CN108283933A - A kind of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst and its preparation method and application - Google Patents
A kind of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst and its preparation method and application Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C07C37/009—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up from waste water
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Abstract
The present invention relates to a kind of catalytic hydrogenation and dechlorination Pd M/NOMC catalyst and its preparation method and application, for the catalyst using the doped meso-porous carbon of synthetic nitrogen as carrier, active component is Pd M.The present invention prepares N doping gold/mesoporous carbon catalyst using one-step synthesis, and infusion process synthesizes Pd M/NOMC catalyst, and the hydrogenation-dechlorination including using it for chlorinated phenol for hydrogen source with hydrogen, formic acid sodium formate, methanol etc. can be used.The present invention adulterates nitrogen-atoms on meso-porous carbon material, and the reaction site of catalysis increases, and improves the activity of catalyst.Nitrogen source can be controlled from source using " one-step method " synthesis, the nitrogen content of addition is more easy to control, and the meso-hole structure of formation is survivable；And the displacement of the minimum combination energy position for causing palladium of nitrogen, the electronics in nitrogen are shifted toward palladium atomic surface, this displacement increases the stability between palladium and material.
Description
Technical field
The invention belongs to wastewater treating technology fields, are related to a kind of catalyst preparation sides catalytic hydrogenation and dechlorination Pd-M/NOMC
Method is related specifically to a kind of preparation method with the difunctional doped meso-porous carbon of support type synthetic nitrogen of absorption-catalysis and its answers
With.
Background technology
Chloro phenol compound is very common industrial chemicals and organic solvent in industries such as chemical industry, medicine.Pesticide,
It is also widely used in dyestuff.But this kind of compound is one kind is difficult to the organic compound degraded, pollution life in the environment
State environment, while also by it is believed that also having very with carcinogenic, teratogenesis, mutagenic effect, and to the health of daily human body
Big influence.Due to containing chlorine element in the organic matter, and chlorine element has a great impact to the pollution of environment, therefore, if will
Chlorine element in compound removes, and can effectively reduce its toxicity sound.2-chlorophenol (2-CP), 2,4 chlorophenesic acids (2,4-DCP),
The organic compounds such as 2,4,6- trichlorophenols (2,4,6-TCP) are paid attention to by Environmental Protection in China office and EPA (U.S.EPA), be included in after
Among the blacklist of continuous processing.
Catalytic hydrogenation and dechlorination (hydrodechlorination, HDC) belongs to one kind in electronation technology, the technology
It is the reactive hydrogen that is provided using catalyst to replace the chlorine atom in chlorinated phenol to reach the dechlorination of Pyrogentisinic Acid.HDC is to pass through
Chlorophenol is restored and generates pollution-free recyclable compound by catalytic hydrogenation, not only can remove chlorinatedorganic, and
And product can be recycled, collection utilizes herein.In order to more effectively remove pollutant, preparation stability is high, and catalytic is strong,
Selectivity waits the catalyst of excellent properties extremely important well.
Ordered mesopore carbon is just because of its duct aligned orderly, and Kong Rong and specific surface ratio normal activated carbon are big, the activity on surface
Position is also more, is shown in fields such as adsorbing separation, super capacitor, energy storage material, catalyst carrier, drug delivery and sustained releases
Very important value uses one-step synthesis method N doping mesoporous carbon, and supported palladium (Pd) herein.
Invention content
For the above the deficiencies in the prior art, a kind of catalytic hydrogenation Pd-M/NOMC catalyst and its preparation are provided
Methods and applications.
Technical scheme is as follows：
The carrier of catalytic hydrogenation Pd-M/NOMC catalyst of the present invention is the doped meso-porous carbon of synthetic nitrogen, removes synthetic nitrogen
Second group other than doped meso-porous carbon is divided into M, and the M is metal, and the preferably described M is one in the metals such as Sn, Au, Cu, Ag
Kind.
