CN106732564B - Aromatic hydrogenation rhodium/activated-carbon catalyst preparation method and application - Google Patents
Aromatic hydrogenation rhodium/activated-carbon catalyst preparation method and application Download PDFInfo
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- CN106732564B CN106732564B CN201611097751.5A CN201611097751A CN106732564B CN 106732564 B CN106732564 B CN 106732564B CN 201611097751 A CN201611097751 A CN 201611097751A CN 106732564 B CN106732564 B CN 106732564B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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- B01J23/892—Nickel and noble metals
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
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- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The present invention provides a kind of aromatic hydrogenation rhodium/activated-carbon catalyst preparation methods, comprising the following steps: one, pre-process to active carbon；Two, the soluble-salt of soluble rhodium compound and auxiliary agent is dissolved in solvent, obtains precursor solution；Three, it will be added in active carbon after precursor solution aerosol dispersion, obtain slurries after mixing evenly, then adjust pH value, filtering and washing；Four, reduction treatment is carried out after being beaten with pure water, is successively filtered, washs and is dried later, obtains aromatic hydrogenation rhodium/activated-carbon catalyst.The present invention also provides the application methods of the catalyst.Catalyst of the present invention is made of active carbon and the metal component being carried on the active carbon, the metal component is rhodium and auxiliary agent, which is suitable for aromatic compound catalytic hydrogenation, and product yield is more than 95%, catalyst performance stabilised, and there is repeatability well.
Description
Technical field
The invention belongs to noble metal catalyst technical fields, and in particular to a kind of aromatic hydrogenation rhodium/activity
The preparation method and application of Pd/carbon catalyst.
Background technique
In the synthesis process of many fine chemicals and its intermediate, the catalytic hydrogenation that can be all related to aromatic compound is anti-
It answers.Relative to carbon-carbon double bond is contained, the catalytic hydrogenation reaction of nitro, the compound of the groups such as carbonyl, aromatic compound will be stranded
It is much more difficult.Typical catalyst used at present such as Raney nickel, needs to be reacted at high temperature under high pressure, and the activity reacted
All poor with selectivity, by-product is more.And load type rhodium catalyst has activity well, Ke Yi to aromatic compound
It is reacted under the conditions of lower pressure and temperature, is especially catalyzed to a variety of containing the aromatic compound of phenyl ring and pyridine ring
Add hydrogen, obtains the reaction of cyclohexyl and piperidines ring derivatives.And the by-product and three deserted citys generated is fewer, and it is green to meet country
The requirement that colour circle is protected.
Currently, the load type rhodium catalyst of aromatic hydrogenation is mainly that activated carbon supported nanometer rhodium metal is urged
Agent, such catalyst common problem be how to be further increased on the basis of existing level catalyst activity and
Selectivity.And suitable absorbent charcoal carrier is selected, and pre-treatment appropriate is carried out, it, can in conjunction with ultrasonic atomizatio dispersing apparatus is utilized
To improve dispersion degree of the noble metal nano particles on absorbent charcoal carrier well, the form of granular size and nano particle,
To further increase rhodium/activated-carbon catalyst activity and selectivity.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of aromatic compound
Object adds hydrogen rhodium/activated-carbon catalyst preparation method.This method is easy to operate, and raw material is easy to get, large-scale industry easy to accomplish
Metaplasia produces, and it is convenient, it can be achieved that the production of noble metal, recycling, reproduction to recycle after the catalyst use of preparation, damages in removal process
It loses less, greatly reduces the production cost of catalyst.The catalyst of this method preparation is suitable for aromatic compound catalysis and adds
Hydrogen, product yield is more than 95%, and catalyst performance stabilised, has repeatability well.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of aromatic hydrogenation rhodium/work
Property Pd/carbon catalyst preparation method, which is characterized in that the catalyst is by active carbon and load metal component group on the activated carbon
At the metal component is rhodium and auxiliary agent, and the mass percentage of rhodium is 1%~5% in the catalyst, the quality hundred of auxiliary agent
Dividing content is 0.1%~1%；The auxiliary agent be platinum, palladium, ruthenium, molybdenum, cobalt and nickel in any one or it is two or more；The catalysis
The preparation method of agent the following steps are included:
Step 1: by active carbon be added to concentration be 10mol/L~15mol/L sodium hydrate aqueous solution in boil 1h~
2h, adopts to be washed with deionized to the pH value of washing lotion after natural cooling and is in neutrality, and pretreated active carbon is obtained after filtering；
Step 2: the soluble-salt of soluble rhodium compound and auxiliary agent is dissolved in solvent, before obtaining after mixing evenly
Drive liquid solution；The solvent is water or alcohol；
Step 3: carrying out ultrasonic atomizatio processing to precursor solution described in step 2 using ultrasonic atomizer, mist is obtained
Change drop, then the atomized drop is passed into and is loaded in the reactor of pretreated active carbon described in step 1, stirs
Dipping, obtains slurries after mixing uniformly, and the pH value of the slurries is then adjusted using lye to 9~12, is continued after stirring 1h~5h
Filtering, obtains filter cake, carries out washing to filter cake using deionized water until the pH value of washing lotion is in neutrality later；Before in the slurries
The additional amount for driving liquid solution, which is that every gram of pretreated active carbon is corresponding, is added 20mL precursor solution；
Step 4: the filter cake after washing in step 3 is beaten with pure water, slurry is obtained, then the slurry is adjusted using lye
The pH value of material is 9~14, and reducing agent then is added into the slurry after adjusting pH value and carries out reduction treatment, successively carried out later
Filter, washing and drying process, obtain aromatic hydrogenation rhodium/activated-carbon catalyst.
