CN104402675B - A kind of method that bionic catalysis oxidation of isobutane prepares the tert-butyl alcohol - Google Patents
A kind of method that bionic catalysis oxidation of isobutane prepares the tert-butyl alcohol Download PDFInfo
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- CN104402675B CN104402675B CN201410669534.3A CN201410669534A CN104402675B CN 104402675 B CN104402675 B CN 104402675B CN 201410669534 A CN201410669534 A CN 201410669534A CN 104402675 B CN104402675 B CN 104402675B
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- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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Abstract
The invention discloses a kind of method that bionic catalysis oxidation of isobutane prepares the tert-butyl alcohol, the method is with iso-butane as raw material, with metal porphyrins as catalyst, with oxygen as oxygen source, add a certain amount of solvent, promoter and radical initiator, controlling reaction temperature is 50 ~ 120 DEG C, and reaction pressure is to carry out catalytic reaction under conditions of 0.5 ~ 2 MPa to obtain the tert-butyl alcohol.It is an advantage of the current invention that reaction condition is gentle, easy to operate, conversion ratio is high, the advantage that selectivity is high.
Description
Technical field
The present invention relates to the preparation method of a kind of tert-butyl alcohol, specifically, relate to a kind of bionic catalysis iso-butane
The method of the tert-butyl alcohol is prepared in oxidation.
Background technology
The tert-butyl alcohol is commonly used to replace n-butyl alcohol as coating and the solvent of medicine, also is used as automotive fuel simultaneously
Additive (preventing carburetor) and antidetonator, the intermediate of organic synthesis and produce tert-butylation compound
Raw material for alkylation, has in terms of producing methyl methacrylate, tert-butyl phenol, the important industrial chemicals of tert-butylamine
Have been widely used.
Propylene/iso-butane cooxidation is a kind of main method of the commercial production tert-butyl alcohol, and U.S. Halcon develops also
On the one hand the method industrialization, the method can be had third by the Oxriane company of composition joint with Arco company
The tert-butyl hydroperoxide cooxidation that alkene and iso-butane are generated generates expoxy propane, on the other hand the coproduction tert-butyl alcohol,
Raw material availability is high, pollutes few, but investment is big and complex process.
Isobutene. hydration is also conventional to prepare the tert-butyl alcohol, wherein with ion exchange resin, ionic liquid or solid acid
Leading (CN 101139251, CN 1714062, CN 1603290) is occupied Deng the direct hydration method for catalyst,
But it is poor with the intersolubility of water that the shortcoming of direct hydration method is isobutene., and therefore conversion ratio is relatively low.Sulfuric acid hydration process
Can obtain the tert-butyl alcohol of high yield, but pollute the problems such as big, equipment corrosion is serious owing to existing, this technology is current
The most gradually eliminate.
Iso-butane is can be obtained by the C-4-fraction produced in petroleum cracking process is separated, abundance, because of
This iso-butane direct oxidation is prepared the tert-butyl alcohol extremely people and is paid close attention to.United States Patent (USP) US 2845461 discloses isobutyl
The method that alkane liquid phase non-catalytic oxidation prepares the tert-butyl alcohol, in reaction temperature 100～150 DEG C, reaction pressure 3.4～4.8
Under conditions of MPa, the conversion ratio of iso-butane is about 20～35%, and the selectivity of the tert-butyl alcohol is 15～20%.China
Patent CN 102807469 discloses prepares the tert-butyl alcohol with metal phthalocyanine for catalyst liquid phase catalytic oxidation iso-butane
Method, in the method, the conversion ratio of iso-butane can reach about 30%, and product tertiary butanol selectivity also can reach
～80%, but required reaction temperature and pressure are the highest, and catalyst amount is big.
Therefore, exploitation reaction condition bionic catalysis gentle, green, efficient iso-butane dioxygen oxidation prepares tertiary fourth
Alcohol technique has important practical significance and application prospect.
Summary of the invention
For the defect overcoming above-mentioned prior art to exist, it is an object of the invention to provide a kind of bionic catalysis different
Butane oxidation prepares the method for the tert-butyl alcohol.
