CN100364956C - Method of distillation and ester exchange reaction for producing dimethyl carbonate and dihydroxyl alcohols - Google Patents
Method of distillation and ester exchange reaction for producing dimethyl carbonate and dihydroxyl alcohols Download PDFInfo
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- CN100364956C CN100364956C CNB2004100535760A CN200410053576A CN100364956C CN 100364956 C CN100364956 C CN 100364956C CN B2004100535760 A CNB2004100535760 A CN B2004100535760A CN 200410053576 A CN200410053576 A CN 200410053576A CN 100364956 C CN100364956 C CN 100364956C
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Abstract
The present invention discloses a method for the joint production of dimethyl carbonate and dihydroxyl alcohol by the ester exchange of reaction rectification, which uses epoxyalkane, carbon dioxide and methanol as a raw material. The present invention comprises that absorbent cyclic carbonic ester comes into contact with mixed gas containing epoxyalkane and carbon dioxide in a mode of counterflow in an absorption tower, the epoxyalkane of absorption liquid of the cyclic carbonic ester containing the epoxyalkane and the carbon dioxide reacts with the carbon dioxide under the existence of a catalyst to generate the cyclic carbonic ester; the synthetic liquid of the cyclic carbonic ester enters a rectifying tower of the cyclic carbonic ester, the cyclic carbonic ester of the tower top enters a rectifying tower by a pipeline to generate an ester exchange reaction with the methanol under the existence of an ester exchange catalyst and generate dimethyl carbonate and dihydroxyl alcohol; then, the dimethyl carbonate and the dihydroxyl alcohol are collected. The present invention greatly improves the single-pass conversion rate of the ester exchange reaction, and simultaneously, the whole flow path can greatly reduce energy consumption by the energy integration of the rectifying tower.
Description
Technical field
The present invention relates to the method for methylcarbonate and dibasic alcohol.
Background of invention
Methylcarbonate (be called for short DMC, down with) is a kind of more basic Organic Chemicals, and its toxicity is very little, (1992 be registered as in Europe " non-toxic chemicals ").Owing to contain active CH in its molecular structure
3-, CH
3O-, CH
3CO-,-CO-, therefore it has multiple reactivity worth, can replace the conducts such as methyl-sulfate, methyl chloride, methyl-chloroformate photoreactive gas of severe toxicity to methylate in many chemical reaction occasions, methoxycarbonylization and carbonylation agent react, and by product only is carbonic acid gas or methyl alcohol.Therefore as a kind of green cleaning industrial chemicals, DMC is used widely in industrial circles such as agricultural chemicals, medicine, plastics, dyestuff, electronic chemical product, fodder additives.In addition, as novel fuel oil additive, DMC also can be used as the substitute of octane promoter and methyl tertiary butyl ether, and it is quite becoming effective aspect raising octane number of fuel oil and the oxygen level.Just because of these peculiar properties and extensive use, a kind of new chemical industrial goods that make DMC become paid attention to by domestic and international chemical circles, and be described as " the new foundation stone " of organic synthesis.
The method of Synthesis of dimethyl carbonate is a lot, but present industrial method has only phosgenation, ester-interchange method, oxidative carbonylation method several.Though phosgenation can industrial-scale production methylcarbonate, problem such as have complex process, raw material severe toxicity, by-product hydrochloric acid corrodibility is strong, environmental pollution is serious, production cost is higher, should not promote.Gas-phase oxidation/carbonylation method and liquid-phase oxidative carbonylation method corrodibility are little, do not use hypertoxic raw material in the production process, be the more method that adopts at present, but facility investment are big, production cost is higher.