Above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst preparation method, which is characterized in that the catalysis
The mass percentage of rhodium is 1%~5% in agent, and the mass percentage of auxiliary agent is 0.4%~0.6%.
Above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst preparation method, which is characterized in that the catalysis
The mass percentage of rhodium is 5% in agent, and the mass percentage of auxiliary agent is 0.5%.
Above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst preparation method, which is characterized in that the catalysis
The partial size of active carbon is 200 mesh~800 mesh in agent, and the specific surface area of the active carbon is 800m2/ g~1500m2/ g, the rhodium
Average grain diameter be 20nm~50nm.
Above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst preparation method, which is characterized in that in step 2
The soluble rhodium compound is rhodium chloride or/and rhodium nitrate.
Above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst preparation method, which is characterized in that in step 2
The soluble-salt of the auxiliary agent is the chloride of auxiliary agent or the nitrate of auxiliary agent.
Above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst preparation method, which is characterized in that in step 4
The reducing agent is sodium borohydride, potassium borohydride, formaldehyde, sodium formate, formic acid or hydrazine hydrate, and the mole of the reducing agent is rhodium
2~5 times of mole, the temperature of the reduction treatment are 50 DEG C~100 DEG C, and the time of the reduction treatment is 1h~3h.
Above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst preparation method, which is characterized in that in step 4
The temperature of the drying process is 80 DEG C~100 DEG C, and the time of the drying process is 5h~12h.
In addition, the present invention also provides a kind of catalyst using above method preparation to be catalyzed to aromatic compound
Add the method for hydrogen, which is characterized in that this method are as follows: aromatic compound, catalysts and solvents are added in autoclave, so
It is passed through hydrogen in backward autoclave, while heating the material in autoclave, makes aromatic compound in reaction under high pressure
Kettle internal pressure is 2MPa~5MPa, and temperature is catalytic hydrogenation reaction 2h~5h under conditions of 80 DEG C~120 DEG C, is obtained after adding hydrogen
Aromatic compound；The additional amount of the catalyst be aromatic compound amount of substance 1%~5%, the solvent be go from
Sub- water or ethyl alcohol.
Above-mentioned method, which is characterized in that the internal pressure of the autoclave is 4MPa, the catalytic hydrogenation reaction
Temperature be 110 DEG C, time of the catalytic hydrogenation reaction is 4h, and the additional amount of the catalyst is aromatic compound amount of substance
3%.
Compared with the prior art, the present invention has the following advantages:
1, rhodium Pd/carbon catalyst prepared by the present invention is to be Noble Metal Rhodium and auxiliary agent using the active carbon of specially treated as carrier
Metallic element is highly dispersed on absorbent charcoal carrier, and rhodium metal particle diameter is 20nm~50nm in catalyst, and in active carbon
It is evenly distributed on carrier, there is good catalytic activity and selectivity.
2, present invention utilizes ultrasonic atomizatio equipment, preparation process can make noble metal active component be uniformly dispersed in work
On property high-area carbon surface, the dispersibility and activity of rhodium Pd/carbon catalyst are improved.
3, the preparation method of catalyst of the present invention is easy to operate, and raw material is easy to get, large-scale industrial production easy to accomplish.Preparation
Catalyst use after recycle it is convenient, it can be achieved that noble metal production-recycling-reproduction, lose in removal process it is less, significantly
Reduce the production cost of catalyst.
4, catalyst prepared by the present invention is suitable for aromatic compound, especially containing phenyl ring and pyridine cycle compound
Catalytic hydrogenation, product yield are more than 95%, substantially increase the yield of product, significantly reduce production cost, and are belonged to efficiently
Green environmental protection technique.
5, catalyst life prepared by the present invention is stablized, and can repeatedly apply, and the cost for reducing single use catalyst is asked
Topic, it is easy to accomplish industrialization.
6, the catalysis process of catalyst of the present invention has the advantages that step simple, mild condition, environmentally protective, urges for such
The large-scale application of agent provides advantageous condition.
Below with reference to embodiment, invention is further described in detail.
