CN108794300B - Pre-separation method of raw material containing ethylene glycol and 1, 2-butanediol and preparation method of epoxybutane - Google Patents
Pre-separation method of raw material containing ethylene glycol and 1, 2-butanediol and preparation method of epoxybutane Download PDFInfo
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Abstract
A preparation method of epoxy butane comprises the following steps: reacting and rectifying a raw material containing ethylene glycol and 1, 2-butanediol with an esterifying agent under the action of an esterification catalyst to respectively obtain a light component containing a reaction product corresponding to the esterifying agent and a heavy component containing ethylene carbonate and butylene carbonate, and rectifying the heavy component containing the ethylene carbonate and the butylene carbonate to respectively obtain ethylene carbonate and butylene carbonate; and (3) decarboxylating the butylene carbonate under the action of a decarboxylation catalyst to obtain the epoxybutane. The preparation method of the epoxybutane comprises the steps of carrying out ester exchange reaction on a raw material containing ethylene glycol and 1, 2-butanediol and an esterifying agent to convert the 1, 2-butanediol into butylene carbonate which does not azeotropy with the ethylene glycol so as to purify the ethylene glycol, and decarboxylating the butylene carbonate formed by converting the 1, 2-butanediol to obtain the epoxybutane with higher added value.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a pre-separation method of raw materials containing ethylene glycol and 1, 2-butanediol and a preparation method of epoxybutane.
Background
By 2016, the global Ethylene Glycol (EG) production capacity reaches 3747 ten thousand tons, and the annual average capacity growth rate reaches more than 5%. At present, two main synthesis methods of ethylene glycol are available, which are respectively: ethylene-ethylene oxide-ethylene glycol lines and synthesis gas (hydrogen and carbon monoxide) -ethylene glycol lines (commonly known as coal-to-ethylene glycol lines).
Due to the abundant domestic coal resources and the obvious cost advantage of the coal-to-ethylene glycol line when the price of crude oil is higher than $ 55/barrel, the technology is pursued by domestic enterprises in recent years. The coal-to-ethylene glycol line mainly comprises three units, namely dimethyl oxalate prepared from synthesis gas, crude ethylene glycol synthesized by hydrogenating dimethyl oxalate and crude ethylene glycol refining. The reaction product of the preparation of the ethylene glycol by the hydrogenation of dimethyl oxalate contains substances with lower boiling points such as methanol and glycolate, and also contains a small amount of substances which have approximate boiling points with the ethylene glycol and are difficult to separate by ordinary rectification, such as 1, 2-propylene glycol, 1, 2-Butanediol (BG), and the like, wherein the boiling points of the 1, 2-butanediol and the ethylene glycol are the closest, and azeotrope is easy to form during the rectification, so that the separation is the most difficult.
Although methods for separating ethylene glycol and 1, 2-butanediol are researched in the prior art, most of the methods have the problems of large equipment investment, long process flow and the like, and the development of the technology for separating ethylene glycol and 1, 2-butanediol is indirectly limited because 1, 2-butanediol is rarely applied industrially and has low economic value.
Butylene Oxide (BO) is an important chemical raw material and is mainly used for synthesizing polyether, phosphate flame retardant and butanediol ether solvents. At present, the synthesis method of butylene oxide is mainly a 1-butene epoxidation method, and typical process lines thereof are a peroxyacid method, a chlorohydrin method, an oxidation method and a hydrogen peroxide direct oxidation method. The peroxyacid method and the chlorohydrin method have been gradually limited and eliminated due to the huge amount of waste water generated; the investment of the co-oxidation method is large; the direct hydrogen peroxide oxidation process requires the use of methanol as a solvent, and has difficulties in product separation due to the close boiling points of methanol and butylene oxide.
In conclusion, the research focus of people is to find a preparation method of epoxy butane, which takes a mixture of ethylene glycol and 1, 2-butanediol as a raw material and purifies ethylene glycol without separating ethylene glycol and 1, 2-butanediol.
Disclosure of Invention
Based on the above, there is a need for a method for preparing butylene oxide by purifying ethylene glycol from a mixture of ethylene glycol and 1, 2-butanediol without separating ethylene glycol and purifying 1, 2-butanediol.
In addition, the application also provides a pre-separation method of the raw material containing the ethylene glycol and the 1, 2-butanediol.
A method for the pre-separation of a feed comprising ethylene glycol and 1, 2-butanediol, comprising the steps of:
reacting and rectifying raw materials containing ethylene glycol and 1, 2-butanediol with an esterifying agent under the action of an esterification catalyst to respectively obtain a light component containing a reaction product corresponding to the esterifying agent and a heavy component containing ethylene carbonate and butylene carbonate, wherein the structural general formula of the esterifying agent is as follows:
wherein X is Cl or NH2OR OR, R is a straight chain OR branched chain alkyl of C1-C4;
and (3) rectifying the heavy components containing the ethylene carbonate and the butylene carbonate to respectively obtain the ethylene carbonate and the butylene carbonate.