For realizing the purpose of the present invention, be the technical scheme is that with iso-butane as raw material, with oxygen as oxygen
Source, adds solvent, auxiliary agent and radical initiator, with logical formula (I) or the mononuclear porphyrin of (II) structure or logical
μ-oxygen-the dinuclear metalloporphyrin of formula (III) structure is catalyst, and controlling in reaction temperature is 50～120 DEG C, reaction
Pressure is to carry out catalytic reaction under conditions of 0.5～2MPa to obtain the tert-butyl alcohol, and catalyst amount is 1～100ppm,
Auxiliary dosage is the 0.5～2mol% of raw material, and the consumption of radical initiator is the 0.05～1mol% of raw material,
M in logical formula (I)1Be metallic atom Mg, Al, Fe, Co, Mn, Ni, Cu or Zn, X be halogen
Element or hydrogen, R1、R2、R3、R4And R5Be selected from hydrogen, halogen, nitro, methyl, hydroxyl, alkoxyl or
Sulfonic group；M in logical formula (II)2It is metallic atom Cr, Mn, Fe, Co, Ni, Cu, Zn or Sn, X
It is halogen or hydrogen, R1、R2、R3、R4And R5It is selected from hydrogen, halogen, nitro, alkyl, alkoxyl, hydroxyl
Base, carboxyl or sulfonic group, dentate X1It is chlorine or imidazoles or pyridine；M in logical formula (III)3It it is metallic atom
Fe, Co, Mn, Ru or Rh, R1、R2、R3、R4And R5Be selected from hydrogen, halogen, nitro, alkyl,
Alkoxyl, hydroxyl, carboxyl or sulfonic group.
In above-mentioned bionic catalysis oxidation of isobutane prepares the method for the tert-butyl alcohol, described radical initiator is selected from
One in HP (NHPI) or derivatives thereof.
In above-mentioned bionic catalysis oxidation of isobutane prepares the method for the tert-butyl alcohol, described auxiliary agent for selected from containing Cr,
One in the inorganic salt of Fe, Mn, Co, V, Ni, Cu, Zn, Pd or Ru, preferred auxiliary agent is for containing
The acetate of Fe, Mn, Co or Pd or chloride.
In above-mentioned bionic catalysis oxidation of isobutane prepares the method for the tert-butyl alcohol, described solvent be selected from acetonitrile,
One in cyanophenyl, ethyl acetate, dichloromethane, acetic acid or 1,2-dichloroethanes.
In above-mentioned bionic catalysis oxidation of isobutane prepares the method for the tert-butyl alcohol, the consumption of described catalyst is
10～50ppm, radical initiator consumption is the 0.1～0.8mol% of raw material, and auxiliary dosage is the 0.8～1.5 of raw material
Mol%, reaction temperature is 60～100 DEG C, and reaction pressure is 0.8～1.5MPa.
The present invention by catalyst uniform dissolution in a solvent, adds radical initiator and auxiliary agent, make iso-butane and
Oxygen carries out catalytic reaction under the effect of catalyst and generates the tert-butyl alcohol.The purpose of the radical initiator added exists
Generating free radical in making system be easier to, the tertiary hydrogen capturing iso-butane generates tert-butyl group free radical, metal under low temperature
Porphyrin has good activation to molecular oxygen thus accelerates the conversion of iso-butane under low temperature.Add the purpose of auxiliary agent
It is that promoting that tert-butyl group free radical decomposes generates the product tert-butyl alcohol, thus improves the conversion of reaction rate, iso-butane
Rate and the selectivity of product.Under the various reaction system of the present invention, the selectivity of the tert-butyl alcohol is high, and product is easily separated,
Catalyst usage amount is few, and radical initiator and auxiliary agent can realize reusing by centrifugal or filtration.
Compared with prior art, there is advantages that
1. the efficiency of the present invention is high, selectivity of product is high, mild condition, and energy consumption reduces.
2. the present invention uses metalloporphyrin to be catalyst, it is to avoid bring due to acidic catalyst in isobutene. hydration method
Equipment heavy corrosion, environmental pollution and security problems.
