CN104418684A - Method for effectively maintaining high activity and high stability of catalyst - Google Patents
Method for effectively maintaining high activity and high stability of catalyst Download PDFInfo
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- CN104418684A CN104418684A CN201310382847.6A CN201310382847A CN104418684A CN 104418684 A CN104418684 A CN 104418684A CN 201310382847 A CN201310382847 A CN 201310382847A CN 104418684 A CN104418684 A CN 104418684A
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Abstract
The invention relates to a catalyst for a hydrogenation and dehalogenation reaction, and particularly relates to a method for effectively maintaining high activity and high stability of a catalyst. According to the method disclosed by the invention, the catalyst is applied to a heterogeneous catalytic hydrogenation and dehalogenation reaction of organic halides in different reaction solvent systems at a reaction pressure of 0.05MPa to 1.0MPa and at a reaction temperature of 20 to 80 DEG C in different reaction solvent systems, wherein the concentration of the catalyst in a reaction solution is 20mg/100ml to 50mg/100ml, and an alkaline proton absorbent is added for absorbing HCl generated in reaction. By changing the properties of a reaction solvent, the method disclosed by the invention can be used for maintaining relatively high activity and stability of the catalyst and is high in hydrogenation and dehalogenation efficiency and moderate in reaction condition, and the catalyst is recyclable.
Description
Technical field
The present invention relates to hydrodehalogenation catalysts, specifically a kind of method of effective maintenance high activity of catalyst and high stability.
Background technology
Heterogeneous catalyzed hydration dehalogenation early has application as a kind of methodology of organic synthesis in the production of fine chemicals, recently also day by day come into one's own in environment protection, it can will be difficult to the height of ordinary method process or cause the halohydrocarbon of Heavy environmental pollution to be converted into low toxicity, tractable or nontoxic recycling compound; Such as by catalytic hydrogenation and dechlorination, it can remove the organochlorines such as chloroparaffin, chlorobenzene, polychlorobiphenyl for the chlorine atom of pollutent, and organo-chlorine pollutant is converted into corresponding alkane, benzene and biphenyl.
Common hydrogenation catalyst is with group VIII metal (load is on carrier) or title complex, carries out catalytic hydrogenation reaction with alcohol, organic acid salt or hydrogen as hydrogen source.European patent (1990, EP352,164) is with Pd (OAc)
2for catalyzer, at PPh
3and NEt
3under existence, chlorobenzene and hydrogen generation hydrodehalogenation react and generate benzene, and transformation efficiency is only 41%; United States Patent (USP) (1986, US4,618,686) is catalyzer with Pd/C, then adds phosphoric acid salt, can make polychlorinated biphenyl dechlorination; United States Patent (USP) (1971, US3,595,931) uses Pd/Al
2o
3as catalyzer, under potassium hydroxide exists, make 2-chloro-p-xylene and hydrogen at high temperature carry out the gas-phase reaction of catalytic hydrogenation and dechlorination, generate dimethylbenzene, transformation efficiency is close to 100%, and during low temperature, transformation efficiency is lower; Chinese patent (2009, CN101565356A) is processed chlorobenzene compound at 200 ~ 400 DEG C with loading type catalyst of phosphatizing nickel, obtains good dechlorination except toxic effect fruit.
In the hydrodehalogenation reaction of organic halogen, can generate hydrogen halide, and the generation of hydrogen halide easily making poisoning of catalyst and inactivation, thus cause the reduction of catalyst activity and the decline of stability, is finally the thorough inactivation of catalyzer.Therefore, the poisoning and deactivation prob solving catalyzer is necessary.
Summary of the invention
The object of this invention is to provide a kind of method of effective maintenance high activity of catalyst and high stability.
For achieving the above object, technical scheme provided by the invention is:
A kind of method of effective maintenance high activity of catalyst and high stability: by catalyzer in differential responses solvent system under 0.05 ~ 1.0MPa reaction pressure, 20 ~ 80 DEG C of temperature of reaction, add alkaline proton absorbent simultaneously and then the heterogeneous catalytic hydrogenation dehalogenation reaction carried out to the organic halogen in differential responses solvent system; Wherein, the concentration of catalyzer in reaction soln is 20 ~ 50mg/100mL; The HCl generated in described alkaline proton absorbent absorption reaction;
Differential responses solvent system is protonic solvent-water two phase solvent system or protonic solvent-methyl alcohol homogeneous solvent system.
Described catalyzer is the catalyzer in hydrodehalogenation reaction system.