Further preferred, the above-mentioned doped meso-porous carbon of synthetic nitrogen is N doping ordered mesopore carbon.Using ordered mesopore carbon its
Duct aligned orderly, Kong Rong and specific surface ratio normal activated carbon are big, and the active sites on surface are also more.
Further preferred, the loaded article of above-mentioned carrier is metal palladium nano-particles.
Above-mentioned catalytic hydrogenation Pd-M/NOMC catalyst is made using one-step synthesis, is as follows：
(1) it weighs corresponding each substance according to different load capacity while being dissolved in the configuration solution of unit carrier water absorption
In, then carry out after fully reacting, take out solid product；
(2) in 60-140 DEG C of dry 4-13h after the sample centrifuge washing obtained above-mentioned steps (1) or dechlorination；
(3) sample that above-mentioned steps (2) obtain is continued to roast under 400-1100 DEG C of nitrogen atmosphere, obtains corresponding nitrogen
Doped meso-porous carbon；
(4) using N doping mesoporous carbon as carrier, in the presence of palladium source and the metal sources M, catalysis is prepared using infusion process and is added
Hydrogen dechlorination Pd-M/NOMC catalyst, the M are a kind of metal.Here the sources metal M can be corresponding M metals compound or
The salt etc. of formation, palladium source can be H2PdCl4Deng.
Catalyst above-mentioned can need to be made each structure and shape according to different, such as can ball be made in catalyst
Shape or bulk use etc..
The temperature of reaction in above-mentioned step (1) is preferably in 70 DEG C-reflux temperature.Be conducive to keep reaction more abundant.Most
It is 3-6 to make the mass ratio of the F127 polymer of step (1), 1,3,5- trimethylbenzenes, resorcinol and urea well：1-1.5：2.0-
3.0：1.5-2.5.
Technical scheme of the present invention compared with prior art, the beneficial effects of the invention are as follows：
1. its duct aligned orderly of ordered mesopore carbon, Kong Rong and specific surface ratio normal activated carbon are big, the active sites on surface
It is more.
2. ordered mesopore carbon adsorbing separation, super capacitor, energy storage material, catalyst carrier, drug delivery with it is slow
It releases equal fields and shows very important value.
3. using the NOMC for the N doping that urea is prepared as nitrogen source, Pd nano particles are loaded, since the doping of nitrogen-atoms improves
The defective bit of carbon material surface, to improve the dispersion degree of Pd particles, and the addition of nitrogen changes the surface of carbon material
Electrochemical state, to improve the stability of Pd nano particles.Show higher hydrogenation-dechlorination activity and stability.
4. the N doping meso-porous carbon material using one-step synthesis method has better hydrothermal stability, and can more preferably improve
The dispersion degree of catalyst granules promotes the activity and stability of catalyst；And it can be more effectively from source using " one-step method "
Upper control nitrogen source, the nitrogen content of addition is more easy to control, and the meso-hole structure of formation is survivable.And " post treatment method " be required for by
The processes such as pickling, duct are easy to cave in；Processing procedure environmental protection, post-processing are mostly hard template method, and process needs high temperature pickling to wait
Journey can pollute.
Description of the drawings
Fig. 1 is the electron microscope for the Pd/NOMC catalyst that the embodiment of the present invention one obtains.
Fig. 2 is SAXRD (A) collection of illustrative plates of the NOMC and Pd/NOMC in the embodiment of the present invention one.
Fig. 3 is WAXRD (B) collection of illustrative plates of the NOMC and Pd/NOMC in the embodiment of the present invention one.
Fig. 4 is the XPS comparison collection of illustrative plates of the Pd/NOMC and Pd/OMC of the embodiment of the present invention one.
Specific implementation mode
Below by specific embodiments and the drawings, the technical solutions of the present invention will be further described, but this
Invention is not limited to these examples.
