CN101757916A - Catalyst for displacement of chlorine from chlorobenzene liquid phase by hydrogen and preparation method thereof - Google Patents
Catalyst for displacement of chlorine from chlorobenzene liquid phase by hydrogen and preparation method thereof Download PDFInfo
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- CN101757916A CN101757916A CN200810154561A CN200810154561A CN101757916A CN 101757916 A CN101757916 A CN 101757916A CN 200810154561 A CN200810154561 A CN 200810154561A CN 200810154561 A CN200810154561 A CN 200810154561A CN 101757916 A CN101757916 A CN 101757916A
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Abstract
The invention discloses a catalyst for the displacement of chlorine from a chlorobenzene liquid phase by hydrogen, which is characterized in that the active ingredients consist of 10 to 80 mass percent of Ni and 20 to 90 mass percent of B. The preparation method of the catalyst is characterized by preparing the catalyst by using a liquid phase reduction process and comprising the following steps: 1, preparing solution; 2, generating a precipitate; and 3, washing and storing the precipitate. The invention has the advantages that: the use of noble metals is avoided, and the cost of the catalyst is effectively reduced; and the preparation method is simple and suitable for large-scale production.
Description
(1) technical field:
The present invention relates to a kind of catalyst of chlorobenzene dechlorination, especially a kind of Catalysts and its preparation method of displacement of chlorine from chlorobenzene liquid phase by hydrogen.
(2) background technology:
Chloro organic cpd is the product after one or several hydrogen atom in aliphatic hydrocarbon, aromatic hydrocarbon and the derivative thereof is replaced by the chlorine atom.Various chlorohydrocarbons are as the base stock or the intermediate of various organic syntheses, and it is industrial to be widely used in organic chemical industry, agricultural chemicals, medicine, dyestuff etc., thereby make the production of chlorohydrocarbon become the very important part of organic chemistry industry.Yet, it is found that multiple chlorinated organics all can constitute a serious threat to the environment and the ecosystem.
At present, the processing method of chlorobenzene is mainly contained seal up for safekeeping, method such as high-temperature process, chemical treatment and biodegradation.Ripe also having of input industry operation: polyethylene glycol/sodium method, polyethylene glycol/alkaline process, non-current reagent method, MODAR oxidizing process and chlorinolysis method, all the other methods are in the laboratory research stage at present mostly, industrializedly also there are all weak points: high-temperature process law part harshness, easily cause secondary pollution, and cost is quite high, equipment is complicated, is not suitable for applying; Method of chemical treatment exists complex process, shortcoming that treatment effeciency is low; Although and biological degradation method is a potential method, the refuse and the speed of the low concentration of can only degrading are slower.At the refuse that contains PCBS that is dispersed in a large number all over the world, press for find a kind of completely, eco-friendly biodegrading process solves this global problem.
Use heterogeneous catalytic hydrogenation, the chlorine atom of chlorobenzene is substituted, and forms new hydrogenation products organic hydrocarbon, and hydrogenation products can reclaim like this, and might be applied in industrial production as raw material.Compare with the method for oxidative degradation, catalytic hydrogenation and dechlorination is a reduction process, can not produce more malicious De dioxins materials.And it is accessory substance that hydrogen chloride is only arranged in the product, is easy to recycle, and this process is the higher green catalysis process of Atom economy.
Catalytic hydrogenation and dechlorination activity of such catalysts component mainly contains Pd, Rh, and Pt, Fe, Ni, wherein the Pd element is considered to be used for the best catalyst of catalytic hydrogenation and dechlorination, thereby also studies at most to the various dechlorination reactions that carry out on the metal Pd are of greatest concern.Usually, use noble metal catalyst such as Pd, Pt, Rh etc. can be under very gentle condition (room temperature, normal pressure) just realize the hydrogenation of chlorobenzene, but because the too high industrial applications that has influenced it of its cost, and less relatively to the dechlorination performance modulation research of non-precious metal catalysts such as Ni.
(3) summary of the invention:
The object of the present invention is to provide a kind of Catalysts and its preparation method of displacement of chlorine from chlorobenzene liquid phase by hydrogen, this catalyst is formed simple, and environmental pollution is little, can reach the purpose of people's expectation.