Protonic solvent all mixes with aqueous phase solvent or methyl alcohol homogeneous solvent by the volume ratio of 20:1 ~ 1:5 by described protonic solvent-aqueous phase solvent system or protonic solvent-methyl alcohol homogeneous solvent system respectively.
Described protonic solvent is propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol or n-Octanol.
In described reaction system, the volume ratio of protonic solvent and water or methyl alcohol is 5:1 ~ 1:3.
Described alkaline proton absorbent is one or more in lithium hydroxide, sodium hydroxide, potassium hydroxide, ammoniacal liquor, triethylamine;
Described alkaline proton absorbent and organic halogen halogen species mol ratio are 1:2 ~ 4:1.
Described alkaline proton absorbent and organic halogen halogen species mol ratio are 1:1 ~ 1.5:1.
Described reaction pressure is 0.05 ~ 1.0MPa, and temperature of reaction is 20 ~ 80 DEG C.
Described catalyzer makees catalyzer for adopting transition metal, and such catalyzer is made up of active ingredient and carrier.Active ingredient is: one or more in Pd, Pt, Rh, Ru, Ni, and active ingredient accounts for 0.5% ~ 5.0% of catalyst quality mark.
The present invention has the following advantages:
1. catalyzer can effectively keep high reactivity reagent high stability.Temperature of reaction provided by the invention and reaction pressure condition comparatively gentle, the Activity and stabill simultaneously keeping higher by regulating dehalogenation reaction solvent polarity can make hydrodechlorination catalysts.
2. hydrodechlorination reaction efficiency is high.Mild reaction conditions provided by the invention can make organic halogen carry out hydrodehalogenation reaction, completely eliminates the halogen atom of organic halogen, reduces stability and the toxicity of organic halogen.
3. reaction conditions is gentle, and operational condition is easy to control, and cost is lower.
4. the present invention's active agent stability of making catalyzer keep higher by changing reaction solvent character, hydrodehalogenation efficiency is high, reaction conditions is gentle, catalyzer is reusable.
Accompanying drawing explanation
The hydrodechlorination reaction effect figure of Pd/C catalysis 4-chlordiphenyl in different properties reaction soln that Fig. 1 provides for the embodiment of the present invention.
Embodiment
Following examples further illustrate of the present invention, but the present invention is not limited thereto.
The preparation of embodiment 1 catalyzer
By 4.15g PdCl
2be dissolved in the dilute hydrochloric acid of 200ml1.0mol/L, add after 5g gac mixes, then add Na
2cO
3solution, regulates pH to 10, stirs 30min, repeatedly wash, until exist without Cl ion in filtrate with deionized water.Then add 5.25g NaBH under agitation
4carry out reductase 12 h, it is neutral for repeatedly washing to filtrate with deionized water, and drying at room temperature, obtains 5.0%Pd/C catalyzer.Palladium-nickel/the C catalyst preparing different content by same method is listed in table 1.
Then according to above-mentioned preparation process, except active ingredient is different with carrier, remaining process is all identical, and preparation can obtain the loaded catalyst of different carriers, different activities composition, and prepared catalyst is listed in table 1.
Table 1 different carriers, different activities component catalyst
The hydrodechlorination of 4-chlordiphenyl in embodiment 2 protonic solvents-water two phase solvent system
Take 5.0%Pd/C catalyzer prepared by 20mg embodiment 1, join in the there-necked flask of 100ml, add containing concentration the protic solvent solution 40ml of the 4-chlordiphenyl being 20g/L, protonic solvent is propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol or n-Octanol, aqueous phase volume is 40ml, sodium hydroxide 0.188g, temperature of reaction controls at 40 DEG C, magnetic stirrer rotating speed is 300r/min, reaction pressure is normal pressure, hydrogen flowing quantity is that 10ml/min, 4-chlordiphenyl hydrodechlorination can good hydrodechlorination in different solvents, and concrete outcome is in table 2.
The hydrodechlorination of 4-chlordiphenyl in table 2 protonic solvent-water two phase solvent system
| Protonic solvent | Mol ratio Cl:Pd | Reaction times/min | Dechlorination efficiency % |
| Propyl carbinol | 452:1 | 90 | 100 |
| Pentyl alcohol | 452:1 | 90 | 100 |
| N-hexyl alcohol | 452:1 | 90 | 98.1 |
| N-Heptyl alcohol | 452:1 | 90 | 95.3 |
| N-Octanol | 452:1 | 90 | 93.2 |
Embodiment 3 temperature is on the impact of 4-chlordiphenyl hydrodechlorination in protonic solvent-water two phase solvent system
Take 5.0%Pd/C catalyzer prepared by 20mg embodiment 1, join in the there-necked flask of 100ml, add containing concentration the protic solvent solution 40ml of the 4-chlordiphenyl being 20g/L, protonic solvent is propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol or n-Octanol, aqueous phase volume is 40ml, sodium hydroxide 0.188g, magnetic stirrer rotating speed is 300r/min, reaction pressure is normal pressure, hydrogen flowing quantity is 10ml/min, under the differing tempss such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 4-chlordiphenyl can good reduction dechlorination, and concrete outcome is in table 3.