Embodiment one
1, about 6.70 grams of resorcinol is weighed, 4.50 grams of hexamethylenetetramines (HMT), 13.00 grams of F127,2.50 gram four
Methyl biphenyl amine (TMB), 300 ml deionized waters, 15 milliliters of ammonium hydroxide (NH4OH, weight percent 28), 5.00 grams of urine
3h is stirred at room temperature after adding in element.
2, air return continuously stirs 10h at a temperature of 85 DEG C in oil bath pan.
3, solid product is taken out after 10h, with centrifuge, washs four with suitable deionized water and ethanol solution respectively
It is secondary.
4, sample taking-up is placed in surface plate after centrifuging, the dry 6-16h at 70-160 DEG C.
5, the sample after drying is put under 450-1200 DEG C of (heating rate is 3 DEG C/min) nitrogen atmosphere and continues to roast 1-
10h。
Catalyst is finally obtained, is packed, is marked and be sealed, the amount of catalyst is 1.5g, catalyst preparation
It is good for use.
6, the preparation of catalyst Pd/NOMC：1g NOMC are weighed with electronic balance, calculate required H2PdCl4Measure (V=
0.835ml).50ml deionized waters and V ml H are added into round-bottomed flask2PdCl4(0.02g/ml) solution stirs under room temperature
0.5h, it is rear that 1g NOMC are added, continue to stir 5h.10V g are configured to the solution of 25ml, are completed in ice-water bath condition 0.5h
Constant pressure addition continues to stir 1h (in ice-water bath).It filters (being washed to neutrality with deionized water and absolute ethyl alcohol), product is placed
Dry 8h, grinding finally obtain the NOMC of Pd loads, are named as Pd/NOMC catalyst in 100 DEG C of drying boxes.
7, when hydrogen source is formic acid-sodium formate, 0.75g 4-CP is weighed and are dissolved in 100ml water, 500ml capacity is then transferred to
Constant volume is for use to 500ml in bottle.
8, configuration formic acid-sodium formate (FASF).Take Pd/NOMC obtained is a certain amount of to be put into clean three-necked flask, then
It pours a certain amount of deionized water, a certain amount of previous 4-CP, a certain amount of FASF into, is finally putting into magnetite, is put into oil bath pan.
9, reaction condition is 30 DEG C of oil baths, and reaction time 60min is sampled every 10min and carried out GC and TOC tests.
10, dichlorobenzene Phenol degradation rate is 92%, phenol product 95%, cyclohexanone 6%, cyclohexanol 2%.
It chooses the corresponding Pd/NOMC catalyst that the present embodiment obtains and carries out corresponding performance test, it can from Fig. 1
Go out, it is survivable that the catalyst that the present invention uses " one-step method " to obtain has the advantages that meso-hole structure makes well；It can be with from Fig. 4
Find out, the displacement of the minimum combination energy position for causing palladium of nitrogen, this is because core electron displacement causes, this also turns out nitrogen
In electronics shifted toward palladium atomic surface, this displacement can increase the stability between palladium and material.
Embodiment two
1, about 3.50 grams of resorcinol is weighed, 2.10 grams of hexamethylenetetramines (HMT), 6.20 grams of F127,1.30 gram four
Methyl biphenyl amine (TMB), 158 ml deionized waters, 7 milliliters of ammonium hydroxide (NH4OH, weight percent 28), 3.6 grams of urine
2h is stirred at room temperature after adding in element.
2, air return continuously stirs 8.5h at a temperature of 85 DEG C in oil bath pan.
3, solid product is taken out after 8.5h, with centrifuge, is washed respectively with suitable deionized water and ethanol solution
Four times.
4, sample taking-up is placed in surface plate after centrifuging, the dry 3-15h at 58-145 DEG C.
5, the sample after drying is put under 390-1200 DEG C of (heating rate is 1 DEG C/min) nitrogen atmosphere and continues to roast 1-
9h。
6, catalyst is finally obtained, is packed, is marked and be sealed, the amount of catalyst is 1.5g, catalyst system
Ready for use.
