CN106732564A - The preparation method and application of aromatic hydrogenation rhodium/activated-carbon catalyst - Google Patents
The preparation method and application of aromatic hydrogenation rhodium/activated-carbon catalyst Download PDFInfo
- Publication number
- CN106732564A CN106732564A CN201611097751.5A CN201611097751A CN106732564A CN 106732564 A CN106732564 A CN 106732564A CN 201611097751 A CN201611097751 A CN 201611097751A CN 106732564 A CN106732564 A CN 106732564A
- Authority
- CN
- China
- Prior art keywords
- rhodium
- catalyst
- activated
- auxiliary agent
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/892—Nickel and noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- 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
- C07D211/40—Oxygen atoms
Abstract
The invention provides a kind of preparation method of aromatic hydrogenation rhodium/activated-carbon catalyst, comprise the following steps:First, activated carbon is pre-processed;2nd, the soluble-salt of soluble rhodium compound and auxiliary agent is dissolved in solvent, obtains precursor solution;3rd, will be added after precursor solution aerosol dispersion in activated carbon, slurries are obtained after stirring, then adjusted pH value, filtering and wash;4th, reduction treatment is carried out after being beaten with pure water, carries out being filtered, washed and dried treatment afterwards successively, obtain aromatic hydrogenation rhodium/activated-carbon catalyst.Present invention also offers the application process of the catalyst.Catalyst of the present invention is made up of activated carbon and the metal component being carried on the activated carbon, the metal component is rhodium and auxiliary agent, and the catalyst is suitable to aromatic compound catalytic hydrogenation, and product yield is more than 95%, catalyst performance stabilised, and with good repeatability.
Description
Technical field
The invention belongs to noble metal catalyst technical field, and in particular to a kind of aromatic hydrogenation rhodium/activity
The preparation method and application of Pd/carbon catalyst.
Background technology
In the building-up process of many fine chemicals and its intermediate, can all be related to the catalytic hydrogenation of aromatic compound anti-
Should.Relative to the compound for containing the groups such as carbon-carbon double bond, nitro, carbonyl, the catalytic hydrogenation reaction of aromatic compound will be stranded
It is much more difficult.Typical catalyst such as the Raney nickel that uses is, it is necessary to reacted at high temperature under high pressure at present, and reaction activity
All poor with selectivity, accessory substance is more.And load type rhodium catalyst has activity well, Ke Yi to aromatic compound
Reacted under the conditions of relatively low pressure and temperature, particularly to various aromatic compound catalysis containing phenyl ring and pyridine ring
Hydrogenation, obtains the reaction of cyclohexyl and piperidines ring derivatives.And the accessory substance and three deserted citys for producing are fewer, meet country green
The requirement that colour circle is protected.
At present, the load type rhodium catalyst of aromatic hydrogenation is mainly activated carbon supported nanometer rhodium metal and urges
Agent, such catalyst common problem be how on the basis of existing level further improve catalyst activity and
Selectivity.And suitable absorbent charcoal carrier is selected, and appropriate pre-treatment is carried out, in conjunction with ultrasonic atomizatio dispersing apparatus are utilized, can
To improve the form of decentralization of the noble metal nano particles on absorbent charcoal carrier, granular size and nano particle well,
So as to further improve the activity and selectivity of rhodium/activated-carbon catalyst.
The content of the invention
The technical problems to be solved by the invention are for above-mentioned the deficiencies in the prior art, there is provided a kind of aromatic compound
The thing hydrogenation preparation method of rhodium/activated-carbon catalyst.The method is simple to operate, and raw material is easy to get, and easily realizes large-scale industry
Metaplasia is produced, and reclaims convenient after the catalyst use of preparation, is capable of achieving production, recovery, the reproduction of noble metal, is damaged in removal process
Mistake is less, greatly reduces the production cost of catalyst.Catalyst prepared by the method is applied to aromatic compound catalysis and adds
Hydrogen, product yield is more than 95%, and catalyst performance stabilised, with good repeatability.
In order to solve the above technical problems, the technical solution adopted by the present invention is:A kind of aromatic hydrogenation rhodium/work
Property Pd/carbon catalyst preparation method, it is characterised in that the catalyst is by activated carbon and load metal component group on the activated carbon
Into the metal component is rhodium and auxiliary agent, and the weight/mass percentage composition of rhodium is 1%~5%, the quality hundred of auxiliary agent in the catalyst
Content is divided to be 0.1%~1%;The auxiliary agent is any one in platinum, palladium, ruthenium, molybdenum, cobalt and nickel or two or more;The catalysis
The preparation method of agent is comprised the following steps:
Step one, activated carbon is added to concentration be 10mol/L~15mol/L sodium hydrate aqueous solution in boil 1h~
2h, is adopted after natural cooling and the pH value to washing lotion is washed with deionized in neutrality, and pretreated activated carbon is obtained after filtering;
Step 2, the soluble-salt of soluble rhodium compound and auxiliary agent is dissolved in solvent, before being obtained after stirring
Drive liquid solution;The solvent is water or alcohol;
Step 3, ultrasonic atomizatio treatment is carried out to precursor solution described in step 2 using ultrasonic atomizer, obtain mist
Change drop, then the atomized drop is passed into is loaded with described in step one in the reactor of pretreated activated carbon, stir
Uniform rear dipping is mixed, slurries are obtained, the pH value of the slurries is then adjusted using alkali lye to 9~12, after continuing stirring 1h~5h
Filtering, obtains filter cake, and washing is carried out to filter cake using deionized water afterwards until the pH value of washing lotion is in neutrality;Before in the slurries
The volume for driving liquid solution is that every gram of pretreated activated carbon correspondence adds 20mL precursor solutions;
Step 4, will be washed in step 3 after filter cake be beaten with pure water, obtain slurry, then the slurry is adjusted using alkali lye
The pH value of material is 9~14, then carries out reduction treatment to addition reducing agent in the slurry after regulation pH value, is carried out successively afterwards
Filter, washing and dried process, obtain aromatic hydrogenation rhodium/activated-carbon catalyst.