3. the catalyst amount that the present invention uses is few, technique is simple, Financial cost is low, green safety, has good
Prospects for commercial application.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, but protection scope of the present invention is not limited to
The scope that embodiment represents.
Embodiment 1
In autoclave, addition 20mL contains 100ppm and has logical formula (I) structural metal porphyrin
(M1=Co, X=H, R1=NO2,R2=R3=R4=R5=H) acetonitrile solution, add 0.005mmol freedom
Base initiator NHPI and 0.02mmolCo (OAc)2, it is filled with 10mmol iso-butane and 2MPa O2, in temperature
Degree stirs under conditions of being 120 DEG C, and through gas chromatographic detection, iso-butane conversion ratio is 41%, the choosing of the tert-butyl alcohol
Selecting property is 96%.
Embodiment 2
In autoclave, addition 20mL contains 50ppm and has logical formula (I) structural metal porphyrin (M1=Mn,
X=F, R3=Cl, R1=R2=R4=R5=H) ethyl acetate solution, add 0.1mmol radical initiator
NHPI and 0.05mmolMn (OAc)2, it is filled with 10mmol iso-butane and 0.5MPa O2, it is 50 DEG C in temperature
Under conditions of stir, through gas chromatographic detection, iso-butane conversion ratio is 38%, and the selectivity of the tert-butyl alcohol is 95%.
Embodiment 3
In autoclave, addition 20mL contains 1ppm and has logical formula (I) structural metal porphyrin (M1=Cu,
X=H, R1=Cl, R2=R3=R4=R5=H) 1,2-dichloroethane solution, add 0.05mmol free radical draw
Send out agent NHPI and 0.08mmolPdCl2, it is filled with 10mmol iso-butane and 0.8MPa O2, it is 60 DEG C in temperature
Under conditions of stir, through gas chromatographic detection, iso-butane conversion ratio is 43%, and the selectivity of the tert-butyl alcohol is 97%.
Embodiment 4
In autoclave, addition 20mL contains 10ppm and has logical formula (I) structural metal porphyrin (M1=Ni,
X=H, R2=DEG C H3,R1=R3=R4=R5=H) dichloromethane solution, add 0.08mmol free radical draw
Send out agent (N-acetyl group phthalimide, NAPI) and 0.1mmolMnCl2, it is filled with 10mmol isobutyl
Alkane and 1MPa O2, stir under conditions of temperature is 80 DEG C, through gas chromatographic detection, iso-butane conversion ratio
Being 42%, the selectivity of the tert-butyl alcohol is 96%.
Embodiment 5
In autoclave, addition 20mL contains 10ppm and has logical formula (II) structural metal porphyrin
(M2=Mn, X1=imidazoles, X=H, R1=NO2,R2=R3=R4=R5=H) cyanophenyl solution, add 0.04mmol
Radical initiator (N-acetyl group phthalimide, NAPI) and 0.12mmolFe (OAc)2, it is filled with
10mmol iso-butane and 1.2MPa O2, stir under conditions of temperature is 100 DEG C, through gas chromatographic detection,
Iso-butane conversion ratio is 45%, and the selectivity of the tert-butyl alcohol is 98%.
Embodiment 6
In autoclave, addition 20mL contains 30ppm and has logical formula (II) structural metal porphyrin (M2=Cr,
X1=Cl, X=H, R3=CH3, R1=R2=R4=R5=H) acetonitrile solution, add 0.03mmol free radical
Initiator (N-acetyl group phthalimide, NAPI) and 0.15mmolFe (OAc)2, it is filled with 10mmol
Iso-butane and 1.2MPa O2, stir under conditions of temperature is 90 DEG C, through gas chromatographic detection, iso-butane
Conversion ratio is 42%, and the selectivity of the tert-butyl alcohol is 96%.