In one embodiment, the molar ratio of the esterifying agent to the mixed alcohol in the raw material containing the ethylene glycol and the 1, 2-butanediol is (1-5): 1.
In one embodiment, the esterification catalyst is selected from at least one of sodium alkoxides, titanates, alkali metal carbonates, organotin, and anion exchange resins; the molar ratio of the esterification catalyst to the mixed alcohol in the raw material containing the ethylene glycol and the 1, 2-butanediol is (0.001-0.1): 1.
In one embodiment, the top temperature of the reactive distillation is 10-100 ℃, the kettle temperature is 50-200 ℃, the number of tower plates is 10-70, and the absolute pressure is 0-10 Bar.
In one embodiment, the light component containing the esterification agent corresponding to the reaction product also contains the esterification agent;
also comprises a step of separating the esterifying agent from light components containing the corresponding reaction products of the esterifying agent for recycling.
In one embodiment, the method further comprises the following steps:
and (3) carrying out reaction rectification on the ethylene carbonate and fatty alcohol to obtain ethylene glycol, wherein the fatty alcohol is C1-C4 primary monohydric alcohol.
In one embodiment, when X is OR and R is a linear alkyl group of C1-C4 in the esterification agent, the corresponding reaction product of the esterification agent is a monohydric primary alcohol of C1-C4;
also comprises a step of separating the reaction product corresponding to the esterifying agent from the light component containing the reaction product corresponding to the esterifying agent for recycling.
In one embodiment, the heavy component containing ethylene carbonate and butylene carbonate also contains ethylene glycol;
also includes the step of separating ethylene glycol from heavy components containing ethylene carbonate and butylene carbonate.
A method for preparing epoxybutane, comprising the steps of the method for pre-separating ethylene glycol and 1, 2-butanediol, further comprising the following steps:
and decarboxylating the butylene carbonate under the action of a decarboxylation catalyst to obtain the epoxybutane.
In one embodiment, the decarboxylation catalyst is selected from at least one of an alkali metal sulfate, an alkali metal chloride, an alkali metal nitrate, an alkylimidazolium salt, an ionic liquid, a supported alkali metal, and a supported alkali metal oxide.
In one embodiment, the absolute pressure of the decarboxylation is 0.1 Bar-10 Bar, the temperature is 60 ℃ to 500 ℃, and the mass space velocity is 0.1h-1～5h-1。
The preparation method of the epoxybutane comprises the steps of carrying out ester exchange reaction on a raw material containing ethylene glycol and 1, 2-butanediol and an esterifying agent to convert the 1, 2-butanediol into butylene carbonate which does not have azeotropic boiling with the ethylene glycol so as to purify the ethylene glycol, and decarboxylating the butylene carbonate formed by converting the 1, 2-butanediol to obtain the epoxybutane with higher added value.
Compared with the traditional preparation method of the epoxybutane, the preparation method of the epoxybutane has the advantages of low equipment investment cost, simple operation, safety and the like.
Drawings
Fig. 1 is a schematic flow diagram of a process for producing butylene oxide according to an embodiment.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
An embodiment of a method for pre-separating a feed comprising ethylene glycol and 1, 2-butanediol comprises the following steps S110 to S160:
s110, reacting and rectifying a raw material containing ethylene glycol and 1, 2-butanediol with an esterifying agent under the action of an esterification catalyst to respectively obtain a light component containing a reaction product corresponding to the esterifying agent and a heavy component containing Ethylene Carbonate (EC) and Butylene Carbonate (BC).
In this embodiment, the raw material containing ethylene glycol and 1, 2-butanediol is a reaction product of dimethyl oxalate and hydrogenation to ethylene glycol.
Further, the raw material containing ethylene glycol and 1, 2-butanediol is a reaction product of preparing ethylene glycol by hydrogenating unpurified dimethyl oxalate containing 95-99.5% of ethylene glycol and 0.5-5% of 1, 2-butanediol; or a reaction product of ethylene glycol prepared by hydrogenation of purified dimethyl oxalate containing 38-90% of ethylene glycol and 10-62% of 1, 2-butanediol.
Wherein, the structural general formula of the esterifying agent is as follows:
in the structural formula, X is Cl or NH2OR OR, R is a straight chain OR branched chain alkyl of C1-C4.
That is, the esterifying agent is phosgene, urea, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, etc., and they are not specifically mentioned here as long as they satisfy the above general formula.
Further, the molar ratio of the esterifying agent to the mixed alcohol in the raw material containing ethylene glycol and 1, 2-butanediol is (1-5): 1.
Further, the esterification catalyst is selected from at least one of sodium alkoxide, titanate, alkali metal carbonate, organotin, and anion exchange resin.