The technology of super critical condition carbon dioxide and the direct Synthesis of dimethyl carbonate of methyl alcohol also has patent report.As the acetate with transition metal described among the CN1243356A is catalyzer, is supercritical medium with the carbonic acid gas; The mixture with MAGNESIUM METAL or salt of wormwood and methyl iodide that the CN1264698A kind is described is a catalyzer, carbonic acid gas and methyl alcohol is placed under the supercritical state of carbonic acid gas directly Synthesis of dimethyl carbonate.What directly the patent of Synthesis of dimethyl carbonate also had the CN1485313A description is raw material with epoxy alkane, methyl alcohol and carbonic acid gas, in employing potassium halide or the salt of wormwood one or more are catalyzer, epoxy alkane: catalyzer=100: 5～10, temperature of reaction is 80～180 ℃, pressure is 5～30MPa, reaction times is 0.5～4 hour direct esterification Synthesis of dimethyl carbonate, simultaneously coproduction dibasic alcohol and cyclic carbonate.Technology with overcritical direct Synthesis of dimethyl carbonate down requires harshness to reaction conditions, is difficult to realize industrialization.
Describe employing inorganic potassium salt compound among patent CN1228358A, the CN1074310C and be impregnated into (massfraction of inorganic potassium salt compound is 11～17%) on the zeolite molecular sieve generates methylcarbonate and dibasic alcohol as methyl alcohol and cyclic carbonate transesterification reaction catalyzer.
Chinese patent CN1308046A has described a kind of method of producing dibasic alcohol and carbonic ether simultaneously, and this method comprises that cyclic carbonate is synthetic, annular carbonic acid esters hydrolysis, dibasic alcohol purification, transesterification reaction, carbonic ether is purified and step such as cyclic carbonate purification.The per pass conversion of this method and yield are subjected to the restriction of transesterification reaction equilibrium conversion, and have relatively high expectations to reaction raw materials is pretreated.
Summary of the invention
The technical issues that need to address of the present invention are the methods that disclose a kind of reactive distillation transesterify co-producing dimethyl carbonate and dibasic alcohol, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
Absorption agent cyclic carbonate and the mixed gas counter current contact in the absorption tower that contains epoxy alkane and carbonic acid gas, epoxy alkane and carbonic acid gas are absorbed in the absorption liquid of cyclic carbonate;
Said epoxy alkane is oxyethane or propylene oxide, and the molar percentage of epoxy alkane is 1～20% in the mixed gas, and the molar percentage of carbonic acid gas is 1～20%, and all the other are air or oxygen;
The working pressure of absorption process is 0.1～20MPa (absolute pressure), preferred 0.1～10MPa, and absorption temperature is-50～250 ℃, is good with-30～100 ℃ especially, vapour-liquid ratio is 0.3～4;
The cyclic carbonate absorption liquid that is rich in epoxy alkane and carbonic acid gas enters in the cyclic carbonate synthesis reactor through pipeline, and in the presence of catalyzer, epoxy alkane and carbon dioxide reaction generate cyclic carbonate; The working pressure of reaction is 0.1～20MPa (absolute pressure), preferred 0.2～10MPa, temperature of reaction is 50～250 ℃, especially be good with 100～250 ℃, the catalyzer that is adopted is halogenide, quaternary amine, organic amine, phosphine thing etc., one or more in preferred tetraethyl-amine bromide, tetrapropyl amine bromide, potassiumiodide, triethylamine, monobromethane, tri-n-butylamine, the Guanidinium carbonate.
The synthetic liquid of the cyclic carbonate that contains catalyzer that comes out from the cyclic carbonate synthesis reactor enters the cyclic carbonate rectifying tower by pipeline, the cat head cyclic carbonate enters reaction fractionating tower again by pipeline, in the presence of transesterification catalyst with methyl alcohol generation transesterification reaction, generate methylcarbonate and dibasic alcohol, said dibasic alcohol is ethylene glycol or propylene glycol, and the mol ratio of methyl alcohol and cyclic carbonate is 1: 1～20: 1;
The working pressure of cyclic carbonate rectifying tower is 0.001～0.1MPa (absolute pressure), is good with 0.001～0.05MPa especially, and temperature is 50～250 ℃, is good with 100～170 ℃ especially;
The working pressure of reactive distillation is 0.001～0.1MPa (absolute pressure), and service temperature is 20～150 ℃, is good with 30～100 ℃ especially;
Transesterification catalyst comprises one or more of alkalimetal oxide, alkali metal hydroxide, alkali metal alcoholate or alkaline carbonate etc., a kind of or its mixture in preferred sodium hydroxide, potassium hydroxide, salt of wormwood, sodium methylate, potassium methylate, sodium ethylate or the potassium ethylate;
The methylcarbonate that comes out from the reactive distillation column overhead and the azeotrope of methyl alcohol, after entering the pressurization knockout tower and separating, cat head obtains the lower thick methyl alcohol of DMC addition, and it is the methylcarbonate product that pressurization separates the Tata still; Alcohol mixture from reactive distillation Tata still comes out enters cut light tower by pipeline, and cat head is a low-boiling-point substance, the tower still obtains to contain hardly the dibasic alcohol crude product of light constituent, enter subsequently in the dibasic alcohol rectifying tower, cat head is a dibasic alcohol again, and the tower still is the alcoholic solution of transesterification catalyst.The working pressure of pressurization knockout tower is 0.1～8.0MPa (absolute pressure), is good with 0.5～3.0MPa especially.
By above-mentioned disclosed technical scheme as seen, the present invention has following characteristics: the present invention directly absorbs the product epoxy alkane and the carbonic acid gas of olefin oxidation by the solvent cyclic carbonate, is rich in epoxy alkane and CO
2The absorption liquid catalytically synthesizing cyclic carbonate ester, then cyclic carbonate under the condition that catalyzer exists with methyl alcohol transesterify Synthesis of dimethyl carbonate and dibasic alcohol.The method of reactive distillation is adopted in transesterify, can improve the per pass conversion of transesterification reaction greatly, and whole flow process is integrated by the energy of rectifying tower simultaneously, can greatly cut down the consumption of energy.
Because CO
2Caused Greenhouse effect more and more become the threat that people face, and it is met the hope of the public to environmental protection as carbon source synthetic organic chemistry product.Therefore, with CO
2, epoxy alkane and methyl alcohol is that the directly synthetic DMC of raw material is the route that has more theory and realistic meaning.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Referring to Fig. 1, method of the present invention comprises the steps:
The gas that contains epoxy alkane and carbonic acid gas counter current contact in absorption tower (1) that absorption agent cyclic carbonate and gas phase oxidation of olefins reaction produce, epoxy alkane and carbonic acid gas are absorbed in the absorption liquid of cyclic carbonate, and tail gas goes the recycle of olefin oxidation operation;
The cyclic carbonate absorption liquid that is rich in epoxy alkane and carbonic acid gas enters in the cyclic carbonate synthesis reactor (2), and in the presence of catalyzer, epoxy alkane and carbon dioxide reaction generate cyclic carbonate; Reactor can adopt tank reactor or tubular reactor;
Enter cyclic carbonate rectifying tower (3) from the cyclic carbonate synthesis reactor synthetic liquid of cyclic carbonate that comes out, the catalyst recirculation of cyclic carbonate rectifying tower (3) bottom is to cyclic carbonate synthesis reactor (2), the cat head cyclic carbonate enters reaction fractionating tower (4), in the presence of transesterification catalyst with methyl alcohol generation transesterification reaction.
The methylcarbonate of reaction fractionating tower (4) cat head and the azeotrope of methyl alcohol enter pressurization knockout tower (5), and cat head obtains the lower thick methyl alcohol of concentration of dimethyl carbonate solution, and the tower still is the methylcarbonate product; The alcohol mixture that reaction fractionating tower (4) tower still comes out, wherein the mass concentration of dibasic alcohol is between 20～70%, enter cut light tower (6) by pipeline, cut light tower (6) cat head is a low-boiling-point substance, the tower still obtains to contain hardly the dibasic alcohol crude product of light constituent, and the dibasic alcohol crude product enters in the dibasic alcohol rectifying tower (7) more subsequently; Dibasic alcohol rectifying tower (7) adopts conventional method to separate, and cat head is a dibasic alcohol, and the tower still is a transesterification catalyst, loops back reaction fractionating tower 4 by pipeline, recycles.
The optimized technical scheme according to the present invention, because epoxy alkane and carbonic acid gas synthesizing annular carbonate are thermopositive reaction, therefore in synthesis reactor (2), react the tower still heating source that the heat that is discharged can be used for that low pressure water vapor takes place or directly is used as reaction fractionating tower (4).
Further, cyclic carbonate distillation tower (3) top heat of condensation can be as low pressure water vapor taking place or directly as the tower still heating source of reaction fractionating tower (4).
Further, methylcarbonate pressure distillation tower (5) overhead condensation heat can be used as and low pressure water vapor takes place or directly as the tower still heating source of reaction fractionating tower (4).
Further, dibasic alcohol knockout tower (7) overhead condensation heat is as low pressure water vapor taking place or directly as the heating source of reaction fractionating tower (4) or Methanol Recovery.
1. oxyethane and carbonic acid gas catalytic esterification generate NSC 11801
Contain oxyethane 1.5mol%, carbonic acid gas 7.5mol% in the gas that oxidation of ethylene obtains, temperature is 45 ℃, 's 1.2 meters packing tower with the flow of 100kg/h by bed height, 45 ℃ NSC 11801 absorption liquid with the flow of 75kg/h under overhead streams, contact with back flow of gas, working pressure is 1.8MPa, and oxyethane and carbonic acid gas are absorbed in the absorption liquid.Analysis revealed, the specific absorption of oxyethane are more than 99.5%, and the specific absorption of carbonic acid gas is more than 90%.
Above-mentioned absorption liquid is mixed in reactor with catalyzer tetraethyl-amine bromide, and be heated to 150 ℃, working pressure is 8MPa, reacts after 45 minutes, and the transformation efficiency of oxyethane is more than 99%, does not detect the generation of other component.
To synthesize liquid and be decompressed to 0.1Mpa, with the carbonic acid gas in the stripping workshop, subsequently with the solution distillation, the control tower top temperature is 130 ℃, and cat head obtains purity and is higher than 99.5% NSC 11801.The tower still obtains being rich in the solution of catalyzer, is back in the NSC 11801 synthesizer.
2. methylcarbonate and ethylene glycol is synthetic
It is that tray column, top are packing tower that reaction fractionating tower adopts the bottom, and tower diameter is 70cm, 50 blocks of column plates.NSC 11801 is with the flow of 10kg/h, the mol ratio of methyl alcohol and NSC 11801 is to be continuously fed in reaction fractionating tower at 2: 1, the reaction fractionating tower working pressure is 0.1Mpa (absolute pressure), tower top temperature is 64 ℃, with the sodium methylate is catalyzer, cat head is the azeotrope (containing methylcarbonate mass concentration 30%) of methylcarbonate and methyl alcohol, the tower still is mainly ethylene glycol and methanol mixture (contains methyl alcohol 58.7%, ethylene glycol 40.2%), the transformation efficiency of transesterification reaction is 99.0%, and selectivity is greater than 99.5%.
3. the separation of methylcarbonate
Being methyl alcohol-dimethyl carbonate azeotrope of 30% with DMC addition adds methylcarbonate compression rectification tower with the flow of 5kg/h, this tower adopts packing tower, packed height is 2.2m, working pressure is 1.5MPa, the control tower top temperature is 155 ℃, the continuous discharging DMC addition of cat head is 7.0% azeotrope, and it is 99.8% methylcarbonate product that the tower still obtains mass concentration.
4. the separation of ethylene glycol
The reaction fractionating tower still is ethylene glycol and methanol mixture (containing methyl alcohol 58.7%, ethylene glycol 40.2%), enters in the cut light tower with the flow of 12kg/h.This tower is a packing tower, tower diameter 70cm, and packed height is 2.0m, and working pressure 0.1MPa (absolute pressure), cat head obtain methanol quality concentration and surpass 98% product, return as the reaction fractionating tower charging, and the tower still obtains quality of glycol concentration and is higher than 99.8% product.
5. the energy of rectifying tower is integrated
In this example, nearly 160 ℃ of the cat head gas phase temperatures of methylcarbonate compression rectification tower, the heating reboiler as reactive distillation Tata still can significantly cut down the consumption of energy.
1. propylene oxide and carbonic acid gas catalytic esterification generate propylene carbonate
Contain propylene oxide 1.5mol%, carbonic acid gas 7.5mol% in the gas that propylene oxidation obtains, temperature is 35 ℃, 's 1.2 meters packing tower with the flow of 100kg/h by bed height, 35 ℃ propylene carbonate absorption liquid with the flow of 75kg/h under overhead streams, contact with back flow of gas, working pressure is 1.6MPa, and propylene oxide and carbonic acid gas are absorbed in the absorption liquid.Analysis revealed, the specific absorption of propylene oxide are more than 99.5%, and the specific absorption of carbonic acid gas is more than 90%.
Above-mentioned absorption liquid is mixed in reactor with catalyzer tetrapropyl amine bromide, and be heated to 150 ℃, working pressure is 8MPa, reacts after 45 minutes, and the transformation efficiency of propylene oxide is more than 99%, does not detect the generation of heavy constituent.
To synthesize liquid and be decompressed to 0.1Mpa, with the carbonic acid gas in the stripping workshop, subsequently with the solution distillation, the control tower top temperature is 130 ℃, and cat head obtains purity and is higher than 99% propylene carbonate.The tower still obtains being rich in the solution of catalyzer, is back in the propylene carbonate synthesizer.
2. methylcarbonate and propylene glycol is synthetic
It is that tray column, top are packing tower that reaction fractionating tower adopts the bottom, and tower diameter is 70cm, 50 blocks of column plates.Propylene carbonate is with the flow of 10kg/h, the mol ratio of methyl alcohol and propylene carbonate is to be continuously fed in reaction fractionating tower at 2: 1, the reaction fractionating tower working pressure is 0.1MPa (absolute pressure), tower top temperature is 64 ℃, with the sodium methylate is catalyzer, cat head is the azeotrope (containing methylcarbonate mass concentration 30%) of methylcarbonate and methyl alcohol, the tower still is mainly propylene glycol and methanol mixture (contains methyl alcohol 58.7%, propylene glycol 40.2%), the transformation efficiency of transesterification reaction is 99.0%, and selectivity is greater than 99.5%.
3. the separation of methylcarbonate.
Being 30% methyl alcohol dimethyl carbonate azeotrope with DMC addition adds methylcarbonate compression rectification tower with the flow of 5kg/h, this tower adopts packing tower, packed height is 2.2m, working pressure is 1.5MPa, the control tower top temperature is 155 ℃, the continuous discharging DMC addition of cat head is 7.0% azeotrope, and it is 99.8% methylcarbonate product that the tower still obtains mass concentration.
4. the separation of propylene glycol.
Reaction fractionating tower still propylene glycol and methanol mixture (containing methyl alcohol 58.7%, propylene glycol 40.2%) enter in the cut light tower with the flow of 12kg/h.This tower is a packing tower, tower diameter 70cm, and packed height is 2.0m, and working pressure 0.1MPa (absolute pressure), cat head obtain methanol quality concentration and surpass 98% product, return as the reaction fractionating tower charging, and the tower still obtains the propylene glycol mass concentration and is higher than 99.8% product.
5. the energy of rectifying tower is integrated
In this example, nearly 160 ℃ of the cat head gas phase temperatures of methylcarbonate compression rectification tower, the heating reboiler as reactive distillation Tata still can significantly cut down the consumption of energy.
Above system is through long-play, quality product and stable yield.
Claims (10)
1. the method for reactive distillation transesterify co-producing dimethyl carbonate and dibasic alcohol is characterized in that, comprises the steps:
The gas that contains epoxy alkane and carbonic acid gas counter current contact in absorption tower (1) that absorption agent cyclic carbonate and gas phase oxidation of olefins reaction produce, epoxy alkane and carbonic acid gas are absorbed in the absorption liquid of cyclic carbonate; Contain in the gas of epoxy alkane and carbonic acid gas, the molar percentage of epoxy alkane is 1～20%, and the molar percentage of carbonic acid gas is 1～20%, and all the other are air or oxygen;
The cyclic carbonate absorption liquid that has absorbed epoxy alkane and carbonic acid gas enters in the cyclic carbonate synthesis reactor (2), and in the presence of catalyzer, epoxy alkane and carbon dioxide reaction generate cyclic carbonate;
Enter cyclic carbonate rectifying tower (3) from cyclic carbonate synthesis reactor (2) the synthetic liquid of cyclic carbonate that comes out, the cat head cyclic carbonate enters reaction fractionating tower (4), with methyl alcohol generation transesterification reaction, the mol ratio of methyl alcohol and cyclic carbonate is 1: 1～20: 1 in the presence of transesterification catalyst;
The methylcarbonate that steams from reaction fractionating tower (4) cat head and the azeotrope of methyl alcohol enter pressurization knockout tower (5), pressurization knockout tower (5) tower still is the methylcarbonate product, alcohol mixture from the discharge of reaction fractionating tower (4) tower still, enter cut light tower (6), cut light tower (6) tower still obtains the dibasic alcohol crude product, and crude product enters in the dibasic alcohol rectifying tower (7) more subsequently; Dibasic alcohol rectifying tower (7) adopts conventional method to separate, and cat head is a dibasic alcohol.
2. method according to claim 1 is characterized in that, the catalyst recirculation of cyclic carbonate rectifying tower (3) bottom is to cyclic carbonate synthesis reactor (2).
3. method according to claim 1 is characterized in that, dibasic alcohol rectifying tower (7) adopts conventional method to separate, and cat head is a dibasic alcohol, and the tower still is a transesterification catalyst, and returns reaction fractionating tower (4) by pipeline, recycles.
4. according to claim 1,2 or 3 described methods, it is characterized in that said epoxy alkane is oxyethane or propylene oxide.
5. according to claim 1,2 or 3 described methods, it is characterized in that the working pressure of absorption process is 0.1～20MPa (absolute pressure), absorption temperature is-50～250 ℃, and vapour-liquid ratio is 0.2～5.
6. according to claim 1,2 or 3 described methods, it is characterized in that the cyclic carbonate absorption liquid that has absorbed epoxy alkane and carbonic acid gas is in the presence of catalyzer, epoxy alkane and carbon dioxide reaction generate cyclic carbonate; The working pressure of reaction is 0.1～20MPa (absolute pressure), and temperature of reaction is 50～250 ℃, and the catalyzer that is adopted is one or more in halogenide, quaternary amine, organic amine or the phosphine thing.
7. according to claim 1,2 or 3 described methods, it is characterized in that the working pressure of cyclic carbonate rectifying tower is 0.001～0.1MPa (absolute pressure), temperature is 50～250 ℃; The working pressure of reactive distillation is 0.001～0.1MPa (absolute pressure), and service temperature is 20～150 ℃.
8. according to claim 1,2 or 3 described methods, it is characterized in that transesterification catalyst comprises one or more of alkalimetal oxide, alkali metal hydroxide, alkali metal alcoholate or alkaline carbonate.
9. according to claim 1,2 or 3 described methods, it is characterized in that the tower still heating source that the heat that reaction is discharged in the synthesis reactor (2) is used to that low pressure water vapor takes place or directly is used as reaction fractionating tower (4).
10. according to claim 1,2 or 3 described methods, it is characterized in that, cyclic carbonate rectifying tower (3) overhead condensation heat is as low pressure water vapor taking place or directly as the tower still heating source of reaction fractionating tower (4), low pressure water vapor is as taking place or directly as the tower still heating source of reaction fractionating tower (4) in methylcarbonate pressure distillation tower (5) overhead condensation heat, and dibasic alcohol knockout tower (7) overhead condensation heat is as low pressure water vapor taking place or directly as the heating source of reaction fractionating tower (4) or Methanol Recovery.
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