The preparation method of above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst, it is characterised in that the catalysis
The weight/mass percentage composition of rhodium is 1%~5% in agent, and the weight/mass percentage composition of auxiliary agent is 0.4%~0.6%.
The preparation method of above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst, it is characterised in that the catalysis
The weight/mass percentage composition of rhodium is 5% in agent, and the weight/mass percentage composition of auxiliary agent is 0.5%.
The preparation method of above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst, it is characterised in that the catalysis
The particle diameter of activated carbon is 200 mesh~800 mesh in agent, and the specific surface area of the activated carbon is 800m2/ g~1500m2/ g, the rhodium
Average grain diameter be 20nm~50nm.
The preparation method of above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst, it is characterised in that in step 2
The soluble rhodium compound is rhodium chloride or/and rhodium nitrate.
The preparation method of above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst, it is characterised in that in step 2
The soluble-salt of the auxiliary agent is the chloride of auxiliary agent or the nitrate of auxiliary agent.
The preparation method of above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst, it is characterised 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 is 50 DEG C~100 DEG C, and the time of the reduction treatment is 1h~3h.
The preparation method of above-mentioned aromatic hydrogenation rhodium/activated-carbon catalyst, it is characterised in that in step 4
The temperature of the dried process is 80 DEG C~100 DEG C, and the time of the dried process is 5h~12h.
In addition, being catalyzed to aromatic compound present invention also offers catalyst prepared by a kind of application above method
The method of hydrogenation, it is characterised in that the method is:By aromatic compound, catalysts and solvents add autoclave in, so
Hydrogen is passed through 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, after being hydrogenated with
Aromatic compound;The addition of the catalyst for aromatic compound amount of substance 1%~5%, the solvent for go from
Sub- water or ethanol.
Above-mentioned method, it is characterised 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 addition of the catalyst is aromatic compound amount of substance
3%.
The present invention has advantages below compared with prior art:
1st, rhodium Pd/carbon catalyst prepared by the present invention be the activated carbon with specially treated as carrier, Noble Metal Rhodium and auxiliary agent
Metallic element is highly dispersed on absorbent charcoal carrier, and rhodium metal particle diameter is 20nm~50nm in catalyst, and in activated carbon
It is evenly distributed on carrier, with good catalysis activity and selectivity.
2nd, 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 dispersed and activity of rhodium Pd/carbon catalyst is improve.
3rd, the preparation method of catalyst of the present invention is easy to operate, and raw material is easy to get, and easily realizes large-scale industrial production.Prepare
Catalyst use after reclaim convenient, be capable of achieving the production-recovery-reproduction of noble metal, lose less in removal process, significantly
Reduce the production cost of catalyst.
4th, catalyst prepared by the present invention is applied to aromatic compound, particularly containing phenyl ring and pyridine cycle compound
Catalytic hydrogenation, product yield substantially increases the yield of product more than 95%, significantly reduces production cost, and belong to efficient
Green environmental protection technique.
5th, the catalyst life stabilization that prepared by the present invention, can time use, reduce and be intended for single use the cost of catalyst and ask
Topic, it is easy to accomplish industrialization.
6th, the catalysis process of catalyst of the present invention has the advantages that simple step, mild condition, environmental protection, is that such is urged
The large-scale application of agent provides favourable condition.
The present invention is described in further detail with reference to embodiment.
