CN107235825A - Diacetone alcohol hydrogenation prepares the method and catalyst of the pentanediol of 2 methyl 2,4 - Google Patents
Diacetone alcohol hydrogenation prepares the method and catalyst of the pentanediol of 2 methyl 2,4 Download PDFInfo
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- CN107235825A CN107235825A CN201710455308.9A CN201710455308A CN107235825A CN 107235825 A CN107235825 A CN 107235825A CN 201710455308 A CN201710455308 A CN 201710455308A CN 107235825 A CN107235825 A CN 107235825A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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Abstract
The present invention is provided prepares 2 methyl 2 by diacetone alcohol hydrogenation, the method and catalyst of 4 pentanediols, methods described includes making DAA react 2 methyl 2 of generation in the presence of a catalyst with hydrogen, 4 pentanediols, wherein the catalyst is the load type metal catalyst that active metal component is supported on hydroxyapatite carrier.The inventive method can be carried out in environment-friendly solvent can also be in solvent-free lower progress, and DAA can be up to the 100% obtained pentanediol of 2 methyl 2,4 of conversion ratio；And the reaction process of the invention by the DAA preparation pentanediol of 2 methyl 2,4 is succinct, equipment is simple, easy to operate, reaction condition is very gentle；While the catalyst preparation of the present invention is simple, cost is low, it is possible to achieve large-scale production, the catalyst hydrothermal stability height of ion-exchange preparation, recycling performance are good；Reaction product and catalyst and dicyandiamide solution are easily separated, and reaction time is short, suitable for industrial production, with boundless application prospect.
Description
Technical field
Field is synthesized the present invention relates to organic catalysis, relates more specifically to diacetone alcohol hydrogenation and prepares 2- methyl -2,4- penta
The method and catalyst of glycol.
Background technology
2- methyl -2,4- pentanediol is the micro- thick liquid of water white transparency, and slightly pure and fresh fragrant and sweet smell is dissolved in water, alcohol, ether
With lower aliphatic hydrocarbon.With water complete miscibility, there is the dissolubility of extra-heavy in senior organic solvent, have well to organic matter
Dispersibility.2- methyl -2,4- pentanediols are a kind of widely used fine chemical products, building materials, cosmetics, textile,
The fields such as agricultural chemicals, coating, Biochemical Engineering, organic synthesis are used widely, and are mainly used as solvent, couplant, emulsifying agent, infiltration
Agent, stabilizer etc..2- methyl -2,4- pentanediol is as coupling agent, and stabilization can be formed by being constituted for proteinase activity in solution
Protein enzyme solution, due to the resin such as PVC, ABS polyacrylate be made with tough and tensile elasticity, the wearability of higher hardness and
Weatherability coating, can be applied to building, ship domain；2- methyl -2,4- pentanediol is as new weaving bleeding agent, for day
So and chemical fibre in, not only better than used various bleeding agents, and product anti-aging can be made, it is anti-corrupt, anticorrosive, improve production
The intensity and suppleness of product；2- methyl -2,4- pentanediol is mainly used in organophosphorus pesticide as agricultural chemicals stabilizer, in 40%ZX
2%2- methyl -2,4- pentanediols are added in cream of isocarbophos, its resolution ratio 69% can be reduced.Therefore, 2- methyl -2,4-
Pentanediol has extraordinary application prospect as the fine chemical product of function admirable.Current 2- methyl -2,4- penta both at home and abroad
The synthetic method of glycol is divided into two kinds according to the difference of raw material route, and one kind is to use 2,4,4,6- tetramethyl -1,3- dioxacyclohexanes
Methanol Decomposition prepare；It is another be with condensation of acetone thing DAA be that raw material hydrogenating reduction is synthesized, later approach is
Current main synthesis and production process both domestic and external.It is being that raw material hydrogenating reduction synthesizes 2- methyl -2,4-PD by DAA
During the application of catalyst be the key link for realizing the reaction, therefore, people have been carried out extensively to the catalyst of the reaction
General research
Wu's generation China et al. proposes the catalyst of hydrogenating reaction of diacetone alcohol in CN1066608A.This application is using nickeliferous
SiO 2 catalyst, utilize metallic vapour method to prepare high dispersive nickel (Ni) metal carrying catalyst (Ni/SiO2) after, by this
Catalyst is used for hydrogenating reaction of diacetone alcohol and prepares the reaction of 2- methyl -2,4- pentanediol, specifically under low temperature (- 78 DEG C), will
Solvent (toluene) changes Ni atom solution and is immersed in SiO2On carrier, and it is stirred vigorously in dipping process, dip time is 6 small
When, room temperature is slowly increased to after dipping, and vacuum sloughs toluene, makes system vacuum up to 10-15Torr, tube sealing, obtained Ni/SiO2
Ni contents are 0.5~20% in catalyst.20mL DAAs are added in 160L does not lure steel reactor, in addition under hydrogen stream
The above-mentioned 2.54%Ni/SiO of 0.30g2Catalyst, is purged with nitrogen after three times and is filled with 3MPa hydrogen, in stirring reaction 5 at 140 DEG C
Hour, DAA conversion ratio is that 95%, 2- methyl -2,4- pentanediols selectively reach 50%.
It is tight holy it is bright et al. proposed in CN102329193A it is a kind of using diacetone alcohol hydrogenation reduction synthesis 2- methyl -2,4-
The production technology of pentanediol, wherein using DAA as raw material, after being mixed with auxiliary agent, in the presence of nickel catalyst, heating
Hydrogen 1.9MPa reduction displacement synthesis 2- methyl -2,4-PD is passed through to 150 DEG C of pressurizations；Auxiliary agent is alkali compounds, as long as
There is no alkaline inorganic compound, the alkaline organic compound of malicious influences, product 2- methyl -2,4- penta 2 to hydrogenation reaction
The purity of alcohol can reach 99.5%, and mass yield brings up to 99%.
Zhu Xuen et al. and Liu Xiaodong et al. proposes 2- methyl -2,4- penta in CN1228354A and CN1565730A respectively
The preparation method of catalyst and the preparation method of DAA synthetic catalyst in the synthesis of glycol, are specifically to be urged with DAA
Change a kind of synthetic method of catalyst in hydrogenating reduction synthesis 2- methyl -2,4- pentanediol reaction, its key problem in technology is:By nickel-
Aluminium alloy is added portionwise in 7~11mol/L NaOH solution, is stirred and is activated at a temperature of 58~62 DEG C for 1 hour, in hydrogen
The nickel-aluminum alloy of activation is washed with distilled water into washing lotion under gas atmosphere to wash in neutrality, then with ethanol, absolute ethyl alcohol is then used
Covering sealing.They also describe is synthesized used in 2- methyl -2,4-PD by DAA catalytic hydrogenating reduction
Catalyst has Ni/SiO2, Ni/ diatomite, activity Pd.Wherein, Ni/SiO2Catalyst is with SiO2For carrier, in reaction temperature
400 DEG C and 1.33 × 10-3Pa dehydrated under vacuum dehydroxylation 4 hours, toluene is after the processing backflow of benzophenone sodium then at Gao Zhen
Upper " freeze-thawing " deoxidation of empty set system three times；Ni/ diatomite catalyst be reaction temperature be 110 DEG C, pressure is 3.5MPa,
Reduced superficial velocity is 0.12h-1Under the conditions of be made；The preparation of solvation Pd atom solution is in U.S. Knotes metallic atom reactors
Middle progress, 140 DEG C of reaction temperature reacts Hydrogen Vapor Pressure 3.0MPa, and the reaction time 5.5 is small to be made at present.
JP54132511A proposes 2- methyl -2,4- pentanediol bottom of towe oil treatment process, using Raney's nickel, thunder Buddhist nun cobalt,
Ni/ diatomite is catalyst.
However, above-mentioned existing literature is used mostly during 2- methyl -2,4- pentanediols are prepared by diacetone alcohol hydrogenation
Ni catalyst series add alkali compounds in Ni catalyst series, and its method for preparing catalyst is more complicated, and Ni bases are urged
Agent has serious loss and unstable, output is small, is unsuitable for enlarged experiment and industrialized production；And these works
Toxic solvent or organic solvent are used during skill so that product separates difficulty, low yield with solvent, and it is high to there is production cost,
Not easy to operate the problems such as.
Therefore, this area needs to develop is catalyzed DAA high-selective and hydrogenating preparation 2- first under the conditions of relatively mild
The new method and raw catelyst of base -2,4-PD are more preferably to meet the demand of commercial Application.
The content of the invention
In view of above-mentioned, in order to solve one or more problems of the prior art, it is an object of the invention to provide one kind
Simply, green, the DAA high-selective and hydrogenating that is catalyzed under the conditions of relatively mild efficiently, stable prepare 2- methyl -2,4-
The method and catalyst of pentanediol.
Therefore, in one aspect, the present invention provides a kind of side that 2- methyl -2,4- pentanediols are prepared by diacetone alcohol hydrogenation
Method, methods described includes making DAA react generation 2- methyl -2,4- pentanediols, wherein institute in the presence of a catalyst with hydrogen
State the load type metal catalyst that catalyst is supported on for active metal component on hydroxyapatite carrier, and wherein described work
Property metal component be the one or more in the periodic table of elements in the transition metal of VIIIB or IB races, the hydroxyl phosphorus
Lime stone carrier has formula Ma(XOb)c(Z)d, wherein M is in group ia, group iia, Y, Ce and Pb in the periodic table of elements
One or more metal cations, X is one or more in Si, P, S, V and As, and Z is to be selected from OH-、CO3 2-、
HCO3 -、F-、Cl-、Br-And I-In one or more contend with anion, and a, b, c and d are in the bar of the formula part valence balance
1-10 is each independently under part.
In preferred embodiments, the reaction is without using solvent.
In preferred embodiments, the reaction is used selected from water, C1-C12 alcohol, C1-C12 alkane and C1-C12 alkyl halides
One or more in hydrocarbon are used as solvent.
In preferred embodiments, in the formula Ma(XOb)c(Z)dIn, M is one in Ca, Mg, Ce, Na and K
Plant or a variety of.
In preferred embodiments, the active metal component is one kind or many in Ru, Pd, Ir, Pt, Ni and Cu
Kind.
In preferred embodiments, the Hydrogen Vapor Pressure in the reaction is 0.1-5MPa.
In preferred embodiments, the reaction temperature of the reaction is 0-200 DEG C, and the reaction time is 1-12h.
In another aspect, the present invention provides a kind of diacetone alcohol hydrogenation catalyst, the catalyst be used for without using
Solvent is used one or more as solvent in water, C1-C12 alcohol, C1-C12 alkane and C1-C12 halogenated alkanes
In the case of catalysis diacetone alcohol hydrogenation prepare the reactions of 2- methyl -2,4- pentanediols, the catalyst is negative for active metal component
The load type metal catalyst on hydroxyapatite carrier is loaded in, wherein the active metal component is in the periodic table of elements
One or more in the transition metal of VIIIB or IB races, the hydroxyapatite carrier has formula Ma(XOb)c(Z)d,
Wherein M is one or more metal cations in group ia, group iia, Y, Ce and Pb in the periodic table of elements, and X is choosing
From the one or more in Si, P, S, V and As, Z is to be selected from OH-、CO3 2-、HCO3 -、F-、Cl-、Br-And I-In one or more
Contend with anion, and a, b, c and d are each independently 1-10 under conditions of the formula part valence balance.
In preferred embodiments, in the formula Ma(XOb)c(Z)dIn, M is one in Ca, Mg, Ce, Na and K
Plant or a variety of.
In preferred embodiments, the active metal component is one kind or many in Ru, Pd, Ir, Pt, Ni and Cu
Kind.
The method of the present invention can carry out carrying out under no solvent in environment-friendly solvent, and dipropyl
2- methyl -2,4-PD is made in the conversion ratio that keto-alcohol can be up to 100%；And the present invention by DAA prepare 2- first
The reaction process of base -2,4-PD is succinct, equipment is simple, easy to operate, reaction condition is very gentle；Simultaneously of the invention urges
Agent preparation process is simple, cost is low, it is possible to achieve large-scale production, catalyst hydrothermal stability prepared by ion-exchange
High, recycling performance is good；Reaction product and catalyst and dicyandiamide solution are easily separated, and reaction time is short, suitable for industrial production,
With boundless application prospect.
Brief description of the drawings
Fig. 1 is calcium hydroxy phosphate Ca used according to the invention5(PO4)3(OH) (HAP) and it is used as carrier system by the use of the HAP
The X of the catalyst (Ru-HAP) of standby obtained calcium hydroxy phosphate load ruthenium and the catalyst (Pd-HAP) of calcium hydroxy phosphate supported palladium
X ray diffraction (XRD) spectrogram.
Fig. 2 is the details in a play not acted out on stage, but told through dialogues ESEM of Pd-HAP prepared in accordance with the present invention (left figure) and Ru-HAP (right figure) catalyst
(HAADF-STEM) photo.
Fig. 3 is the gas chromatogram that the product prepared is reacted according to one embodiment of the invention.
Embodiment
The chemical equation for being converted into 2- methyl -2,4-PD by DAA is as follows：
In order to provide a kind of simple, green, the catalysis DAA high selectivity under the conditions of relatively mild efficiently, stable
Hydrogenation is for the method and catalyst of 2- methyl -2,4- pentanediols, and the present inventor is by furtheing investigate unexpectedly
It was found that, metallic catalyst of the Metal Supported prepared using such as ion-exchange on hydroxy apatites carrier, energy
Enough fcc raw material DAAs under conditions of quite gently (may be up to high conversion (up to 100%), high selectivity
100%) 2- methyl -2,4-PD is prepared.
It is not intended to be bound by any theory, the present inventor thinks, above-mentioned catalyst is in catalysis DAA to 2-
Have in the course of reaction of methyl -2,4- pentanediol it is higher catalytic activity main reason is that, it is more warm in reaction temperature
With under conditions of, above-mentioned reaction raw materials are difficult polymerization, while alkalescence, which is presented, in carrier hydroxyapatite (HAP) can substantially suppress two
Coking in pyruvic alcohol conversion process is formed；The carrier has very strong ion-exchange capacity simultaneously, can make the work of load
The dispersion effect of property metal component is very good, thus shows higher catalytic activity；In addition, the carrier HAP surfaces are contained
Sour site can have preferable suction-operated to carbonyl, the factor in terms of these can all cause the present invention catalyst performance
Go out good hydrogenation activity.
Found based on more than, 2- methyl -2 prepared by diacetone alcohol hydrogenation there is provided one kind in one aspect of the invention,
The method of 4- pentanediols, methods described includes making DAA react generation in the presence of diacetone alcohol hydrogenation catalyst with hydrogen
2- methyl -2,4- pentanediols, wherein the catalyst is the support type that active metal component is supported on hydroxyapatite carrier
Metallic catalyst.
In the present invention, the reaction can be used selected from water, C1-C12 alcohol, C1- without using solvent, or the reaction
One or more in C12 alkane and C1-C12 halogenated alkanes are used as solvent.
In another aspect of the present invention there is provided a kind of diacetone alcohol hydrogenation catalyst, the catalyst is used for not
Using solvent or use one or more as molten in water, C1-C12 alcohol, C1-C12 alkane and C1-C12 halogenated alkanes
The reaction that diacetone alcohol hydrogenation prepares 2- methyl -2,4- pentanediols is catalyzed in the case of agent, the catalyst is active metal group
Divide the load type metal catalyst being supported on hydroxyapatite carrier.
Preferably, the catalyst includes the weight % of 0.1 weight %~10, and the weight %'s of preferably 0.5 weight %~5 is described
Active metal component.
It is used to without using solvent or make there is provided above-mentioned diacetone alcohol hydrogenation catalyst in another aspect of the present invention
With in water, C1-C12 alcohol, C1-C12 alkane and C1-C12 halogenated alkanes one or more as solvent in the case of urge
Change the purposes that the reaction for preparing 2- methyl -2,4-PD is reacted by DAA and hydrogen.
In the catalyst of the present invention, the active metal component is VIIIB the or IB races in the periodic table of elements
One or more in transition metal, the hydroxyapatite carrier has formula Ma(XOb)c(Z)d, wherein M is selected from element
One or more metal cations in periodic table in group ia, group iia, Y, Ce and Pb, X is in Si, P, S, V and As
One or more, Z be selected from OH-、CO3 2-、HCO3 -、F-、Cl-、Br-And I-In one or more contend with anion, and
A, b, c and d are each independently 1-10 under conditions of the formula part valence balance.
Preferably, the active metal component is the one or more in Ru, Pd, Ir, Pt, Ni and Cu.
Preferably, in the carrier, M is the one or more in Ca, Mg, Ce, Na and K, particularly preferably Ca.
Preferably, in the carrier, X is P or V.
Preferably, in the carrier, Z is OH-、F-Or Cl-。
Preferably, in the presence of solvent, the solvent is preferably water.
Preferably, the reaction temperature of the reaction is 0-200 DEG C, more preferably preferably 60-160 DEG C, 80-140 DEG C.
Preferably, the hydrogen in reaction pressure is 0.1-5MPa, more preferably preferably 0.5-2MPa, 1-2MPa.
Preferably, the reaction time of the reaction is 1-12h, preferably 3-6h.
Preferably, catalyst of the invention is to be supported on using what ion-exchange was prepared on phosphorus ash stone carrier
Load type metal catalyst.
Embodiment
Further detailed complete explanation is done to the present invention with reference to instantiation.Such as without special theory in following embodiments
Bright, method therefor is conventional method, and agents useful for same is commercially obtained.The embodiments described below is exemplary
, it is only used for explaining the present invention, and be not construed as limiting the claims.
Catalyst preparation example
Load type metal catalyst used in the present invention, can be prepared as follows：
Ruthenium supported catalyst：50-150mL concentration is respectively adopted in 250mL round-bottomed flask for 0.126-1.265mg/
ML RuCl3·xH2O acetone soln (being purchased from Aladdin reagent Co., Ltd) dipping 0.50-1.00g apatite carrier is such as
Ca5(PO4)3(OH)、Mg2Ca3(PO4)3(OH)、Ce5(VO4)6(OH)2、Ca5(PO4)3(HCO3)、Ca5(PO4)3F or Na10(PO4)3
Etc. (OH) (it is purchased from Aladdin reagent Co., Ltd), magnetic stirrer 12-24h is reached after adsorption equilibrium, vavuum pump suction filtration
And washed with acetone, 6-12h is dried under the conditions of 20-100 DEG C in drying box, then using tubular reduction furnace at 150-400 DEG C
Under use H2Reduction 1-6 hours, obtains the ruthenium in table 1 with 0.5 weight %-5 weight % supported ruthenium catalyst.
Palladium supported catalyst：50-150mL concentration is respectively adopted in 250mL round-bottomed flask for 0.228-2.28mg/mL
Pd (OAC)2Acetone soln (be purchased from Aladdin reagent Co., Ltd) dipping 0.50-1.00g phosphorus ash stone carrier such as Ca5
(PO4)3(OH)、Mg2Ca3(PO4)3(OH)、Ce5(VO4)6(OH)2、Ca5(PO4)3(HCO3)、Ca5(PO4)3F or Na10(PO4)3
(OH) etc. (being purchased from Aladdin reagent Co., Ltd), magnetic stirrer 12-24h is reached after adsorption equilibrium, vacuum pumping
Filter and washed with acetone, 6-12h is dried under the conditions of 20-100 DEG C in drying box, then using tubular reduction furnace in 150-400
H is used at DEG C2Reduction 1-6 hours, obtains the palladium in table 1 with 0.5 weight %-5 weight % loaded palladium catalyst.
Fig. 1 is calcium hydroxy phosphate Ca used according to the invention5(PO4)3(OH) (HAP) and it is used as carrier by the use of the HAP
The catalyst (Pd-HAP) and calcium hydroxy phosphate of the calcium hydroxy phosphate supported palladium prepared load the catalyst (Ru-HAP) of ruthenium
X-ray diffraction (XRD) spectrogram.It will be seen from figure 1 that passing through the pattern contrast table before and after hydroxyapatite carrier to load metal
It is bright, the diffraction maximum of any metal species is not observed after supported active metals component on the XRD spectra of hydroxyapatite, this
Illustrate that metal disperses on carrier HAP highly uniform, while also illustrate that the stability of hydroxyapatite carrier appearance structure is non-
Chang Hao.
Fig. 2 is the HAADF-STEM photos of Pd-HAP and Ru-HAP catalyst prepared in accordance with the present invention.From Fig. 2 details in a play not acted out on stage, but told through dialogues
Electron microscope can be seen that active metal component and load to after carrier HAP, and the active metal component disperses non-on carrier HAP
It is often uniform, metallic particles is counted and calculated, the average grain diameter of active metal component Pd metals only has 0.9nm, it is living
The average grain diameter of property metal component Ru metals only has 1.2nm, illustrates the metal dimension loaded on hydroxy apatites carrier all
It is very small.
Two or more combinations in other metals Ir, Pt, Ni or Cu or various metals Ru, Pd, Ir, Pt, Ni and Cu are born
Carried catalyst：It is identical that its preparation process and above-mentioned Ru or Pd load to hydroxyapatite supported catalyst preparation method, obtains
The catalyst arrived is as shown in table 1.
Load type metal catalyst explained below using above-mentioned preparation is catalyzed DAA high-selective and hydrogenating system
The application examples of standby 2- methyl -2,4-PD.
Application examples 1-8
The catalyst prepared using said process is under 120 DEG C, 1MPa hydrogen, in aqueous solvent, reacts 3h, is catalyzed dipropyl
Keto-alcohol Hydrogenation is for 2- methyl -2,4- pentanediols, and detailed process is as follows：
100mg DAAs are added in 50mL Parr reactors, the corresponding carried metal shown in table 1 is utilized respectively
Catalyst (1 weight % active metal components), adds 10mL water, and Hydrogen Vapor Pressure is set to 1MPa, ramped heating schedule to 120
DEG C, under magnetic agitation, after reacting 3 hours, cooling, opening reactor are slowly deflated, and catalyst is divided with reaction solution by centrifugation
From after reaction solution ethanol dilutes, with gas-chromatography (being purchased from Ke Xiao Instrument Ltd.) analysis.GC conditions are as follows：
GC1690 gas-chromatography fid detectors, capillary chromatographic column (Innowax, 30m × 0.250mm × 0.25 μm), take program liter
Temperature, starting column temperature is 40 DEG C, and rising to 250 DEG C with 10 DEG C/min heating rate is kept for 10 minutes.Carrier gas for 99.99% it is high-purity
N2, flow velocity is 1mL/min.Three times repetition experiment gas chromatographic analysis result its results detailed in Table 1 and Fig. 3.Fig. 3 is according to this
The gas chromatogram of product prepared by the reaction of invention one embodiment, Fig. 3 reflects internal standard method and reaction yield is quantified, its
Middle t=12.015min, 2- methyl -2,4- pentanediol；T=8.148min, internal standard compound n-hexyl alcohol.
Application examples 9-14
The Metal Supported of different loads amount (0.5-5 weight % active metal components) as shown in table 1 is carried in apatite
Metallic catalyst on body is at 60 DEG C, and 2MPa hydrogen in alcohol solvent, reacts 4h, catalysis diacetone alcohol hydrogenation prepares 2- first
Base -2,4- pentanediol, detailed process is as follows：
100mg DAAs are added in 50mL Parr reactors, the corresponding carried metal shown in table 1 is utilized respectively
Catalyst, adds 10mL ethanol, and Hydrogen Vapor Pressure is set to 2MPa, is heated to after 60 DEG C, under stirring condition, 4 hours of reaction, cold
But, deflate, centrifuge, catalyst is separated with reaction solution, after reaction solution ethanol dilutes, use gas chromatographic analysis.Gas-chromatography
Condition is as follows：GC1690 gas-chromatography fid detectors, capillary chromatographic column (Innowax, 30m × 0.250mm × 0.25 μm),
Temperature programming is taken, starting column temperature is 40 DEG C, rising to 250 DEG C with 10 DEG C/min heating rate is kept for 10 minutes.Carrier gas is
99.99% high-purity N2, flow velocity is 1mL/min.The gas chromatographic analysis of three repetition experiments the results are shown in Table 1.
Application examples 15-25
By metal supported catalyst (the 1 weight % activity of different single-activity metal components as shown in table 1 and combinations thereof
Metal component) at 40 DEG C, 2MPa hydrogen in isopropanol solvent, reacts 4h, catalysis diacetone alcohol hydrogenation prepares 2- methyl -2,
4- pentanediols, detailed process is as follows：
100mg DAAs are added in 50mL Parr reactors, the corresponding carried metal shown in table 1 is utilized respectively
Catalyst, adds 10mL isopropanol, and Hydrogen Vapor Pressure is set to 2MPa, is heated to after 40 DEG C, under stirring condition, 4 hours of reaction,
Cooling, deflation, centrifugation, make catalyst be separated with reaction solution, after reaction solution ethanol dilutes, use gas chromatographic analysis.Gas phase color
Spectral condition is as follows：GC1690 gas-chromatography fid detectors, the capillary chromatographic column (μ of Innowax, 30m × 0.250mm × 0.25
M), temperature programming is taken, starting column temperature is 40 DEG C, rising to 250 DEG C with 10 DEG C/min heating rate is kept for 10 minutes.Carrier gas is
99.99% high-purity N2, flow velocity is 1mL/min.The gas chromatographic analysis of three repetition experiments the results are shown in Table 1.
Application examples 26-38
By catalyst (2 weight % active metal components) as shown in table 1 in 100 DEG C, 3MPa hydrogen, different solvents condition
Under, reaction 5h catalysis diacetone alcohol hydrogenations prepare 2- methyl -2,4- pentanediols, and detailed process is as follows：
100mg DAAs are added in 50mL Parr reactors, the corresponding carried metal shown in table 1 is utilized respectively
Catalyst, adds 10mL solvents, and Hydrogen Vapor Pressure is set to 3MPa, is heated to after 100 DEG C, under stirring condition, 5 hours of reaction, cold
But, deflate, centrifuge, catalyst is separated with reaction solution, after reaction solution ethanol dilutes, use gas chromatographic analysis.Gas-chromatography
Condition is as follows：GC1690 gas-chromatography fid detectors, capillary chromatographic column (Innowax, 30m × 0.250mm × 0.25 μm),
Temperature programming is taken, starting column temperature is 40 DEG C, rising to 250 DEG C with 10 DEG C/min heating rate is kept for 10 minutes.Carrier gas is
99.99% high-purity N2, flow velocity is 1mL/min.The gas chromatographic analysis of three repetition experiments the results are shown in Table 1.
Application examples 39-49
By catalyst (5 weight % active metal components) as shown in table 1 under condition of different temperatures (0-200 DEG C),
1MPa hydrogen, using C6-C12 alkane or halogenated alkane as solvent, reaction 6h catalysis diacetone alcohol hydrogenations prepare 2- methyl -2,4- penta
Glycol, detailed process is as follows：
100mg DAAs are added in 50mL Parr reactors, the corresponding carried metal shown in table 1 is utilized respectively
Catalyst, adds 10mL n-hexane, Hydrogen Vapor Pressure is 1MPa, is heated under design temperature, stirring condition, reacts 6 hours
Afterwards, cool down, deflate, centrifuge, catalyst is separated with reaction solution, after reaction solution ethanol dilutes, use gas chromatographic analysis.Gas phase
Chromatographic condition is as follows：GC1690 gas-chromatography fid detectors, the capillary chromatographic column (μ of Innowax, 30m × 0.250mm × 0.25
M), temperature programming is taken, starting column temperature is 40 DEG C, rising to 250 DEG C with 10 DEG C/min heating rate is kept for 10 minutes.Carrier gas is
99.99% high-purity N2, flow velocity is 1mL/min.The gas chromatographic analysis of three repetition experiments the results are shown in Table 1.
Application examples 50-55
By catalyst (1 weight % active metal components) (0.1- under different hydrogen pressure condition as shown in table 1
4MPa), 140 DEG C, in aqueous solvent, 3h is reacted, catalysis diacetone alcohol hydrogenation prepares 2- methyl -2,4- pentanediols, detailed process
It is as follows：
100mg DAAs are added in 50mL Parr reactors, the corresponding carried metal shown in table 1 is utilized respectively
Catalyst, adds 10mL water, and Hydrogen Vapor Pressure is added to setting hydrogen pressure, is heated to 140 DEG C, under stirring condition, reacts 3 hours
Afterwards, cool down, deflate, centrifuge, catalyst is separated with reaction solution, after reaction solution ethanol dilutes, use gas chromatographic analysis.Gas phase
Chromatographic condition is as follows：GC1690 gas-chromatography fid detectors, the capillary chromatographic column (μ of Innowax, 30m × 0.250mm × 0.25
M), temperature programming is taken, starting column temperature is 40 DEG C, rising to 250 DEG C with 10 DEG C/min heating rate is kept for 10 minutes.Carrier gas is
99.99% high-purity N2, flow velocity is 1mL/min.The gas chromatographic analysis of three repetition experiments the results are shown in Table 1.
Application examples 56-63
By catalyst (2 weight % active metal components) as shown in table 1 under differential responses time conditions (1-10h),
160 DEG C, 1MPa hydrogen, catalysis diacetone alcohol hydrogenation prepares 2- methyl -2,4- pentanediols in aqueous solvent, and detailed process is as follows：
100mg DAAs are added in 50mL Parr reactors, the corresponding carried metal shown in table 1 is utilized respectively
Catalyst, adds 10mL water, and Hydrogen Vapor Pressure is set to 1MPa, is heated to after 160 DEG C, under stirring condition, reaction setting time, cold
But, deflate, centrifuge, catalyst is separated with reaction solution, after reaction solution ethanol dilutes, use gas chromatographic analysis.Gas-chromatography
Condition is as follows：GC1690 gas-chromatography fid detectors, capillary chromatographic column (Innowax, 30m × 0.250mm × 0.25 μm),
Temperature programming is taken, starting column temperature is 40 DEG C, rising to 250 DEG C with 10 DEG C/min heating rate is kept for 10 minutes.Carrier gas is
99.99% high-purity N2, flow velocity is 1mL/min.The gas chromatographic analysis of three repetition experiments the results are shown in Table 1.
Application examples 64-72
By catalyst (1 weight % or 5 weight % active metal components) as shown in table 1 at 60-160 DEG C, 2MPa hydrogen,
Without using under solvent condition, reaction 3h catalysis diacetone alcohol hydrogenations prepare 2- methyl -2,4- pentanediols.
100mg DAAs are added in 50mL Parr reactors, the corresponding carried metal shown in table 1 is utilized respectively
Catalyst, is added without solvent, and Hydrogen Vapor Pressure is set to 2MPa, is heated under specified temp, stirring condition, cold after 3 hours of reaction
But, deflate, centrifuge, catalyst is separated with reaction solution, after reaction solution ethanol dilutes, use gas chromatographic analysis.Gas-chromatography
Condition is as follows：GC1690 gas-chromatography fid detectors, capillary chromatographic column (Innowax, 30m × 0.250mm × 0.25 μm),
Temperature programming is taken, starting column temperature is 40 DEG C, rising to 250 DEG C with 10 DEG C/min heating rate is kept for 10 minutes.Carrier gas is
99.99% high-purity N2, flow velocity is 1mL/min.The gas chromatographic analysis of three repetition experiments the results are shown in Table 1.
Table 1
Note：--- represent solvent-free.
It is can be seen that from the reaction result of table 1 using hydroxyapatite and be used as prepared by carrier loaded active metal component urging
Agent can be catalyzed two in water, alcohols, alkane or halogenated alkane solvents or under solvent-free under gentle reaction condition
Pyruvic alcohol prepares target product 2- methyl -2,4-PD with high conversion, high yield.
Moreover, use above example result shows, the present invention by hydroxyapatite and metal (Ru, Pd, Ir, Pt, Ni, Cu and
Its various metals is combined) loaded catalyst that is prepared by the method for ion exchange, under conditions of quite gentle
(100-160 DEG C, 1-2MPa H2, 3-6h) and can be with high conversion (up to 100%), in high yield (up to 100%) prepare
2- methyl -2,4- pentanediols, realize a kind of simple, green, efficient catalyst compared with being catalyzed DAA under temperate condition
High-selective and hydrogenating prepares 2- methyl -2,4- pentanediol better methods, can better meet industrial applications demand.
Although the embodiment of the present invention has obtained detailed description, it will be understood to those of skill in the art that.Root
According to disclosed all teachings, various modifications and replacement can be carried out to those details, these change the guarantor in the present invention
Within the scope of shield.The four corner of the present invention is provided by appended claims and its any equivalent.
Claims (10)
1. a kind of method that 2- methyl -2,4- pentanediols are prepared by diacetone alcohol hydrogenation, methods described include making DAA with
Hydrogen reacts generation 2- methyl -2,4- pentanediols in the presence of a catalyst, wherein the catalyst loads for active metal component
Load type metal catalyst on hydroxyapatite carrier, and wherein described active metal component is selected from the periodic table of elements
In VIIIB or IB races transition metal in one or more, the hydroxyapatite carrier has formula Ma(XOb)c
(Z)d, wherein M is one or more metals in the periodic table of elements in group ia, group iia, Y, Ce and Pb, X be selected from
One or more in Si, P, S, V and As, Z is to be selected from OH-、CO3 2-、HCO3 -、F-、Cl-、Br-And I-In one or more resist
Weigh anion, and a, b, c and d are each independently 1-10 under conditions of the formula part valence balance.
2. according to the method described in claim 1, it is characterised in that the reaction is without using solvent.
3. according to the method described in claim 1, it is characterised in that the reaction is used selected from water, C1-C12 alcohol, C1-C12 alkane
One or more in hydrocarbon and C1-C12 halogenated alkanes are used as solvent.
4. according to the method described in claim 1, it is characterised in that in the formula Ma(XOb)c(Z)dIn, M be selected from Ca, Mg,
One or more in Ce, Na and K.
5. according to the method described in claim 1, it is characterised in that the active metal component is selected from Ru, Pd, Ir, Pt, Ni
With the one or more in Cu.
6. according to the method described in claim 1, it is characterised in that the Hydrogen Vapor Pressure in the reaction is 0.1-5MPa.
7. according to the method described in claim 1, it is characterised in that the reaction temperature of the reaction is 0-200 DEG C, reaction time
For 1-12h.
8. a kind of diacetone alcohol hydrogenation catalyst, the catalyst be used for without using solvent or using selected from water, C1-C12 alcohol,
In C1-C12 alkane and C1-C12 halogenated alkanes one or more as solvent in the case of be catalyzed diacetone alcohol hydrogenation prepare
The reaction of 2- methyl -2,4- pentanediols, the catalyst is the load that active metal component is supported on hydroxyapatite carrier
Type metallic catalyst, wherein the active metal component is in the transition metal of VIIIB or IB races in the periodic table of elements
One or more, the hydroxyapatite carrier has formula Ma(XOb)c(Z)d, wherein M is the in the periodic table of elements
One or more metals in IA races, group iia, Y, Ce and Pb, X is the one or more in Si, P, S, V and As, and Z is
Selected from OH-、CO3 2-、HCO3 -、F-、Cl-、Br-And I-In one or more contend with anion, and a, b, c and d are described logical
1-10 is each independently under conditions of formula part valence balance.
9. diacetone alcohol hydrogenation catalyst according to claim 8, it is characterised in that in the formula Ma(XOb)c(Z)d
In, M is the one or more in Ca, Mg, Ce, Na and K.
10. diacetone alcohol hydrogenation catalyst according to claim 8, it is characterised in that the active metal component is choosing
From the one or more in Ru, Pd, Ir, Pt, Ni and Cu.
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| CN110721715B (en) * | 2019-11-12 | 2022-08-05 | 万华化学集团股份有限公司 | Catalyst and method for preparing isohexide by using same |
| CN111298816A (en) * | 2020-03-03 | 2020-06-19 | 苏州彼定新材料科技有限公司 | Preparation method of porous hydroxyapatite supported platinum catalyst |
| CN111298816B (en) * | 2020-03-03 | 2023-05-16 | 苏州彼定新材料科技有限公司 | Preparation method of porous hydroxyapatite supported platinum catalyst |
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