CN105709735B - A kind of chlorobenzene catalytic converting catalyst and its preparation method and application - Google Patents
A kind of chlorobenzene catalytic converting catalyst and its preparation method and application Download PDFInfo
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- CN105709735B CN105709735B CN201610040826.XA CN201610040826A CN105709735B CN 105709735 B CN105709735 B CN 105709735B CN 201610040826 A CN201610040826 A CN 201610040826A CN 105709735 B CN105709735 B CN 105709735B
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Abstract
The invention discloses a kind of chlorobenzene catalytic converting catalyst, catalyst is made of carrier and active component；Preparation method is to weigh soluble palladium salt, lanthanum nitrate and cerous nitrate in proportion, it is configured to and the aqueous solution of weighed active carbon total pore volume same volume, it is dry under vacuum state to weigh active carbon, after, it is cooled to dipping temperature, by configured solution, active carbon is sufficiently impregnated with treated, then it is dried under vacuum anaerobic state, deionized water mashing is added, a few hours are restored in a hydrogen atmosphere, potassium borohydride/sodium water solution reduction is added dropwise later, most washs through deionized water to neutrality, is directly sealed up for safekeeping after filtering afterwards；And its application in the reaction of phenyl ether organic matter is generated in chlorobenzene catalyzed conversion.Catalyst catalytic performance of the invention is good, applies often, and conversion ratio may be implemented the coupling of catalytic hydrogenation and dechlorination reaction and chlorobenzene and alcohol substitution reaction, more there is the phenyl ether type organic of application value up to 100%, 99% or more selectivity.
Description
Technical field
The invention belongs to chlorobenzene degradation environmental protection technical field more particularly to a kind of catalysis of chlorobenzene catalytic hydroconversion
Agent and preparation method thereof, and a kind of method that chlorobenzene catalytic hydroconversion is used at phenyl ether is provided.
Background technique
Chlorobenzene is a kind of important raw material of industry, is answered extensively as organic synthesis raw material and fine chemicals intermediate etc.
For each field such as chemical industry, medicine, pesticide, dyestuff.However, this kind of compound usually has residual, bioconcentration, low waves
Hair property and high toxicity (carcinogenic, teratogenesis, mutagenesis), and be not easy to be decomposed or natural degradation, long-term accumulation can be to lifes in environment
State environmental and human health impacts constitute a serious threat.Therefore, how to degrade chlorobenzene, nontoxicization processing is carried out to it just becomes ring
It is badly in need of the important subject urgently solved in border protection field.
Currently, chlorinatedorganic processing method mainly have biological degradation method (Environmental Pollution and Control, 2013,35 (l):
86), (persistence organic pollutant forum 2009 and the 4th persistence organic pollutant whole nation are learned for high temperature incineration, catalysis oxidation
Art conference Papers collection .p155), electronation dechlorination facture (CN1539693, CN1183316A, CN1470300A, (China
Environmental science, 2012,32 (12): 2213-2218)), photocatalysis (catalysis journal, 2004,25 (9): 753) and catalytic hydrogenation take off
Chlorine etc..Biological degradation method is that organic matter is converted to CO under the catalytic action of microbial enzyme2And H2O or other innocuous substances
Process is an ideal potential processing method.But microorganism is more sensitive, influences vulnerable to the external world, especially
In high concentration chlorinatedorganic environment, degradation efficiency is low, degrades not thorough enough；High temperature incineration method is needed using a large amount of combustion heat
It is risen to 1100 degree or more in seconds, is otherwise readily generated the bigger dioxin of toxicity；Catalytic oxidation is at home
Development is very fast, but still remains a series of problems, such as at high cost, energy consumption is high, processing is not thorough, easily causes secondary pollution；Chemistry is also
Former dechlorination facture mostly be under certain temperature and catalyst action, using the antichlors such as metal or metal oxygen/hydride with have
Chemical reaction occurs for machine chloride to reach dealuminated USY cataluyst purpose, limitation of the dechlorinating ability vulnerable to antichlor quantity, therefore is somebody's turn to do
Method is usually used in the processing of low concentration organic chloride；Catalytic hydrogenation and dechlorination method is hydrogen and C-Cl key under the action of catalyst
Hydrogenolysis dechlorination reaction occurs, generates HCl and alkane, benzene or biphenyl etc..This method does not destroy C-C key substantially, will not generate greenhouse
Gas CO2Or the secondary pollutions such as bigger dioxin of toxicity.It is the higher green catalysis process of Atom economy, it is considered to be
Eliminate the dechlorination method of one kind of chlorinatedorganic environmental pollution efficiently, safe.