Further, sodium alkoxide is sodium methoxide, sodium ethoxide, or the like; titanate is tetrabutyl titanate, etc.; the alkali metal carbonate is sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, etc.; the organic tin is stannous oxalate and the like; the anion exchange resin is weak base anion exchange resin.
Further, the molar ratio of the esterification catalyst to the mixed alcohol in the raw material containing ethylene glycol and 1, 2-butanediol is (0.001-0.1): 1.
Further, the top temperature of the reaction rectification is 10-100 ℃, the kettle temperature is 50-200 ℃, the number of tower plates is 10-70, and the absolute pressure is 0-10 Bar.
S120, rectifying the heavy components containing the ethylene carbonate and the butylene carbonate to respectively obtain the ethylene carbonate and the butylene carbonate.
The heavy components containing ethylene carbonate and butylene carbonate further contain an esterification catalyst.
In addition, since the reactivity of 1, 2-butanediol with the esterifying agent is superior to that of ethylene glycol with the esterifying agent, ethylene glycol may be contained in the above-mentioned heavy components containing ethylene carbonate and butylene carbonate.
When the heavy component containing ethylene carbonate and butylene carbonate further contains ethylene glycol, the pre-separation method further comprises a step of separating ethylene glycol from the heavy component containing ethylene carbonate and butylene carbonate (denoted as step S130).
In this embodiment, the method for separating ethylene carbonate, butylene carbonate, esterification catalyst and ethylene glycol is three-stage rectification.
Specifically, heavy components containing ethylene carbonate and butylene carbonate are subjected to primary rectification, high-purity ethylene glycol is extracted from the top of the tower, a mixture of the ethylene carbonate, the butylene carbonate and an esterification catalyst is extracted from the bottom of the tower, the mixture of the ethylene carbonate, the butylene carbonate and the esterification catalyst is subjected to secondary rectification, high-purity butylene carbonate is extracted from the top of the tower, a mixture of the ethylene carbonate and the esterification catalyst is extracted from the bottom of the tower, the mixture of the ethylene carbonate and the esterification catalyst is subjected to tertiary rectification, high-purity ethylene carbonate is extracted from the top of the tower, and the esterification catalyst is extracted from the bottom of the tower for recycling.
Wherein the top temperature of the primary rectification is 50-200 ℃, the kettle temperature is 70-300 ℃, the number of column plates is 30-80, the feeding position is the position of 15-45 column plates, and the absolute pressure is 0-1 Bar.
The top temperature of the secondary rectification is 130-250 ℃, the kettle temperature is 150-270 ℃, the number of column plates is 60-200, the feeding position is the position of column plate number 40-100, and the absolute pressure is 0-1 Bar.
The top temperature of the three-stage rectification is 100-260 ℃, the kettle temperature is 160-300 ℃, the number of column plates is 1-30, the feeding position is the position of the column plate number is 1-29, and the absolute pressure is 0-1 Bar.
It is understood that the above-mentioned method for rectifying a heavy component comprising ethylene glycol, ethylene carbonate and butylene carbonate is not limited to the above-described process as long as ethylene glycol, ethylene carbonate, butylene carbonate and an esterification catalyst can be separated, and for example, step S120 and step S130 are performed simultaneously, that is, ethylene glycol, ethylene carbonate, butylene carbonate and an esterification agent are separated simultaneously.
If ethylene glycol is completely converted to ethylene carbonate, the above-mentioned rectification method is only required to separate ethylene carbonate, butylene carbonate and the esterification catalyst, and step S130 may be omitted.
In addition, the above light fraction containing the esterification agent corresponding to the reaction product may contain an unreacted esterification agent. When the light component containing the esterification agent corresponding to the reaction product contains the esterification agent, the pre-separation method further comprises a step of separating the esterification agent from the light component containing the esterification agent corresponding to the reaction product for recycling (denoted as step S140).
In this embodiment, the step of separating the esterification agent from the light fraction containing the reaction product corresponding to the esterification agent for recycling is specifically:
and (3) performing pressure swing rectification on the light component containing the esterification agent corresponding to the reaction product to obtain the esterification agent for recycling.
If recycling of the esterification agent is not considered, the step S140 may be omitted.
It will be understood that when the esterifying agent is an esterifying agent in which X is Cl in the general structural formula (i.e., the esterifying agent is phosgene), the corresponding reaction product is HCl, and when the esterifying agent is an esterifying agent in which X is NH in the general structural formula2When the esterifying agent (i.e., the esterifying agent is urea), the corresponding reaction product is NH3When the esterifying agent is an esterifying agent in which X is OR in the structural general formula (namely the esterifying agent is dialkyl carbonate), the corresponding reaction product is ROH, and R is a linear chain OR branched chain alkyl of C1-C4.
In the present embodiment, the pre-separation method further includes the following step S150:
and (3) reacting and rectifying the ethylene carbonate and the fatty alcohol to obtain the ethylene glycol.