Specific embodiment
Embodiment 1
The catalyst that the present embodiment need to be prepared be aromatic hydrogenation rhodium/activated-carbon catalyst, the catalyst by
Active carbon and the metal component being carried on the active carbon form, and the partial size of active carbon is 200 mesh~300 mesh, the activity
The specific surface area of charcoal is 1200m2/ g, the metal component are rhodium and auxiliary agent, and the average grain diameter of the rhodium is 20nm~50nm, is helped
Agent be platinum, palladium, ruthenium, molybdenum, cobalt and nickel in any one or it is two or more, the auxiliary agent that the present embodiment is specifically selected be cobalt, it is described
The mass percentage of rhodium is 5% in catalyst, and the mass percentage of auxiliary agent is 1%.The present embodiment aromatic compound adds
Hydrogen rhodium/activated-carbon catalyst preparation method the following steps are included:
It is stirred evenly Step 1: 10g active carbon is added in the sodium hydrate aqueous solution that concentration is 12mol/L, then
2h is boiled in heating, stops heating later, after the mixed material natural cooling after boiling, be washed with deionized to the pH of washing lotion
Value is in neutrality, and pretreated active carbon is obtained after filtering；
Step 2: the soluble-salt of soluble rhodium compound and auxiliary agent is added in solvent together, stirring fills solute
Divide and be dissolved in solvent, obtains precursor solution after mixing evenly；The solvent is water or alcohol；The soluble rhodium compound is
Rhodium chloride or/and rhodium nitrate, the soluble-salt of the auxiliary agent are the chloride of auxiliary agent or the nitrate of auxiliary agent；The present embodiment tool
The soluble rhodium compound that body uses is rhodium chloride, and the soluble-salt of the auxiliary agent specifically used is cobalt chloride ammonium；The trichlorine
The additional amount for changing rhodium is to guarantee rhodium content 0.5g, and the additional amount of the cobalt chloride is to guarantee cobalt content 0.1g；
It is added in reactor Step 3: weighing pretreated active carbon described in 9.4g step 1, it will be in step 2
The precursor solution is passed into reactor after ultrasonic atomizer aerosol dispersion is at atomized drop, makes precursor solution and pre-
Active carbon stirring that treated obtains slurries after impregnating 2h, and then under agitation, with weak lye, (mass concentration is 1%
Sodium hydroxide solution) to adjust the pH value of the slurries be 10, continue to filter after stirring 3h, obtain filter cake, uses deionization later
The pH value of Washing of Filter Cake to washing lotion is in neutrality by water；The additional amount of the precursor solution is every gram of pretreated active carbon pair
20mL precursor solution should be added, 188mL precursor solution is added in the present embodiment into reactor altogether；
Step 4: being beaten washing in step 3 to neutral 20 times of pure water of filter cake, slurry is obtained, then use weak lye
(sodium hydroxide solution that mass concentration is 1%) adjusts the pH value of the slurry to 9, then adds into the slurry after adjusting pH value
Enter reducing agent and carry out reduction treatment, be successively filtered, wash and be dried later, the temperature of drying process is 100 DEG C, is done
The time of dry processing is 5h, obtains aromatic hydrogenation rhodium/activated-carbon catalyst；The reducing agent be sodium borohydride,
Potassium borohydride, formaldehyde, sodium formate, formic acid or hydrazine hydrate, the reducing agent that the present embodiment specifically uses is sodium borohydride, the reduction
The mole of agent is 3 times of rhodium mole, and the temperature of the reduction treatment is 60 DEG C, and the time of reduction treatment is 2h.
Embodiment 2
The present embodiment is same as Example 1, wherein the difference is that only: the auxiliary agent is platinum, palladium, ruthenium, molybdenum, cobalt and nickel
In at least two.