Specific embodiment
Embodiment 1
The catalyst that the present embodiment need to be prepared be aromatic hydrogenation rhodium/activated-carbon catalyst, the catalyst by
Activated carbon and the metal component composition being carried on the activated carbon, the particle diameter of activated carbon is 200 mesh~300 mesh, the activity
The specific surface area of charcoal is 1200m2/ g, the metal component is rhodium and auxiliary agent, and the average grain diameter of the rhodium is 20nm~50nm, is helped
Agent is any one in platinum, palladium, ruthenium, molybdenum, cobalt and nickel or two or more, and the auxiliary agent that the present embodiment is specifically selected is cobalt, described
The weight/mass percentage composition of rhodium is 5% in catalyst, and the weight/mass percentage composition of auxiliary agent is 1%.The present embodiment aromatic compound adds
The preparation method of hydrogen rhodium/activated-carbon catalyst is comprised the following steps:
Step one, 10g activated carbons are added to concentration be 12mol/L sodium hydrate aqueous solution in stir, then
2h is boiled in heating, and heating is stopped afterwards, after the mixed material natural cooling after boiling, is washed with deionized to the pH of washing lotion
Value obtains pretreated activated carbon in neutrality 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, precursor solution is obtained after stirring;The solvent is water or alcohol;The soluble rhodium compound is
Rhodium chloride or/and rhodium nitrate, the soluble-salt of the auxiliary agent is the chloride of auxiliary agent or the nitrate of auxiliary agent;The present embodiment has
The soluble rhodium compound that body is used is rhodium chloride, and the soluble-salt of the specific auxiliary agent for using is cobalt chloride ammonium;The trichlorine
Change the addition of rhodium to ensure rhodium content 0.5g, the addition of the cobalt chloride is guarantee cobalt content 0.1g;
Step 3, weigh pretreated activated carbon described in 9.4g steps one and be added in reactor, by step 2
The precursor solution, into being passed into reactor after atomized drop, makes precursor solution and pre- through ultrasonic atomizer aerosol dispersion
Slurries are obtained after activated carbon stirring dipping 2h after treatment, then under agitation, (mass concentration is 1% with weak lye
Sodium hydroxide solution) to adjust the pH value of the slurries be 10, continues to be filtered after stirring 3h, filter cake is obtained, afterwards using deionization
Water is by the pH value of Washing of Filter Cake to washing lotion in neutrality;The addition of the precursor solution is every gram of pretreated activated carbon pair
20mL precursor solutions should be added, the present embodiment is altogether to addition 188mL precursor solutions in reactor;
Step 4, will be washed in step 3 to neutral filter cake and be beaten with 20 times of pure water, obtain slurry, then use weak lye
(mass concentration is 1% sodium hydroxide solution) adjusts the pH value of the slurry to 9, then in the slurry after regulation pH value plus
Entering reducing agent carries out reduction treatment, carries out being filtered, washed and dried treatment afterwards successively, and the temperature of dried process is 100 DEG C, is done
The time of dry treatment 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 is specifically used 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
Activated carbon and the metal component composition being carried on the activated carbon, the particle diameter of activated carbon is 200 mesh~400 mesh, the activity
The specific surface area of charcoal is 1500m2/ g, the metal component is rhodium and auxiliary agent, and the average grain diameter of the rhodium is 20nm~50nm, is helped
Agent is any one in platinum, palladium, ruthenium, molybdenum, cobalt and nickel or two or more, and the auxiliary agent that the present embodiment is specifically selected is ruthenium, described
The weight/mass percentage composition of rhodium is 5% in catalyst, and the weight/mass percentage composition of auxiliary agent is 0.5%.The present embodiment aromatic compound
The preparation method of hydrogenation rhodium/activated-carbon catalyst is comprised the following steps:
Step one, 10g activated carbons are added to concentration be 15mol/L sodium hydrate aqueous solution in stir, then
1h is boiled in heating, and heating is stopped afterwards, after the mixed material natural cooling after boiling, is washed with deionized to the pH of washing lotion
Value obtains pretreated activated carbon in neutrality 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, precursor solution is obtained after stirring;The solvent is water or alcohol;The soluble rhodium compound is
Rhodium chloride or/and rhodium nitrate, the soluble-salt of the auxiliary agent is the chloride of auxiliary agent or the nitrate of auxiliary agent;The present embodiment has
The soluble rhodium compound that body is used is rhodium chloride and rhodium nitrate, and the soluble-salt of the specific auxiliary agent for using is ruthenium trichloride;
To ensure rhodium content 0.4g, the addition of the rhodium nitrate is 0.1g, institute to ensure rhodium content to the addition of the rhodium chloride
The addition of ruthenium trichloride is stated to ensure ruthenium content 0.05g;
Step 3, weigh pretreated activated carbon described in 9.45g steps one and be added in reactor, by step 2
The precursor solution, into being passed into reactor after atomized drop, makes precursor solution and pre- through ultrasonic atomizer aerosol dispersion
Slurries are obtained after activated carbon stirring dipping 6h after treatment, then under agitation, (mass concentration is 1% with weak lye
Sodium hydroxide solution) to adjust the pH value of the slurries be 9, continues to be filtered after stirring 1h, filter cake is obtained, afterwards using deionized water
By the pH value of Washing of Filter Cake to washing lotion in neutrality;The addition of the precursor solution is every gram of pretreated activated carbon correspondence
20mL precursor solutions are added, the present embodiment is altogether to addition 189mL precursor solutions in reactor;
Step 4, will be washed in step 3 to neutral filter cake and be beaten with 20 times of pure water, obtain slurry, then use weak lye
(mass concentration is 1% sodium hydroxide solution) adjusts the pH value of the slurry to 14, then in the slurry after regulation pH value
Adding reducing agent carries out reduction treatment, carries out being filtered, washed and dried treatment afterwards successively, and the temperature of dried process is 120 DEG C,