CN103406150A discloses a kind of macromolecule loading metal palladium complex catalyst and its preparation method and application.
This method is made polyacrylic acid through Phen nitrification, amination, acylation, polymerization reaction first and loads acrylamido -1 5-,
Then carried metal palladium complex catalyst is made in palladium load by 10 Phen compounds on this compound.Dechlorination reaction
In anhydrous ethanol solvent, under triethylamine and sodium borohydride collective effect, hydrogenation-dechlorination is carried out in 0.1MPa hydrogen atmosphere
12h is reacted, chlorinated aromatic hydrocarbons can be degraded to accordingly without chlorine organic.
CN101037374A discloses a kind of method of chlorinated aromatic hydrocarbons catalytic hydrogenation and dechlorination.This method is with support type nickel phosphide
For catalyst, in normal pressure, 200~400 degree, 10~10000h of hydrogen gas space velocity-1It is 0.01 with chlorobenzene, dichloro-benzenes or trichloro-benzenes air speed
~10h-1In the case where carry out the reaction of gas and solid phase catalyzing hydrogenation-dechlorination.For chlorobenzene transformation ratio up to 99%, catabolite is benzene.
CN101979141A has been made modified nickel phosphide hydrogenation-dechlorination using the hydrogen treat containing a small amount of oxygen or vapor and has urged
Agent.And normal pressure, 150~250 degree, hydrogen gas space velocity be 10~500h-1, chlorobenzene compound air speed be 2~6h-1Condition
Under reacted.Chlorobenzene transformation ratio is 80% or so.
CN101757916A discloses a kind of catalyst and preparation method thereof of displacement of chlorine from chlorobenzene liquid phase by hydrogen, it is characterised in that
The active component of catalyst is made of Ni and B, and dechlorination reaction is under 0.5~1.5MPa of hydrogen pressure, 50~150 degree of reaction temperature, alkali
It is carried out in the anhydrous ethanol solvent of property.93% or more dechlorination conversion ratio.
CN102921143A discloses a kind of method of efficient degradation chloro phenol compound, and this method is with support type VIII
Race's bimetallic is catalyst, in organic-water two-phase solvent of alkalinity, in 0.05~0.15MPa of reaction pressure and reaction temperature
30~50 degree of lower progress hydrogenation-dechlorination reactions, are degraded to phenol for chloro phenol compound.
CN101462967B using charcoal carry Pd or Ni catalyst, 1.5~3.0MPa of Hydrogen Vapor Pressure, reaction temperature 80~
It can be monochlor-benzene amine compounds by polystream amine compounds catalytic hydrogenation in the presence of organic solvent and alkali under 120 degree.
CN102512783A uses loading transition metallic catalyst, in organic-water two-phase of alkalinity, in Hydrogen Vapor Pressure
Under the reaction condition that 0.05~1.0MPa and temperature are 20~80 degree, acted on by phase transfer reagent, by low aqueous solubility persistence
Halogenated organic pollutant catalytic hydrodehalogenation is degraded to accessible organic matter.
As can be seen that existing catalytic hydrogenation and dechlorination method degradation polystream is mainly in Pd or Ni from published document
Under metallic catalyst effect, the stabilization of phenyl ring in former chlorinatedorganic is kept, is reacted by catalytic hydrogenation and dechlorination and removes Cl, it is raw
Mixture both at low chlorobenzene (monochloro-benzene or dichloro-benzenes) or benzene, then either, dechlorination conversion ratio is between 80~99%.Cause
This, the purpose of polystream degradation is only the organic matter converted it into convenient for being for further processing using other methods.