Wherein the fatty alcohol is C1-C4 primary monohydric alcohol.
If it is not considered to further convert the ethylene carbonate into ethylene glycol, step S150 may be omitted.
It can be understood that if the esterifying agent is an esterifying agent in which X is OR in the structural formula (i.e. the esterifying agent is dialkyl carbonate), and R is a linear alkyl group of C1-C4, the corresponding reaction product is a monohydric primary alcohol of C1-C4, and the corresponding reaction product of the esterifying agent can be recycled. Namely, the pre-separation method further comprises a step of separating the reaction product corresponding to the esterifying agent from the light component containing the reaction product corresponding to the esterifying agent for recycling (denoted as step S160).
If the recycling of the reaction product corresponding to the esterification agent is not considered, step S160 may be omitted.
Further, it should be noted that step S140 and step S150 may be performed simultaneously, for example: and (3) performing pressure swing rectification on the light components containing the esterification agent corresponding reaction products to respectively obtain the esterification agent and the corresponding reaction products of the esterification agent.
The pre-separation method of the raw material containing the ethylene glycol and the 1, 2-butanediol comprises the steps of carrying out reaction rectification on the raw material containing the ethylene glycol and the 1, 2-butanediol and an esterifying agent, respectively converting the ethylene glycol and the 1, 2-butanediol into the ethylene carbonate and the butylene carbonate, and then separating the ethylene carbonate and the butylene carbonate according to the boiling point difference of the ethylene carbonate and the butylene carbonate, so that the direct separation of the ethylene glycol and the 1, 2-butanediol which are easy to form azeotrope and difficult to separate is avoided, and the method has the advantages of low equipment investment cost, safe operation, simplicity and the like.
Referring to fig. 1, a flow chart of a method for preparing butylene oxide according to an embodiment of the present invention is shown, wherein the method for preparing butylene oxide includes the following steps S210 to S260:
s210, reacting and rectifying a raw material containing ethylene glycol and 1, 2-butanediol with an esterification agent under the action of a catalyst to respectively obtain a light component containing a reaction product corresponding to the esterification agent and a heavy component containing ethylene carbonate and butylene carbonate.
Wherein, the structural general formula of the esterifying agent is as follows:
in the structural formula, X is Cl or NH2OR OR, R is a straight chain OR branched chain alkyl of C1-C4.
That is, the esterifying agent is phosgene, urea, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, etc., and they are not specifically mentioned here as long as they satisfy the above general formula.
In the present embodiment, the esterifying agent is a linear alkyl group having a structure in which X is OR and R is C1-C4.
Further, the molar ratio of the esterifying agent to the mixed alcohol in the raw material containing ethylene glycol and 1, 2-butanediol is (1-5): 1.
Further, the esterification catalyst is selected from at least one of sodium alkoxide, titanate, alkali metal carbonate, organotin, and anion exchange resin.
Further, sodium alkoxide is sodium methoxide, sodium ethoxide, or the like; titanate is tetrabutyl titanate, etc.; the alkali metal carbonate is sodium carbonate, potassium carbonate, cesium carbonate, rubidium carbonate, etc.
Further, the molar ratio of the esterification catalyst to the mixed alcohol in the raw material containing ethylene glycol and 1, 2-butanediol is (0.001-0.1): 1.
Further, the top temperature of the reaction rectification is 10-100 ℃, the kettle temperature is 50-200 ℃, the number of tower plates is 10-70, and the absolute pressure is 0-10 Bar.
S220, rectifying the heavy components containing the ethylene carbonate and the butylene carbonate to respectively obtain the ethylene carbonate and the butylene carbonate.
The heavy components containing ethylene carbonate and butylene carbonate further contain an esterification catalyst.
In this embodiment, the heavy component containing ethylene carbonate and butylene carbonate further contains ethylene glycol.
Further, the rectification method is three-stage rectification.
Specifically, the heavy component containing ethylene glycol, ethylene carbonate and butylene carbonate is subjected to primary rectification, high-purity ethylene glycol is extracted from the top of the tower, a mixture of ethylene carbonate, butylene carbonate and an esterification catalyst is extracted from the bottom of the tower, the mixture of ethylene carbonate, butylene carbonate and the esterification catalyst is subjected to secondary rectification, high-purity butylene carbonate is extracted from the top of the tower, a mixture of ethylene carbonate and the esterification catalyst is extracted from the bottom of the tower, the mixture of ethylene carbonate and the esterification catalyst is subjected to tertiary rectification, high-purity ethylene carbonate is extracted from the top of the tower, and the esterification catalyst is extracted from the bottom of the tower for recycling.
Wherein the top temperature of the primary rectification is 50-200 ℃, the kettle temperature is 70-300 ℃, the number of column plates is 30-80, the feeding position is the position of 15-45 column plates, and the absolute pressure is 0-1 Bar.
