CN107469813B - A kind of carried noble metal hydrogenation catalyst and its preparation and application - Google Patents
A kind of carried noble metal hydrogenation catalyst and its preparation and application Download PDFInfo
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- CN107469813B CN107469813B CN201710602465.8A CN201710602465A CN107469813B CN 107469813 B CN107469813 B CN 107469813B CN 201710602465 A CN201710602465 A CN 201710602465A CN 107469813 B CN107469813 B CN 107469813B
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- 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
- B01J23/42—Platinum
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- 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
- B01J23/44—Palladium
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention discloses a kind of carried noble metal hydrogenation catalysts and its preparation and application, the catalyst to be prepared in accordance with the following steps: 1) preparing the mixed liquor being made of water, alcohol, ethyl orthosilicate；2) active carbon stirring is poured into the mixed liquor that step 1) obtains；Then soluble precious-metal salt is added, adjusts slurry pH value to 0.5~2.5, stirs aging later and obtain reacting slurry；3) lye pH adjustment value is added into reacting slurry to 7.5~14, alkaline matter in lye is selected from the combination of one or more of potassium hydroxide, cesium hydroxide, potassium acetate, cesium acetate, potassium carbonate, cesium carbonate, continue to stir, is finally filtered, washed to obtain catalyst precursor；4) catalyst precursor obtains carried noble metal hydrogenation catalyst through reduction.Application in amino phenyl ether compound shown in the compound hydrogenation synthesis Formula II shown in catalysis type I that the present invention provides the catalyst, conversion ratio reach 100%, selectively can reach 99.5% or more, catalyst can be applied 50 times or more.
Description
(1) technical field
The present invention relates to a kind of hydrogenation catalyst and its preparations and application, and in particular to a kind of carried noble metal adds hydrogen to urge
Agent and preparation method thereof and the application in catalytic hydrogenating reduction synthesizing amino phenyl ether compound.
(2) technical background
Amino phenyl ether compound is a kind of important fine-chemical intermediate, be widely used in medicine, dyestuff, feed,
The fields such as fragrance, rubber.Its synthetic method mainly using nitrobenzene ether compounds as raw material through electronation or catalytic hydrogenation also
Original is made.Chemical reduction method is that chemistry meter occurs using the reducing property and raw material of the chemical reagent such as iron powder, vulcanized sodium, hydrazine hydrate
The redox reaction of amount.Therefore, this method three wastes are more, large labor intensity, poor product quality, are forced by existing environmental regulation
It eliminates.For catalytic hydrogenation method using gaseous hydrogen as reducing medium, oxidation product is water, has environmentally protective, operating environment
The high advantage of good, high degree of automation, product yield, becomes a kind of Nitro group reduction technology generallyd use both at home and abroad.
Forefathers have been carried out some fruitful grind in terms of selective catalytic hydrogenation synthesizing amino phenyl ether compound
Study carefully work.
[2006,23 (5): fine chemistry industry 514] reports the preparation pair of skeletal isomerzation selective catalytic hydrogenation to Yuan Zhongyi etc.
The research of aminoanisole.This article is using Raney-RuNiC as catalyst, and tetrahydrofuran (THF) is solvent, in autoclave hydrogenation reaction
The hydrogenation reaction of paranitroanisole is carried out in device.Suitable reaction condition are as follows: paranitroanisole 32.6mmol, THF15ml,
Catalyst 0.65g, 90-100 DEG C of temperature, pressure 1.1-1.5Mpa.Conversion ratio 100%, yield 99.4%, the service life 63 hours.
CN100494159C is disclosed with the technique of chlorobenzene production nitro phenylate, amino phenylate and amide groups phenylate.Wherein
In catalytic hydrogenation step, which is solvent by catalyst, alcohol of Raney Ni, is 120 DEG C, reaction pressure in reaction temperature
Under the process conditions of 1.6MPa, can intermittent catalysis p-nitrophenyl ether, adjacent nitro phenylate and 2,4- Nitroanisole hydrogenating reduction
It is respectively synthesized corresponding p-aminophenyl ether, adjacent amino phenylate and 2,4- aminoanisole.It can also be in 120 DEG C, reaction pressure
Under conditions of 4.0MPa, 1.0% that Raney Ni dosage is nitro compounds, continous way is catalyzed in three-phase fixed-bed catalytic reactor
2,4- Nitroanisole hydrogenating reduction synthesizes 2,4- aminoanisole.Amino phenylate conversion ratio is up to 98% or more.
CN101798272A discloses the method for paranitroanisole catalytic hydrogenation synthesis paraphenetidine.The invention is adopted
With load type palladium catalyst, Catalysis p-nitroanisole hydrogenating reduction generates paraphenetidine in supercritical CO 2 medium.
Reaction condition are as follows: 50-80 DEG C of reaction temperature, hydrogen partial pressure 1-6MPa, stagnation pressure 10-18MPa.99% or more paraphenetidine yield.
[apply chemical industry, 2005,34 (3): 165] for report using Raney Ni as catalyst, dehydrated alcohol is molten to Lu Lihua etc.
Under agent, 80 DEG C of reaction temperature and Hydrogen Vapor Pressure 1.0MPa, o-aminoanisole yield is up to 90%.
CN103073436A, which is disclosed, prepares adjacent ammonia with ortho-nitroanisole and the reduction of paranitroanisole hydrogenation mixture
The method of base methyl phenyl ethers anisole and paraphenetidine.For this method using adjacent, paranitroanisole as raw material, methanol is solvent, 10%Pt/
C is catalyst, and catalytic hydrogenating reduction reaction is carried out under 40 DEG C of reaction temperature and Hydrogen Vapor Pressure 0.4MPa.
[2005,24 (7): chemical industry progress 767] has studied ortho-nitroanisole catalytic hydrogenation and synthesizes adjacent amino Cao Xiaoqun etc.
Methyl phenyl ethers anisole, instead of traditional vulcanized sodium reducing process.The optimum process condition determined are as follows: 40 DEG C of reaction temperature and hydrogen pressure
Power 0.4MPa, 5%Pd/C catalyst (self-control) dosage 0.9% (to account in terms of ortho-nitroanisole quality), solvent methanol and adjacent nitre
Base methyl phenyl ethers anisole mass ratio is 0.75:1.Compared with vulcanized sodium reducing process, the reaction time was contracted the catalytic hydrogenation process by 6 hours
It is short to 1.75 hours, product yield is increased to 93.8% by 90.5%.
[2010,27 (4): Speciality Petrochemicals 7] is prepared for Ni/Al with infusion process to Gao Chuanlin etc.2O3Catalyst, and by its
Para aminophenyl ethyl ether is prepared for paranitrophenetole plus hydrogen.Optimum reaction condition are as follows: nickel loading 30%, reaction temperature control
At 86-95 DEG C, solvent methanol and paranitrophenetole volume ratio are 1:1, when stirring rate 800r/min, paranitrophenetole
The selectivity of conversion ratio and para aminophenyl ethyl ether is higher than 99.3%.After catalyst applies 35 times, the selection of para aminophenyl ethyl ether
There is downward trend in property.
[2000,8 (5): chemical science and technology 19] has studied Production of O-methoxyaniline By Liquid Phase Hydrogenation of O-Nitroanisole to Sun Yan etc.
Catalytic hydrogenation process.It was found that appropriate process conditions are as follows: 60 DEG C of reaction temperature, reaction pressure 2.0MPa, Raney Ni catalyst
Additive amount 1% (with nitro compounds poidometer), mixing speed 800r/min, solvent methanol and nitro compounds mass ratio 1:1.Ortho-nitrophenyl
99.9% or more methyl ether conversion ratio, it is selective close to 100%.But simultaneously, it was also found that the o-nitrochlorobenzene in raw material adds life after hydrogen
At aniline, product quality is influenced, while also increasing catalyst consumption.Author thinks that most effective method is reduced in raw material
Nitro-chlorobenzene content.
It is most studies have shown that nitryl group catalytic hydrogenating reduction mechanism be related to nitro, nitroso, azanol until arylamine by
Grade hydro-reduction process, the low hydrogenation reaction rate of reaction energy barrier is fast, and target product arylamine selectivity is high.But by hydrogenation catalyst
Catalytic performance and reaction process condition influence, and intermediary nitrous substratess and azanol etc. easily undergo coupling reaction to produce azo
Object is closed, this is more generally existing one of main by-product during Nitro group reduction.For example, document
[ZhaoyinHou, et al, Ind.Eng.Chem.Res., 2010,49,4664] report, using Ni as catalyst, ethyl alcohol is solvent
When, in Catalytic Hydrogenation of Nitrobenzene reaction product containing 0.3~2.9% azo compound.Theoretically, azo chemical combination
Object can continue plus hydrogen hydrogenolysis is arylamine, but usually require harsher reaction condition (such as high temperature and pressure).Therefore, in routine
Under hydroconversion condition, azo compound can be stable in the presence of in hydrogenation products.This not only largely effects on product yield, generates big
The industrial waste of amount, can also wrap up or blocking catalyst duct, seriously affect the service life of catalyst, increase production cost.
This is main problem existing for nitryl group hydrogenation reduction in aromatic nitro compound catalytic hydrogenation.
When increasing alkoxy base on the phenyl ring in nitrobenzene molecular structure, i.e. nitrobenzene ether compounds, fragrant nitro
Compound for catalysis hydrogenation process becomes increasingly complex.In addition to the coupling side reaction of the generations such as the above-mentioned nitrous substratess addressed and azanol
Except, the amino group N in amino phenylate molecular structure easily sloughs one point with the O in the alkoxy of another amino phenylate molecule
Sub- alcohol is coupled, and with alcohols solvent similar reaction can also occur for intermediary azanol, generates N- alkoxy aromatic amine compounds；
In addition, nitro phenylate is usually often to remain about 1% or so chloronitrobenzene class from the etherified reaction of nitro-chlorobenzene
It closes object, hydrogenolysis dechlorination reaction easily occurs in hydrogenation system and generates HCl (being dissolved in is hydrochloric acid solution in product water).Due to N- alkane
The generation of oxygroup aromatic amine compounds can not only reduce principal product yield, but also itself boiling point is high, dissolubility is poor, viscosity is big,
It will cause the irreversible duct blocking property inactivation of catalyst；The strong acid characteristic of another by-product hydrochloric acid can to catalyst, reactor and its
Follow-up equipment generates fatal corrosivity damage.This is main problem present in nitrobenzene ether compounds catalytic hydrogenation.
Therefore, how to improve amino phenylate selectivity, control azo compound, N- alkoxy aromatic amine compounds with
And the generation of the by-products such as hydrochloric acid, improving catalyst stability is nitro phenylate catalytic hydrogenation synthesizing amino phenyl ether compound
Technological difficulties and critical problem.However, the nitro phenylate Catalytic Hydrogenation Techniques that above-mentioned existing document is addressed only are rested on to original
There are Process Exploration and the exploitation of the substitution Catalytic Hydrogenation Techniques of chemical reduction process, or addresses only one or two kinds of side reactions
Influence, selectivity, yield and catalyst life and reduce production cost etc. and still need to be greatly improved.So far, obvious
The synthesis of three kinds of side reactions effectively inhibits to study during open report p-nitrophenyl ether hydrogenating reduction.
(3) summary of the invention
The first purpose of the invention is to provide a kind of carried noble metal hydrogenation catalyst, the catalyst filtration speed
Fastly, stability is good, and can effectively modify cloud density and the distribution of noble-metal-cluster particle, modulation by introducing silicon alkoxide structure
The adsorption desorption characteristic of reactant, product and intermediary molecule during hydrogenating reduction, effectively inhibition side reaction, the progress for promoting main reaction.
A second object of the present invention is to provide a kind of preparation methods of carried noble metal hydrogenation catalyst.
Third object of the present invention is to provide the carried noble metal hydrogenation catalysts to close in catalytic hydrogenating reduction method
At the application in amino phenyl ether compound, have the characteristics that high conversion rate, selectivity is good, stability is good.
In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical scheme:
The present invention provides a kind of carried noble metal hydrogenation catalyst, the carried noble metal hydrogenation catalyst according to
It is prepared by following steps:
1) mixed liquor being made of water, alcohol, ethyl orthosilicate is prepared, wherein the molar ratio of water and alcohol is 0.1~5:1, just
The molar ratio of silester and water is 1:15~150；
2) active carbon is poured into the mixed liquor that step 1) obtains, and is stirred 1~5 hour in 15~50 DEG C；Then it is added
Soluble precious-metal salt, noble metal is in the form of forming anion complex with other ions in the soluble precious-metal salt
In the presence of, and slurry pH value is adjusted to 0.5~2.5 with acid solution, it stirs aging 5~36 hours, obtains anti-at 15~50 DEG C later
Answer slurries；Wherein the feed ratio of soluble precious-metal salt and ethyl orthosilicate with the molar ratio computing of noble metal and silicon be 0.99~
The feed ratio of 10:1, soluble precious-metal salt and active carbon is calculated as 0.50~10.0:100 with the mass ratio of noble metal and active carbon；
3) lye pH adjustment value is added into the reacting slurry that step 2) obtains to 7.5~14, it is small to continue constant temperature stirring 1~12
When, it finally filters, with ethanol washing to filtrate pH value to neutrality, obtains catalyst precursor；The concentration of the lye be 5~
15wt%, alkaline matter therein in potassium hydroxide, cesium hydroxide, potassium acetate, cesium acetate, potassium carbonate, cesium carbonate one
Kind or several combinations；
4) catalyst precursor that step 3) obtains is restored under hydrogen atmosphere using temperature-programmed reduction method, is obtained
Carried noble metal hydrogenation catalyst.
Further, the carrier active carbon, wherein mesoporous proportion be not less than 50%, specific surface area be 600~
1100m20.5~2.5mL/g of/g, Kong Rongwei.
Further, in step 1), alcohol preferred alcohol or propyl alcohol.
Further, in step 2), the feed ratio of soluble precious-metal salt and active carbon is with the quality of noble metal and active carbon
It is preferably 1.0~8.0wt% than meter.
Further, in step 2), the soluble precious-metal salt preferably wherein noble metal to form yin with other ions
The form of ionic complex exists.Specifically, the soluble precious-metal salt can be chlorine palladium acid (by dissolving with hydrochloric acid palladium chloride system
), the combination of chlorine palladium acid sodium, chloroplatinic acid, one or more of platinic sodium chloride.
Further, acid solution described in step 2) can be hydrochloric acid, acetic acid, nitric acid etc..
Further, in step 3), after tune pH value to 7.5~14, continuing mixing time is preferably 2~8 hours.
Further, reducing condition described in step 4) are as follows: 100 are risen to from room temperature with the rate of 0.1~0.5 DEG C/min~
150 DEG C, then 200~250 DEG C are risen to the rate of 0.5~2.0 DEG C/min, last constant temperature 1~5 hour.
Carried noble metal hydrogenation catalyst produced by the present invention, in its preparation process, using acid precious metal salt
Precursor participates in the hydrolysis and polymerization process of ethyl orthosilicate, by precious metal ion association in silica polymer particle；
In addition, combining using acid, basic hydrolysis, silanol structure and its coordinating group can be effectively adjusted, it is total to generate hydroxyl, potassium and/or caesium
The silicon alkoxide structure deposited, the noble metal interaction after the reduction of silicon alkoxide structure and association in silicon dioxide granule,
Coexist in absorbent charcoal carrier surface.Therefore, carried noble metal hydrogenation catalyst of the present invention, says from structural point, be
On absorbent charcoal carrier, be evenly distributed with silicon dioxide granule, silica particle surface have association noble-metal-cluster particle and
The silicon alkoxides structures such as silicone hydroxyl, silanol potassium/caesium.In this structure, silicon alkoxide structure has effectively modified the electricity of noble-metal-cluster particle
Sub- cloud density and distribution, the suction of reactant (nitro), product (amino) and intermediary molecule is de- during modulation hydrogenating reduction
Attached characteristic, effectively inhibition side reaction, the progress for promoting main reaction.
The present invention provides a kind of preparation methods of carried noble metal hydrogenation catalyst, and the method is in accordance with the following steps
It carries out:
1) mixed liquor being made of water, alcohol, ethyl orthosilicate is prepared, wherein the molar ratio of water and alcohol is 0.1~5:1, just
The molar ratio of silester and water is 1:15~150；
2) active carbon is poured into the mixed liquor that step 1) obtains, and is stirred 1~5 hour in 15~50 DEG C；Then it is added
Soluble precious-metal salt, noble metal is in the form of forming anion complex with other ions in the soluble precious-metal salt
In the presence of, and slurry pH value is adjusted to 0.5~2.5 with acid solution, it stirs aging 5~36 hours, obtains anti-at 15~50 DEG C later
Answer slurries；Wherein the feed ratio of soluble precious-metal salt and ethyl orthosilicate with the molar ratio computing of noble metal and silicon be 0.99~
The feed ratio of 10:1, soluble precious-metal salt and active carbon is calculated as 0.50~10.0:100 with the mass ratio of noble metal and active carbon；
3) lye pH adjustment value is added into the reacting slurry that step 2) obtains to 7.5~14, it is small to continue constant temperature stirring 1~12
When, it finally filters, with ethanol washing to filtrate pH value to neutrality, obtains catalyst precursor；The concentration of the lye be 5~
15wt%, alkaline matter therein in potassium hydroxide, cesium hydroxide, potassium acetate, cesium acetate, potassium carbonate, cesium carbonate one
Kind or several combinations；
4) catalyst precursor that step 3) obtains is restored under hydrogen atmosphere using temperature-programmed reduction method, is obtained
Carried noble metal hydrogenation catalyst.
Above-mentioned steps 1) -4) preparation details be same as above, details are not described herein.
Invention further provides carried noble metal hydrogenation catalyst compounds shown in catalysis type I, and hydrogen to be added to close
At the application in amino phenyl ether compound shown in Formula II, the application specifically: by compound shown in Formulas I and the load
Type noble metal hydrogenation catalyst is put into high-pressure hydrogenation reaction kettle, closed reactor, and hydrogen is filled with after displaced air and opens stirring,
Catalytic hydrogenation reaction is carried out under conditions of temperature is 20~100 DEG C, Hydrogen Vapor Pressure is 0.1~3.0MPa, is reacted in carrying out, it is real
When monitor on-line hydrogenation liquid pH value, so that hydrogenation liquid pH value in kettle is maintained at 6.0~7.5, linkage lye is adjusted in real time, institute
The alkaline matter in lye stated be one of potassium hydroxide, cesium hydroxide, potassium acetate, cesium acetate, potassium carbonate, cesium carbonate or
It is several, and controlling the ion concentration of potassium and/or caesium in hydrogenation liquid is 0.05~2.0g/L, sampling shown in chromatography detection Formulas I through changing
When conjunction object content is 0, stop reaction, hydrogenation liquid is post-treated to obtain compound shown in Formula II；
Rn represents the substituent group on phenyl ring, n≤5, and wherein at least one is OCH3、OCH2CH3Or OCH2CH2CH3,
Complementary basis group respectively stands alone as H, CH3、OH、CH2CH3、NO2Or NH2.In this reaction, only nitro is reduced to amino, other groups
Reaction front and back remains unchanged.
Further, Formulas I compound represented preferably is selected from one of following: ortho-nitroanisole, paranitroanisole, adjacent nitro
Phenetole, paranitrophenetole, to nitro neighbour's benzene diethyl ether, ortho-nitrophenyl propyl ether, p-nitrophenyl propyl ether, 2,4- dinitrobenzene first
Ether, 2,4- dinitrobenzene ether.
In the application, recommend the matter that feeds intake of compound shown in the Formulas I Yu the carried noble metal hydrogenation catalyst
Amount is than being 100:0.1~4, preferably 100:0.2~2.0.
In the application, preferable reaction temperature is 35~100 DEG C, and preferably Hydrogen Vapor Pressure is 0.2~2.5MPa.
Compound shown in the Formulas I can carry out hydrogenation reaction in a solvent, and applicable solvent is water, compound shown in Formula II
One or both of arbitrary proportion mixed solvent, recommend the volumetric usage of the solvent with compound shown in substrate Formulas I
Quality is calculated as 0.5~2.0mL/g.
Compound shown in the Formulas I can also carry out hydrogenation reaction under solvent-free conditions.When carrying out solvent-free hydrogenation reaction,
Raw material preheating must be melted to liquid first, then rise to reaction temperature and carry out hydrogenation reaction.
When carrying out hydrogenation reaction in a kettle, the method for the hydrogenation liquid post-processing are as follows: hydrogenation liquid filters to isolate
Catalyst, filtrate is used to apply through stratification recycling aqueous phase solution as linkage lye, up to formula after organic phase distillation dehydration
Compound shown in II；Filtering gained catalyst may return to reaction kettle progress catalyst and apply.When carrying out in a fluidized bed plus hydrogen
When reaction, gas phase repressurization after vapor-liquid separation is back to gas handling system, realizes hydrogen circulation；Mistake built in the reacted device of solid liquid phase
Catalyst granules is trapped in reactor by filter, liquid phase be similar to reaction kettle in filtrate, subsequent processing method successively into
Row, obtains compound shown in product Formula II.
Compared with prior art, the beneficial effects of the present invention are embodied in:
1) carried noble metal hydrogenation catalyst of the present invention, is evenly distributed with silica on absorbent charcoal carrier
Particle, active carbon mechanical strength can be remarkably reinforced in this, weaken the sad filter of catalyst and noble metal caused by due to active carbon dusting
The problem of loss, keeps catalyst filtration speed fast, and stability is good.And have in silicon dioxide granule the noble-metal-cluster particle of association with
And the silicon alkoxides structure such as silicone hydroxyl, silanol potassium/caesium, silicon alkoxide structure can effectively modify the cloud density of noble-metal-cluster particle with
It is distributed, the adsorption desorption characteristic of reactant (nitro), product (amino) and intermediary molecule during modulation hydrogenating reduction effectively presses down
Side reaction processed, the progress for promoting main reaction.Therefore, which is alkylated the N of azanol or arylamine group and alkoxy grp secondary
The coupling reaction of generations and the hydrogenolysis dechlorination side reactions to chlorinated aromatic nitro compound such as reaction, nitrous substratess and azanol,
All there is significantly inhibiting effect.
2) preparation method of carried noble metal hydrogenation catalyst of the present invention, before acid precious metal salt
The hydrolysis and polymerization process and ethyl orthosilicate that body participates in ethyl orthosilicate uses in conjunction with sour, basic hydrolysis, forms uniqueness
Catalyst structure.
3) catalyst of the invention is in the reaction of catalytic hydrogenation method synthesizing amino ether compound, conversion ratio 100%, selection
Property can reach 99.5% or more, and catalyst can be applied 50 times or more.
4) catalytic hydrogenation of the present invention does not use organic solution or solvent-free, enormously simplifies technique stream
Journey improves the utilization efficiency of reaction kettle one-pot, reduces solvent recovery energy consumption and solvent volatility loss.
(4) specific embodiment
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto:
Embodiment one
10g active carbon is weighed, the specific surface area of active carbon is 1000m2/ g, mesopore proportion 50%, Kong Rong 0.8mL/g.Claim
It takes 1g water, 8g ethyl alcohol, 0.1g ethyl orthosilicate in beaker, is stirred well to and is completely dissolved.Active carbon is poured into mixed liquor,
It is stirred 2 hours at 25 DEG C.Then the chloroplatinic acid containing 0.2g platinum is added, and then with hydrochloric acid adjust active carbon slurries pH to
1.0, and aging 20 hours at 25 DEG C.Active carbon slurries pH to 9.0 is adjusted with 5wt% potassium hydroxide solution later, is continued permanent
Warm aging 5 hours, filtering, with ethanol washing to filtrate pH value to neutrality, obtains catalyst precursor.Finally in a hydrogen atmosphere
It is risen to 150 DEG C (final temperatures 1) from room temperature with 0.1 DEG C/min (heating rate 1), then rises to 250 with 0.5 DEG C/min (heating rate 2)
DEG C (final temperature 2), constant temperature 2 hours.Up to the catalyst sample.
Embodiment two is to embodiment ten third is that according to catalyst prepared by one preparation process of embodiment, design parameter is as shown in table 1.
Comparative example 1
Conventional carbon-carried palladium catalyst preparation method: being 1100m by specific surface area2The active carbon of/g, Kong Rongwei 0.80mL/g
In 110 DEG C vacuum dehydration 4 hours；Pipetting 10mL concentration is the chlorine palladium acid solution of 0.05g/mL in 50mL deionized water,
Make its pH value in 0.8 with hydrochloric acid adjusting；Then the 10g active carbon Jing Guo vacuum dehydration is dipped in palladium liquid, 80 DEG C sufficiently
Stirring dipping 6 hours adjusts pH value to 8~10 with 5wt% sodium hydroxide solution；After 1 hour, dropwise addition 2.5mL hydrazine hydrate, 35
DEG C reductase 12 hour.It is down to room temperature, reaction system filtering later, filter cake is washed with deionized to neutrality, 110 DEG C of drying and dehydratings 4
Hour, obtain simple substance supported palladium catalyst.
Embodiment 14 is urged to embodiment 20 sixth is that catalyst made from above-mentioned preparation method is applied to nitro phenylate
Change the example of hydrogenation synthesis amino phenyl ether compound.
Embodiment 14
100g paranitrophenetole, one catalyst of 0.8g embodiment are added in 500mL autoclave, reaction is closed
Kettle displaces air in reactor with nitrogen, then with hydrogen displacement nitrogen, opens stirring, agitation revolution 1400r/min, dimension
50 DEG C of reaction temperature are held, Hydrogen Vapor Pressure 1.0MPa is reacted.During reaction carries out, real time on-line monitoring hydrogenation liquid pH value is in parallel
Dynamic cesium hydroxide lye is adjusted in real time, and hydrogenation liquid pH value in kettle is made to be maintained at 6.0~7.5, and control in hydrogenation liquid caesium from
Sub- concentration is 0.5g/L.Sampling through chromatography detection paranitrophenetole content be 0 when, stop reaction, filtration catalytic agent.Filtrate warp
Phase is product after dividing water and vacuum distillation dehydration, and through chromatographic quantitative analysis (molar percentage), result is hydrogenation reaction
Conversion ratio 100%, selectivity 99.5%.
Embodiment 15 to embodiment 26 is hydrogenation catalyst application obtained by embodiment two to embodiment 13
Catalytic performance in the reaction of nitrobenzene ether compounds catalytic hydrogenation synthesizing amino phenyl ether compound, the results are shown in Table 2.
Comparative example 2
100g paranitrophenetole, 1 catalyst of 0.8g comparative example are added in 500mL autoclave, reaction kettle is closed,
Air in reactor is displaced with nitrogen, then with hydrogen displacement nitrogen, opens stirring, agitation revolution 1400r/min remains anti-
Temperature 50 C is answered, Hydrogen Vapor Pressure 1.0MPa is reacted.During reaction carries out, real time on-line monitoring hydrogenation liquid pH value, linkage hydrogen
Cesium oxide lye is adjusted in real time, so that hydrogenation liquid pH value in kettle is maintained at 6.0~7.5, and it is dense to control cesium ion in hydrogenation liquid
Degree is 0.5g/L.Sampling through chromatography detection paranitrophenetole content be 0 when, stop reaction, filtration catalytic agent.Filtrate is through phase point
It is product from dividing after water and vacuum distillation dehydration, through chromatographic quantitative analysis (molar percentage), result is hydrogenation reaction conversion
Rate 100%, selectivity 94.5%.
Comparative example 3
100g paranitrophenetole, 1 catalyst of 0.8g comparative example are added in 500mL autoclave, reaction kettle is closed,
Air in reactor is displaced with nitrogen, then with hydrogen displacement nitrogen, opens stirring, agitation revolution 1400r/min remains anti-
Temperature 50 C is answered, Hydrogen Vapor Pressure 1.0MPa is reacted.When sampling through chromatography detection paranitrophenetole content is 0, stop anti-
It answers, filtration catalytic agent.Filtrate is product after mutually being separated point water and vacuum distillation dehydration, through chromatographic quantitative analysis (moles hundred
Divide ratio), result is hydrogenation reaction conversion ratio 100%, selectivity 90.5%.
Comparative example 4
100g paranitrophenetole, one catalyst of 0.8g embodiment are added in 500mL autoclave, reaction is closed
Kettle displaces air in reactor with nitrogen, then with hydrogen displacement nitrogen, opens stirring, agitation revolution 1400r/min, dimension
50 DEG C of reaction temperature are held, Hydrogen Vapor Pressure 1.0MPa is reacted.Sampling through chromatography detection paranitrophenetole content be 0 when, stop
It only reacts, filtration catalytic agent.Filtrate is product after mutually being separated point water and vacuum distillation dehydration, (is rubbed through chromatographic quantitative analysis
That percentage), result is hydrogenation reaction conversion ratio 100%, selectivity 97.4%.
Embodiment 27 is that the catalyst of embodiment 14 applies experiment, and the results are shown in Table 3.
The catalyst of 3. embodiment 27 of table applies experimental result
Claims (10)
1. a kind of carried noble metal hydrogenation catalyst, the carried noble metal hydrogenation catalyst is made in accordance with the following steps
It is standby:
1) mixed liquor being made of water, alcohol, ethyl orthosilicate is prepared, wherein the molar ratio of water and alcohol is 0.1~5:1, positive silicic acid
The molar ratio of ethyl ester and water is 1:15~150；
2) active carbon is poured into the mixed liquor that step 1) obtains, and is stirred 1~5 hour in 15~50 DEG C；Then it is added solvable
Property precious metal salt, noble metal is deposited in the form of forming anion complex with other ions in the soluble precious-metal salt
, and slurry pH value is adjusted to 0.5~2.5 with acid solution, it stirs aging 5~36 hours, is reacted at 15~50 DEG C later
Slurries；Wherein the feed ratio of soluble precious-metal salt and ethyl orthosilicate is with the molar ratio computing of noble metal and silicon for 0.99~10:
1, the feed ratio of soluble precious-metal salt and active carbon is calculated as 0.50~10.0:100 with the mass ratio of noble metal and active carbon；
3) lye pH adjustment value is added into the reacting slurry that step 2) obtains to 7.5~14, continues constant temperature and stirs 1~12 hour,
It finally filters, with ethanol washing to filtrate pH value to neutrality, obtains catalyst precursor；The concentration of the lye be 5~
15wt%, alkaline matter therein in potassium hydroxide, cesium hydroxide, potassium acetate, cesium acetate, potassium carbonate, cesium carbonate one
Kind or several combinations；
4) catalyst precursor that step 3) obtains is restored under hydrogen atmosphere using temperature-programmed reduction method, is loaded
Type noble metal hydrogenation catalyst.
2. carried noble metal hydrogenation catalyst as described in claim 1, it is characterised in that: the carrier active carbon, wherein
Mesoporous proportion is not less than 50%, and specific surface area is 600~1100m20.5~2.5mL/g of/g, Kong Rongwei.
3. carried noble metal hydrogenation catalyst as claimed in claim 1 or 2, it is characterised in that: in step 1), alcohol is ethyl alcohol
Or propyl alcohol.
4. carried noble metal hydrogenation catalyst as claimed in claim 1 or 2, it is characterised in that: soluble expensive in step 2)
The feed ratio of metal salt and active carbon is calculated as 1.0~8.0wt% with the mass ratio of noble metal and active carbon.
5. carried noble metal hydrogenation catalyst as claimed in claim 1 or 2, it is characterised in that: in step 2), described can
Dissolubility precious metal salt is the combination of one or more of chlorine palladium acid, chlorine palladium acid sodium, chloroplatinic acid, platinic sodium chloride.
6. carried noble metal hydrogenation catalyst as claimed in claim 1 or 2, it is characterised in that: restored described in step 4)
Condition are as follows: rise to 100~150 DEG C from room temperature with the rate of 0.1~0.5 DEG C/min, then with the rate liter of 0.5~2.0 DEG C/min
To 200~250 DEG C, last constant temperature 1~5 hour.
7. a kind of preparation method of carried noble metal hydrogenation catalyst, the method carry out in accordance with the following steps:
1) mixed liquor being made of water, alcohol, ethyl orthosilicate is prepared, wherein the molar ratio of water and alcohol is 0.1~5:1, positive silicic acid
The molar ratio of ethyl ester and water is 1:15~150；
2) active carbon is poured into the mixed liquor that step 1) obtains, and is stirred 1~5 hour in 15~50 DEG C；Then it is added solvable
Property precious metal salt, noble metal is deposited in the form of forming anion complex with other ions in the soluble precious-metal salt
, and slurry pH value is adjusted to 0.5~2.5 with acid solution, it stirs aging 5~36 hours, is reacted at 15~50 DEG C later
Slurries；Wherein the feed ratio of soluble precious-metal salt and ethyl orthosilicate is with the molar ratio computing of noble metal and silicon for 0.99~10:
1, the feed ratio of soluble precious-metal salt and active carbon is calculated as 0.50~10.0:100 with the mass ratio of noble metal and active carbon；
3) lye pH adjustment value is added into the reacting slurry that step 2) obtains to 7.5~14, continues constant temperature and stirs 1~12 hour,
It finally filters, with ethanol washing to filtrate pH value to neutrality, obtains catalyst precursor；The concentration of the lye be 5~
15wt%, alkaline matter therein in potassium hydroxide, cesium hydroxide, potassium acetate, cesium acetate, potassium carbonate, cesium carbonate one
Kind or several combinations；
4) catalyst precursor that step 3) obtains is restored under hydrogen atmosphere using temperature-programmed reduction method, is loaded
Type noble metal hydrogenation catalyst.
8. carried noble metal hydrogenation catalyst as described in claim 1 compound hydrogenation synthesis Formula II shown in catalysis type I
Shown in application in amino phenyl ether compound, the application specifically: by compound shown in Formulas I and the expensive gold of the support type
Belong in hydrogenation catalyst investment high-pressure hydrogenation reaction kettle, closed reactor, is filled with hydrogen after displaced air and opens stirring, in temperature
Catalytic hydrogenation reaction is carried out under conditions of being 0.1~3.0MPa for 20~100 DEG C, Hydrogen Vapor Pressure, is reacted in carrying out, real-time online
Hydrogenation liquid pH value is monitored, so that hydrogenation liquid pH value in kettle is maintained at 6.0~7.5, linkage lye is adjusted in real time, the alkali
Alkaline matter in liquid is one or more of potassium hydroxide, cesium hydroxide, potassium acetate, cesium acetate, potassium carbonate, cesium carbonate,
And controlling the ion concentration of potassium and/or caesium in hydrogenation liquid is 0.05~2.0g/L, sampling contains through compound shown in chromatography detection Formulas I
When amount is 0, stop reaction, hydrogenation liquid is post-treated to obtain compound shown in Formula II；
Rn represents the substituent group on phenyl ring, n≤5, and wherein at least one is OCH3、OCH2CH3Or OCH2CH2CH3, complementary basis
Group respectively stands alone as H, CH3、OH、CH2CH3、NO2Or NH2, in this reaction, only nitro is reduced to amino, and other groups are anti-
Front and back is answered to remain unchanged.
9. application as claimed in claim 8, it is characterised in that: Formulas I compound represented is selected from one of following: ortho-nitrophenyl first
Ether, paranitroanisole, o-nitrophenetole, paranitrophenetole, to nitro neighbour's benzene diethyl ether, ortho-nitrophenyl propyl ether, to nitre
Base propyl phenyl ether, 2,4- dinitroanisol, 2,4- dinitrobenzene ether.
10. application as claimed in claim 8 or 9, it is characterised in that: compound shown in the Formulas I is in a solvent or without molten
Carry out hydrogenation reaction under the conditions of agent, solvent is the mixed solvent of one or both of water, compound shown in Formula II arbitrary proportion.
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| CN109701574B (en) * | 2018-11-28 | 2022-04-19 | 浙江工业大学 | Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of pyridine ring compounds |
| CN109569686B (en) * | 2018-11-28 | 2021-10-15 | 浙江工业大学 | Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of halogenated nitrobenzene |
| CN109759109B (en) * | 2018-11-28 | 2022-04-19 | 浙江工业大学 | Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of nitrobenzene compounds |
| CN109701522B (en) * | 2018-12-31 | 2021-06-08 | 浙江工业大学 | Preparation of supported ruthenium-based hydrogenation catalyst and application of supported ruthenium-based hydrogenation catalyst in catalytic hydrogenation of dimethyl terephthalate |
| CN114618569B (en) * | 2020-12-10 | 2023-06-06 | 中国科学院大连化学物理研究所 | Catalyst and preparation method and application thereof |
| CN113145121B (en) * | 2021-05-10 | 2022-03-01 | 中国矿业大学 | Nickel-carbon catalyst with high specific surface area and preparation method and application thereof |
| CN116239549B (en) * | 2023-03-16 | 2024-02-20 | 南京工业大学 | Method for using platinum-based catalyst in hydrogenation reaction of 2-methylfuran |
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