CN103691464A discloses a kind of for the low-temperature catalyzed aluminium hydroxide supported palladium for adding hydrogen to eliminate of chlorobenzene phenolic compound in water
Catalyst, the catalyst can convert cyclohexanone and phenol for chlorobenzene phenolic compound.But the catalyst be only applicable to it is low dense
The chlorobenzene phenolic compound processing in (1000~2000mg/L) aqueous solution is spent, and there are also 15 for phenol content in its catabolite
~40% or so.
Summary of the invention
Present invention aims at provided for deficiency of the prior art a kind of chlorobenzene catalytic converting catalyst and
The technical solution of preparation method and application, this method is reacted using catalytic hydrogenation and dechlorination and the coupling of chlorobenzene and alcohol substitution reaction
It closes, can not only promote the dechlorination process of chlorobenzene, can also more be there is the phenyl ether type organic of application value.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme:
A kind of chlorobenzene catalytic converting catalyst, it is characterised in that: catalyst is made of carrier and active component, and carrier is to live
Property charcoal, active component are made of palladium, lanthanum, cerium and boron, and mass percent is respectively (3.0%~15.0%) of carrier quality:
(0.1%~5.0%): (0.1%~5.0%): (0.1%~2.5%).
Preferably, the material of active carbon is coconut husk, and ash is less than 5.0wt%, and specific surface area is greater than 750m2/ g, Kong Rong great
In 0.5ml/g.
Preferably, the mass percent of palladium, lanthanum, cerium and boron is respectively (4.0%~12.0%) of carrier quality: (0.2%
~3.5%): (0.2%~3.5%): (0.15%~1.5%).
The method of preparation such as above-mentioned a kind of chlorobenzene catalytic converting catalyst, it is characterised in that include the following steps:
A) by mass percentage be respectively carrier quality (4.0%~12.0%): (0.2%~3.5%): (0.2%~
3.5%) soluble palladium salt, lanthanum nitrate and cerous nitrate are weighed, is configured to water-soluble with weighed active carbon total pore volume same volume
Liquid is placed in constant pressure funnel, and is inserted on three-necked flask；
B) active carbon is weighed to be dried under vacuum state, drying temperature be 100~200 DEG C, preferably 120.0~
180.0 DEG C, drying time is 1.0~5.0h, and preferably 1.5~3.5h, vacuum degree is -0.08~-0.1MPa, after drying,
It is cooled to dipping temperature, dipping temperature is 1.0~100 DEG C；
C) constant pressure funnel valve is opened, it will be configured containing processing in palladium, lanthanum, the aqueous solution of cerium and step b) in step a)
Active carbon afterwards is sufficiently impregnated, and it is dry then to carry out temperature programming under vacuum anaerobic state, and vacuum degree is -0.08~-
0.1MPa, remaining gas are nitrogen, and temperature programming drying is since dipping temperature with the heating rate liter of 5.0~25.0 DEG C/min
200.0~250.0 DEG C are risen to 100.0~200.0 DEG C, then with the heating rate of 0.5~5.0 DEG C/min, last constant temperature 0.5~
4.0h rises to 120.0~180.0 DEG C preferably since dipping temperature with the heating rate of 10.0~20.0 DEG C/min, then with 1.0
The heating rate of~4.0 DEG C/min rises to 200.0~230.0 DEG C, last 1.0~4.0h of constant temperature；
D) vacuum is closed, under nitrogen protection, deionized water mashing is added by constant pressure funnel, the dosage of deionized water is
3.0~10.0 times of active carbon total pore volume volume, stir evenly, while potassium borohydride/sodium solution being added into constant pressure funnel, so
It is restored in a hydrogen atmosphere afterwards, reduction temperature is 20.0~95.0 DEG C, and the recovery time is 1.0~8.0h, preferably reduction temperature
Degree is 35.0~80.0 DEG C, and the recovery time is 2.0~6.0h, and potassium borohydride/sodium water solution reduction is added dropwise later, and reduction temperature is
1.0~100.0 DEG C, the recovery time be 1.0~8.0h, preferably reduction temperature be 5.0~80.0 DEG C, the recovery time be 2.0~
6.0h, potassium borohydride/sodium dosage are most to wash afterwards through deionized water to neutrality, are directly sealed up for safekeeping after filtering.
