CN104607249A - Chelating type porous catalyst for synthesizing carbonic acid dialkyl ester by liquid-phase oxidative carbonylation, and preparation method of chelating type porous catalyst - Google Patents
Chelating type porous catalyst for synthesizing carbonic acid dialkyl ester by liquid-phase oxidative carbonylation, and preparation method of chelating type porous catalyst Download PDFInfo
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- CN104607249A CN104607249A CN201510037567.0A CN201510037567A CN104607249A CN 104607249 A CN104607249 A CN 104607249A CN 201510037567 A CN201510037567 A CN 201510037567A CN 104607249 A CN104607249 A CN 104607249A
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Abstract
The invention provides a chelating type porous catalyst for synthesizing carbonic acid dialkyl ester by liquid-phase oxidative carbonylation, and a preparation method of the chelating type porous catalyst. The chelating type porous catalyst comprises a copper compound and an MOFs porous material having a tooth-shaped Schiff alkali functional-group structure, wherein the copper compound and the Schiff alkali functional-group structure are combined together through metal organic coordination bonds. The preparation method of the chelating type porous catalyst comprises the following steps: placing the microcrystalline powder of the MOFs porous material having a tooth-shaped Schiff alkali functional-group structure in a solvent under a temperature of 0-100 DEG C, stirring the microcrystalline powder and the solvent for suspension and dispersion, and slowly adding the copper compound; after adding the copper compound, continuing to stir the mixture for 1-3h; after the reaction, performing filtering separation on the mixed liquid, and performing vacuum drying on the separated solid substances under the condition of 150-200 DEG C, wherein the vacuum range is 0.5-5mmHg. The chelating type porous catalyst fundamentally avoids the phenomenon that the ligand of the catalyst is carried by high-airspeed process gases under the premise of keeping or improving activity selectivity. Therefore, the requirements for massive industrial production are satisfied.
Description
Technical field
The present invention relates to catalyst field technology, a kind of chelating type porous catalyst for liquid-phase oxidative carbonylation synthesis of dialkyl carbonates and preparation method thereof is particularly provided
.
Background technology
The dialkyl carbonate being representative with dimethyl carbonate (Dimethyl Carbonate, DMC) is the important green chemical of a class.Not only self is outstanding to the solvability of gas chromatography, and can also form mixed solvent with various alcohol, ether, ketone with arbitrary proportion.Of particular concern is, the low-carbon alcohols such as dimethyl carbonate and butanols carries out the mix products of ester exchange reaction, modulation boiling point is carried out by its ester exchange degree of modulation, temperature range can cover traditional poisonous and harmful solvent such as triphen and cyclohexanone completely, forms a series of clean replacement scheme in application widely.In addition, dimethyl carbonate molecule has the structures such as methyl, carbonyl and methoxycarbonyl group, traditional hypertoxic raw materials such as alternative dimethyl suflfate, phosgene, realizes clean synthesis.Numerous technology and Industrial form has been defined in fields such as organic carbonate, Merlon, isocyanates and polyurethane.Visible, be that the dialkyl carbonates chemicals of representative has considerable market capacity and commercial value with dimethyl carbonate.
The conventional production methods of dimethyl carbonate is phosgenation, due to the factor such as Environmental security hidden danger is serious and equipment corrosion is strong, is now replaced by technology such as oxidative carbonylation of methanol method, ester-interchange method, alcoholysis of urea.Wherein oxidative carbonylation of methanol method is with methyl alcohol, carbon monoxide and oxygen for raw material, and single step reaction obtains dimethyl carbonate, and water byproduct cleans harmless, meets Green Chemistry Theory.
Oxidative carbonylation of methanol method is divided into vapor phase method and liquid phase method two kinds, wherein vapor phase method with Japanese Ube company through the indirect vapor phase method of methyl nitrite and with the direct vapor phase method of DOW company of the U.S. for representative, all face respective technical barrier at present.Liquid phase method technique is realized industrialization (EP 0460732, EP 0460735) by Italy Enichem company the earliest, the catalyst of use for CuCl reaction equation as follows:
The corrosivity of CuCl catalyst is serious, requires higher to the material of equipment; There is gas, liquid, solid three-phase in reaction system, mass-and heat-transfer is complicated; Especially this catalyst is more responsive to system water content, easily causes catalysqt deactivation, causes selectively sharply declining.