The top temperature of the secondary rectification is 130-250 ℃, the kettle temperature is 150-270 ℃, the number of column plates is 60-200, the feeding position is the position of column plate number 40-100, and the absolute pressure is 0-1 Bar.
The top temperature of the three-stage rectification is 100-260 ℃, the kettle temperature is 160-300 ℃, the number of column plates is 1-30, the feeding position is the position of the column plate number is 1-29, and the absolute pressure is 0-1 Bar.
It is understood that the above-described method for rectifying the heavy components comprising ethylene glycol, ethylene carbonate and butylene carbonate is not limited to the above-described process as long as ethylene glycol, ethylene carbonate, butylene carbonate and the esterification catalyst can be separated.
And S230, decarboxylating the butylene carbonate under the action of a decarboxylation catalyst to obtain the epoxybutane.
Wherein the decarboxylation catalyst is at least one selected from alkali metal sulfate, alkali metal chloride, alkali metal nitrate, alkyl imidazole salt, ionic liquid, supported alkali metal and supported alkali metal oxide.
Further, the alkali metal sulfate is sodium sulfate, zinc sulfate, tin sulfate, magnesium sulfate, aluminum sulfate, or the like; the alkali metal chloride is sodium chloride, green zinc, stannic chloride, magnesium chloride, etc.; the alkali metal nitrate is sodium nitrate, zinc nitrate, tin nitrate, magnesium nitrate, aluminum nitrate, etc.
Further, the supported alkali metal is supported alkali metal taking silicon oxide, an X-type molecular sieve or a Y-type molecular sieve as a carrier, wherein the alkali metal is sodium, zinc, tin, magnesium, aluminum and the like; the supported alkali metal oxide is supported alkali metal oxide taking silicon oxide, an X-type molecular sieve or a Y-type molecular sieve as a carrier, wherein the alkali metal oxide is sodium oxide, zinc oxide, tin oxide, magnesium oxide, aluminum oxide and the like.
Further, the absolute pressure of decarboxylation is 0.1 Bar-10 BarThe temperature is 60 ℃ to 500 ℃, and the mass space velocity is 0.1h-1～5h-1。
In this embodiment, the light fraction containing the esterification agent-corresponding reaction product further contains an unreacted esterification agent. When the light component containing the esterification agent corresponding to the reaction product contains the esterification agent, the pre-separation method further comprises the following steps:
s240, performing pressure swing rectification on the light component containing the esterification agent corresponding reaction product to respectively obtain the esterification agent and the esterification agent corresponding reaction product.
Wherein, the esterification agent obtained by pressure swing distillation can be recycled.
If recycling of the esterification agent is not considered, step S240 may be omitted.
In this embodiment, the preseparation method further includes the steps of:
and S250, reacting and rectifying the ethylene carbonate and the fatty alcohol to obtain the ethylene glycol.
Wherein the fatty alcohol is C1-C4 primary monohydric alcohol.
In this embodiment, the esterification agent is an esterification agent in which X is OR in the structural formula (i.e., the esterification agent is dialkyl carbonate), and R is a linear alkyl group of C1 to C4, so that the corresponding reaction product is a monohydric primary alcohol of C1 to C4, and at this time, the corresponding reaction product of the esterification agent can be recycled.
It should be noted that step S250 may be omitted if no further conversion of ethylene carbonate to ethylene glycol is contemplated.
That is, in the present embodiment, the preliminary separation method further includes the steps of:
s260, circularly applying the esterification agent obtained by pressure swing rectification to the corresponding reaction product.
If the recycling of the reaction product corresponding to the esterification agent is not considered, step S260 may be omitted.
According to the preparation method of the epoxybutane, raw materials containing ethylene glycol and 1, 2-butanediol and an esterifying agent are subjected to reactive distillation, the reactivity of the 1, 2-butanediol and the esterifying agent is superior to that of the ethylene glycol and the esterifying agent, so that the 1, 2-butanediol is almost completely converted into the butylene carbonate, the ethylene glycol is possibly only partially converted into the ethylene carbonate, then the ethylene glycol with higher added value can be purified according to the boiling point difference of the ethylene glycol, the ethylene carbonate and the butylene carbonate, and the butylene carbonate is subjected to decarboxylation to obtain the epoxybutane with higher added value.
Compared with the traditional preparation method of the epoxybutane, the preparation method of the epoxybutane by using the ethylene glycol and the 1, 2-butanediol as the raw materials has the advantages of simple product separation, low investment cost, no three wastes, safety, environmental protection and higher selectivity and purity of the epoxybutane.
The following are specific examples
Example 1
The method comprises the following steps of carrying out reaction rectification on raw materials containing 95% of ethylene glycol and 5% of 1, 2-butanediol and dimethyl carbonate under the action of sodium methoxide to obtain a light component containing methanol and dimethyl carbonate and a heavy component containing ethylene carbonate and butylene carbonate, wherein the top temperature of the reaction rectification is 64 ℃, the kettle temperature is 100 ℃, the number of tower plates is 50, the absolute pressure is 1Bar, the molar ratio of the dimethyl carbonate to mixed alcohol in the raw materials is 1.3:1, and the molar ratio of the sodium methoxide to the mixed alcohol in the raw materials is 0.01: 1.