Further, the soluble palladium salt in step a) is K2PdCl4、H2PdCl4、Na2PdCl4One or more of
Mixture.
Preferably, the dipping temperature in step b) is 5.0~80.0 DEG C.
A kind of application of chlorobenzene catalytic converting catalyst, it is characterised in that include the following steps: chlorobenzene, pure and mild catalyst
Be according to the proportion (100g): (150~1500ml): (0.1~4.0g), sodium hydroxide/potassium hydroxide rub with chlorine atom in chlorobenzene
You put into high-pressure hydrogenation reaction kettle, the volume that feeds intake is 70%, closes reaction kettle, is displaced instead with nitrogen than being 1.0~2.0
The air in device is answered, then with hydrogen displacement nitrogen, and is stirred, maintaining reaction temperature is 70~200 DEG C, and Hydrogen Vapor Pressure is
Catalysis reaction is carried out under the conditions of 0.3~3.0MPa (preferable reaction temperature is 80~150 DEG C, and Hydrogen Vapor Pressure is 0.5~2.0MPa),
Until stopping absorbing hydrogen, stop reaction, filter cake is back to progress catalyst in reaction kettle and applied, filtered by filtration catalytic agent
Liquid carries out solvent and separates with product, and solvent is recycled.
Further, chlorobenzene isWherein-R1、-R2、-R3、-R4、-R5It is each independently selected from following groups :-
H、-Cl、-CH3、-CH2CH3、-NO2、-NH2、-OCH3、-OCH2CH3、-C6H6、-C6ClxH5-x(0≤x≤5)、-COOCH3。
Further, alcohol is one in methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol
Kind or two or more mixtures.
Preferably, chlorobenzene, pure and mild catalyst proportion be (100g): (200~1000ml): (0.2~2.0g).
The purpose of existing chlorobenzene degradation is converted it into convenient for passing through catalysis using the organic matter of other methods processing
Hydrogenation-dechlorination reaction removes Cl, generates low chlorobenzene (monochloro-benzene or dichloro-benzenes) or benzene, then the mixture of either the two, dechlorination
Conversion ratio is between 80~99%.
The present invention is by adopting the above-described technical solution, have the advantages that
1, the catalytic converting catalyst and preparation method thereof being made of palladium, lanthanum, cerium and boron, catalyst catalytic performance is good, set
With often；
2, the conversion ratio of catalyzed conversion is up to 100%, selective 99% or more；
3, catalytic hydrogenation and dechlorination reaction and chlorobenzene and alcohol substitution reaction may be implemented in the catalyzed conversion suitable for a variety of chlorobenzenes
Coupling, more had the phenyl ether type organic of application value.
Specific embodiment
A kind of chlorobenzene catalytic converting catalyst of the present invention, catalyst are made of carrier and active component, and carrier is active carbon,
Preferably, the material of active carbon is coconut husk, and ash is less than 5.0wt%, and specific surface area is greater than 750m2/ g, Kong Rong are greater than 0.5ml/
G, active component are made of palladium, lanthanum, cerium and boron, and mass percent is respectively (3.0%~15.0%) of carrier quality:
(0.1%~5.0%): (0.1%~5.0%): (0.1%~2.5%), it is preferred that the mass percent of palladium, lanthanum, cerium and boron
Respectively (4.0%~12.0%) of carrier quality: (0.2%~3.5%): (0.2%~3.5%): (0.15%~
1.5%).