Embodiment 7
In autoclave, addition 20mL contains 80ppm and has logical formula (II) structural metal porphyrin (M2=Co,
X1=Cl, X=H, R1=NO2,R2=R3=R4=R5=H) ethyl acetate solution, add 0.06mmol freedom
Base initiator NHPI and 0.09mmolZnCl2, it is filled with 10mmol iso-butane and 1.2MPa O2, in temperature
Stirring under conditions of being 100 DEG C, through gas chromatographic detection, iso-butane conversion ratio is 45%, the selection of the tert-butyl alcohol
Property is 97%.
Embodiment 8
In autoclave, addition 20mL contains 50ppm and has logical formula (II) structural metal porphyrin (M2=Fe,
X1=pyridine, X=H, R1=R2=R3=R4=R5=H) acetic acid solution, add 0.02mmol free radical cause
Agent NHPI and 0.18mmolCuCl2, it is filled with 10mmol iso-butane and 1.5MPa O2, it is 80 DEG C in temperature
Under conditions of stir, through gas chromatographic detection, iso-butane conversion ratio is 46%, and the selectivity of the tert-butyl alcohol is 96%.
Embodiment 9
In autoclave, addition 20mL contains 40ppm and has logical formula (III) structural metal porphyrin
(M3=Fe, R1=R2=R3=R4=R5=H) acetonitrile solution, add 0.07mmol radical initiator
NHPI and 0.12mmolPd (OAc)2, it is filled with 10mmol iso-butane and 1.3MPa O2, it is 90 DEG C in temperature
Under conditions of stir, through gas chromatographic detection, iso-butane conversion ratio is 56%, and the selectivity of the tert-butyl alcohol is 97%.
Embodiment 10
In autoclave, addition 20mL contains 50ppm and has logical formula (III) structural metal porphyrin
(M3=Mn, R1=Cl, R2=R3=R4=R5=H) dichloromethane solution, add 0.1mmol free radical draw
Send out agent (3-picolyl-HP, Py-NHPI) and 0.14mmolCo (OAc)2,
It is filled with 10mmol iso-butane and 1.2MPa O2, stir under conditions of temperature is 90 DEG C, through gas chromatogram
Detection, iso-butane conversion ratio is 40%, and the selectivity of the tert-butyl alcohol is 97%.
Embodiment 11
In autoclave, addition 20mL contains 20ppm and has logical formula (III) structural metal porphyrin
(M3=Ru, R1=R2=R3=R4=R5=H) ethyl acetate solution, add 0.01mmol free radical cause
Agent (3-picolyl-HP, Py-NHPI) and 0.18mmolMnCl2, it is filled with
10mmol iso-butane and 1MPa O2, stir under conditions of temperature is 120 DEG C, through gas chromatographic detection,
Iso-butane conversion ratio is 48%, and the selectivity of the tert-butyl alcohol is 96%.
Embodiment 12
In autoclave, addition 20mL contains 50ppm and has logical formula (III) structural metal porphyrin
(M3=Rh, R1=R2=R3=R4=R5=H) 1,2-dichloroethane solution, add 0.08mmol free radical
NHPI and 0.12mmolC DEG C of l of initiator2, it is filled with 10mmol iso-butane and 1.2MPa O2, in temperature it is
Stirring under conditions of 80 DEG C, through gas chromatographic detection, iso-butane conversion ratio is 46%, and the selectivity of the tert-butyl alcohol is
95%.
Claims (10)
1. the method that a bionic catalysis oxidation of isobutane prepares the tert-butyl alcohol, it is characterised in that with iso-butane as raw material,
With oxygen as oxygen source, add solvent, auxiliary agent and radical initiator, with the monokaryon gold of logical formula (I) or (II) structure
μ-oxygen-the dinuclear metalloporphyrin belonging to porphyrin or logical formula (III) structure is catalyst, control in reaction temperature be
50～120 DEG C, reaction pressure is to carry out catalytic reaction under conditions of 0.5～2MPa to obtain the tert-butyl alcohol, and catalyst is used
Amount is 1～100ppm, and auxiliary dosage is the 0.5～2mol% of raw material, and the consumption of radical initiator is raw material
0.05～1mol%,
M in logical formula (I)1It is metallic atom Mg, Al, Fe, Co, Mn, Ni, Cu or Zn, R1、R2、
R3、R4And R5It is selected from hydrogen, halogen, nitro, methyl, hydroxyl, alkoxyl or sulfonic group；Logical formula (II)
In M2It is metallic atom Cr, Mn, Fe, Co, Ni, Cu, Zn or Sn, R1、R2、R3、R4With
R5It is selected from hydrogen, halogen, nitro, alkyl, alkoxyl, hydroxyl, carboxyl or sulfonic group, dentate X1It is
Chlorine or imidazoles or pyridine；M in logical formula (III)3It is metallic atom Fe, Co, Mn, Ru or Rh, R1、
R2、R3、R4And R5It is selected from hydrogen, halogen, nitro, alkyl, alkoxyl, hydroxyl, carboxyl or sulfonic group.