After the heavy components containing the ethylene carbonate and the butylene carbonate are subjected to primary rectification, high-purity ethylene glycol is extracted from the top of the tower, the mixture of the ethylene carbonate, the butylene carbonate and sodium methoxide is extracted from the bottom of the tower, the mixture of the ethylene carbonate, the butylene carbonate and the sodium methoxide is rectified in the second stage to obtain high-purity butylene carbonate from the top of the tower, the mixture of the ethylene carbonate and the sodium methoxide is rectified in the third stage to obtain high-purity ethylene carbonate from the top of the tower, and the sodium methoxide is recycled from the bottom of the tower, wherein the top temperature of the first-stage rectification is 80 ℃, the kettle temperature is 160 ℃, the number of tower plates is 35, and the absolute pressure is 0.1Bar, the top temperature of the second-stage rectification is 145 ℃, the kettle temperature is 201 ℃, the number of tower plates is 130, and the absolute pressure is 0.1Bar, the top temperature of the third-stage rectification is 160 ℃, the kettle temperature is 165 ℃, the number of tower plates is 1, and the absolute pressure is 0.1 Bar.
The butylene carbonate is decarboxylated under the action of zinc nitrate to obtain a ringOxybutane, wherein the absolute pressure of decarboxylation is 0.4Bar, the temperature is 230 ℃ and the mass space velocity is 1.1h-1。
And (3) reacting and rectifying the ethylene carbonate and methanol to obtain the ethylene glycol.
And (3) performing pressure swing rectification on the light components containing the methanol and the dimethyl carbonate to respectively obtain the dimethyl carbonate and the methanol, recycling the dimethyl carbonate and recycling the methanol.
The detection proves that the conversion rate of BC is 99.0%, the selectivity of BO is 97.2%, the purity of EG is 98.4% and the purity of BO is 96.1%.
Example 2
The method comprises the following steps of carrying out reactive distillation on a raw material containing 40% of ethylene glycol and 60% of 1, 2-butanediol and diethyl carbonate under the action of tetrabutyl titanate to obtain a light component containing ethanol and diethyl carbonate and a heavy component containing ethylene carbonate and butylene carbonate, wherein the top temperature of the reactive distillation is 90 ℃, the kettle temperature is 130 ℃, the number of tower plates is 69, the absolute pressure is 1Bar, the molar ratio of diethyl carbonate to mixed alcohol in the raw material is 4:1, and the molar ratio of tetrabutyl titanate to mixed alcohol in the raw material is 0.05: 1.
After heavy components containing ethylene carbonate and butylene carbonate are subjected to primary rectification, high-purity ethylene glycol is extracted from the top of the tower, a mixture of ethylene carbonate, butylene carbonate and tetrabutyl titanate is extracted from the bottom of the tower, the mixture of the ethylene carbonate, the butylene carbonate and the tetrabutyl titanate is subjected to secondary rectification to extract high-purity butylene carbonate from the top of the tower, a mixture of the ethylene carbonate and the tetrabutyl titanate is extracted from the bottom of the tower, the mixture of the ethylene carbonate and the tetrabutyl titanate is subjected to tertiary rectification to extract high-purity ethylene carbonate from the top of the tower, and the tetrabutyl titanate is recycled, wherein the top temperature of the primary rectification is 134 ℃, the kettle temperature is 198 ℃, the number of plates is 56, the absolute pressure is 0.4Bar, the top temperature of the secondary rectification is 241 ℃, the kettle temperature is 249 ℃, the number of plates is 155, the absolute pressure is 0.9Bar, the top temperature of the secondary rectification is 160 ℃, the kettle temperature is 165 ℃, the number of plates, Absolute pressure 0.1 Bar.
The butylene carbonate is decarboxylated under the action of sodium chloride to obtain the epoxybutane, wherein the absolute pressure of decarboxylation is 3Bar, the temperature is 270 ℃, and the mass space velocity is 3.2h-1。
And (3) reacting and rectifying the ethylene carbonate and ethanol to obtain the ethylene glycol.
And (3) performing pressure swing rectification on the light component containing the ethanol and the diethyl carbonate to respectively obtain diethyl carbonate and ethanol, recycling the diethyl carbonate and the ethanol.
The detection proves that the conversion rate of BC is 99.5%, the selectivity of BO is 99.8%, the purity of EG is 99.1% and the purity of BO is 99.5%.