Embodiment 3
The catalyst that the present embodiment need to be prepared be aromatic hydrogenation rhodium/activated-carbon catalyst, the catalyst by
Active carbon and the metal component being carried on the active carbon form, and the partial size of active carbon is 200 mesh~400 mesh, the activity
The specific surface area of charcoal is 1500m2/ g, the metal component are rhodium and auxiliary agent, and the average grain diameter of the rhodium is 20nm~50nm, is helped
Agent be platinum, palladium, ruthenium, molybdenum, cobalt and nickel in any one or it is two or more, the auxiliary agent that the present embodiment is specifically selected be ruthenium, it is described
The mass percentage of rhodium is 5% in catalyst, and the mass percentage of auxiliary agent is 0.5%.The present embodiment aromatic compound
Add hydrogen rhodium/activated-carbon catalyst preparation method the following steps are included:
It is stirred evenly Step 1: 10g active carbon is added in the sodium hydrate aqueous solution that concentration is 15mol/L, then
1h is boiled in heating, stops heating later, after the mixed material natural cooling after boiling, be washed with deionized to the pH of washing lotion
Value is in neutrality, and pretreated active carbon is obtained after filtering；
Step 2: the soluble-salt of soluble rhodium compound and auxiliary agent is added in solvent together, stirring fills solute
Divide and be dissolved in solvent, obtains precursor solution after mixing evenly；The solvent is water or alcohol；The soluble rhodium compound is
Rhodium chloride or/and rhodium nitrate, the soluble-salt of the auxiliary agent are the chloride of auxiliary agent or the nitrate of auxiliary agent；The present embodiment tool
The soluble rhodium compound that body uses is rhodium chloride and rhodium nitrate, and the soluble-salt of the auxiliary agent specifically used is ruthenium trichloride；
The additional amount of the rhodium chloride is to guarantee rhodium content 0.4g, and the additional amount of the rhodium nitrate is to guarantee that rhodium content is 0.1g, institute
The additional amount of ruthenium trichloride is stated to guarantee ruthenium content 0.05g；
It is added in reactor Step 3: weighing pretreated active carbon described in 9.45g step 1, it will be in step 2
The precursor solution is passed into reactor after ultrasonic atomizer aerosol dispersion is at atomized drop, makes precursor solution and pre-
Active carbon stirring that treated obtains slurries after impregnating 6h, and then under agitation, with weak lye, (mass concentration is 1%
Sodium hydroxide solution) to adjust the pH value of the slurries be 9, continue to filter after stirring 1h, obtain filter cake, uses deionized water later
The pH value of Washing of Filter Cake to washing lotion is in neutrality；The additional amount of the precursor solution is that every gram of pretreated active carbon is corresponding
20mL precursor solution is added, 189mL precursor solution is added in the present embodiment into reactor altogether；
Step 4: being beaten washing in step 3 to neutral 20 times of pure water of filter cake, slurry is obtained, then use weak lye
(sodium hydroxide solution that mass concentration is 1%) adjusts the pH value of the slurry to 14, then into the slurry after adjusting pH value
Reducing agent is added and carries out reduction treatment, is successively filtered, washs and is dried later, the temperature of drying process is 120 DEG C,
The time of drying process is 5h, obtains aromatic hydrogenation rhodium/activated-carbon catalyst；The reducing agent is hydroboration
Sodium, potassium borohydride, formaldehyde, sodium formate, formic acid or hydrazine hydrate, the reducing agent that the present embodiment specifically uses are described for potassium borohydride
The mole of reducing agent is 3 times of rhodium mole, and the temperature of the reduction treatment is 60 DEG C, and the time of reduction treatment is 2h.
Embodiment 4
The present embodiment is same as Example 3, wherein the difference is that only: the auxiliary agent be platinum, palladium, cobalt or nickel, or
For at least two in platinum, ruthenium, palladium, cobalt and nickel.
Embodiment 5
The catalyst that the present embodiment need to be prepared be aromatic hydrogenation rhodium/activated-carbon catalyst, the catalyst by
Active carbon and the metal component being carried on the active carbon form, and the partial size of active carbon is 250 mesh~300 mesh, the activity
The specific surface area of charcoal is 1200m2/ g, the metal component are rhodium and auxiliary agent, and the average grain diameter of the rhodium is 20nm~50nm, is helped
Agent be platinum, palladium, ruthenium, molybdenum, cobalt and nickel in any one or it is two or more, the auxiliary agent that the present embodiment is specifically selected be platinum, ruthenium and
Nickel, the mass percentage of rhodium is 5% in the catalyst, and the mass percentage of auxiliary agent is 0.4%.The present embodiment aromatic series
Compound add hydrogen rhodium/activated-carbon catalyst preparation method the following steps are included:
It is stirred evenly Step 1: 10g active carbon is added in the sodium hydrate aqueous solution that concentration is 10mol/L, then
2h is boiled in heating, stops heating later, after the mixed material natural cooling after boiling, be washed with deionized to the pH of washing lotion
Value is in neutrality, and pretreated active carbon is obtained after filtering；
Step 2: the soluble-salt of soluble rhodium compound and auxiliary agent is added in solvent together, stirring fills solute
Divide and be dissolved in solvent, obtains precursor solution after mixing evenly；The solvent is water or alcohol；The soluble rhodium compound is
Rhodium chloride or/and rhodium nitrate, the soluble-salt of the auxiliary agent are the chloride of auxiliary agent or the nitrate of auxiliary agent；The present embodiment tool
The soluble rhodium compound that body uses is rhodium chloride and rhodium nitrate, and the soluble-salt of the auxiliary agent specifically used is platinum chloride, three
Ruthenic chloride and nickel nitrate；The additional amount of the rhodium chloride is to guarantee rhodium content 0.1g, and the additional amount of the rhodium nitrate is to guarantee
Rhodium content is 0.4g, and the additional amount of the ruthenium trichloride is to guarantee ruthenium content 0.01g, and the additional amount of the cobalt chloride is to guarantee cobalt