For improving the combination property of CuCl, the main thought of follow-up study work concentrates on to be introduced on auxiliary agent and part.Typical part is heterocyclic Schiff base compounds, can be divided into imidazoles and the large class (CN101664697A, CN101234965A, CN102059147A, CN1333086A etc.) of pyridine two.For reducing catalytic erosion further, even have also appeared free from chloride complex technology, as CN104086236A, but the part used remains based on heterocyclic Schiff base class.
The tooth type structures of heterocyclic Schiff base class part uniqueness can form metastable coordination metasable state easily with univalent copper ion, improve Cu (OCH
3) formation of Cl intermediate and the insertion of carbon monoxide.At raising catalyst activity optionally simultaneously, also Cl is effectively reduced
-corrosivity.
Although heterocyclic Schiff base and Cu
+chelate have larger stability constant when normal temperature, but under oxidation carbonylation condition, not only temperature has brought up to 120 ~ 150 DEG C, and constantly there is the redox reaction between positive monovalence and positive divalence in copper, and forming the intermediates such as methoxyl group copper, this makes the stability constant of chelate significantly decline.In plant-scale continuous flow procedure, the heterocyclic Schiff base monomer of past release chelating is easily taken out of by the technique carrier gas of large air speed, causes catalytic component to run off and activity decrease.For head it off, must consider that a kind of mode improves the immobilized effect of heterocyclic Schiff base, fundamentally eliminate this leakage.Common way is by active constituent loading in the solid bed reaction of the enterprising promoting the circulation of qi of certain carrier, i.e. gas-phase process (CN103071497A, CN102941114A).This kind of scheme often address only the immobilized of metal active constituent, but does not usually use Schiff auxiliary agent, cannot tackle the problem at its root.
In recent years, rapid to metal-organic framework materials (Metal Organic Framework materials, MOFs) progress.MOFs is a kind of coordination polymer with three-D pore structure, is generally tie point with metal ion, and organic ligand position supports Special composition 3D and extends, and forms the Large ratio surface porous material of specific area much larger than similar duct molecular sieve.
The present invention attempts to search out and had a kind ofly both played the advantage of Schiff auxiliary agent in homogeneous reaction, can strengthen again the immobilized effect of Schiff tooth-shape structure, reduce the method for catalyst loss, to meet the technological requirement of large air speed carrier gas, realize industrial applications.
Summary of the invention
In view of this, the present invention is directed to the disappearance of prior art existence, the invention provides a kind of chelating type porous catalyst for liquid-phase oxidative carbonylation synthesis of dialkyl carbonates and preparation method thereof; Be particularly useful for the saturated low-carbon alcohols liquid-phase oxidative carbonylation reaction of C1 ~ C6 alkyl; This catalyst, under the prerequisite kept or improve active selectable, is fundamentally eliminated the phenomenon that catalyst ligand is carried secretly by large air speed process gas, is met large industrial requirement.
For achieving the above object, the present invention adopts following technical scheme:
For a chelating type porous catalyst for liquid-phase oxidative carbonylation synthesis of dialkyl carbonates, include copper compounds and there is the MOFs porous material of flute profile Schiff structure of functional groups; Described copper compounds and Schiff structure of functional groups are combined by metal organic coordination bond.
As a kind of preferred version, the general formula of described copper compounds is CuX
n; This CuX
nin X be Cl
-, Br
-, CH
3o
-, CH
3cH
2o
-, CH
3cOO
-, CO
3 2-, HCO
3 -, SO
4 2-, NO
3 -, NO
2 -, OH
-, this CuX
nin n be valent state equilibrium number.
As a kind of preferred version, described copper compounds is CuCl or CuCl
2.
As a kind of preferred version, described in there is flute profile Schiff structure of functional groups MOFs porous material contain the molecule fragment of two dimension or tridimensional network; The structural formula of this molecule fragment is:
。
As a kind of preferred version, the R in described molecule fragment is the single or multiple functional groups with flute profile Schiff base structure, and the general formula of this functional group is:
or
As a kind of preferred version, the R in described R functional group
1and R
2for one or more in protium or alkyl, phenyl, benzo base, amino, nitro, halogeno-group, sulfonic group.Radical position can be positioned at other position any ring removed outside profile of tooth Schiff base structure position and R and Outer groups link position.
As a kind of preferred version, described M is metallic element, comprises the metallic element in main group IA ~ VIA and subgroup IB ~ VIII, preferred Zn, Al, Cu, Fe, Co, Gr, Ni, Gd, Ga, Zr, Mn.R ' and R " can be other organo-functional group without profile of tooth Schiff base structure, can presence or absence, can be identical or not identical.