The time of dried 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 is specifically used is potassium borohydride, described
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
It is 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
Activated carbon and the metal component composition being carried on the activated carbon, the particle diameter of activated carbon is 250 mesh~300 mesh, the activity
The specific surface area of charcoal is 1200m2/ g, the metal component is 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 present embodiment specifically select auxiliary agent for platinum, ruthenium and
Nickel, the weight/mass percentage composition of rhodium is 5% in the catalyst, and the weight/mass percentage composition of auxiliary agent is 0.4%.The present embodiment aromatic series
The preparation method of compound hydrogenation rhodium/activated-carbon catalyst is comprised the following steps:
Step one, 10g activated carbons are added to concentration be 10mol/L sodium hydrate aqueous solution in stir, then
2h is boiled in heating, and heating is stopped afterwards, after the mixed material natural cooling after boiling, is washed with deionized to the pH of washing lotion
Value obtains pretreated activated carbon in neutrality 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, precursor solution is obtained after stirring;The solvent is water or alcohol;The soluble rhodium compound is
Rhodium chloride or/and rhodium nitrate, the soluble-salt of the auxiliary agent is the chloride of auxiliary agent or the nitrate of auxiliary agent;The present embodiment has
The soluble rhodium compound that body is used is rhodium chloride and rhodium nitrate, and the soluble-salt of the specific auxiliary agent for using is platinum chloride, three
Ruthenic chloride and nickel nitrate;To ensure rhodium content 0.1g, the addition of the rhodium nitrate is guarantee to the addition of the rhodium chloride
Rhodium content is 0.4g, and to ensure ruthenium content 0.01g, the addition of the cobalt chloride is guarantee cobalt to the addition of the ruthenium trichloride
Content 0.01g, the addition of the nickel nitrate is guarantee nickel content 0.02g;
Step 3, weigh pretreated activated carbon described in 9.46g steps one and be added in reactor, by step 2
The precursor solution, into being passed into reactor after atomized drop, makes precursor solution and pre- through ultrasonic atomizer aerosol dispersion
Slurries are obtained after activated carbon stirring dipping 3h after treatment, then under agitation, (mass concentration is 1% with weak lye
Sodium hydroxide solution) to adjust the pH value of the slurries be 11, continues to be filtered after stirring 5h, filter cake is obtained, afterwards using deionization
Water is by the pH value of Washing of Filter Cake to washing lotion in neutrality;The addition of the precursor solution is every gram of pretreated activated carbon pair
20mL precursor solutions should be added, the present embodiment is altogether to addition 189.2mL precursor solutions in reactor;
Step 4, will be washed in step 3 to neutral filter cake and be beaten with 20 times of pure water, obtain slurry, then use weak lye
(mass concentration is 1% sodium hydroxide solution) adjusts the pH value of the slurry to 11, then in the slurry after regulation pH value
Adding reducing agent carries out reduction treatment, carries out being filtered, washed and dried treatment afterwards successively, and the temperature of dried process is 80 DEG C,
The time of dried 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 is specifically used is hydrazine hydrate, described to go back
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 more than four kinds, or be three kinds in ruthenium, palladium, cobalt and nickel, or be two kinds in palladium, cobalt and nickel and platinum
Mixture, or be palladium or cobalt and platinum and the mixture of ruthenium.
Embodiment 7
The catalyst that the present embodiment need to be prepared be aromatic hydrogenation rhodium/activated-carbon catalyst, the catalyst by
Activated carbon and the metal component composition being carried on the activated carbon, the particle diameter of activated carbon is 300 mesh~500 mesh, the activity
The specific surface area of charcoal is 800m2/ g, the metal component is rhodium and auxiliary agent, and the average grain diameter of the rhodium is 20nm~50nm, is helped
Agent is any one in platinum, palladium, ruthenium, molybdenum, cobalt and nickel or two or more, and the auxiliary agent that the present embodiment is specifically selected is cobalt, ruthenium, palladium
And nickel, the weight/mass percentage composition of rhodium is 5% in the catalyst, and the weight/mass percentage composition of auxiliary agent is 0.6%.The present embodiment fragrance
The preparation method of compounds of group hydrogenation rhodium/activated-carbon catalyst is comprised the following steps:
Step one, 10g activated carbons are added to concentration be 15mol/L sodium hydrate aqueous solution in stir, then
1.5h is boiled in heating, and heating is stopped afterwards, after the mixed material natural cooling after boiling, is washed with deionized to washing lotion
PH value obtains pretreated activated carbon in neutrality 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, precursor solution is obtained after stirring;The solvent is water or alcohol;The soluble rhodium compound is
Rhodium chloride or/and rhodium nitrate, the soluble-salt of the auxiliary agent is the chloride of auxiliary agent or the nitrate of auxiliary agent;The present embodiment has
The soluble rhodium compound that body is used is rhodium chloride, and the soluble-salt of the specific auxiliary agent for using is cobalt chloride, ruthenium trichloride, nitre
Sour palladium and nickel nitrate;To ensure rhodium content 0.5g, the addition of the ruthenium trichloride is guarantee to the addition of the rhodium chloride
Ruthenium content 0.01g, to ensure cobalt content 0.01g, the addition of the nickel nitrate is to ensure that nickel contains to the addition of the cobalt chloride
Amount 0.01g, the addition of the palladium nitrate is guarantee palladium content 0.01g;
Step 3, weigh pretreated activated carbon described in 9.44g steps one and be added in reactor, by step 2
The precursor solution, into being passed into reactor after atomized drop, makes precursor solution and pre- through ultrasonic atomizer aerosol dispersion
Slurries are obtained after activated carbon stirring dipping 4h after treatment, then under agitation, (mass concentration is 1% with weak lye