A kind of method of preparation such as above-mentioned chlorobenzene catalytic converting catalyst, includes the following steps:
A) by mass percentage be respectively carrier quality (4.0%~12.0%): (0.2%~3.5%): (0.2%~
3.5%) soluble palladium salt, lanthanum nitrate and cerous nitrate are weighed, is configured to water-soluble with weighed active carbon total pore volume same volume
Liquid is placed in constant pressure funnel, and is inserted on three-necked flask, and soluble palladium salt is K2PdCl4、H2PdCl4、Na2PdCl4One of
Or two or more mixtures；
B) active carbon is weighed to be dried under vacuum state, drying temperature be 100~200 DEG C, preferably 120.0~
180.0 DEG C, drying time is 1.0~5.0h, and preferably 1.5~3.5h, vacuum degree is -0.08~-0.1MPa, after drying,
It is cooled to dipping temperature, dipping temperature is 1.0~100 DEG C, it is preferred that dipping temperature is 5.0~80.0 DEG C；
C) constant pressure funnel valve is opened, it will be configured containing processing in palladium, lanthanum, the aqueous solution of cerium and step b) in step a)
Active carbon afterwards is sufficiently impregnated, and it is dry then to carry out temperature programming under vacuum anaerobic state, and vacuum degree is -0.08~-
0.1MPa, remaining gas are nitrogen, and temperature programming drying is since dipping temperature with the heating rate liter of 5.0~25.0 DEG C/min
200.0~250.0 DEG C are risen to 100.0~200.0 DEG C, then with the heating rate of 0.5~5.0 DEG C/min, last constant temperature 0.5~
4.0h rises to 120.0~180.0 DEG C preferably since dipping temperature with the heating rate of 10.0~20.0 DEG C/min, then with 1.0
The heating rate of~4.0 DEG C/min rises to 200.0~230.0 DEG C, last 1.0~4.0h of constant temperature；
D) vacuum is closed, under nitrogen protection, deionized water mashing is added by constant pressure funnel, the dosage of deionized water is
3.0~10.0 times of active carbon total pore volume volume, stir evenly, while potassium borohydride/sodium solution being added into constant pressure funnel, so
It is restored in a hydrogen atmosphere afterwards, reduction temperature is 20.0~95.0 DEG C, and the recovery time is 1.0~8.0h, preferably reduction temperature
Degree is 35.0~80.0 DEG C, and the recovery time is 2.0~6.0h, and potassium borohydride/sodium water solution reduction is added dropwise later, and reduction temperature is
1.0~100.0 DEG C, the recovery time be 1.0~8.0h, preferably reduction temperature be 5.0~80.0 DEG C, the recovery time be 2.0~
6.0h, potassium borohydride/sodium dosage are most to wash afterwards through deionized water to neutrality, are directly sealed up for safekeeping after filtering.
A kind of application of chlorobenzene catalytic converting catalyst, include the following steps: be according to the proportion by chlorobenzene, pure and mild catalyst
(100g): (150~1500ml): (0.1~4.0g), chlorobenzene areWherein-R1、-R2、-R3、-R4、-R5Respectively
It is independently selected from following groups :-H ,-Cl ,-CH3、-CH2CH3、-NO2、-NH2、-OCH3、-OCH2CH3、-C6H6、-C6ClxH5-x(0≤
x≤5)、-COOCH3, alcohol is one in methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol
Kind or two or more mixtures, it is preferred that chlorobenzene, pure and mild catalyst proportion be (100g): (200~1000ml): (0.2~
2.0g), sodium hydroxide/potassium hydroxide and chlorine atom molar ratio in chlorobenzene are 1.0~2.0, put into high-pressure hydrogenation reaction kettle, throw
Expect that volume is 70%, closes reaction kettle, displace the air in reactor with nitrogen, then with hydrogen displacement nitrogen, and carry out
Stirring, maintaining reaction temperature are 70~200 DEG C, and Hydrogen Vapor Pressure is that (preferable reaction temperature is 80~150 DEG C to 0.3~3.0MPa, hydrogen
Atmospheric pressure is carries out catalysis reaction under the conditions of 0.5~2.0MPa), until stopping absorbing hydrogen, stops reaction, filtration catalytic
Filter cake is back to progress catalyst in reaction kettle and applied by agent, and filtrate carries out solvent and separates with product, and solvent, which carries out circulation, to be made
With.