Content 0.01g, the additional amount of the nickel nitrate are to guarantee nickel content 0.02g；
It is added in reactor Step 3: weighing pretreated active carbon described in 9.46g step 1, it will be in step 2
The precursor solution is passed into reactor after ultrasonic atomizer aerosol dispersion is at atomized drop, makes precursor solution and pre-
Active carbon stirring that treated obtains slurries after impregnating 3h, and then under agitation, with weak lye, (mass concentration is 1%
Sodium hydroxide solution) to adjust the pH value of the slurries be 11, continue to filter after stirring 5h, obtain filter cake, uses deionization later
The pH value of Washing of Filter Cake to washing lotion is in neutrality by water；The additional amount of the precursor solution is every gram of pretreated active carbon pair
20mL precursor solution should be added, 189.2mL precursor solution is added in the present embodiment into reactor altogether；
Step 4: being beaten washing in step 3 to neutral 20 times of pure water of filter cake, slurry is obtained, then use weak lye
(sodium hydroxide solution that mass concentration is 1%) adjusts the pH value of the slurry to 11, then into the slurry after adjusting pH value
Reducing agent is added and carries out reduction treatment, is successively filtered, washs and is dried later, the temperature of drying process is 80 DEG C,
The time of drying process is 12h, obtains aromatic hydrogenation rhodium/activated-carbon catalyst；The reducing agent is hydroboration
Sodium, potassium borohydride, formaldehyde, sodium formate, formic acid or hydrazine hydrate, the reducing agent that the present embodiment specifically uses are described to go back for hydrazine hydrate
The mole of former agent is 2 times of rhodium mole, and the temperature of the reduction treatment is 70 DEG C, and the time of reduction treatment is 3h.
Embodiment 6
The present embodiment is same as Example 5, wherein the difference is that only: the auxiliary agent is in platinum, ruthenium, palladium, cobalt and nickel
One kind, two kinds or four kinds or more, be perhaps ruthenium, three kinds in palladium, cobalt and nickel or be two kinds and platinum in palladium, cobalt and nickel
Mixture, or be palladium or the mixture of cobalt and platinum and ruthenium.
Embodiment 7
The catalyst that the present embodiment need to be prepared be aromatic hydrogenation rhodium/activated-carbon catalyst, the catalyst by
Active carbon and the metal component being carried on the active carbon form, and the partial size of active carbon is 300 mesh~500 mesh, the activity
The specific surface area of charcoal is 800m2/ g, the metal component are rhodium and auxiliary agent, and the average grain diameter of the rhodium is 20nm~50nm, is helped
Agent be platinum, palladium, ruthenium, molybdenum, cobalt and nickel in any one or it is two or more, the auxiliary agent that the present embodiment is specifically selected be cobalt, ruthenium, palladium
And nickel, the mass percentage of rhodium is 5% in the catalyst, and the mass percentage of auxiliary agent is 0.6%.The present embodiment fragrance
Compounds of group add hydrogen rhodium/activated-carbon catalyst preparation method the following steps are included:
It is stirred evenly Step 1: 10g active carbon is added in the sodium hydrate aqueous solution that concentration is 15mol/L, then
1.5h is boiled in heating, stops heating later, after the mixed material natural cooling after boiling, be washed with deionized to washing lotion
PH value is in neutrality, and pretreated active carbon is obtained after filtering；
Step 2: the soluble-salt of soluble rhodium compound and auxiliary agent is added in solvent together, stirring fills solute
Divide and be dissolved in solvent, obtains precursor solution after mixing evenly；The solvent is water or alcohol；The soluble rhodium compound is
Rhodium chloride or/and rhodium nitrate, the soluble-salt of the auxiliary agent are the chloride of auxiliary agent or the nitrate of auxiliary agent；The present embodiment tool
The soluble rhodium compound that body uses is rhodium chloride, and the soluble-salt of the auxiliary agent specifically used is cobalt chloride, ruthenium trichloride, nitre
Sour palladium and nickel nitrate；The additional amount of the rhodium chloride is to guarantee rhodium content 0.5g, and the additional amount of the ruthenium trichloride is to guarantee
Ruthenium content 0.01g, the additional amount of the cobalt chloride are to guarantee cobalt content 0.01g, and the additional amount of the nickel nitrate is to guarantee that nickel contains
0.01g is measured, the additional amount of the palladium nitrate is to guarantee palladium content 0.01g；
It is added in reactor Step 3: weighing pretreated active carbon described in 9.44g step 1, it will be in step 2
The precursor solution is passed into reactor after ultrasonic atomizer aerosol dispersion is at atomized drop, makes precursor solution and pre-
Active carbon stirring that treated obtains slurries after impregnating 4h, and then under agitation, with weak lye, (mass concentration is 1%
Sodium hydroxide solution) to adjust the pH value of the slurries be 12, continue to filter after stirring 2h, obtain filter cake, uses deionization later
The pH value of Washing of Filter Cake to washing lotion is in neutrality by water；The additional amount of the precursor solution is every gram of pretreated active carbon pair
20mL precursor solution should be added, 188mL precursor solution is added in the present embodiment into reactor altogether；
Step 4: being beaten washing in step 3 to neutral 30 times of pure water of filter cake, slurry is obtained, then use weak lye
(sodium hydroxide solution that mass concentration is 1%) adjusts the pH value of the slurry to 12, then into the slurry after adjusting pH value
Reducing agent is added and carries out reduction treatment, is successively filtered, washs and is dried later, the temperature of drying process is 90 DEG C,
The time of drying process is 10h, obtains aromatic hydrogenation rhodium/activated-carbon catalyst；The reducing agent is hydroboration
Sodium, potassium borohydride, formaldehyde, sodium formate, formic acid or hydrazine hydrate, the reducing agent that the present embodiment specifically uses is formic acid, the reduction
The mole of agent is 3 times of rhodium mole, and the temperature of the reduction treatment is 100 DEG C, and the time of reduction treatment is 2h.
