CN103772327A - Extraction method for epoxy chloro-propane - Google Patents
Extraction method for epoxy chloro-propane Download PDFInfo
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- CN103772327A CN103772327A CN201210413367.7A CN201210413367A CN103772327A CN 103772327 A CN103772327 A CN 103772327A CN 201210413367 A CN201210413367 A CN 201210413367A CN 103772327 A CN103772327 A CN 103772327A
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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Abstract
The invention provides an extraction method for epoxy chloro-propane. The method comprises the following steps: a solution containing epoxy chloro-propane, methanol, 3-chloropropylene and water is continuously extracted in two extracting tower, wherein in the first extracting tower, 3-chloropropylene flows from the top down to be in countercurrent contact with a material flow, which contains the solution containing epoxy chloro-propane, methanol, 3-chloropropylene and water as well as water serving as an extracting agent, so as to obtain an extract phase rich in epoxy chloro-propane, and the weight ratio of water serving as an extracting agent to 3-chloropropylene is 1:(0.5-2); in the second extracting tower, the extract phase rich in epoxy chloro-propane flows from the bottom up to be in countercurrent contact with water so as to obtain a raffinate phase rich in epoxy chloro-propane and 3-chloropropylene. The raffinate phase rich in epoxy chloro-propane, obtained according the method provided by the invention, doesn't or approximately doesn't contain methanol; meanwhile, the method provided by the invention can achieve higher epoxy-propare extraction rate.
Description
Technical field
The present invention relates to a kind of extracting process of epoxy chloropropane.
Background technology
Epoxy chloropropane is a kind of important basic organic chemical industry raw material and intermediate, is widely used in synthetic epoxy resin, glycerine, chlorohydrin rubber, medicine and agricultural chemicals etc.
For reducing wastewater discharge and waste residue intractability, epoxy chloropropane can, by under the existence of titanium-silicon molecular sieve catalyst TS-1 and organic solvent, contact chlorallylene with hydrogen peroxide, carries out epoxidation reaction and prepares.Described organic solvent requirement and chlorallylene and hydrogen peroxide have preferably compatibility, generally select the alcoholic solvents such as methyl alcohol, ethanol, propyl alcohol and butanols, take methyl alcohol as good.The water generating with reaction that the liquid phase that solid-liquid separation obtains of carrying out the mixture that contact is obtained contains that unreacted chlorallylene, the methyl alcohol as solvent, target product epoxy chloropropane, hydrogen peroxide charging bring into conventionally and a small amount of by product propylene glycol of chlorine monomethyl ether and propylene glycol of chlorine.Therefore need the liquid phase that solid-liquid separation is obtained to separate, to obtain reaction product epoxy chloropropane, and reclaim solvent methanol and unreacted chlorallylene.
At present, the method that separates epoxy chloropropane is generally the liquid phase that solid-liquid separation is obtained and distills, thereby isolates epoxy chloropropane; Or liquid phase solid-liquid separation being obtained with extraction agent extracts, thereby isolate epoxy chloropropane.But in the time there is first alcohol and water, in still-process, epoxy chloropropane can react with first alcohol and water, generate the by products such as propylene glycol of chlorine monomethyl ether and propylene glycol of chlorine, thereby reduce the yield of epoxy chloropropane.
US6350888 discloses a kind of by the method for extraction agent extracting and separating epoxy chloropropane, the method is by adding a kind of organic extractant to extract the epoxidation product through solid-liquid separation, obtain the liquid phase that contains epoxy chloropropane, then distill out the extraction agent in the liquid phase that contains epoxy chloropropane obtaining, separate and obtain epoxy chloropropane.Although the method can reach the object that separates epoxy chloropropane, but, need a large amount of extraction agents owing to extracting epoxy chloropropane and isolate methyl alcohol from epoxidation reaction product, and fractionation by distillation epoxy chloropropane and recovery extraction agent, also need to consume a large amount of energy, and the method is also difficult to realize epoxy chloropropane and separates with the thorough of methyl alcohol, in still-process epoxy chloropropane also can with methyl alcohol generation side reaction, generate the by products such as propylene glycol of chlorine monomethyl ether, reduce the yield of epoxy chloropropane.