Technical scheme of the present invention: a kind of catalyst of displacement of chlorine from chlorobenzene liquid phase by hydrogen, it is characterized in that the activity of such catalysts component is made up of Ni, B, wherein the mass percent of Ni is 10-80%, the mass percent of B is 20%-90%.
A kind of displacement of chlorine from chlorobenzene liquid phase by hydrogen Preparation of catalysts method is characterized in that catalyst adopts the method for liquid-phase reduction, and concrete steps are as follows:
(1) configuration solution: the NiSO that will contain Ni
4Soluble in water, the ammoniacal liquor of adding 5-20ml fully dissolves its solution;
(2) generate sediment: drip the NaBH that contains B in the solution that in step (1), obtains
4Solution, reaction is carried out immediately and is sent hydrogen, obtains the black precipitate NiB that form is an amorphous alloy, and promptly the catalyst n iB of displacement of chlorine from chlorobenzene liquid phase by hydrogen maintains the temperature in the course of reaction in 10-80 ℃; And the feeding inert gas shielding, not oxidized to guarantee product;
(3) washing precipitate and preservation: treat that no hydrogen emits, use deionized water washing sediment, then the black precipitate NiB that obtains is kept in the absolute ethyl alcohol.
The inert gas that feeds in the above-mentioned said step (2) is N
2Or Ar.
The Application of Catalyst that a kind of said method makes is characterized in that it plays catalytic action in displacement of chlorine from chlorobenzene liquid phase by hydrogen reaction; Its catalytic reaction condition is: adopt autoclave, H
2Pressurization 0.5-1.5MPa, adds black precipitate NiB as catalyst and chlorobenzene, absolute ethyl alcohol, NaOH, rotating speed 600-1000rpm, reaction time 1.0-2.0h by reaction temperature 50-150 ℃.
Above-mentioned said reactor is got 100ml.
Above-mentioned said catalyst is got 0.3g.
Above-mentioned said chlorobenzene is got 2.0g, and absolute ethyl alcohol is got 60ml, and NaOH is got 1.0g.
Superiority of the present invention is: 1. avoid using noble metal, reduced the catalyst cost effectively; 2. the preparation method is simple, helps large-scale production.
(4) specific embodiment:
Embodiment 1: take by weighing nickel sulfate hexahydrate 1g adding 50ml deionized water and be mixed with nickel sulfate solution, add 5ml ammoniacal liquor in solution, stirred 1 hour; The 0.4g sodium borohydride is joined in the 10ml deionized water; Under the room temperature sodium borohydride solution is added drop-wise in the solution containing nickel, reaction is carried out immediately and is sent hydrogen, drips, and treats that no hydrogen emits, and spends deionised water, then the black solid that obtains is kept in the absolute ethyl alcohol.
The catalyst of preparation is used for the displacement of chlorine from chlorobenzene liquid phase by hydrogen reaction, reaction condition is: 70 ℃ of reaction temperatures, pressure 1.0MPa, adopt the 100ml reactor, add 0.3g black precipitate NiB as catalyst and 2.0g chlorobenzene, 60ml absolute ethyl alcohol, 1.0g NaOH, rotating speed 700rpm, the reaction time is 1 hour; Final result, catalyst chlorobenzene conversion ratio is 93%.
Embodiment 2: take by weighing nickel sulfate hexahydrate 1g adding 50ml deionized water and be mixed with nickel sulfate solution, add 10ml ammoniacal liquor in solution, stirred 1 hour; The 0.6g sodium borohydride is joined in the 10ml deionized water; Under the room temperature sodium borohydride solution is added drop-wise in the solution containing nickel, reaction is carried out immediately and is sent hydrogen, drips, and treats that no hydrogen emits, and spends deionised water, then the black solid that obtains is kept in the absolute ethyl alcohol.