Embodiment 8
The present embodiment is same as Example 7, wherein the difference is that only: the auxiliary agent is in platinum, ruthenium, palladium, cobalt and nickel
At most four kinds.
Embodiment 9
The catalyst that the present embodiment need to be prepared be aromatic hydrogenation rhodium/activated-carbon catalyst, the catalyst by
Active carbon and the metal component being carried on the active carbon form, and the partial size of active carbon is 500 mesh~800 mesh, the activity
The specific surface area of charcoal is 1500m2/ g, the metal component are rhodium and auxiliary agent, and the average grain diameter of the rhodium is 20nm~50nm, is helped
Agent be platinum, palladium, ruthenium, molybdenum, cobalt and nickel in any one or it is two or more, the auxiliary agent that the present embodiment is specifically selected be cobalt and nickel,
The mass percentage of rhodium is 5% in the catalyst, and the mass percentage of auxiliary agent is 0.1%.The present embodiment aromatic series
Close object add hydrogen rhodium/activated-carbon catalyst preparation method the following steps are included:
It is stirred evenly Step 1: 10g active carbon is added in the sodium hydrate aqueous solution that concentration is 14mol/L, then
2h is boiled in heating, stops heating later, after the mixed material natural cooling after boiling, be washed with deionized to the pH of washing lotion
Value is in neutrality, and pretreated active carbon is obtained after filtering；
Step 2: the soluble-salt of soluble rhodium compound and auxiliary agent is added in solvent together, stirring fills solute
Divide and be dissolved in solvent, obtains precursor solution after mixing evenly；The solvent is water or alcohol；The soluble rhodium compound is
Rhodium chloride or/and rhodium nitrate, the soluble-salt of the auxiliary agent are the chloride of auxiliary agent or the nitrate of auxiliary agent；The present embodiment tool
The soluble rhodium compound that body uses is rhodium nitrate, and the soluble-salt of the auxiliary agent specifically used is cobalt nitrate and nickel nitrate；It is described
The additional amount of rhodium nitrate is to guarantee rhodium content 0.5g, and the additional amount of the cobalt nitrate is to guarantee cobalt content 0.005g, the nitric acid
The additional amount of nickel is to guarantee nickel content 0.005g；
It is added in reactor Step 3: weighing pretreated active carbon described in 9.49g step 1, it will be in step 2
The precursor solution is passed into reactor after ultrasonic atomizer aerosol dispersion is at atomized drop, makes precursor solution and pre-
Active carbon stirring that treated obtains slurries after impregnating 4h, and then under agitation, with weak lye, (mass concentration is 1%
Sodium hydroxide solution) to adjust the pH value of the slurries be 10, continue to filter after stirring 4h, obtain filter cake, uses deionization later
The pH value of Washing of Filter Cake to washing lotion is in neutrality by water；The additional amount of the precursor solution is every gram of pretreated active carbon pair
20mL precursor solution should be added, 189.8mL precursor solution is added in the present embodiment into reactor altogether；
Step 4: being beaten washing in step 3 to neutral 25 times of pure water of filter cake, slurry is obtained, then use weak lye
(sodium hydroxide solution that mass concentration is 1%) adjusts the pH value of the slurry to 10, then into the slurry after adjusting pH value
Reducing agent is added and carries out reduction treatment, is successively filtered, washs and is dried later, the temperature of drying process is 120 DEG C,
The time of drying process is 8h, obtains aromatic hydrogenation rhodium/activated-carbon catalyst；The reducing agent is hydroboration
Sodium, potassium borohydride, formaldehyde, sodium formate, formic acid or hydrazine hydrate, the reducing agent that the present embodiment specifically uses are described to go back for sodium formate
The mole of former agent is 2 times of rhodium mole, and the temperature of the reduction treatment is 50 DEG C, and the time of reduction treatment is 1h.