Embodiment one is to embodiment ten
Provide catalyst activity component content, proportion and its preparation condition (as shown in Table 1 and Table 2).Catalyst is specific
Preparation process is as follows: claiming by the 4.0-12.0%:0.2-3.5%:0.2-3.5% that mass content percentage is respectively carrier quality
Take soluble palladium salt, lanthanum nitrate and cerous nitrate, be configured to the aqueous solution of weighed active carbon total pore volume same volume, be placed in perseverance
It presses in funnel, and is inserted on three-necked flask.Then drying is mounted in three-necked flask under vacuum state, 120.0-180.0 degree
Active carbon 1.5-3.5 hours.After drying, it is cooled to 5.0-80.0 degree, opens constant pressure funnel valve, is made containing palladium, lanthanum and cerium
Aqueous solution sufficiently soaked with active carbon.Then under vacuum anaerobic state, with 10.0-20.0 degree min since dipping temperature
The heating rate of clock rises to 120.0-180.0 degree, then rises to 180.0-230.0 degree with 1.0-4.0 degrees/min of heating rate,
Last constant temperature 1.0-4.0 hours.Vacuum is closed, under the protection of nitrogen, it is total that active carbon is approximately equivalent to by constant pressure funnel injection
Hole holds the deionized water of 3.0-10.0 times of volume, stirs evenly, while potassium borohydride/sodium solution being added into constant pressure funnel.So
Afterwards reductase 12 .0-6.0 hours under hydrogen atmosphere, 35.0-80.0 degree.Then at 5.0-80.0 degree, 1.0-4.0 times of lanthanum+cerium is instilled
The potassium borohydride of metal ion molar ratio/sodium reduction 2.0-6.0 hours.Finally, washing is directly sealed up for safekeeping after filtering to neutrality.
Table 1
Table 2
Embodiment 11 is to embodiment 35
Catalyst made from above-mentioned preparation method is applied to the reaction of chlorobenzene catalytic hydrogenation and dechlorination and chlorobenzene and alcohol replaces instead
The coupling answered more is had the example (as shown in Table 3 and Table 4) of the phenyl ether organic compound of application value.Specifically plus hydrogen turns
Change process is as follows: being according to the proportion 100g:200-1000ml:0.2-2.0g, chlorobenzene and sodium hydroxide by chlorobenzene, alcohol, catalyst
Molar ratio is 1.0-2.0, is put into 500ml high-pressure hydrogenation reaction kettle, and the volume that feeds intake is 70%.Reaction kettle is closed, is set with nitrogen
Swap out air in reactor, then with hydrogen displacement nitrogen, opens stirring, maintaining reaction temperature is 80-150 DEG C, Hydrogen Vapor Pressure
0.5-2.0MPa stops reaction, filtration catalytic agent until not inhaling hydrogen.Filtrate gas chromatographic analysis.
Table 3
Table 4
Embodiment 36
It is that catalyst prepared by embodiment ten is applied applied to the catalyst of the obtained phenetole reaction of hexachloro-benzene catalyzed conversion
Situation (as shown in table 5).Specific hydroconversion process is as follows: be according to the proportion 100g by hexachloro-benzene, ethyl alcohol, catalyst:
600ml:1.0g, hexachloro-benzene and sodium hydroxide molar ratio are 1.5, are put into 500ml high-pressure hydrogenation reaction kettle, the volume that feeds intake is
70%.Reaction kettle is closed, displaces air in reactor with nitrogen, then with hydrogen displacement nitrogen, stirring is opened, maintains reaction
Temperature is 90-110 DEG C or so, between Hydrogen Vapor Pressure 0.5-1.2MPa, until not inhaling hydrogen, stops reaction, filtration catalytic agent.
Using low-temperature evaporation method precipitated sodium chloride, ethyl alcohol and sodium hydroxide recycling and reusing.Filtrate gas chromatographic analysis.
The catalyst of 5 embodiment ten of table preparation applies situation in the reaction of hexachloro-benzene catalyzed conversion synthesis of phenyl ether
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to realize essentially identical technical effect, made ground simple change, equivalent replacement or modification etc. are all covered
Among protection scope of the present invention.