Sodium hydroxide solution) to adjust the pH value of the slurries be 12, continues to be filtered after stirring 2h, filter cake is obtained, afterwards using deionization
Water is by the pH value of Washing of Filter Cake to washing lotion in neutrality;The addition of the precursor solution is every gram of pretreated activated carbon pair
20mL precursor solutions should be added, the present embodiment is altogether to addition 188mL precursor solutions in reactor;
Step 4, will be washed in step 3 to neutral filter cake and be beaten with 30 times of pure water, obtain slurry, then use weak lye
(mass concentration is 1% sodium hydroxide solution) adjusts the pH value of the slurry to 12, then in the slurry after regulation pH value
Adding reducing agent carries out reduction treatment, carries out being filtered, washed and dried treatment afterwards successively, and the temperature of dried process is 90 DEG C,
The time of dried 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 is specifically used 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
Activated carbon and the metal component composition being carried on the activated carbon, the particle diameter of activated carbon is 500 mesh~800 mesh, the activity
The specific surface area of charcoal is 1500m2/ g, the metal component is 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 present embodiment specifically select auxiliary agent be cobalt and nickel,
The weight/mass percentage composition of rhodium is 5% in the catalyst, and the weight/mass percentage composition of auxiliary agent is 0.1%.The present embodiment aromatic series
The preparation method of compound hydrogenation rhodium/activated-carbon catalyst is comprised the following steps:
Step one, 10g activated carbons are added to concentration be 14mol/L sodium hydrate aqueous solution in stir, then
2h is boiled in heating, and heating is stopped afterwards, after the mixed material natural cooling after boiling, is washed with deionized to the pH of washing lotion
Value obtains pretreated activated carbon in neutrality 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, precursor solution is obtained after stirring;The solvent is water or alcohol;The soluble rhodium compound is
Rhodium chloride or/and rhodium nitrate, the soluble-salt of the auxiliary agent is the chloride of auxiliary agent or the nitrate of auxiliary agent;The present embodiment has
The soluble rhodium compound that body is used is rhodium nitrate, and the soluble-salt of the specific auxiliary agent for using is cobalt nitrate and nickel nitrate;It is described
To ensure rhodium content 0.5g, the addition of the cobalt nitrate is guarantee cobalt content 0.005g, the nitric acid to the addition of rhodium nitrate
The addition of nickel is guarantee nickel content 0.005g;
Step 3, weigh pretreated activated carbon described in 9.49g steps one and be added in reactor, by step 2
The precursor solution, into being passed into reactor after atomized drop, makes precursor solution and pre- through ultrasonic atomizer aerosol dispersion
Slurries are obtained after activated carbon stirring dipping 4h after treatment, then under agitation, (mass concentration is 1% with weak lye
Sodium hydroxide solution) to adjust the pH value of the slurries be 10, continues to be filtered after stirring 4h, filter cake is obtained, afterwards using deionization
Water is by the pH value of Washing of Filter Cake to washing lotion in neutrality;The addition of the precursor solution is every gram of pretreated activated carbon pair
20mL precursor solutions should be added, the present embodiment is altogether to addition 189.8mL precursor solutions in reactor;
Step 4, will be washed in step 3 to neutral filter cake and be beaten with 25 times of pure water, obtain slurry, then use weak lye
(mass concentration is 1% sodium hydroxide solution) adjusts the pH value of the slurry to 10, then in the slurry after regulation pH value
Adding reducing agent carries out reduction treatment, carries out being filtered, washed and dried treatment afterwards successively, and the temperature of dried process is 120 DEG C,
The time of dried 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 is specifically used is sodium formate, described to go back
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 the way of being bought from market, the quality percentage of rhodium in the catalyst
Content is 5%, and the particle diameter of rhodium metal is 20nm~50nm.
Catalyst of the present invention carries out the concrete application method of catalytic hydrogenation to aromatic compound by embodiment 10 to reality
Example 13 is applied to be described.
Embodiment 10
The present embodiment carries out catalysis to aromatic compound and adds using embodiment 1,3,5,7,9 and the catalyst of comparative example 1
Hydrogen is:During aromatic compound, catalysts and solvents are added into autoclave, then to being passed through hydrogen in autoclave,
The material in autoclave being heated simultaneously, making aromatic compound be 4MPa in autoclave internal pressure, temperature is 110
Catalytic hydrogenation reaction 4h under conditions of DEG C, the aromatic compound after being hydrogenated with;The addition 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 and adds using embodiment 1,3,5,7,9 and the catalyst of comparative example 1
Hydrogen is:During aromatic compound, catalysts and solvents are added into autoclave, then to being passed through hydrogen in autoclave,
The material in autoclave being heated simultaneously, making aromatic compound be 2MPa in autoclave internal pressure, temperature is 80
Catalytic hydrogenation reaction 5h under conditions of DEG C, the aromatic compound after being hydrogenated with;The addition 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 ethanol.
Embodiment 12
The present embodiment carries out catalysis to aromatic compound and adds using embodiment 1,3,5,7,9 and the catalyst of comparative example 1
Hydrogen is:During aromatic compound, catalysts and solvents are added into autoclave, then to being passed through hydrogen in autoclave,
The material in autoclave being heated simultaneously, making aromatic compound be 5MPa in autoclave internal pressure, temperature is 100
Catalytic hydrogenation reaction 2h under conditions of DEG C, the aromatic compound after being hydrogenated with;The addition of the catalyst is aromatic series
The 1% of compound quality, in the present embodiment, the aromatic compound is 3- pyridones, and the solvent is deionized water.