For a preparation method for the chelating type porous catalyst of liquid-phase oxidative carbonylation synthesis of dialkyl carbonates, it is characterized in that: comprise the steps:
A, first, under the condition of 0 ~ 100 DEG C, puts into the dispersion of solvent stirring suspension, slowly adds copper compounds, after reinforced, continue stirring 1 ~ 3h by the MOFs porous material powder crystallite with flute profile Schiff structure of functional groups;
After b, question response terminate, by above-mentioned mixed liquor isolated by filtration, by isolated solids under 150 ~ 200 DEG C of conditions, vacuum drying 18 ~ 24h; Vacuum ranges is 0.5 ~ 5mmHg;
As a kind of preferred version, described solvent includes water, C1 ~ C6 saturated alkyl low-carbon alcohols, N, dinethylformamide, N, N-diethyl acetamide, dialkyl carbonate (alkyl length is C1 ~ C6), methyl acetate, ethyl acetate, propyl acetate, butyl acetate, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, butyl glycol ether acetic acid esters, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propandiol butyl ether acetic acid esters, oxolane, 1-METHYLPYRROLIDONE, acetone, MEK, cyclohexanone, espeleton, benzene, toluene, dimethylbenzene, acetonitrile, one or more mixture in carbon disulfide.
The present invention compared with prior art has obvious advantage and beneficial effect, the catalyst prepared by the present invention is had both to play the advantage of Schiff auxiliary agent in homogeneous reaction, the immobilized effect of Schiff tooth-shape structure can be strengthened again, reduce the method for catalyst loss, to meet the technological requirement of large air speed carrier gas, realize industrial applications.This kind of MOFs material with bidentate Schiff functional structure all has Large ratio surface three-D pore structure, all can produce the absorption of Van der Waals type, and adsorption capacity is considerable to multiple gases.
This catalyst can meet following requirement simultaneously:
(1) Large ratio surface structure can guarantee that gas component fully spreads and participates in reaction, makes this heterogeneous catalyst can reach the active effect of homogeneous catalyst, guarantees high activity and the high selectivity of low-carbon alcohols oxidation carbonylation;
(2) bidentate Schiff functional group achieves immobilized by forming Large ratio surface three-D pore structure material, thoroughly solves loss of active component problem;
(3) active component is combined with MOFs material by chelating mode, effectively can reduce catalytic erosion.
Detailed description of the invention
[example one]
Take 100g Al (OH) (bpydc) (MOF-253) powder crystallite, at 25 DEG C, dispersed with stirring is in 1000g methyl alcohol, by anhydrous for 35.4g CuCl
2powder slowly adds wherein, carries out metallic ion coordination reaction under agitation; All raw materials add rear continuation and stir 1h; Filter the solids that obtains and put into vacuum drying oven, at 200 DEG C, dry 8h under 0.5mmHg vacuum, finally obtain 134.6g catalyst.
[example two]
Take 100g Al (OH) (bpydc) (MOF-253) powder crystallite, at 35 DEG C, dispersed with stirring is in 1000g ethanol, anhydrous for 26g CuCl powder is slowly added wherein, carries out metallic ion coordination reaction under agitation; All raw materials add rear continuation and stir 3h.Filter the solids that obtains and put into vacuum drying oven, at 175 DEG C, dry 20h under 3mmHg vacuum, finally obtain 125.2g catalyst.
[example three]
Take 100g Al (OH) (bpydc) (MOF-253) powder crystallite, at 40 DEG C, dispersed with stirring is in 1000g butyl acetate, anhydrous for 30g CuCl powder is slowly added wherein, carries out metallic ion coordination reaction under agitation; All raw materials add rear continuation and stir 2h; Filter the solids that obtains and put into vacuum drying oven, at 150 DEG C, dry 24h under 5mmHg vacuum, finally obtain 121.6g catalyst.
[example four]
Take 100g Al (OH) (bpydc) (MOF-253) powder crystallite, at 0 DEG C, dispersed with stirring is in 1000g methyl alcohol, by anhydrous for 48g CuCl
2powder slowly adds wherein, carries out metallic ion coordination reaction under agitation; All raw materials add rear continuation and stir 1.5h; Filter the solids that obtains and put into vacuum drying oven, at 160 DEG C, dry 22h under 2mmHg vacuum, finally obtain 131.4g catalyst.
[example five]
Take 100g Al (OH) (bpydc) (MOF-253) powder crystallite, at 100 DEG C, dispersed with stirring is in 1000g butanols, anhydrous for 25g CuCl powder is slowly added wherein, carries out metallic ion coordination reaction under agitation; All raw materials add rear continuation and stir 2h; Filter the solids that obtains and put into vacuum drying oven, at 180 DEG C, dry 20h under 4mmHg vacuum, finally obtain 98.5g catalyst.
[example six]
Take 100g Al (OH) (bpydc) (MOF-253) powder crystallite, at 80 DEG C, dispersed with stirring is in 1000g propyl acetate, by anhydrous for 56g CuCl
2powder slowly adds wherein, carries out metallic ion coordination reaction under agitation; All raw materials add rear continuation and stir 2h; Filter the solids that obtains and put into vacuum drying oven, at 150 DEG C, dry 18h under 4.5mmHg vacuum, finally obtain 136.9g catalyst.
Anhydrous CuCl powder described in embodiment 1 ~ 6 or anhydrous CuCl
2powder is that (general formula is CuX to copper compounds
n) in two kinds, this CuX
nin X can be Cl
-, Br
-, CH
3o
-, CH
3cH
2o
-, CH
3cOO
-, CO
3 2-, HCO
3 -, SO
4 2-, NO
3 -, NO
2 -, OH
-, the present invention can adopt with one or more upper mixture, and this type of formula all belongs to protection scope of the present invention.
[Application Example one]
In 250ml autoclave, add 50ml methyl alcohol, add example controlling catalyst 3g; With air in nitrogen displacement still, with the process gas (CO 92%, O prepared in advance
28%) nitrogen in still is replaced.Then by process gas, 40kgf/cm is pressurized to autoclave
2, at 120 ~ 140 DEG C, react 20min.After cooling, by liquid-phase reaction product gas chromatographic analysis.Dimethyl carbonate selective 99.9%, catalyst productivity 2.3gDMC/g.cat.h.
[Application Example two]
In 250ml autoclave, add 50ml methyl alcohol, add example two controlling catalyst 2.5g.With air in nitrogen displacement still, with the process gas (CO 92%, O prepared in advance
28%) nitrogen in still is replaced.Then by process gas, 40kgf/cm is pressurized to autoclave
2, at 120 ~ 140 DEG C, react 15min.After cooling, by liquid-phase reaction product gas chromatographic analysis.Dimethyl carbonate selective 99.9%, catalyst productivity 3.6gDMC/g.cat.h.
[Application Example three]
In 250ml autoclave, add 50ml methyl alcohol, add example three controlling catalyst 2.8g.With air in nitrogen displacement still, with the process gas (CO 92%, O prepared in advance
28%) nitrogen in still is replaced.Then by process gas, 40kgf/cm is pressurized to autoclave
2, at 120 ~ 140 DEG C, react 15min.After cooling, by liquid-phase reaction product gas chromatographic analysis.Dimethyl carbonate selective 99.9%, catalyst productivity 2.9gDMC/g.cat.h.
[Application Example four]
In the Φ 152mm tubular reactor of 10 liter capacities, add 7 liters of methyl alcohol in advance, and the catalyst obtained by 250g example two.System nitrogen displaced air, then uses process gas (CO 95.5%, O
24.5%) nitrogen is replaced.Keep process gas to pass into from reactor bottom continuously, system is warmed up to 150 DEG C, pressure 30kgf/cm
2carry out methanol oxidation carbonylation, product D MC is with gas phase extraction, and the methyl alcohol that reaction consumes and the methyl alcohol that gasification is flowed out are supplemented by the delivery pump of reactor bottom.Product gas chromatographic analysis, the extraction speed of selective 99.9%, the DMC of being of DMC is 332.1g/h, and catalyst productivity is about 1.33gDMC/g.cat.h.Any catalytic component with profile of tooth Schiff structure of functional groups is not detected in process tail gas.
The invention provides a kind of chelating type porous catalyst for liquid-phase oxidative carbonylation synthesis of dialkyl carbonates, its main feature is: under the prerequisite kept or improve catalyst activity, fundamentally eliminate the phenomenon that catalyst ligand is carried secretly by large air speed process gas, effectively extend catalyst life, reduce use cost, meet large industrial requirement.
The above, it is only preferred embodiment of the present invention, not technical scope of the present invention is imposed any restrictions, thus every according to technical spirit of the present invention to any trickle amendment made for any of the above embodiments, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (7)
1. for a chelating type porous catalyst for liquid-phase oxidative carbonylation synthesis of dialkyl carbonates, it is characterized in that: include copper compounds and there is the MOFs porous material of flute profile Schiff structure of functional groups; Described copper compounds and Schiff structure of functional groups are combined by metal organic coordination bond.
2. a kind of chelating type porous catalyst for liquid-phase oxidative carbonylation synthesis of dialkyl carbonates according to claim 1, is characterized in that: the general formula of described copper compounds is CuX
n; This CuX
nin X be Cl
-, Br
-, CH
3o
-, CH
3cH
2o
-, CH
3cOO
-, CO
3 2-, HCO
3 -, SO
4 2-, NO
3 -, NO
2 -, OH
-, this CuX
nin n be valent state equilibrium number.
3. a kind of chelating type porous catalyst for liquid-phase oxidative carbonylation synthesis of dialkyl carbonates according to claim 1, is characterized in that: described in there is flute profile Schiff structure of functional groups MOFs porous material contain the molecule fragment of two dimension or tridimensional network; The structural formula of this molecule fragment is:
。
4. a kind of chelating type porous catalyst for liquid-phase oxidative carbonylation synthesis of dialkyl carbonates according to claim 3, it is characterized in that: the R in described molecule fragment is the single or multiple functional groups with flute profile Schiff base structure, and the general formula of this functional group is:
or
According to claim 4 for a chelating type porous catalyst for liquid-phase oxidative carbonylation synthesis of dialkyl carbonates, it is characterized in that: the R in described R functional group
1and R
2for one or more in protium or alkyl, phenyl, benzo base, amino, nitro, halogeno-group, sulfonic group.
5. a kind of chelating type porous catalyst for liquid-phase oxidative carbonylation synthesis of dialkyl carbonates according to claim 3, is characterized in that: in described molecule fragment, M is metallic element.
6. according to any one of claim 1 ~ 6 for a preparation method for the chelating type porous catalyst of liquid-phase oxidative carbonylation synthesis of dialkyl carbonates, it is characterized in that, comprise the steps:
A, first, under the condition of 0 ~ 100 DEG C, puts into the dispersion of solvent stirring suspension, slowly adds copper compounds, after reinforced, continue stirring 1 ~ 3h by the MOFs porous material powder crystallite with flute profile Schiff structure of functional groups;
After b, question response terminate, by above-mentioned mixed liquor isolated by filtration, by isolated solids under 150 ~ 200 DEG C of conditions, vacuum drying 18 ~ 24h; Vacuum ranges is 0.5 ~ 5mmHg.
7. the preparation method of a kind of chelating type porous catalyst for liquid-phase oxidative carbonylation synthesis of dialkyl carbonates according to claim 7, it is characterized in that: described solvent includes water, C1 ~ C6 saturated alkyl low-carbon alcohols, N, dinethylformamide, N, N-diethyl acetamide, dialkyl carbonate (alkyl length is C1 ~ C6), methyl acetate, ethyl acetate, propyl acetate, butyl acetate, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, butyl glycol ether acetic acid esters, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propandiol butyl ether acetic acid esters, oxolane, 1-METHYLPYRROLIDONE, acetone, MEK, cyclohexanone, espeleton, benzene, toluene, dimethylbenzene, acetonitrile, one or more mixture in carbon disulfide.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111617803A (en) * | 2020-07-10 | 2020-09-04 | 四川弘征科技有限公司 | Catalyst for synthesizing dimethyl carbonate by oxidative carbonylation, preparation method and application thereof |
| CN112827510A (en) * | 2021-02-08 | 2021-05-25 | 福州大学 | Porous composite material for catalytic synthesis of propylene carbonate and preparation method thereof |
-
2015
- 2015-01-26 CN CN201510037567.0A patent/CN104607249A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111617803A (en) * | 2020-07-10 | 2020-09-04 | 四川弘征科技有限公司 | Catalyst for synthesizing dimethyl carbonate by oxidative carbonylation, preparation method and application thereof |
| CN112827510A (en) * | 2021-02-08 | 2021-05-25 | 福州大学 | Porous composite material for catalytic synthesis of propylene carbonate and preparation method thereof |
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Application publication date: 20150513 |