Method the most according to claim 1, it is characterised in that described radical initiator is selected from N-
One in hydroxyphthalimide or derivatives thereof.
Method the most according to claim 1, it is characterised in that described auxiliary agent for selected from containing Cr, Fe,
One in the inorganic salt of Mn, Co, V, Ni, Cu, Zn, Pd or Ru.
Method the most according to claim 1, it is characterised in that auxiliary agent is containing Fe, Mn, Co or Pd
Acetate or chloride.
Method the most according to claim 1, it is characterised in that described solvent be selected from acetonitrile, cyanophenyl,
One in ethyl acetate, dichloromethane, acetic acid or 1,2-dichloroethanes.
Method the most according to claim 1, it is characterised in that the consumption of catalyst is 10～50ppm.
Method the most according to claim 1, it is characterised in that described radical initiator consumption is former
The 0.1～0.8mol% of material.
Method the most according to claim 1, it is characterised in that described auxiliary dosage is the 0.8～1.5 of raw material
Mol%.
Method the most according to claim 1, it is characterised in that reaction temperature is 60～100 DEG C.
Method the most according to claim 1, it is characterised in that reaction pressure is 0.8～1.5MPa.
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| CN201410669534.3A CN104402675B (en) | 2014-11-20 | 2014-11-20 | A kind of method that bionic catalysis oxidation of isobutane prepares the tert-butyl alcohol |
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| CN104402675B true CN104402675B (en) | 2016-11-30 |
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| CN110483244B (en) * | 2019-08-21 | 2022-07-08 | 中山大学 | Preparation method of tert-butyl alcohol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0471561A2 (en) * | 1990-08-16 | 1992-02-19 | Sun Refining and Marketing Company | Metal coordination complex catalysts containing a halogenated ligand for hydrocarbon oxidation |
| CN1546457A (en) * | 2003-12-18 | 2004-11-17 | 北京工业大学 | Preparation of o-nitrobenzaldehyde by biomimetic catalysis oxidation of o-nitrotoluene with oxygen |
-
2014
- 2014-11-20 CN CN201410669534.3A patent/CN104402675B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0471561A2 (en) * | 1990-08-16 | 1992-02-19 | Sun Refining and Marketing Company | Metal coordination complex catalysts containing a halogenated ligand for hydrocarbon oxidation |
| CN1546457A (en) * | 2003-12-18 | 2004-11-17 | 北京工业大学 | Preparation of o-nitrobenzaldehyde by biomimetic catalysis oxidation of o-nitrotoluene with oxygen |
Non-Patent Citations (3)
| Title |
|---|
| Recent progress in aerobic oxidation of hydrocarbons by N-hydroxyimides;Yasutaka Ishii，et al.;《Catalysis Today》;20060630;第117卷;105-113 * |
| SELECTIVE LOW TEMPERATURE HYDROXYLATION OF ISOBUTANE BY MOLECULAR OXYGEN CATALYZED BY AN IRON PERHALOPORPHYRIN COMPLEX;James E. LYONS，et al.;《Catalysis Letters》;19911231;第8卷;45-52 * |
| 水溶性金属卟啉应用于催化反应的研究进展;任清刚等;《有机化学》;20101130;第30卷(第11期);1605-1614 * |
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