Embodiment 13
The present embodiment carries out catalysis to aromatic compound and adds using embodiment 1,3,5,7,9 and the catalyst of comparative example 1
Hydrogen is:During aromatic compound, catalysts and solvents are added into autoclave, then to being passed through hydrogen in autoclave,
The material in autoclave being heated simultaneously, making aromatic compound be 4MPa in autoclave internal pressure, temperature is 120
Catalytic hydrogenation reaction 3h under conditions of DEG C, the aromatic compound after being hydrogenated with;The addition 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 ethanol.
According to embodiment 10 to the methods described of embodiment 13, embodiment 1,3,5,7,9 is respectively adopted and comparative example 1 is catalyzed
Agent carries out catalytic hydrogenation experiment to aromatic compound, and test result analysis process is:5mL is extracted reaction solution, after filtering, with anhydrous
Ethanol is diluted to 50mL, is analyzed with Shimadzu high performance liquid chromatography LC-15C, and analysis result is shown in Table 1.
The different catalysts of table 1 are catalyzed the result of the test of aromatic hydrogenation
, it is apparent that being added suitable for above-mentioned several aromatic compounds using catalyst prepared by the present invention from table 1
Hydrogen, compared with rhodium/activated-carbon catalyst in the market, the product yield of catalytic hydrogenation reaction is greatly improved, and yield surpasses
Cross 95%.
According to embodiment 10 to the methods described of embodiment 13, embodiment 1,3,5,7,9 is respectively adopted and comparative example 1 is catalyzed
Agent carries out catalytic hydrogenation replica test to dehydroepiandros-sterone, and result of the test is shown in Table 2.
The different catalysts of table 2 repeat to be catalyzed the result of the test of aromatic hydrogenation
, it is apparent that the catalyst performance stabilised of method of the present invention preparation, repeats with good from table 2
Property.
It follows that aromatic hydrogenation rhodium/activated-carbon catalyst that the present invention is provided, it is prepared and catalysis side
Method is simple to operate, and raw material is easy to get, and easily realizes large-scale industrial production, reclaims convenient after the catalyst use of preparation, can be real
Production, recovery, the reproduction of existing noble metal, lose less in removal process, greatly reduce the production cost of catalyst.This is urged
Agent is applied to aromatic compound catalytic hydrogenation, and product yield is more than 95%, and catalyst performance stabilised, with well may be used
Repeatability.
The above, is only presently preferred embodiments of the present invention, and not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art is substantially made to above example, still fall within technical solution of the present invention
Protection domain in.
Claims (10)
1. the preparation method of a kind of aromatic hydrogenation rhodium/activated-carbon catalyst, it is characterised in that the catalyst is by living
Property charcoal and load on the activated carbon metal component composition, the metal component be rhodium and auxiliary agent, the quality of rhodium in the catalyst
Percentage composition is 1%~5%, and the weight/mass percentage composition 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 is comprised the following steps:
Step one, activated carbon is added to concentration be 10mol/L~15mol/L sodium hydrate aqueous solution in boil 1h~2h,
Adopted after natural cooling and the pH value to washing lotion is washed with deionized in neutrality, pretreated activated 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 stirring
Solution;The solvent is water or alcohol;
Step 3, ultrasonic atomizatio treatment, atomized liquid are carried out to precursor solution described in step 2 using ultrasonic atomizer
Drop, then the atomized drop is passed into is loaded with described in step one in the reactor of pretreated activated carbon, stirring is equal
Dipping, obtains slurries after even, and the pH value of the slurries is then adjusted using alkali lye to 9~12, continues to be filtered after stirring 1h~5h,
Filter cake is obtained, washing is carried out to filter cake using deionized water afterwards until the pH value of washing lotion is in neutrality;Presoma in the slurries
The volume of solution is that every gram of pretreated activated carbon correspondence adds 20mL precursor solutions;
Step 4, will be washed in step 3 after filter cake be beaten with pure water, obtain slurry, then the slurry is adjusted using alkali lye
PH value is 9~14, then carries out reduction treatment to addition reducing agent in the slurry after regulation pH value, filtered successively afterwards,
Washing and dried process, obtain aromatic hydrogenation rhodium/activated-carbon catalyst.
2. the preparation method of aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst, its feature exists
In the weight/mass percentage composition of rhodium is 1%~5% in the catalyst, and the weight/mass percentage composition of auxiliary agent is 0.4%~0.6%.
3. the preparation method of aromatic hydrogenation according to claim 2 rhodium/activated-carbon catalyst, its feature exists
In the weight/mass percentage composition of rhodium is 5% in the catalyst, and the weight/mass percentage composition of auxiliary agent is 0.5%.
4. the preparation method of aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst, its feature exists
In the particle diameter of activated carbon is 200 mesh~800 mesh in the catalyst, and the specific surface area of the activated carbon is 800m2/ g~
1500m2/ g, the average grain diameter of the rhodium is 20nm~50nm.
5. the preparation method of aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst, its feature exists
In soluble rhodium compound described in step 2 is rhodium chloride or/and rhodium nitrate.