7, the preparation of catalyst Pd-Cu/NOMC：1g NOMC are weighed with electronic balance, calculate required H2PdCl4Measure (V=
0.835ml) and chlorination amount of copper (m=10V g).50ml deionized waters and V ml H are added into round-bottomed flask2PdCl4
(0.02g/ml) solution stirs 0.5h under room temperature, rear that 1g NOMC are added, and continues to stir 5h.10V g are configured to the molten of 25ml
Liquid completes constant pressure addition in ice-water bath condition 0.5h, continues to stir 1h (in ice-water bath).It filters (with deionized water and anhydrous
Ethyl alcohol is washed to neutrality), product is placed in 100 DEG C of drying boxes dry 8h, grinding finally obtains the NOMC of Pd-Cu loads,
It is named as Pd-Cu/NOMC catalyst.
8, it weighs 3.75g substrates parachlorphenol (4-CP) to be dissolved in 400ml deionized waters, then pours into volumetric flask.
9, it takes 100ml water in clean three-necked flask, while substrate (1.8g/L), 20mg systems that 50ml has been configured is added
The Pd-Cu/NOMC catalyst got ready.
10, reaction condition is：27 DEG C of oil baths, 0.2MPa H2, stirring is opened, timing is started simultaneously at.
11, reaction time 350min is sampled, promoting the circulation of qi analysis of hplc sample composition of going forward side by side every 25min.
12, dichlorobenzene Phenol degradation rate is 96%, phenol product 93%, cyclohexanone 6%, cyclohexanol 2%.
Embodiment three
1, about 5.00 grams of resorcinol is weighed, 3.80 grams of hexamethylenetetramines (HMT), 8.10 grams of F127,3.00 gram four
Methyl biphenyl amine (TMB), 220 ml deionized waters, 10 milliliters of ammonium hydroxide (NH4OH, weight percent 28), 5.0 grams of urine
2.5h is stirred at room temperature after adding in element.
2, air return continuously stirs 9h at a temperature of 80 DEG C in oil bath pan.
3, solid product is taken out after 9h, with centrifuge, washs four with suitable deionized water and ethanol solution respectively
It is secondary.
4, sample taking-up is placed in surface plate after centrifuging, the dry 4-15h at 55-140 DEG C.
5, the sample after drying is put under 390-1200 DEG C of (heating rate is 1 DEG C/min) nitrogen atmosphere and continues to roast 1-
8h。
6, catalyst is finally obtained, is packed, is marked and be sealed, the amount of catalyst is 1.5g, catalyst system
Ready for use.
7, the preparation of catalyst Pd-Au/NOMC：1g NOMC are weighed with electronic balance, calculate required H2PdCl4Measure (V=
0.835ml) and gold chloride amount (m=10V g).50ml deionized waters and V ml H are added into round-bottomed flask2PdCl4
(0.02g/ml) solution stirs 0.5h under room temperature, rear that 1g NOMC are added, and continues to stir 5h.10V g are configured to the molten of 25ml
Liquid completes constant pressure addition in ice-water bath condition 0.5h, continues to stir 1h (in ice-water bath).It filters (with deionized water and anhydrous
Ethyl alcohol is washed to neutrality), product is placed in 100 DEG C of drying boxes dry 8h, grinding finally obtains the NOMC of Pd-Au loads,
It is named as Pd/NOMC catalyst.
8,1.70g substrates 2 are weighed, 4- chlorophenesic acids (2,4-DCP) are dissolved in 250ml deionized waters, then pour into capacity
In bottle.
9, it takes 50ml water in clean three-necked flask, while substrate (2.1g/L), 10mg systems that 30ml has been configured is added
The Pd/NOMC catalyst got ready.
10, reaction condition is：25 DEG C of oil baths, 0.1MPa H2, stirring is opened, timing is started simultaneously at.
11, reaction time 250min is sampled, promoting the circulation of qi analysis of hplc sample composition of going forward side by side every 30min.
12, dichlorobenzene Phenol degradation rate is 98%, phenol product 95%, cyclohexanone 7%, cyclohexanol 3%.
Example IV
1, about 2.00 grams of resorcinol is weighed, 1.20 grams of hexamethylenetetramines (HMT), 3.60 grams of F127,0.70 gram four
Methyl biphenyl amine (TMB), 100 ml deionized waters, 4 milliliters of ammonium hydroxide (NH4OH, weight percent 28), 1.40 grams of urine
1.5h is stirred at room temperature after adding in element.
2, air return continuously stirs 7.5h at a temperature of 82 DEG C in oil bath pan.
3, solid product is taken out after 7.5h, with centrifuge, is washed respectively with suitable deionized water and ethanol solution
Four times.
4, sample taking-up is placed in surface plate after centrifuging, the dry 4-12h at 50-145 DEG C.
5, the sample after drying is put under 400-1300 DEG C of (heating rate is 2 DEG C/min) nitrogen atmosphere and continues to roast 1-
9h。
Catalyst is finally obtained, is packed, is marked and be sealed, the amount of catalyst is 1.5g, catalyst preparation
It is good for use.
6, the preparation of catalyst Pd/NOMC：1g NOMC are weighed with electronic balance, calculate required H2PdCl4Measure (V=
0.8351ml) and nitric acid silver content (m=10V g).50ml deionized waters and V ml H are added into round-bottomed flask2PdCl4
(0.02g/ml) solution stirs 0.5h under room temperature, rear that 1g NOMC are added, and continues to stir 5h.10V g are configured to the molten of 25ml
Liquid completes constant pressure addition in ice-water bath condition 0.5h, continues to stir 1h (in ice-water bath).It filters (with deionized water and anhydrous
Ethyl alcohol is washed to neutrality), product is placed in 100 DEG C of drying boxes dry 8h, grinding finally obtains the NOMC of Pd-Ag loads,
It is named as Pd/NOMC catalyst.
7, it weighs 2,4,6- trichlorophenol, 2,4,6,-T (2,4,6-TCP) of 1.5g substrates to be dissolved in 200ml deionized waters, then pours into appearance
In measuring bottle.
8, it takes 20ml water in clean three-necked flask, while substrate (1.3g/L), 5mg that 9ml has been configured is added and prepares
Good Pd/NOMC catalyst.
9, reaction condition is：30 DEG C of oil baths, 0.2MPa H2, stirring is opened, timing is started simultaneously at.
10, reaction time 210min is sampled, promoting the circulation of qi analysis of hplc sample composition of going forward side by side every 30min.
11, dichlorobenzene Phenol degradation rate is 95%, phenol product 94%, cyclohexanone 5%, cyclohexanol 2%.
Embodiment five
1, about 2.20 grams of resorcinol is weighed, 1.40 grams of hexamethylenetetramines (HMT), 4.00 grams of F127,0.80 gram 1,
3,5- trimethylbenzenes (TMB), 104 ml deionized waters, 4 milliliters of ammonium hydroxide (NH4OH, weight percent 28), 1.60 grams
1h is stirred at room temperature after adding in urea.
2, air return continuously stirs 8h at a temperature of 80 DEG C in oil bath pan.
3, solid product is taken out after 8h, with centrifuge, washs four with suitable deionized water and ethanol solution respectively
It is secondary.
4, sample taking-up is placed in surface plate after centrifuging, the dry 4-13h at 60-140 DEG C.
5, the sample after drying is put under 400-1100 DEG C of (heating rate is 1 DEG C/min) nitrogen atmosphere and continues to roast 1-
8h。
6, catalyst is finally obtained, is packed, is marked and be sealed, the amount of catalyst is 1.5g, catalyst system
Ready for use.