Example 3
The method comprises the following steps of carrying out reactive distillation on a raw material containing 85% of ethylene glycol and 15% of 1, 2-butanediol and urea under the action of amino anion exchange resin to obtain a light component containing ammonia gas and urea and a heavy component containing ethylene carbonate and butylene carbonate, wherein the top temperature of the reactive distillation is 30 ℃, the kettle temperature is 72 ℃, the number of tower plates is 34, the absolute pressure is 1Bar, the molar ratio of the urea to mixed alcohol in the raw material is 2.6:1, and the molar ratio of the amino anion exchange resin to the mixed alcohol in the raw material is 0.1: 1.
After heavy components containing ethylene carbonate and butylene carbonate are subjected to primary rectification, high-purity ethylene glycol is extracted from the top of the tower, a mixture of the ethylene carbonate, the butylene carbonate and amino anion exchange resin is extracted from the bottom of the tower, the mixture of the ethylene carbonate, the butylene carbonate and the amino anion exchange resin is subjected to secondary rectification, high-purity butylene carbonate is extracted from the top of the tower, a mixture of the ethylene carbonate and the amino anion exchange resin is extracted from the bottom of the tower, the mixture of the ethylene carbonate and the amino anion exchange resin is subjected to tertiary rectification, high-purity ethylene carbonate is extracted from the top of the tower, the amino anion exchange resin is extracted from the bottom of the tower for recycling, wherein the top temperature of the primary rectification is 158 ℃, the tower plate temperature of the tower is 199 ℃, the number of 75, the absolute pressure is 0.8Bar, the top temperature of the secondary rectification is 167 ℃, the tower plate temperature of the tower is 234 ℃, the number of the tower plates is 200, the top temperature of the three-stage rectification is 192 ℃, the kettle temperature is 195 ℃, the number of tower plates is 20, and the absolute pressure is 0.4 Bar.
The butylene carbonate is decarboxylated under the action of hexadecyl imidazole chloride to obtain the epoxybutane, wherein the absolute pressure of decarboxylation is 7.1Bar, the temperature is 350 ℃, and the mass space velocity is 4.0h-1。
And (3) reacting and rectifying the ethylene carbonate and methanol to obtain the ethylene glycol.
And (3) performing pressure swing rectification on the light components containing ammonia gas and urea to respectively obtain urea and ammonia gas, and recycling the urea.
The detection proves that the conversion rate of BC is 99.9%, the selectivity of BO is 99.3%, the purity of EG is 99.5%, and the purity of BO is 99.3%.
Example 4
The method comprises the steps of carrying out reaction rectification on a raw material containing 56% of ethylene glycol and 44% of 1, 2-butanediol and phosgene under the action of sodium carbonate to obtain a light component containing hydrogen chloride and phosgene and a heavy component containing ethylene carbonate and butylene carbonate, wherein the top temperature of the reaction rectification is 5 ℃, the kettle temperature is 26 ℃, the number of tower plates is 5, and the absolute pressure is 8Bar, the molar ratio of the phosgene to mixed alcohol in the raw material is 1:1, and the molar ratio of the sodium carbonate to the mixed alcohol in the raw material is 0.002: 1.
After the heavy components containing the ethylene carbonate and the butylene carbonate are subjected to primary rectification, high-purity ethylene glycol is extracted from the top of the tower, a mixture of the ethylene carbonate, the butylene carbonate and sodium carbonate is extracted from the bottom of the tower, the mixture of the ethylene carbonate, the butylene carbonate and the sodium carbonate is subjected to secondary rectification to obtain high-purity butylene carbonate from the top of the tower, the mixture of the ethylene carbonate and the sodium carbonate from the bottom of the tower, the mixture of the ethylene carbonate and the sodium carbonate is subjected to tertiary rectification to obtain high-purity ethylene carbonate from the top of the tower, and the sodium carbonate from the bottom of the tower is recycled, wherein the top temperature of the first-stage rectification is 115 ℃, the kettle temperature is 172 ℃, the number of plates is 80, the absolute pressure is 0.3Bar, the top temperature of the second-stage rectification is 225 ℃, the kettle temperature is 241 ℃, the number of plates is 189, the absolute pressure is 0.6Bar, the top temperature of the third-stage rectification is 251 ℃, the kettle temperature is 255 ℃, the number of plates is 10, and the absolute pressure is 0.9 Bar.
Decarboxylating butylene carbonate under the action of magnesium sulfate to obtain epoxybutane, wherein the absolute pressure of decarboxylation is 10Bar, the temperature is 470 ℃, and the mass space velocity is 0.6h-1。
And (3) reacting and rectifying the ethylene carbonate and methanol to obtain the ethylene glycol.
And (3) performing pressure swing rectification on the light components containing the phosgene and the hydrogen chloride to respectively obtain the phosgene and the hydrogen chloride, and recycling the phosgene.
The detection proves that the conversion rate of BC is 98.2%, the selectivity of BO is 95.0%, the purity of EG is 99.6%, and the purity of BO is 93.2%.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A method for the pre-separation of a feed comprising ethylene glycol and 1, 2-butanediol, comprising the steps of:
reacting and rectifying raw materials containing ethylene glycol and 1, 2-butanediol with an esterifying agent under the action of an esterification catalyst to respectively obtain a light component containing a reaction product corresponding to the esterifying agent and a heavy component containing ethylene carbonate and butylene carbonate, wherein the structural general formula of the esterifying agent is as follows:
wherein X is Cl or NH2OR OR, R is a straight chain OR branched chain alkyl of C1-C4;
rectifying the heavy components containing the ethylene carbonate and the butylene carbonate to respectively obtain the ethylene carbonate and the butylene carbonate;
reacting and rectifying the ethylene carbonate and fatty alcohol to obtain ethylene glycol;
the top temperature of the reactive distillation is 10-100 ℃, the kettle temperature is 50-200 ℃, the number of column plates is 10-70, and the absolute pressure is 0-10 Bar.
2. The method for pre-separating the raw material containing ethylene glycol and 1, 2-butanediol according to claim 1, wherein the molar ratio of the esterification agent to the mixed alcohol in the raw material containing ethylene glycol and 1, 2-butanediol is (1-5): 1.
3. The method for pre-separating a raw material containing ethylene glycol and 1, 2-butanediol according to claim 1, wherein the esterification catalyst is at least one selected from sodium alkoxide, titanate, alkali metal carbonate, organotin and anion exchange resin; the molar ratio of the esterification catalyst to the mixed alcohol in the raw material containing the ethylene glycol and the 1, 2-butanediol is (0.001-0.1): 1.
4. The method for the pre-separation of a feed comprising ethylene glycol and 1, 2-butanediol as claimed in claim 1, characterized in that the top temperature of the reactive distillation is 64 ℃, the pot temperature is 100 ℃, the number of plates is 50, and the absolute pressure is 1 Bar.
5. The pre-separation method of raw materials containing ethylene glycol and 1, 2-butanediol according to any one of claims 1 to 4, characterized in that the light component of the reaction product corresponding to the esterification agent further contains an esterification agent;
also comprises a step of separating the esterifying agent from the light component containing the corresponding reaction product of the esterifying agent for recycling.
6. The process for the pre-separation of a feed comprising ethylene glycol and 1, 2-butanediol as claimed in claim 1,
the fatty alcohol is C1-C4 primary monohydric alcohol.
7. The method for pre-separating a raw material containing ethylene glycol and 1, 2-butanediol as claimed in claim 6, wherein when X is OR and R is a linear alkyl group of C1-C4 in the esterification agent, the corresponding reaction product of the esterification agent is a monohydric primary alcohol of C1-C4;
also comprises a step of separating the reaction product corresponding to the esterifying agent from the light component containing the reaction product corresponding to the esterifying agent for recycling.
8. The method for pre-separating a raw material containing ethylene glycol and 1, 2-butanediol according to any one of claims 1 to 4, wherein the heavy component containing ethylene carbonate and butylene carbonate further contains ethylene glycol;
also includes the step of separating ethylene glycol from heavy components containing ethylene carbonate and butylene carbonate.
9. A method for producing an epoxybutane, comprising the step of the method for pre-separating ethylene glycol and 1, 2-butanediol according to any one of claims 1 to 8, further comprising the steps of:
and decarboxylating the butylene carbonate under the action of a decarboxylation catalyst to obtain the epoxybutane.
10. The method for producing butylene oxide according to claim 9, wherein the decarboxylation catalyst is at least one selected from the group consisting of an alkali metal sulfate, an alkali metal chloride, an alkali metal nitrate, an alkylimidazolium salt, an ionic liquid, a supported alkali metal, and a supported alkali metal oxide.
11. The method for preparing butylene oxide according to claim 9, wherein the absolute pressure of decarboxylation is 0.1 Bar-10 Bar, the temperature is 60 ℃ to 500 ℃, and the mass space velocity is 0.1h-1～5h-1。
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| CN111978274B (en) * | 2019-05-22 | 2022-09-30 | 广州大有精细化工厂 | Method for preparing butylene oxide |
| CN114478190B (en) * | 2020-10-27 | 2024-03-05 | 中国石油化工股份有限公司 | Ethylene glycol refining method |
| CN115304454B (en) * | 2021-05-07 | 2024-07-23 | 中国石油化工股份有限公司 | Separation method and system for recycling glycol in polyester production process |
| CN113387890B (en) * | 2021-06-17 | 2022-11-15 | 中国科学院过程工程研究所 | Ionic liquid, polyionic liquid and preparation method and application thereof |
| CN114539025A (en) * | 2022-03-11 | 2022-05-27 | 广西科技大学 | Method for separating dihydric alcohol through ester exchange reaction |
| CN114456040A (en) * | 2022-03-11 | 2022-05-10 | 广西科技大学 | Method for separating dihydric alcohol through carbonyl transfer reaction |
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