CN101293882B discloses a kind of separation method of epoxy chloropropane, the method comprises and will contain epoxy chloropropane, methyl alcohol, the solution of chlorallylene and water separates after mixing with extraction agent, the liquid phase that obtains being rich in the liquid phase of epoxy chloropropane and be rich in methyl alcohol, the liquid phase that is rich in epoxy chloropropane that distillation obtains, obtain epoxy chloropropane, wherein, described extraction agent comprises extraction agent A and extraction agent B, extraction agent A and extraction agent B are immiscible, the ability of extraction agent A extraction methyl alcohol is higher than extraction agent B, the ability of extraction agent B extraction epoxy chloropropane is higher than extraction agent A, the boiling point of extraction agent B is different from the boiling point of epoxy chloropropane.The energy consumption of this separation method significantly reduces, and the yield of epoxy chloropropane also increases simultaneously, can reach 97-99 % by weight.
Summary of the invention
The object of the present invention is to provide a kind of extracting process of epoxy chloropropane, in the liquid phase that contains epoxy chloropropane being obtained by the method, do not contain or substantially contain methyl alcohol, thereby can obtain higher epoxy chloropropane yield.
The present inventor finds in practice process, adopts the disclosed method of CN101293882B to extract in the liquid phase that contains epoxy chloropropane obtaining and still contains a certain amount of methyl alcohol.For further reducing the methanol content extracting in the liquid phase that contains epoxy chloropropane obtaining, the present inventor conducts in-depth research, find: in two extraction towers, extract, wherein, first extraction tower adopts water and chlorallylene as extraction agent, and chlorallylene is sent into from the top of first extraction tower, with contain as the water of extraction agent and containing epoxy chloropropane, methyl alcohol, counter current contact is carried out in the logistics of the solution of chlorallylene and water, and make as the water of extraction agent with weight ratio as the chlorallylene of extraction agent within the scope in 1:0.5-2, can obtain the extraction phase that is rich in epoxy chloropropane as heavy-fluid phase, the extraction phase that is rich in epoxy chloropropane is sent into from the bottom of second extraction tower, carry out counter current contact with water, can obtain the liquid phase that is rich in epoxy chloropropane and chlorallylene as light liquid phase, and the liquid phase that is rich in epoxy chloropropane and chlorallylene obtaining does not contain or substantially contains methyl alcohol, thereby can avoid in follow-up still-process, the epoxy chloropropane yield causing due to the existence of methyl alcohol reduces.Complete on this basis the present invention.
The extracting process that the invention provides a kind of epoxy chloropropane, the method comprises the following steps:
(1) the second extraction agent is flowed in the first extraction tower from top to bottom, with contain the first extraction agent and treat that the logistics of extraction liquid carries out the first counter current contact, obtain as first extraction phase that is rich in epoxy chloropropane of heavy-fluid phase and as first extracting phase that is rich in methyl alcohol of light liquid phase, describedly treat that extraction liquid is the solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water
Described the first extraction agent is water, and described the second extraction agent is chlorallylene, and the weight ratio of described the first extraction agent and the second extraction agent is 1:0.5-2;
(2) described the first extraction phase is flowed in the second extraction tower from bottom to top, carry out the second counter current contact with the 3rd extraction agent, obtain as second extracting phase that is rich in epoxy chloropropane and chlorallylene of light liquid phase and as second extraction phase that contains methyl alcohol of heavy-fluid phase, described the 3rd extraction agent is water.
Extracting process of the present invention, adopt two extraction towers to carry out continuous extraction, the second extracting phase that is rich in epoxy chloropropane finally obtaining not containing or substantially containing methyl alcohol, thereby can avoid in follow-up still-process, the epoxy chloropropane yield causing due to the existence of methyl alcohol reduces.And method of the present invention can also obtain higher epoxy chloropropane percentage extraction.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.
Fig. 1 is for illustrating the extracting process of epoxy chloropropane of the present invention.
Embodiment
Comprise step (1) according to the extracting process of epoxy chloropropane of the present invention: the second extraction agent is flowed in the first extraction tower from top to bottom, with contain the first extraction agent and treat that the logistics of extraction liquid carries out the first counter current contact, obtain as first extraction phase that is rich in epoxy chloropropane of heavy-fluid phase and as first extracting phase that is rich in methyl alcohol of light liquid phase, described in treat that extraction liquid is the solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water.
