CN102199088B - Synthesis process of alkyl carbonate - Google Patents
Synthesis process of alkyl carbonate Download PDFInfo
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- CN102199088B CN102199088B CN 201110078015 CN201110078015A CN102199088B CN 102199088 B CN102199088 B CN 102199088B CN 201110078015 CN201110078015 CN 201110078015 CN 201110078015 A CN201110078015 A CN 201110078015A CN 102199088 B CN102199088 B CN 102199088B
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Abstract
The invention relates to a synthesis process of alkyl carbonate. The process comprises the following steps of: firstly adding alcohol to a reaction container, carrying out reaction with a CuSCN or CuSCN complex as a catalyst and stirring to obtain alkyl carbonate, wherein the mol ratio of the alcohol to the catalyst is 1:(0.001-0.1), reaction temperature is 80-200 DEG C, reaction pressure is 0.5-5 MPa and stirring speed is 1-1000 r/m and stirring time is 0.5-10 hours. The synthesis process has the characteristics that the catalyst preparation process is simple, and the catalyst has high activity, high selectivity, high stability and no halogen ion, thus solving the corrosion problem of chlorine ion in industrial CuCl catalyst on equipment and facilitating industrial production.
Description
Technical field
The present invention relates to a kind of synthesis technique of alkyl carbonate.
Background technology
Methylcarbonate (being called for short DMC) and diethyl carbonate (vehicle economy C) are a kind of green chemicals, as solvent, can be with immiscible organic solvents such as any ratio and alcohol, ether, ketone, and evaporation rate is relatively moderate, becomes " new lover " of coating use solvent; As chemical reagent, contain alkyl, alkoxyl group, carbalkoxy and carbonyl in molecule, can substitute phosgene, methyl-sulfate, halogenated alkane etc., be widely used in the industries such as chemical industry, medicine, agricultural chemicals, food, be described as " the new matrix " of organic synthesis; Its oxygen level is high simultaneously, is expected to substitute methyl tertiary butyl ether as the oxygenated additive of gasoline, diesel oil, and the market demand potential is huge.The synthetic method of DMC and DEC has phosgenation, ester-interchange method, oxidative carbonylation method, alcoholysis of urea etc.Wherein the oxidative carbonylation method is with methyl alcohol, CO and O
2Be raw material, synthetic through catalytic one-stage, by product only has harmless water, meets the requirement of Green Chemistry, is the green chemistry process of generally acknowledging in the world, becomes both at home and abroad the competitively focus of exploitation.
Italy Eni chem company takes the lead in the technique of synthesizing methyl carbonate by methanol liquid phase oxidation oxonation has been realized industrialization (Ind.Chim.21 (1), 1985) in the eighties take cuprous chloride as catalyzer mid-term.But cuprous chloride has strong corrosion to reaction unit, must add the impregnating material such as upper glass or enamel lining at reactor wall, makes device be difficult to realize maximizing.In addition, the solvability extreme difference due to cuprous chloride in reaction system must use the cuprous chloride of high density to obtain enough speed of response in Eni chem technique.
Chinese patent open file CN1197792A (1998) is take cuprous chloride as Primary Catalysts, magnesium chloride, calcium chloride etc. are auxiliary agent, prepare the composite catalyst of alkaline-earth metal salt decorative, improved to a certain extent the solvability of cuprous chloride in reaction solution, improve catalyst activity, but there is no to solve the etching problem to equipment.
Chinese patent open file CN1333086A (2002) has announced take cuprous chloride as Primary Catalysts, with nitrogenous heterogeneous ring compound or the composite catalyst of high-molecular complex formation, further improved the solvability of cuprous chloride in reaction solution, improved catalyst activity and selectivity, and reaction system is decreased to the corrodibility of equipment, but still there is corrosive chlorion in reaction, is unfavorable for industrialized use.
Summary of the invention
Problem to be solved by this invention is to propose a kind of synthesis technique take CuSCN or CuSCN complex compound as the alkyl carbonate of catalyzer for above-mentioned prior art, not only selectivity is good for it, transformation efficiency is high, and corrodibility is low, can without corrosion-proof lining, be conducive to suitability for industrialized production.
The present invention is that the solution that the problem of the above-mentioned proposition of solution adopts is: the synthesis technique of alkyl carbonate, it is characterized in that adding alcohol in reaction vessel, and advance reaction take CuSCN or CuSCN complex compound as catalyzer, wherein alcohol is 1: 0.001～0.1 with the mol ratio of catalyzer, temperature of reaction is 80～200 ℃, and reaction pressure is 0.5～5MPa, 0.5～10 hour reaction times, 1～1000 rev/min of stir speed (S.S.) can obtain alkyl carbonate.Catalyst productivity is 10-62mol alkyl carbonate/molCu, the selectivity of alkyl carbonate 〉=90%.
Press such scheme, described alcohol is methyl alcohol or ethanol.
Press such scheme, described alkyl carbonate is methylcarbonate or diethyl carbonate.