Comparative example 1
This comparative example obtains rhodium/activated-carbon catalyst in a manner of buying from market, the quality percentage of rhodium in the catalyst
Content is 5%, and the partial size of rhodium metal is 20nm~50nm.
The concrete application method that catalyst of the present invention carries out catalytic hydrogenation to aromatic compound passes through embodiment 10 to reality
Example 13 is applied to be described.
Embodiment 10
The present embodiment carries out catalysis to aromatic compound using embodiment 1,3,5,7,9 and 1 catalyst of comparative example and adds
Hydrogen are as follows: aromatic compound, catalysts and solvents are added in autoclave, hydrogen is then passed through into autoclave,
The material in autoclave is heated simultaneously, makes aromatic compound in autoclave internal pressure 4MPa, temperature 110
Catalytic hydrogenation reaction 4h under conditions of DEG C obtains adding the aromatic compound after hydrogen；The additional amount of the catalyst is aromatic series
The 3% of compound quality, in the present embodiment, the aromatic compound is benzoic acid, and the solvent is deionized water.
Embodiment 11
The present embodiment carries out catalysis to aromatic compound using embodiment 1,3,5,7,9 and 1 catalyst of comparative example and adds
Hydrogen are as follows: aromatic compound, catalysts and solvents are added in autoclave, hydrogen is then passed through into autoclave,
The material in autoclave is heated simultaneously, makes aromatic compound in autoclave internal pressure 2MPa, temperature 80
Catalytic hydrogenation reaction 5h under conditions of DEG C obtains adding the aromatic compound after hydrogen；The additional amount of the catalyst is aromatic series
The 5% of compound quality, in the present embodiment, the aromatic compound is terephthalic acid (TPA), and the solvent is ethyl alcohol.
Embodiment 12
The present embodiment carries out catalysis to aromatic compound using embodiment 1,3,5,7,9 and 1 catalyst of comparative example and adds
Hydrogen are as follows: aromatic compound, catalysts and solvents are added in autoclave, hydrogen is then passed through into autoclave,
The material in autoclave is heated simultaneously, makes aromatic compound in autoclave internal pressure 5MPa, temperature 100
Catalytic hydrogenation reaction 2h under conditions of DEG C obtains adding the aromatic compound after hydrogen；The additional amount of the catalyst is aromatic series
The 1% of compound quality, in the present embodiment, the aromatic compound is 3- pyridone, and the solvent is deionized water.
Embodiment 13
The present embodiment carries out catalysis to aromatic compound using embodiment 1,3,5,7,9 and 1 catalyst of comparative example and adds
Hydrogen are as follows: aromatic compound, catalysts and solvents are added in autoclave, hydrogen is then passed through into autoclave,
The material in autoclave is heated simultaneously, makes aromatic compound in autoclave internal pressure 4MPa, temperature 120
Catalytic hydrogenation reaction 3h under conditions of DEG C obtains adding the aromatic compound after hydrogen；The additional amount of the catalyst is aromatic series
The 3% of compound quality, in the present embodiment, the aromatic compound is p-phenylenediamine, and the solvent is ethyl alcohol.
According to embodiment 10 to 13 the method for embodiment, embodiment 1,3,5,7,9 is respectively adopted and comparative example 1 is catalyzed
Agent carries out catalytic hydrogenation test, test result analysis process are as follows: extract reaction solution 5mL, after filtering, use is anhydrous to aromatic compound
Ethyl alcohol is diluted to 50mL, is analyzed with Shimadzu high performance liquid chromatography LC-15C, and analysis the results are shown in Table 1.
The test result of 1 different catalysts of table catalysis aromatic hydrogenation
Add from table 1, it is apparent that being suitable for above-mentioned several aromatic compounds using catalyst prepared by the present invention
Hydrogen, compared with rhodium/activated-carbon catalyst currently on the market, the product yield of catalytic hydrogenation reaction is greatly improved, and yield is super
Cross 95%.
According to embodiment 10 to 13 the method for embodiment, embodiment 1,3,5,7,9 is respectively adopted and comparative example 1 is catalyzed
Agent carries out catalytic hydrogenation repetitive test to dehydroepiandros-sterone, and test result is shown in Table 2.
2 different catalysts of table repeat the test result for being catalyzed aromatic hydrogenation
, it is apparent that catalyst performance stabilised prepared by method of the invention, has repeatable well from table 2
Property.