Polychlorobiphenyl hydrodechlorination under table 3 differing temps
| Temperature/DEG C | Solvent | Mol ratio Cl:Pd | Reaction times/min | Dechlorination efficiency % |
| 20 | N-butanol-water | 452:1 | 90 | 85.3 |
| 30 | N-butanol-water | 452:1 | 90 | 98.8 |
| 40 | N-butanol-water | 452:1 | 90 | 100 |
| 50 | N-butanol-water | 452:1 | 90 | 100 |
| 20 | Pentyl alcohol-water | 452:1 | 90 | 81.7 |
| 30 | Pentyl alcohol-water | 452:1 | 90 | 95.9 |
| 40 | Pentyl alcohol-water | 452:1 | 90 | 100 |
| 50 | Pentyl alcohol-water | 452:1 | 90 | 100 |
The hydrodechlorination of 4-chlordiphenyl in embodiment 4 protonic solvents-methyl alcohol homogeneous solvent system
Take 5.0%Pd/C catalyzer prepared by 20mg embodiment 1, join in the there-necked flask of 100ml, add containing concentration the protic solvent solution 40ml of the 4-chlordiphenyl being 20g/L, protonic solvent is propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol or n-Octanol, methyl alcohol volume is 40ml, sodium hydroxide 0.188g, temperature of reaction controls at 40 DEG C, magnetic stirrer rotating speed is 300r/min, reaction pressure is normal pressure, hydrogen flowing quantity is that 10ml/min, 4-chlordiphenyl hydrodechlorination can good hydrodechlorination in different solvents, and concrete outcome is in table 4.
The hydrodechlorination of polychlorobiphenyl under table 4 different concns
| Solvent | Mol ratio Cl:Pd | Reaction times/min | Dechlorination efficiency % |
| Propyl carbinol-methyl alcohol | 452:1 | 120 | 100 |
| Pentyl alcohol-methyl alcohol | 452:1 | 120 | 99.9 |
| N-hexyl alcohol-methyl alcohol | 452:1 | 120 | 97.1 |
| N-Heptyl alcohol-methyl alcohol | 452:1 | 120 | 91.2 |
| N-Octanol-methyl alcohol | 452:1 | 120 | 88.7 |
Embodiment 5 propyl carbinol is on the impact of 4-chlordiphenyl Hydrodechlorinating catalyst stability
Take 5.0%Pd/C catalyzer prepared by 25mg embodiment 1, join in the there-necked flask of 100ml, add containing concentration the butanol solution 80ml of the 4-chlordiphenyl being 10g/L, sodium hydroxide 0.188g, temperature of reaction controls at 40 DEG C, magnetic stirrer rotating speed is 300r/min, reaction pressure is normal pressure, hydrogen flowing quantity is 10ml/min, reaction 2.5h, reclaims after post catalyst reaction filters, is re-applied in reaction next time after washing three times with water, recycling like this 10 times, the recycling of catalyzer in propyl carbinol the results are shown in Figure 1.
Embodiment 6 propyl carbinols-methyl alcohol is on the impact of 4-chlordiphenyl Hydrodechlorinating catalyst stability
Take 5.0%Pd/C catalyzer prepared by 25mg embodiment 1, join in the there-necked flask of 100ml, add containing concentration the butanol solution 40ml of the 4-chlordiphenyl being 20g/L, methyl alcohol 40ml, sodium hydroxide 0.188g, temperature of reaction controls at 40 DEG C, magnetic stirrer rotating speed is 300r/min, reaction pressure is normal pressure, hydrogen flowing quantity is 10ml/min, reaction 2.5h, post catalyst reaction reclaims after filtering, be re-applied in reaction next time after washing three times with water, recycling like this 10 times, the recycling of catalyzer in propyl carbinol-methyl alcohol the results are shown in Figure 1.