6. the preparation method of aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst, its feature exists
In the soluble-salt of auxiliary agent described in step 2 is the chloride of auxiliary agent or the nitrate of auxiliary agent.
7. the preparation method of aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst, its feature exists
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
It is 1h~3h.
8. the preparation method of aromatic hydrogenation according to claim 1 rhodium/activated-carbon catalyst, its feature exists
In the temperature of dried process described in step 4 is 80 DEG C~120 DEG C, and the time of the dried process is 5h~12h.
9. it is a kind of to apply the catalyst prepared such as any claim in claim 1 to 8 to be catalyzed aromatic compound
The method of hydrogenation, it is characterised in that the method is:By aromatic compound, catalysts and solvents add autoclave in, so
Hydrogen is passed through 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, after being hydrogenated with
Aromatic compound;The addition of the catalyst for aromatic compound amount of substance 1%~5%, the solvent for go from
Sub- water or ethanol.
10. method according to claim 9, it is characterised in that the internal pressure of the autoclave is 4MPa, described
The temperature of catalytic hydrogenation reaction is 110 DEG C, and the time of the catalytic hydrogenation reaction is 4h, and the addition of the catalyst is fragrance
The 3% of compounds of group quality.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611097751.5A CN106732564B (en) | 2016-12-03 | 2016-12-03 | Aromatic hydrogenation rhodium/activated-carbon catalyst preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611097751.5A CN106732564B (en) | 2016-12-03 | 2016-12-03 | Aromatic hydrogenation rhodium/activated-carbon catalyst preparation method and application |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106732564A true CN106732564A (en) | 2017-05-31 |
CN106732564B CN106732564B (en) | 2019-06-14 |
Family
ID=58884297
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611097751.5A Active CN106732564B (en) | 2016-12-03 | 2016-12-03 | Aromatic hydrogenation rhodium/activated-carbon catalyst preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106732564B (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107442134A (en) * | 2017-08-30 | 2017-12-08 | 江苏大学 | A kind of rhodium/nickel alloy nanocatalyst and its preparation method and application |
CN107715870A (en) * | 2017-10-13 | 2018-02-23 | 西安凯立新材料股份有限公司 | A kind of preparation method and application for preparing L aminopropanol ruthenium Pd/carbon catalysts |
CN108786804A (en) * | 2018-05-31 | 2018-11-13 | 王鹏飞 | Hydrogenation catalyst, preparation method and application |
CN110624537A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Preparation method of phthalate hydrogenation catalyst |
CN110624571A (en) * | 2019-09-27 | 2019-12-31 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing 3, 5-dichloroaniline and preparation method and application thereof |
CN110743567A (en) * | 2019-11-07 | 2020-02-04 | 西安凯立新材料股份有限公司 | α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde and preparation method and application thereof |
CN110743544A (en) * | 2019-11-07 | 2020-02-04 | 西安凯立新材料股份有限公司 | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof |
CN110756198A (en) * | 2019-11-07 | 2020-02-07 | 西安凯立新材料股份有限公司 | Ruthenium-aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane and preparation method and application thereof |
CN112108139A (en) * | 2020-09-29 | 2020-12-22 | 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 |
CN113121368A (en) * | 2021-03-29 | 2021-07-16 | 安徽华恒生物科技股份有限公司 | Method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof |
CN115106087A (en) * | 2022-06-30 | 2022-09-27 | 西安凯立新材料股份有限公司 | Preparation method of biomass oil hydrogenation catalyst |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101549292A (en) * | 2009-05-08 | 2009-10-07 | 西安凯立化工有限公司 | Catalyst for synthesizing cyclohexene by hydrogenation of benzene ring and preparing method thereof |
CN102476052A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Supported ruthenium catalyst and preparation method thereof |
CN102746087A (en) * | 2012-08-01 | 2012-10-24 | 厦门大学 | Method for preparing cyclohexane by catalyzing and hydrogenising benzene at room temperature |
CN103084183A (en) * | 2011-10-27 | 2013-05-08 | 中国石油化工股份有限公司 | Fixed bed catalyst preparation method and fixed bed catalyst |
CN104399455A (en) * | 2014-12-18 | 2015-03-11 | 陕西瑞科新材料股份有限公司 | Preparation method of palladium-carbon catalyst |
-
2016
- 2016-12-03 CN CN201611097751.5A patent/CN106732564B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101549292A (en) * | 2009-05-08 | 2009-10-07 | 西安凯立化工有限公司 | Catalyst for synthesizing cyclohexene by hydrogenation of benzene ring and preparing method thereof |
CN102476052A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Supported ruthenium catalyst and preparation method thereof |
CN103084183A (en) * | 2011-10-27 | 2013-05-08 | 中国石油化工股份有限公司 | Fixed bed catalyst preparation method and fixed bed catalyst |
CN102746087A (en) * | 2012-08-01 | 2012-10-24 | 厦门大学 | Method for preparing cyclohexane by catalyzing and hydrogenising benzene at room temperature |
CN104399455A (en) * | 2014-12-18 | 2015-03-11 | 陕西瑞科新材料股份有限公司 | Preparation method of palladium-carbon catalyst |