Claims (7)
1. a kind of method of chlorobenzene catalytic converting catalyst, it is characterised in that include the following steps:
A) 4.0%~12.0%:0.2%~3.5%:0.2%~3.5% of respectively carrier quality weighs by mass percentage
Soluble palladium salt, lanthanum nitrate and cerous nitrate, be configured to the aqueous solution of weighed active carbon total pore volume same volume, be placed in constant pressure
In funnel, and it is inserted on three-necked flask；
B) active carbon is weighed to be dried under vacuum state, drying temperature be 100~200 DEG C, drying time be 1.0~
5.0h, vacuum degree are -0.08~-0.1MPa, after drying, are cooled to dipping temperature, the dipping temperature is 1.0~100
℃；
C) constant pressure funnel valve is opened, it will be configured containing treated in palladium, lanthanum, the aqueous solution of cerium and step b) in step a)
The active carbon is sufficiently impregnated, and it is dry then to carry out temperature programming under vacuum anaerobic state, and vacuum degree is -0.08~-
0.1MPa, remaining gas are nitrogen, and described program heating is dry fast with the heating of 5.0~25.0 DEG C/min since dipping temperature
Degree rises to 100.0~200.0 DEG C, then rises to 200.0~250.0 DEG C with the heating rate of 0.5~5.0 DEG C/min, last constant temperature
0.5~4.0h；
D) vacuum is closed, under nitrogen protection, deionized water mashing is added by constant pressure funnel, the dosage of the deionized water is
3.0~10.0 times of the active carbon total pore volume volume, stir evenly, while addition potassium borohydride/sodium is molten into constant pressure funnel
Liquid；Then it is restored in a hydrogen atmosphere, reduction temperature is 20.0~95.0 DEG C, and the recovery time is 1.0~8.0h, is dripped later
Add potassium borohydride/sodium water solution reduction, reduction temperature is 1.0~100.0 DEG C, and the recovery time is 1.0~8.0h, the hydroboration
Potassium/sodium dosage is 1.0-4.0 times of lanthanum+ce metal ion molar ratio, is most washed afterwards through deionized water to neutrality, straight after filtering
It connects and seals up for safekeeping.
2. a kind of preparation method of chlorobenzene catalytic converting catalyst according to claim 1, it is characterised in that: in step a)
The soluble palladium salt be K2PdCl4、H2PdCl4、Na2PdCl4One or more mixtures of.
3. a kind of preparation method of chlorobenzene catalytic converting catalyst according to claim 1, it is characterised in that: in step b)
The dipping temperature be 5.0~80.0 DEG C.
4. a kind of application of chlorobenzene catalytic converting catalyst as described in claim 1, it is characterised in that include the following steps: by
Chlorobenzene, pure and mild catalyst are 100g:150~1500ml:0.1~4.0g according to the proportion, in sodium hydroxide/potassium hydroxide and chlorobenzene
Chlorine atom molar ratio is 1.0~2.0, is put into high-pressure hydrogenation reaction kettle, and the volume that feeds intake is 70%, closes reaction kettle, uses nitrogen
The air in reactor is displaced, then with hydrogen displacement nitrogen, and is stirred, maintaining reaction temperature is 70~200 DEG C, hydrogen
Atmospheric pressure carries out catalysis reaction under the conditions of being 0.3~3.0MPa, until stopping absorbing hydrogen, stops reacting, filtration catalytic agent,
Filter cake is back to progress catalyst in reaction kettle to apply, filtrate carries out solvent and separates with product, and solvent is recycled.
5. a kind of application of chlorobenzene catalytic converting catalyst according to claim 4, it is characterised in that: the chlorobenzene isWherein-R1、-R2、-R3、-R4、-R5It is each independently selected from following groups :-H ,-Cl ,-CH3、-CH2CH3、-
NO2、-NH2、-OCH3、-OCH2CH3、-C6H6、-C6ClxH5-x 0≤x≤5、-COOCH3。
6. a kind of application of chlorobenzene catalytic converting catalyst according to claim 4, it is characterised in that: the alcohol is first
One of alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol and tert-butyl alcohol or more than one mixtures.
7. a kind of application of chlorobenzene catalytic converting catalyst according to claim 4, it is characterised in that: the chlorobenzene, institute
The proportion for stating the pure and mild catalyst is 100g:200~1000ml:0.2~2.0g.
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