It follows that aromatic hydrogenation provided by the invention rhodium/activated-carbon catalyst, preparation and catalysis side
Method is easy to operate, and raw material is easy to get, large-scale industrial production easy to accomplish, and it is convenient to recycle after the catalyst use of preparation, can be real
Production, the recycling, reproduction of existing noble metal, lose in removal process less, greatly reduce the production cost of catalyst.This is urged
Agent is suitable for aromatic compound catalytic hydrogenation, and product yield is more than 95%, and catalyst performance stabilised, has and well may be used
Repeatability.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (10)
1. a kind of aromatic hydrogenation rhodium/activated-carbon catalyst preparation method, which is characterized in that the catalyst is by living
Property charcoal and load metal component composition on the activated carbon, the metal component is rhodium and auxiliary agent, the quality of rhodium in the catalyst
Percentage composition is 1%~5%, and the mass percentage of auxiliary agent is 0.1%~1%；The auxiliary agent be platinum, palladium, ruthenium, molybdenum, cobalt and
In nickel any one or it is two or more；The preparation method of the catalyst the following steps are included:
1h~2h is boiled Step 1: active carbon is added in the sodium hydrate aqueous solution that concentration is 10mol/L~15mol/L,
It adopts to be washed with deionized to the pH value of washing lotion after natural cooling and be in neutrality, pretreated active carbon is obtained after filtering；
Step 2: the soluble-salt of soluble rhodium compound and auxiliary agent is dissolved in solvent, presoma is obtained after mixing evenly
Solution；The solvent is water or alcohol；
Step 3: carrying out ultrasonic atomizatio processing, atomized liquid to precursor solution described in step 2 using ultrasonic atomizer
Drop, then the atomized drop is passed into and is loaded in the reactor of pretreated active carbon described in step 1, stirring is equal
Dipping, obtains slurries after even, then adjusts the pH value of the slurries to 9~12 using lye, continues to filter after stirring 1h~5h,
Filter cake is obtained, washing is carried out to filter cake using deionized water until the pH value of washing lotion is in neutrality later；Presoma in the slurries
The additional amount of solution, which is that every gram of pretreated active carbon is corresponding, is added 20mL precursor solution；
Step 4: the filter cake after washing in step 3 is beaten with pure water, slurry is obtained, then the slurry is adjusted using lye
PH value is 9~14, and reducing agent then is added into the slurry after adjusting pH value and carries out reduction treatment, be successively filtered later,
Washing and drying process, obtain aromatic hydrogenation rhodium/activated-carbon catalyst.
2. aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst preparation method, feature exist
In the mass percentage of rhodium is 1%~5% in the catalyst, and the mass percentage of auxiliary agent is 0.4%~0.6%.
3. aromatic hydrogenation according to claim 2 rhodium/activated-carbon catalyst preparation method, feature exist
In the mass percentage of rhodium is 5% in the catalyst, and the mass percentage of auxiliary agent is 0.5%.
4. aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst preparation method, feature exist
In the partial size of active carbon is 200 mesh~800 mesh in the catalyst, and the specific surface area of the active carbon is 800m2/ g~
1500m2/ g, the average grain diameter of the rhodium are 20nm~50nm.
5. aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst preparation method, feature exist
In soluble rhodium compound described in step 2 is rhodium chloride or/and rhodium nitrate.
6. aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst preparation method, feature exist
In the soluble-salt of auxiliary agent described in step 2 is the chloride of auxiliary agent or the nitrate of auxiliary agent.
7. aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst preparation method, feature exist
In reducing agent described in step 4 is sodium borohydride, potassium borohydride, formaldehyde, sodium formate, formic acid or hydrazine hydrate, the reducing agent
Mole be 2~5 times of rhodium mole, the temperature of the reduction treatment is 50 DEG C~100 DEG C, the time of the reduction treatment
For 1h~3h.
8. aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst preparation method, feature exist
In the temperature of drying process described in step 4 is 80 DEG C~120 DEG C, and the time of the drying process is 5h~12h.
9. a kind of application is catalyzed aromatic compound such as the catalyst of any claim preparation in claim 1 to 8
Add the method for hydrogen, which is characterized in that this method are as follows: aromatic compound, catalysts and solvents are added in autoclave, so
It is passed through hydrogen in backward autoclave, while heating the material in autoclave, makes aromatic compound in reaction under high pressure
Kettle internal pressure is 2MPa~5MPa, and temperature is catalytic hydrogenation reaction 2h~5h under conditions of 80 DEG C~120 DEG C, is obtained after adding hydrogen
Aromatic compound；The additional amount of the catalyst be aromatic compound amount of substance 1%~5%, the solvent be go from
Sub- water or ethyl alcohol.
10. according to the method described in claim 9, it is characterized in that, the internal pressure of the autoclave be 4MPa, it is described
The temperature of catalytic hydrogenation reaction is 110 DEG C, and the time of the catalytic hydrogenation reaction is 4h, and the additional amount of the catalyst is fragrance
The 3% of compounds of group quality.
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| CN108786804B (en) * | 2018-05-31 | 2021-01-26 | 王鹏飞 | Hydrogenation catalyst, preparation method and application thereof |
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| CN110743544B (en) * | 2019-11-07 | 2023-02-24 | 西安凯立新材料股份有限公司 | Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof |
| CN112108139B (en) * | 2020-09-29 | 2023-05-09 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing aniline by nitrobenzene liquid phase hydrogenation and preparation method thereof |
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