7, the preparation of catalyst Pd-Sn/NOMC：1g NOMC are weighed with electronic balance, calculate required H2PdCl4Measure (V=
0.835ml) and stannous chloride amount (m=10V g).50ml deionized waters and the H of V ml are added into round-bottomed flask2PdCl4
(0.02g/ml) solution stirs 0.5h under room temperature, rear that 1g NOMC are added, and continues to stir 5h.10V g are configured to the molten of 25ml
Liquid completes constant pressure addition in ice-water bath condition 0.5h, continues to stir 1h (in ice-water bath).It filters (with deionized water and anhydrous
Ethyl alcohol is washed to neutrality), product is placed in 100 DEG C of drying boxes dry 8h, grinding, the nitrogen for finally obtaining Pd-Sn loads is mixed
Miscellaneous mesoporous carbon (NOMC), is named as Pd/NOMC catalyst.
8, it weighs 0.75g substrates 2-chlorophenol (2-CP) to be dissolved in 100ml deionized waters, then pours into volumetric flask.
9, it takes 25ml water in clean three-necked flask, while substrate (1.5g/L), 5mg that 10ml has been configured is added and prepares
Good Pd/NOMC catalyst.
10, reaction condition is：25 DEG C of oil baths, 0.1MPa H2, stirring is opened, timing is started simultaneously at.
11, reaction time 250min is sampled, promoting the circulation of qi analysis of hplc sample composition of going forward side by side every 30min.
12, dichlorobenzene Phenol degradation rate is 99%, phenol product 90%, cyclohexanone 8%, cyclohexanol 2%.
Specific embodiment described in the present invention is only an illustration of the spirit of the invention.Technology belonging to the present invention is led
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
It is skilled to this field although present invention has been described in detail and some specific embodiments have been cited
For technical staff, as long as it is obvious that can make various changes or correct without departing from the spirit and scope of the present invention.
Claims (8)
1. a kind of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst, which is characterized in that the carrier of the catalyst is that synthesis N doping is situated between
Hole carbon；Second group is divided into M, and the M is a kind of metal.
2. a kind of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst according to claim 1, which is characterized in that the M is
Sn, Au, Cu or Ag.
3. a kind of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst according to claim 1, which is characterized in that Jie
Hole carbon is N doping ordered mesopore carbon.
4. a kind of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst according to claim 1, which is characterized in that the carrier
Loaded article be metal palladium nano-particles.
5. a kind of preparation method of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst, which is characterized in that catalytic hydrogenation and dechlorination Pd-
M/NOMC catalyst is made using one-step synthesis, is as follows：
(1) F127 polymer, 1,3,5- trimethylbenzenes, resorcinol and urea are proportionally added at one time in water, use ammonia
Water adjusts solution to alkalescent, then carries out after fully reacting, and takes out solid product；
(2) after the sample centrifuge washing obtained above-mentioned steps (1) or dechlorination, processing is dried；
(3) sample that above-mentioned steps (2) obtain is continued to roast under nitrogen atmosphere, obtains corresponding N doping mesoporous carbon；
(4) using N doping mesoporous carbon as carrier, in the presence of palladium source and the metal sources M, it is de- that catalytic hydrogenation is prepared using infusion process
Chlorine Pd-M/NOMC catalyst, the M are a kind of metal.
6. being existed according to a kind of preparation method of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst, feature described in claim 5
In the temperature of the drying process described in step (2) is 60-140 DEG C, and the time of drying process is 4-13h；Step (3) described roasting
It is 400-1100 DEG C to burn temperature, roasting time 1-8h.
7. a kind of application of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst, which is characterized in that use Pd- described in claim 1
M/NOMC catalyst carries out catalytic hydrogenation and dechlorination.
8. the application of catalytic hydrogenation and dechlorination Pd-M/NOMC catalyst according to claim 7, which is characterized in that the catalysis
The hydrogen source that hydrogen uses is added to be selected from hydrogen, formic acid-sodium formate, methanol, ethyl alcohol or ethylene glycol.
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