Press such scheme, the part in described CuSCN complex compound is nitrogen-containing heterocycle compound or nitrogen containing polymer compound.
Press such scheme, described nitrogen-containing heterocycle compound is the mixing of any one or two kinds in phenanthroline, N-Methylimidazole, Polypyridine, pyrimidine, multi-joint pyrimidine, N-Methyl pyrrolidone, imidazoles aminopyridine and 4-phenylpyridine.
Press such scheme, described nitrogen containing polymer compound is polyvinyl pyridine or polyvinylpyrrolidone.
Press such scheme, the Cu/N element mol ratio in described CuSCN complex compound is 1: 2-7.0.
The objective of the invention is with CuSCN or nitrogen-containing heterocycle compound and nitrogen containing polymer compound is part, makes catalyzer with the CuSCN complex compound that CuSCN forms, and implements the reaction of the synthetic methylcarbonate of methyl alcohol or oxidation of ethanol carbonylation or diethyl carbonate.
Oxidative carbonylation synthesis of alkyl carbonic ether is generally followed following reaction mechanism:
2CuSCN+2ROH+1/2 O
2→2Cu(OR)(SCN)+H
2O (1)
CuSCN+CO→Cu(CO)(SCN) (2)
Cu(CO)(SCN)·Cu(OR)(SCN)→Cu(COOR)(SCN)+CuSCN (4)
Cu(COOR)(SCN)+Cu(OR)(SCN)→ROCOOR+2CuSCN (5)
In reaction process, carbonylation is cuprous forms by negatively charged ion the key that bridged complex is oxidation carbonylation with alkoxide copper, and namely reactions steps (2) is the synthetic committed step of alkyl carbonate.Because the thiocyanate ion in the present invention is an amphiphilic ions, sulphur atom wherein is easy to cuprous complexing, and nitrogen-atoms is easy to the cupric complexing, and bridged complex easily forms like this, so combined coefficient is higher; Simultaneously, can promote the dissolving of cuprous salt after nitrogenous compound on cupric coordination, improve its concentration in reaction solution, therefore active the raising.
Characteristics of the present invention are, catalyst preparation process is simple, and catalytic activity is high, selectivity and good stability, and not halogen-containing ion in catalyzer, thereby fundamentally solved the corrosion problems of chlorion to equipment in industrial CuCl catalyzer, be conducive to industrialized production.
Embodiment
The present invention will be further described below in conjunction with embodiment, but can not be construed as limiting the invention.
Embodiment 1
Add 50ml (1.236mol) methyl alcohol in the 300ml autoclave, 0.006mol CuSCN catalyzer is used gas mixture (O under room temperature
2: 5%, CO:95%) air in the metathesis reactor, then be forced into 4.0MPa with gas mixture.600 rev/mins of stir speed (S.S.)s, under 120 ℃ of temperature of reaction, reaction is 4 hours.Get the final proof gas chromatographic analysis after cooling.DMC selectivity 97.8%, the catalyzed reaction number of catalyzer are 23mol DMC/ (molCu).
Embodiment 2
Under argon shield, 0.1mol CuSCN is suspended in 100ml methyl alcohol, adds the methanol solution of 0.1mol phenanthroline, back flow reaction 24 hours, recovery methyl alcohol, vacuum-drying get 0.1mol CuSCN-phenanthroline complex compound.
The CuSCN-phenanthroline complex compound (Cu/N element mol ratio is 1: 3) of getting the above-mentioned preparation of 0.006mol is catalyzer, and all the other conditions are with example 1.The DMC selectivity is 98.9%, and the catalyzed reaction number of catalyzer is 20.3mol DMC/ (molCu).
Embodiment 3
Replace outside phenanthroline with dipyridyl, other condition prepares the CuSCN-bipyridyl complexes with embodiment 2.
Make catalyzer with 0.006mol CuSCN-bipyridyl complexes (Cu/N element mol ratio is 1: 3), under 900 rev/mins of stir speed (S.S.)s, 150 ℃ of temperature of reaction, reaction is 2 hours, and all the other conditions are with example 1.The DMC selectivity is 95.1%, and the catalyzed reaction number of catalyzer is 33.8mol DMC/ (molCu).
Embodiment 4
Replace outside phenanthroline with the N-Methylimidazole, other condition prepares CuSCN-N-Methylimidazole complex compound with embodiment 2.
Add 50ml (1.236mol) methyl alcohol in the 300ml autoclave, 0.01mol CuSCN-N-Methylimidazole complex compound (Cu/N element mol ratio is 1: 2) is made catalyzer, use gas mixture (O2:6% under room temperature, CO:94%) air in metathesis reactor, then be forced into 4.5MPa with gas mixture.400 rev/mins of stir speed (S.S.)s, under 120 ℃ of temperature of reaction, reaction is 1.5 hours.Get the final proof gas chromatographic analysis after cooling.The DMC selectivity is 97.3%, and the catalyzed reaction number of catalyzer is 36.5molDMC/ (molCu).