Non-Patent Citations (3)
Title |
---|
厉嘉云等: ""碱处理对活性炭载体及负载钯催化剂性能的影响"", 《石油化工》 * |
粟云彦等: ""活性炭载体的改性对钯炭催化剂性能影响研究进展"", 《贵金属》 * |
鞠景喜等: ""Rh/C催化剂的制备及其催化性能研究"", 《浙江冶金》 * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107442134A (en) * | 2017-08-30 | 2017-12-08 | 江苏大学 | A kind of rhodium/nickel alloy nanocatalyst and its preparation method and application |
CN107715870A (en) * | 2017-10-13 | 2018-02-23 | 西安凯立新材料股份有限公司 | A kind of preparation method and application for preparing L aminopropanol ruthenium Pd/carbon catalysts |
CN108786804B (en) * | 2018-05-31 | 2021-01-26 | 王鹏飞 | Hydrogenation catalyst, preparation method and application thereof |
CN108786804A (en) * | 2018-05-31 | 2018-11-13 | 王鹏飞 | Hydrogenation catalyst, preparation method and application |
CN110624537A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Preparation method of phthalate hydrogenation catalyst |
CN110624537B (en) * | 2018-06-25 | 2022-08-23 | 中国石油化工股份有限公司 | Preparation method of phthalate hydrogenation catalyst |
CN110624571A (en) * | 2019-09-27 | 2019-12-31 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing 3, 5-dichloroaniline and preparation method and application thereof |
CN110624571B (en) * | 2019-09-27 | 2022-07-05 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing 3, 5-dichloroaniline and preparation method and application thereof |
CN110743567A (en) * | 2019-11-07 | 2020-02-04 | 西安凯立新材料股份有限公司 | α -iridium carbon catalyst for selective hydrogenation of unsaturated aldehyde and preparation method and application thereof |
CN110743544A (en) * | 2019-11-07 | 2020-02-04 | 西安凯立新材料股份有限公司 | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof |
CN110756198A (en) * | 2019-11-07 | 2020-02-07 | 西安凯立新材料股份有限公司 | Ruthenium-aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane and preparation method and application thereof |
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 |
CN112108139A (en) * | 2020-09-29 | 2020-12-22 | 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 |
CN113121368A (en) * | 2021-03-29 | 2021-07-16 | 安徽华恒生物科技股份有限公司 | Method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof |
CN115106087A (en) * | 2022-06-30 | 2022-09-27 | 西安凯立新材料股份有限公司 | Preparation method of biomass oil hydrogenation catalyst |
Also Published As
Publication number | Publication date |
---|---|
CN106732564B (en) | 2019-06-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106732564B (en) | Aromatic hydrogenation rhodium/activated-carbon catalyst preparation method and application | |
CN105214686B (en) | A kind of charcoal carries multicomponent catalyst and preparation method and application | |
CN100369673C (en) | Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation | |
CN101549292B (en) | Catalyst for synthesizing cyclohexene by hydrogenation of benzene ring and preparing method thereof | |
CN101502800B (en) | Catalyst for one-step synthesis of alkyl cyclohexanone from alkylphenol and preparation method thereof | |
CN110743544B (en) | Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
CN109078655B (en) | High-dispersion Pd-IL/Al2O3Preparation of catalyst and application thereof in selective hydrogenation reaction of acetylene | |
CN109939676A (en) | Monatomic palladium catalyst and its preparation and the application in selective hydrogenation of acetylene | |
CN104399535B (en) | The preparation method and application that a kind of magnetic partner is catalyst based | |
CN107899581B (en) | Loaded on SiO2Preparation method and application of nickel catalyst on microspheres | |
CN114054061B (en) | Nitrogen-doped carbon-supported palladium catalyst and preparation method and application thereof | |
CN102179245B (en) | Application of palladium/active carbon catalyst in synthesizing N,N'-dibenzylethylenediamine | |
CN107694563A (en) | Palladium carbon catalyst and its preparation method and application | |
CN103769088A (en) | Preparation method of size-controllable nano Pd/C catalyst | |
CN104772141B (en) | A kind of preparation method and applications for the catalyst that low-carbon dihydric alcohol is prepared available for glucose hydrogenolysis | |
CN107362797A (en) | Nano ruthenium carbon catalyst and preparation method thereof and its application in 4,4 ' diamino-dicyclohexyl methanes are synthesized | |
CN113600181A (en) | Preparation method of nano palladium supported catalyst | |
CN105195147A (en) | Dehydrogenation catalyst with copper nanoparticles loaded inside carbon nano tube and preparation method of dehydrogenation catalyst | |
CN107715870A (en) | A kind of preparation method and application for preparing L aminopropanol ruthenium Pd/carbon catalysts | |
CN106607020A (en) | Preparation method for high-activity palladium-carbon catalyst | |
CN114436852A (en) | Method for preparing hexamethylene diamine by hydrogenation of adiponitrile | |
CN102861573A (en) | Carrier type platinum-ruthenium catalyst and application to hydrogenation of halide-containing nitro compound | |
CN114849694B (en) | Catalyst for hydrogenation of nitroaromatic hydrocarbon based on metal-loaded tungsten oxide, preparation method and application thereof | |
CN111039755A (en) | Application of nickel boride catalyst in selective hydrogenation of alkynol | |
CN106582757B (en) | Dehydroepiandros-sterone adds hydrogen palladium/calcium carbonate catalyst preparation method and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |