CN101565357A - Method of low-temperature catalytic dechlorination of chlorophenol - Google Patents
Method of low-temperature catalytic dechlorination of chlorophenol Download PDFInfo
- Publication number
- CN101565357A CN101565357A CNA200910052474XA CN200910052474A CN101565357A CN 101565357 A CN101565357 A CN 101565357A CN A200910052474X A CNA200910052474X A CN A200910052474XA CN 200910052474 A CN200910052474 A CN 200910052474A CN 101565357 A CN101565357 A CN 101565357A
- Authority
- CN
- China
- Prior art keywords
- dechlorination
- reaction
- chlorophenol
- catalyzer
- equivalent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method of low-temperature catalytic dechlorination of chlorinated aromatic hydrocarbons. The method uses chlorophenol as pollutant, in the presence of Pd, uses hydrogen as a reducing agent and hydrogen pressure as atmospheric pressure, controls temperature in the range of 258 to 273k, adds an ammonium acetate dechlorination reagent in batches, carries out catalytic hydrogenation and dechlorination reaction in organic solvent, and can remove 8 to 26 moles of chlorine per mole of Pd catalyst per minute, and phenol produced in a high selectivity way can be recycled. Through simple filtration, the Pd catalyst can be reused for plural times without losing activity. The process of the invention can be effectively used for low-temperature catalytic hydrogenation and dechlorination for chlorinated aromatic compounds, and has good prospect for industrialization in environmental protection.
Description
Technical field
The invention belongs to the catalysis dechlorination environmental protection technical field, specially refer to a kind of method that the low-temperature catalyzed hydrodechlorination of chloro virtue phenol is eliminated environment chlorination aromatic hydrocarbon pollutant that is used for.
Background technology
Chlorinated aromatic hydrocarbons has a wide range of applications, and can be used as solvent, sweetener, wormer, the intermediate of sterilant and many organic syntheses.But because therefore its hypertoxicity and intensive bioconcentration have caused the concern of people for healthy and environment.This compound is difficult to degraded, and the enrichment meeting in fatty tissue causes transgenation and causes cancer.Be difficult to chlorinated aromatic hydrocarbons is decomposed into CO fully by direct burning and biodegradable method
2, H
2O and HCl, Many researchers is devoted to a kind of new dechlorination method now, can reduce the toxicity of chlorinated aromatic hydrocarbons significantly, and wherein the catalytic hydrogenation and dechlorination method is comparatively effective, is a kind of practicable method.
The catalytic hydrogenation and dechlorination reaction of chlorinated aromatic hydrocarbons is a kind of simple, safety, and effective means, by product HCl can separate easily, and product aromatic hydrocarbons can be recycled.Report and use group VIII transition metal, in the Fatty Alcohol(C12-C14 and C12-C18) medium, the dechlorination reaction of liquid phase can take place under the condition of gentleness as catalyzer.It is nearest that to studies show that solvent plays a part in this process very important, the efficient and the selectivity of influence reaction, and methyl alcohol and 2-propyl alcohol can be used as the solvent of the dechlorination reaction of Pd catalyst polystream usually.Have the catalyzer of bibliographical information working load Ni that the hydrodechlorination reaction of gas phase at high temperature can take place, and the catalyzer of load P d is mainly used in the liquid-phase hydrogenatin dechlorination reaction under the mild conditions.Because gac has high specific surface area and good supporting, is often used as the carrier of Pd catalyzer.
The catalytic hydrodechlorination reaction of present most of Pd all is at room temperature to carry out, and lower temperature is not found bibliographical information as yet.
Summary of the invention
The technical issues that need to address of the present invention are the methods that disclose a kind of chlorinated aromatic hydrocarbons by low-temperature catalysis dechlorination, the present invention is pollutent with the chlorophenol, in the presence of Pd, as reductive agent, hydrogen pressure is a normal atmosphere with hydrogen, and temperature is controlled at 258～273K scope, add ammonium acetate dechlorination reagent in the batch-wise mode, in organic solvent, carry out the catalytic hydrogenation and dechlorination reaction, can remove 8～26 moles chlorine on every mole of Pd catalyzer of per minute.By simple filtering, the repeated use that the Pd catalyzer can be repeatedly and non-inactivation.The present invention improves the catalytic performance of Pd catalyzer by adding bases dechlorination compositions and methods in batches, makes reaction be able to carry out effectively at low temperatures, to overcome the low defective of reaction efficiency under the low temperature that prior art exists.
The method of the said chlorophenol low-temperature catalytic dechlorination of the present invention comprises the steps:
In the presence of Pd, with hydrogen as reductive agent, hydrogen pressure is a normal atmosphere, and temperature is controlled at 258～273K scope, adds bases dechlorination reagent in the mode that drips, in organic solvent, carry out the catalytic hydrogenation and dechlorination reaction, reaction times 1～10h, the kind difference of chlorophenol, the efficient of hydrodechlorination changes thereupon, and the needed time of dechlorination also changes thereupon fully.Reaction product is a phenol.
According to the present invention, said Pd catalyzer is by carrier stable in the organic solution and metal Pd are constituted;
Said carrier can be commercially available gac, a kind of in silicon oxide and the aluminum oxide, and its amount is 90～99wt.% of total catalyst weight;
The content of Pd is 1～10wt.% in the said Pd catalyzer;
The salt solution impregnation method load P d component that said Preparation of catalysts adopts document to mention usually.
Catalyst consumption is pressed the atomic ratio 1: 100～1: 200 of Cl in Pd and the chlorophenol.Catalyst levels is too low, and the reaction times is longer.
Said organic solvent is a kind of in methyl alcohol, ethanol, the Virahol;
Said chlorination aromatic hydrocarbon compound can be that a chlorine replaces, and also can be that many chlorine replace; Content in organic solvent is 10～10000ppm (weight);
The consumption of said dechlorination reagent ammonium acetate is the equivalent of Cl in the reactant, adds in batches; Add for the first time 0.1 equivalent; After reaching 0.1 equivalent, the inversion quantity of reactant adds 0.1 equivalent again; After reaching 0.2 equivalent, the inversion quantity of reactant adds 0.1 equivalent again, and the like.
Said temperature of reaction is 253～273K, and the temperature of reaction height helps the raising of efficient;
Said reaction pressure is a normal atmosphere.
Under above-mentioned processing condition, the hydrodechlorination efficient of Pd catalyzer is higher, can remove 8～26 moles chlorine on every mole of Pd catalyzer of per minute, and highly selective produces phenol, can recycle.By simple filtering Pd catalyzer can be repeatedly repeated use and non-inactivation.The present invention is by add ammonium acetate dechlorination compositions and methods in batches; improve the catalytic performance of Pd catalyzer; make reaction be able to carry out effectively at low temperatures; technology of the present invention can effectively be used for the catalytic hydrogenation and dechlorination of chlorination aromatic hydrocarbon compound, has excellent industrial application foreground aspect environment protection.
Specific embodiments
Embodiment 1
Cocoanut active charcoal is ground, sieve 300～400 purpose active carbon powders, a certain amount of activated carbon is joined in the 10wt.% nitric acid, at 80 ℃ of stirred in water bath 2h, filter then, distilled water wash is to neutral.Handle with water vapour again, oven dry, standby.Palladous chloride is dissolved in the 10wt.% aqueous hydrochloric acid, is made into 1.7 * 10
-2The palladium chloride solution of mol/L.The 10g gac that nitric acid treatment is crossed joins in the palladium chloride aqueous solution that 165ml prepares, and dipping 2h adds the reduction of 8ml formaldehyde again, drips saturated sodium hydrogen carbonate solution simultaneously, and control pH value is about 9, reacts constant to the pH value.It is the 5wt.%Pd/C catalyzer that filtering drying promptly obtains Pd content.
Reaction process is that 0.648g (5mmol) para-chlorophenol, 0.385g (5mmol) ammonium acetate, 0.10g 5wt.%Pd/C catalyzer, 50ml methanol solution are added to the 100ml there-necked flask that has mechanical stirring device, with cryosel solution bath controlled temperature at-15～-10 ℃, hydrogen with the displacement in the still 6 times after, at hydrogen pressure is under the atmospheric condition, open mechanical stirring, rotational speed rate is 500rpm, reaction 10h.By certain time interval, serial sampling is learnt with gas chromatographic analysis, and reaction product is a phenol, does not detect other compound and generates.The results are shown in Table 1.
Embodiment 2
Palladous chloride is dissolved in the 10wt.% aqueous hydrochloric acid, is made into 1.7 * 10
-2The palladium chloride solution of mol/L, get 83ml, add 10g and press cocoanut active charcoal (300 order) the dipping 2h that embodiment 1 method is handled, add the reduction of 8ml formaldehyde again, drip saturated sodium hydrogen carbonate solution simultaneously, control pH value is about 9, reacts constant to the pH value, and it is the 2.5wt.%Pd/C catalyzer that filtering drying promptly obtains Pd content.
Reaction process is that 0.648g para-chlorophenol, 0.20g 2.5wt.%Pd/C catalyzer, 50ml methanol solution are added to the 100ml there-necked flask that has mechanical stirring device, with cryosel solution bath controlled temperature at-15～-10 ℃, hydrogen with the displacement in the still 6 times after, at hydrogen pressure is under the atmospheric condition, open mechanical stirring, rotational speed rate is 500rpm, begins every reaction 1h from reaction in reaction process, add 0.096g (1.25mmol) ammonium acetate, add altogether 4 times.By certain time interval, serial sampling is learnt with gas chromatographic analysis, and reaction product is a phenol, does not detect other compound and generates.The results are shown in Table 1.
Embodiment 3
Get embodiment 1 prepared 5wt.%Pd/C catalyzer 0.10g, ortho chloro phenol 0.643g, ammonium acetate 0.385g and put into the 50ml methanol solution, make suspension, be added to the 100ml there-necked flask that has mechanical stirring device, other reaction conditions is identical with embodiment 1, by certain time interval, serial sampling is learnt with gas chromatographic analysis, reaction product is a phenol, does not detect other compound and generates.The results are shown in Table 1.
Embodiment 4
Get embodiment 1 prepared 5wt.%Pd/C catalyzer 0.10g, ortho chloro phenol 0.643g and put into the 50ml methanol solution, make suspension, be added to the 100ml there-necked flask that has mechanical stirring device, other reaction conditions is identical with embodiment 2, by certain time interval, serial sampling gets with gas chromatographic analysis, reaction product is a phenol, does not detect other compound and generates.The results are shown in Table 1.
Embodiment 5
Get the prepared 5wt.%Pd/C catalyzer 0.20g, 2 of embodiment 1,4-chlorophenesic acid 0.824g, ammonium acetate 0.770g put into the 50ml methanol solution, make suspension, be added to the 100ml there-necked flask that has mechanical stirring device, other reaction conditions is identical with embodiment 1, by certain time interval, serial sampling, get with gas chromatographic analysis, reaction product is phenol, ortho chloro phenol, para-chlorophenol, does not detect other compound and generates.The results are shown in Table 2.
Embodiment 6
Get the prepared 5wt.%Pd/C catalyzer 0.20g, 2 of embodiment 1,4-chlorophenesic acid 0.824g puts into the 50ml methanol solution, make suspension, be added to the 100ml there-necked flask that has mechanical stirring device, other reaction conditions is identical with embodiment 2, in reaction process,, add 0.096g (1.25mmol) ammonium acetate, add altogether 8 times from the every reaction 0.5h of reaction beginning.By certain time interval, serial sampling gets with gas chromatographic analysis, and reaction product is phenol, ortho chloro phenol, para-chlorophenol, does not detect other compound and generates.The results are shown in Table 2.
Embodiment 7
Get embodiment 1 prepared 5wt.%Pd/C catalyzer 0.05g, 0.324g para-chlorophenol and 0.193g ammonium acetate and put into the 50ml methanol solution, make suspension, be added to the 100ml there-necked flask that has mechanical stirring device, other reaction conditions is identical with embodiment 2, by certain time interval, serial sampling gets with gas chromatographic analysis, reaction product is a phenol, does not detect other compound and generates.The results are shown in Table 1.
Embodiment 8
The 5wt.%Pd/C that 0.10g embodiment 1 is prepared, put into the 50ml methanol solution together with 0.648g para-chlorophenol and 0.385g ammonium acetate, make suspension, be added to the 100ml there-necked flask that has mechanical stirring device, other reaction conditions is identical with embodiment 2, by certain time interval, serial sampling, get with gas chromatographic analysis, reaction product is a phenol, does not detect other compound and generates.After the reaction, with reaction mother liquor and catalyzer centrifugation, used catalyzer and 0.01g live catalyst, put into the 50ml methanol solution together with para-chlorophenol 0.648g, make suspension once more, be added to the 100ml there-necked flask that has mechanical stirring device, other reaction conditions is identical with embodiment 2, and catalyzer is applied mechanically 10 times continuously.The results are shown in Table 1 the tenth time.
Table 1 monochloro phenol dechlorination transformation efficiency (%) over time
Table 2 2,4 dichloro phenol dechlorination transformation efficiency (%) over time
Claims (7)
1. the method for chlorophenol low-temperature catalytic dechlorination is characterized in that, comprises the steps: in the presence of the Pd catalyzer, as reductive agent, add bases dechlorination reagent in the mode that drips, with hydrogen in organic solvent, chlorination aromatic hydrocarbon compound and H-H reaction, reaction product are phenol;
Said chlorination aromatic hydrocarbon compound is a kind of of chlorine replacement or many chlorine fortified phenol;
Said catalyzer is by carrier stable in the organic solution and metal Pd are constituted;
Said carrier can be commercially available gac, a kind of in silicon oxide and the aluminum oxide, and its amount is 90～99wt.% of total catalyst weight;
The content of Pd is 1～10wt.% in the said Pd catalyzer.
2. method according to claim 1 is characterized in that, catalyst consumption is pressed the atomic ratio 1: 100～1: 200 of Cl in Pd and the chlorophenol.
3. method according to claim 1 is characterized in that organic solvent is a kind of in methyl alcohol, ethanol, the Virahol.
4. method according to claim 1 is characterized in that dechlorination reagent is Ammoniom-Acetate, and its consumption is the equivalent of Cl in the reactant.
5. method according to claim 1 is characterized in that the adding in batches of dechlorination reagent, adds 0.1 equivalent for the first time; After reaching 0.1 equivalent, the inversion quantity of reactant adds 0.1 equivalent again; After reaching 0.2 equivalent, the inversion quantity of reactant adds 0.1 equivalent again, and the like.
6. method according to claim 1, its feature are in temperature of reaction, and its scope is at-15～0 ℃.
7. method according to claim 1, its feature is 10～10000ppm (weight) in the concentration of chlorophenol in reaction mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200910052474XA CN101565357A (en) | 2009-06-04 | 2009-06-04 | Method of low-temperature catalytic dechlorination of chlorophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200910052474XA CN101565357A (en) | 2009-06-04 | 2009-06-04 | Method of low-temperature catalytic dechlorination of chlorophenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101565357A true CN101565357A (en) | 2009-10-28 |
Family
ID=41281753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200910052474XA Pending CN101565357A (en) | 2009-06-04 | 2009-06-04 | Method of low-temperature catalytic dechlorination of chlorophenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101565357A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461575A (en) * | 2015-12-31 | 2016-04-06 | 江苏尚莱特医药化工材料有限公司 | Preparation method of 4,6-diamidoresorcinol or salts thereof |
| CN106902489A (en) * | 2017-04-16 | 2017-06-30 | 内蒙古佳瑞米精细化工有限公司 | A kind of residual processing method of CTC rectifying stills |
| CN109942388A (en) * | 2019-04-18 | 2019-06-28 | 绍兴市上虞沿江生物科技有限公司 | The preparation method of 1,4- cyclohexanedione |
| CN111790377A (en) * | 2019-12-26 | 2020-10-20 | 东北石油大学 | Monoatomic catalyst, preparation method and application thereof |
-
2009
- 2009-06-04 CN CNA200910052474XA patent/CN101565357A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461575A (en) * | 2015-12-31 | 2016-04-06 | 江苏尚莱特医药化工材料有限公司 | Preparation method of 4,6-diamidoresorcinol or salts thereof |
| CN106902489A (en) * | 2017-04-16 | 2017-06-30 | 内蒙古佳瑞米精细化工有限公司 | A kind of residual processing method of CTC rectifying stills |
| CN106902489B (en) * | 2017-04-16 | 2020-02-07 | 内蒙古佳瑞米精细化工有限公司 | Method for treating CTC (CTC) distillation still residues |
| CN109942388A (en) * | 2019-04-18 | 2019-06-28 | 绍兴市上虞沿江生物科技有限公司 | The preparation method of 1,4- cyclohexanedione |
| CN111790377A (en) * | 2019-12-26 | 2020-10-20 | 东北石油大学 | Monoatomic catalyst, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Upare et al. | Selective hydrogenation of levulinic acid to γ-valerolactone over carbon-supported noble metal catalysts | |
| CN101565356A (en) | Method of low-temperature catalytic dechlorination of chlorophenol | |
| CN103977795B (en) | A kind of preparation method of catalyst of hexachloro-benzene of degrading | |
| CN100467432C (en) | Synthesis method of substituted cyclohexanone and/or substituted cyclohexanol | |
| CN101143328A (en) | Catalyst used for preparing tetrachloroethylene and its preparation method and use | |
| CN101450308A (en) | Carbon loaded type noble metal catalyst and preparation method thereof | |
| CN106034401B (en) | The improved method of the reduction amination and selective hydration of substrate containing selected halogen | |
| CN101049560A (en) | Catalyst for preparing dichloroaniline through hydrogenization for dichloronitrobenzene, and preparation method | |
| CN104028283A (en) | Metal-loaded magnetic carbon material catalyst and method for catalyzing dechlorination of chlorinated phenol through metal-loaded magnetic carbon material catalyst | |
| CN103183355A (en) | Precious metal modification method of titanium silicalite molecular sieve | |
| CN106693961B (en) | Palladium carbon catalyst and preparation method and application | |
| CN101565357A (en) | Method of low-temperature catalytic dechlorination of chlorophenol | |
| CN103977744A (en) | Method for catalytic degradation of hexachlorobenzene | |
| CN102553584A (en) | Modified palladium-carbon catalyst for producing chloroacetic acid and preparation method for catalyst | |
| CN101767016A (en) | Aromatic aldehyde selective hydrogenation catalyst for refining terephthalic acid | |
| CN105693490B (en) | It is a kind of to aoxidize the method for preparing 2,3,5 trimethylbenzoquinones | |
| CN104276951A (en) | Method for using water phase to catalytically oxidize lactates for preparing pyruvates | |
| TW201503956A (en) | Method for regenerating catalyst for hydrogenation reaction, and method for producing hydride of polyhydric alcohol | |
| CN104549254A (en) | Catalyst for preparing 1,6-hexanediol through direct reduction of adipic acid | |
| CN103894209B (en) | A kind of catalyst for chlorination aromatic hydrocarbon dechlorination hydrogenation and preparation and application | |
| Yao et al. | Hydrazine as a facile and highly efficient hydrogen source for reduction of NaHCO3 into formic acid over Ni and ZnO catalysts | |
| CN109134201A (en) | The heterogeneous catalytic hydrogenation defluorination processing method of efficient degradation fluorobenzene phenolic compound | |
| CN104741117A (en) | Method and catalyst for preparing benzene and cyclohexane by catalytically hydrogenating liquid phase of aryl chloride | |
| CN101693643B (en) | Novel process for catalytic conversion of tetrachloromethane on non-hydrogen condition | |
| CN105622347B (en) | A kind of method that xylose prepares 1,2- pentanediols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20091028 |