Embodiment 5
Except stir speed (S.S.) is adjusted to 50 rev/mins, other condition is with embodiment 4, and the DMC selectivity is 98.7%, and the catalyzed reaction number of catalyzer is 15.2mol DMC/ (molCu).
Embodiment 6
Except the polyvinylpyrrolidone (take the basis of V-Pyrol RC monomer as calculating) with 0.5mol replaces the phenanthroline of 0.1mol, other condition prepares CuSCN-polyvinylpyrrolidone complex compound with embodiment 2.
Add 50ml (1.236mol) methyl alcohol in the 300ml autoclave, 1.5g CuSCN-polyvinylpyrrolidone (Cu/N element mol ratio is 1: 6) is made catalyzer, uses gas mixture (O under room temperature
2: 5%, CO:95%) air in the metathesis reactor, then be forced into 3.0MPa with gas mixture.400 rev/mins of stir speed (S.S.)s, under 130 ℃ of temperature of reaction, reaction is 2.5 hours.Get the final proof gas chromatographic analysis after cooling.The DMC selectivity is 98.4%, and the catalyzed reaction number of catalyzer is 20.5molDMC/ (molCu).
Embodiment 7
Under argon shield, 0.1mol CuSCN is suspended in 100ml methyl alcohol, adds the methanol solution that is dissolved with 0.1mol dipyridyl and 0.1mol N-Methylimidazole, back flow reaction 24 hours, recovery methyl alcohol, vacuum-drying get CuSCN-dipyridyl-N-Methylimidazole complex compound.
Be catalyzer with 0.006mol CuSCN-dipyridyl-N-Methylimidazole complex compound (Cu/N element mol ratio is 1: 4), reacted 2 hours, all the other conditions are with example 1.The DMC selectivity is 98.6%, and the catalyzed reaction number of catalyzer is 38.3mol DMC/ (molCu).
Embodiment 8
Add 50ml (0.857mol) dehydrated alcohol in the 300ml autoclave, 0.006mol CuSCN catalyzer is used gas mixture (O under room temperature
2: 5%, CO:95%) air in the metathesis reactor, then be forced into 4.0MPa with gas mixture.400 rev/mins of stir speed (S.S.)s, under 120 ℃ of temperature of reaction, reaction is 3 hours.Get the final proof gas chromatographic analysis after cooling.The DEC selectivity is 96.5%, and the catalyzed reaction number of catalyzer is 22.8mol DEC/ (molCu).
Embodiment 9
Make catalyzer with 0.01mol CuSCN-N-Methylimidazole complex compound (mol ratio of Cu and N-Methylimidazole is 1: 3), all the other conditions are with example 7, and the DEC selectivity is 99.5%, and the catalyzed reaction number of catalyzer is 30.2mol DEC/ (molCu).
Claims (5)
1. the synthesis technique of alkyl carbonate, it is characterized in that adding alcohol in reaction vessel, described alcohol is methyl alcohol or ethanol, and advances reaction take CuSCN or CuSCN complex compound as catalyzer, and wherein alcohol is 1: 0.001 ~ 0.1 with the mol ratio of catalyzer, temperature of reaction is 80 ~ 200 ℃, reaction pressure is 0.5 ~ 5MPa, 0.5 ~ 10 hour reaction times, 1 ~ 1000 rev/min of stir speed (S.S.), can obtain alkyl carbonate, described alkyl carbonate is methylcarbonate or diethyl carbonate.
2. by the synthesis technique of alkyl carbonate claimed in claim 1, it is characterized in that the part in described CuSCN complex compound is nitrogen-containing heterocycle compound or nitrogen containing polymer compound.
3. by the synthesis technique of alkyl carbonate claimed in claim 2, it is characterized in that described nitrogen-containing heterocycle compound is the mixing of any one or two kinds in phenanthroline, N-Methylimidazole, Polypyridine, pyrimidine, multi-joint pyrimidine, N-Methyl pyrrolidone, imidazoles aminopyridine and 4-phenylpyridine.
4. by the synthesis technique of alkyl carbonate claimed in claim 2, it is characterized in that described nitrogen containing polymer compound is polyvinyl pyridine or polyvinylpyrrolidone.
5. by the synthesis technique of alkyl carbonate claimed in claim 1, it is characterized in that the Cu/N element mol ratio in described CuSCN complex compound is 1: 2 – 7.0.
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| CN101856625A (en) * | 2010-06-17 | 2010-10-13 | 南京工业大学 | Non-noble metal homogeneous catalysis system for alcohol oxidative carbonylation and use method thereof |
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Effective date of registration: 20160229 Address after: 431600 Dongfanghong village, Hanchuan Economic Development Zone, Hubei Patentee after: Hubei golden leaf new Mstar Technology Ltd Address before: 430074 Wuhan, Hongshan Province District, hung Chu street, No. 693 Patentee before: Wuhan Institute of Technology |
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