0.1%) 100 grams fill in fixed bed reactors, temperature programming is alsoWith air speed 20h-1Pass into hydrogen to 350 DEG C of reaction temperatures, then improve hydrogen gas space velocity to 50h-1, by 1,2,3-trichloro-benzenes,After the mixture heating vaporization of pentachlorobenzene and hexachloro-benzene taking air speed as 8h-1Speed pass into fixed bed reactors reactions, productAfter water absorbs, adopt gas chromatographic analysis gaseous product content, result is as table 1.
The reaction result of table 1 embodiment 1～5
In the present invention, the preparation of used catalyst and reduction activation method are as follows:
It is 1: 1 group according to volume ratio that the carrier coconut husk charcoal of catalyst is added by 0.1mol/L nitric acid and 0.3mol/L hydrochloric acidBecome nitration mixture in, boil 4～10 hours, then filter, wash to the pH value of filtrate be 5～7, the coconut husk charcoal of gainedBe dried 5～10 hours at 120 DEG C, obtain the coconut husk charcoal of acid treatment; By proportioning, the soluble salt of palladium and nickel is mixed with and is soakedStain liquid, adds maceration extract to flood the coconut husk charcoal of acid treatment, 60～90 DEG C of dipping temperatures, dip time 3～7Hour, obtain catalyst precursor; Catalyst precursor under nitrogen protection in 160～200 DEG C dry 10～16 hours,Obtain catalyst of the present invention. Then with the aqueous formic acid of 10～15wt% at 70～120 DEG C of reduction activation catalyst11～13 hours, reducing loaded palladium, nickel on coconut husk charcoal, after activating and reducing completes again under nitrogen protection,At 180～220 DEG C, dry 10～15h, obtains the catalyst after reduction activation.
Claims (1)
1. chlorination aromatic hydrocarbon dechlorination Hydrogenation is for a method for cyclohexane, by two palladium/Ni the type after reduction activation gold100 grams of metal catalysts fill in fixed bed reactors, temperature programming with air speed 20h-1Pass into hydrogen to reaction temperature200 DEG C, then improve hydrogen gas space velocity to 40h-1, by after chlorobenzene heating vaporization taking air speed as 5h-1Speed pass into fixed bedReactor reaction, is characterized in that described palladium/Ni type bimetallic catalyst is taking coconut husk charcoal as carrier, in active componentThe mass percentage content of nickel is 5%, the mass percentage content of palladium is 5%, and the palladium/Ni type after reduction activation is twoThe preparation of metallic catalyst and reduction activation method are as follows:
It is 1: 1 group according to volume ratio that the carrier coconut husk charcoal of catalyst is added by 0.1mol/L nitric acid and 0.3mol/L hydrochloric acidBecome nitration mixture in, boil 4～10 hours, then filter, wash to the pH value of filtrate be 5～7, the coconut husk charcoal of gainedBe dried 5～10 hours at 120 DEG C, obtain the coconut husk charcoal of acid treatment; By proportioning, the soluble salt of palladium and nickel is mixed with and is soakedStain liquid, adds maceration extract to flood the coconut husk charcoal of acid treatment, 60～90 DEG C of dipping temperatures, dip time 3～7Hour, obtain catalyst precursor; Catalyst precursor under nitrogen protection in 160～200 DEG C dry 10～16 hours,Obtain palladium/Ni type bimetallic catalyst, then live 70～120 DEG C of reduction with the aqueous formic acid of 10～15wt%Change palladium/Ni type bimetallic catalyst 11～13 hours, reducing loaded palladium, nickel on coconut husk charcoal, activating and reducing is completeCheng Houzai is under nitrogen protection, and dry 10～15h at 180～220 DEG C, obtains the palladium/Ni type pair after reduction activationMetallic catalyst.
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| CN107602318B (en) * | 2017-09-08 | 2020-06-05 | 郑州大学 | Method for liquid-phase reduction dehalogenation of halogenated aromatic hydrocarbon under mild condition |
| CN108822107B (en) * | 2018-06-08 | 2020-07-31 | 福建师范大学福清分校 | Method for dehalogenation and reduction of polyhalogenated perylene diimide aromatic hydrocarbon by nickel catalysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101007280A (en) * | 2007-01-26 | 2007-08-01 | 南开大学 | Preparation method of a novel hydrogenation and dechlorination catalyst |
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| CN101632931B (en) * | 2009-08-14 | 2012-06-27 | 西安近代化学研究所 | Hydrodechlorination catalyst |
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Non-Patent Citations (4)
| Title |
|---|
| Catalytic hydrodechlorination of chloroaromatic gas streams promoted by Pd and Ni: The role of hydrogen spillover;Claudia Amorim等;《Journal of Hazardous Materials》;20121231;第211-212卷;第208-217页 * |
| Characterization and reactivity of Al2O3 supported Pd-Ni bimetallic catalysts for hydrodechlorination of chlorobenzene;N. Seshu Babu等;《Applied Catalysis B: Environmental》;20111013;第111-112卷;第1300-1306页 * |
| Performance of supported nickel and other metal catalysts in the hydrodechlorination of chlorobenzene and 1-chlorohexane;Vincent de Jong等;《Applied Catalysis A: General》;20041231;第271卷;第153-163页 * |
| The hydrodechlorination of chlorobenzene in the vapor phase in the presence of metal-carbon nanocomposites based on nickel, palladium, and iron;E.S.Lokteva等;《RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A》;20091231;第83卷(第8期);第309-316页 * |
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