The catalyst of preparation is used for the displacement of chlorine from chlorobenzene liquid phase by hydrogen reaction, reaction condition is: 75 ℃ of reaction temperatures, pressure 0.9MPa, adopt the 100ml reactor, add 0.3g black precipitate NiB as catalyst and 2.0g chlorobenzene, 60ml absolute ethyl alcohol, 1.0g NaOH, rotating speed 800rpm, the reaction time is 1.5 hours; Final result, catalyst chlorobenzene conversion ratio is 95%
Embodiment 3: take by weighing six water nickel nitrate 1g adding 50ml deionized water and be mixed with nickel sulfate solution, add 10ml ammoniacal liquor in solution, stirred 1 hour; The 0.4g sodium borohydride is joined in the 10ml deionized water; Under the room temperature sodium borohydride solution is added drop-wise in the solution containing nickel, reaction is carried out immediately and is sent hydrogen, drips, and treats that no hydrogen emits, and spends deionised water, then the black solid that obtains is kept in the absolute ethyl alcohol.
The catalyst of preparation is used for the displacement of chlorine from chlorobenzene liquid phase by hydrogen reaction, reaction condition is: 80 ℃ of reaction temperatures, pressure 1.2MPa, adopt the 100ml reactor, add 0.3g black precipitate NiB as catalyst and 2.0g chlorobenzene, 60ml absolute ethyl alcohol, 1.0g NaOH, rotating speed 900rpm, the reaction time is 2 hours; Final result, catalyst chlorobenzene conversion ratio is 90%.
Claims (7)
1. the catalyst of a displacement of chlorine from chlorobenzene liquid phase by hydrogen is characterized in that the activity of such catalysts component is made up of Ni, B, and wherein the mass percent of Ni is 10-80%, and the mass percent of B is 20%-90%.
2. a displacement of chlorine from chlorobenzene liquid phase by hydrogen Preparation of catalysts method is characterized in that catalyst adopts the method for liquid-phase reduction, and concrete steps are as follows:
(1) configuration solution: the NiSO that will contain Ni
4Soluble in water, the ammoniacal liquor of adding 5-20ml fully dissolves its solution;
(2) generate sediment: drip the NaBH that contains B in the solution that in step (1), obtains
4Solution, reaction is carried out immediately and is sent hydrogen, obtains the black precipitate NiB that form is an amorphous alloy, and promptly the catalyst n iB of displacement of chlorine from chlorobenzene liquid phase by hydrogen maintains the temperature in the course of reaction in 10-80 ℃; And the feeding inert gas shielding, not oxidized to guarantee product;
(3) washing precipitate and preservation: treat that no hydrogen emits, use deionized water washing sediment, then the black precipitate NiB that obtains is kept in the absolute ethyl alcohol.
3. according to the said a kind of displacement of chlorine from chlorobenzene liquid phase by hydrogen Preparation of catalysts method of claim 2, it is characterized in that the inert gas that feeds in the said step (2) is N
2Or Ar.
4. Application of Catalyst that makes according to the method for claim 3 is characterized in that it plays catalytic action in the displacement of chlorine from chlorobenzene liquid phase by hydrogen reaction; Its catalytic reaction condition is: adopt autoclave, H
2Pressurization 0.5-1.5MPa, adds black precipitate NiB as catalyst and chlorobenzene, absolute ethyl alcohol, NaOH, rotating speed 600-1000rpm, reaction time 1.0-2h by reaction temperature 50-150 ℃.
5. according to the said a kind of Application of Catalyst that makes according to the method for claim 3 of claim 4, it is characterized in that said reactor gets 100ml.
6. according to the said a kind of Application of Catalyst that makes according to the method for claim 3 of claim 4, it is characterized in that said catalyst gets 0.3g.
7. according to the said a kind of Application of Catalyst that makes according to the method for claim 3 of claim 4, it is characterized in that said chlorobenzene gets 2.0g, absolute ethyl alcohol is got 60ml, and NaOH is got 1.0g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810154561A CN101757916A (en) | 2008-12-25 | 2008-12-25 | Catalyst for displacement of chlorine from chlorobenzene liquid phase by hydrogen and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810154561A CN101757916A (en) | 2008-12-25 | 2008-12-25 | Catalyst for displacement of chlorine from chlorobenzene liquid phase by hydrogen and preparation method thereof |
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| CN101757916A true CN101757916A (en) | 2010-06-30 |
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| CN200810154561A Pending CN101757916A (en) | 2008-12-25 | 2008-12-25 | Catalyst for displacement of chlorine from chlorobenzene liquid phase by hydrogen and preparation method thereof |
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Open date: 20100630 |