Embodiment 7 n-butanol-water is on the impact of 4-chlordiphenyl Hydrodechlorinating catalyst stability
Take 5.0%Pd/C catalyzer prepared by 25mg embodiment 1, join in the there-necked flask of 100ml, add containing concentration the butanol solution 40ml of the 4-chlordiphenyl being 20g/L, water 40ml, sodium hydroxide 0.188g, temperature of reaction controls at 40 DEG C, magnetic stirrer rotating speed is 300r/min, reaction pressure is normal pressure, hydrogen flowing quantity is 10ml/min, reaction 2.5h, post catalyst reaction reclaims after filtering, be re-applied in reaction next time after washing three times with water, recycling like this 10 times, the recycling of catalyzer in propyl carbinol-methyl alcohol the results are shown in Figure 1.
By other catalyzer described in above-described embodiment 1, and the catalyzer in the acted on hydrodehalogenation reaction system to be obtained by prior art all can completely eliminate the halogen atom of organic halogen in described protonic solvent-water two phase solvent system or protonic solvent-methyl alcohol homogeneous solvent system, reduce stability and the toxicity of organic halogen, and catalyzer can keep higher promoting agent and stability, can reuse simultaneously.
Claims (9)
1. effectively keep a method for high activity of catalyst and high stability, it is characterized in that:
By catalyzer in differential responses solvent system under 0.05 ~ 1.0MPa reaction pressure, 20 ~ 80 DEG C of temperature of reaction, add alkaline proton absorbent simultaneously and then the heterogeneous catalytic hydrogenation dehalogenation reaction carried out to the organic halogen in differential responses solvent system; Wherein, the concentration of catalyzer in reaction soln is 20 ~ 50mg/100mL;
Differential responses solvent system is protonic solvent-water two phase solvent system or protonic solvent-methyl alcohol homogeneous solvent system.
2. press the method for effective maintenance high activity of catalyst according to claim 1 and high stability, it is characterized in that: described catalyzer is the catalyzer in hydrodehalogenation reaction system.
3. press the method for effective maintenance high activity of catalyst according to claim 1 and high stability, it is characterized in that: protonic solvent all mixes with aqueous phase solvent or methyl alcohol homogeneous solvent by the volume ratio of 20:1 ~ 1:5 by described protonic solvent-aqueous phase solvent system or protonic solvent-methyl alcohol homogeneous solvent system respectively.
4., by the method for effective maintenance high activity of catalyst described in claim 1 or 3 and high stability, it is characterized in that: described protonic solvent is propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol or n-Octanol.
5. press the method for effective maintenance high activity of catalyst according to claim 3 and high stability, it is characterized in that: in described reaction system, the volume ratio of protonic solvent and water or methyl alcohol is 5:1 ~ 1:3.
6. by the method for effective maintenance high activity of catalyst according to claim 1 and high stability, it is characterized in that: described alkaline proton absorbent is one or more in lithium hydroxide, sodium hydroxide, potassium hydroxide, ammoniacal liquor, triethylamine.
7. press the method for effective maintenance high activity of catalyst according to claim 6 and high stability, it is characterized in that: described alkaline proton absorbent and organic halogen halogen species mol ratio are 1:2 ~ 4:1.
8. press the method for effective maintenance high activity of catalyst according to claim 7 and high stability, it is characterized in that: described alkaline proton absorbent and organic halogen halogen species mol ratio are 1:1 ~ 1.5:1.
9. press the method for effective maintenance high activity of catalyst according to claim 1 and high stability, it is characterized in that: described reaction pressure is 0.05 ~ 1.0MPa, temperature of reaction is 20 ~ 80 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102923A (en) * | 2018-01-05 | 2018-06-01 | 茂名市金阳热带海珍养殖有限公司 | A kind of selection of high activity and the strong egg capsule algae algae of resistance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830924A (en) * | 2005-03-08 | 2006-09-13 | 中国科学院大连化学物理研究所 | Method for keeping activity and stability of catalyst during dehalogenation reaction |
| CN1830925A (en) * | 2005-03-08 | 2006-09-13 | 中国科学院大连化学物理研究所 | Method for preventing catalyst from being poisoning and inactivation during liquid phase dehalogenation reaction |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830924A (en) * | 2005-03-08 | 2006-09-13 | 中国科学院大连化学物理研究所 | Method for keeping activity and stability of catalyst during dehalogenation reaction |
| CN1830925A (en) * | 2005-03-08 | 2006-09-13 | 中国科学院大连化学物理研究所 | Method for preventing catalyst from being poisoning and inactivation during liquid phase dehalogenation reaction |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102923A (en) * | 2018-01-05 | 2018-06-01 | 茂名市金阳热带海珍养殖有限公司 | A kind of selection of high activity and the strong egg capsule algae algae of resistance |
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Application publication date: 20150318 |