In the present invention, described heavy-fluid refers in the two-phase forming after liquid liquid separates mutually, the liquid phase that density is relatively large, and described light liquid refers in the two-phase forming after liquid liquid separates mutually, the liquid phase that density is relatively little.
According to extracting process of the present invention, described in contain the first extraction agent and treat that the logistics of extraction liquid can be by being obtained by mixing described solution and described the first extraction agent containing epoxy chloropropane, methyl alcohol, chlorallylene and water.Can be before entering the first extraction tower, described solution and described the first extraction agent containing epoxy chloropropane, methyl alcohol, chlorallylene and water is obtained by mixing, also can be obtained by mixing by the described solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water and described the first extraction agent are sent into respectively to same position in described the first extraction tower.Preferably, before entering the first extraction tower, described solution and described the first extraction agent containing epoxy chloropropane, methyl alcohol, chlorallylene and water is obtained by mixing to the described logistics that contains the first extraction agent and treat extraction liquid.In the various mixing devices that can commonly use in this area, described solution and the first extraction agent containing epoxy chloropropane, methyl alcohol, chlorallylene and water is obtained by mixing to the described logistics that contains the first extraction agent and treat extraction liquid, described mixing device can be for example line mixer or stirring tank, is preferably line mixer.
According to extracting process of the present invention, described the first extraction agent is water, and described the second extraction agent is chlorallylene.The weight ratio of described the first extraction agent and the second extraction agent is 1:0.5-2.In the time that the ratio of described the first extraction agent and the second extraction agent is outside above-mentioned scope, in the first extraction tower, is difficult to realize liquid liquid and separates.From the percentage extraction of further raising epoxy chloropropane, and the angle of methanol content in the liquid phase that contains epoxy chloropropane that further reduction finally obtains is set out, the weight ratio of described the first extraction agent and described the second extraction agent is preferably 1:0.6-1.8, more preferably 1:0.6-1.6.
The consumption of described the first extraction agent and the second extraction agent can carry out appropriate selection according to the amount of the described solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water.Usually, with respect to the solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water described in 100 weight parts, the consumption of described the second extraction agent can be 10-200 weight part.From the angle of the percentage extraction of further raising epoxy chloropropane, with respect to 100 weight part epoxidation reaction mixtures, the consumption of described the second extraction agent is preferably 40-100 weight part, more preferably 50-80 weight part.
Can be conventional selection as the purity of the chlorallylene of the second extraction agent, usually, can be 95-100 % by weight as the purity of the chlorallylene of the second extraction agent, is preferably 97-99 % by weight.
The second extraction agent can be sent into from the top of the first extraction tower, thus with come from containing the first extraction agent and treating that the logistics of extraction liquid carries out the first counter current contact of described the first extraction tower bottom.
Extracting process of the present invention comprises step (2): described the first extraction phase is flowed from bottom to top in the second extraction tower, carry out the second counter current contact with the 3rd extraction agent, obtain as second extracting phase that is rich in epoxy chloropropane and chlorallylene of light liquid phase and as second extraction phase that contains methyl alcohol of heavy-fluid phase, described the 3rd extraction agent is water.
The consumption of described the 3rd extraction agent is as the criterion as second extracting phase that is rich in epoxy chloropropane and chlorallylene of light liquid phase and as second extraction phase that contains methyl alcohol of heavy-fluid phase can obtain.Usually, with respect to the solution that contains epoxy chloropropionate alkene, methyl alcohol, chlorallylene and water described in 100 weight parts, the consumption of described the 3rd extraction agent can be 10-100 weight part.The angle of the methanol content the second extracting phase obtaining from further reduction, with respect to the solution containing epoxy chloropropionate alkene, methyl alcohol, chlorallylene and water described in 100 weight parts, the consumption of described the 3rd extraction agent is preferably 30-80 weight part, more preferably 40-70 weight part.
According to extracting process of the present invention, the second extracting phase that is rich in epoxy chloropropane and chlorallylene does not contain or substantially contains methyl alcohol.In the present invention, the total amount that term " substantially not containing methyl alcohol " refers to the second extracting phase that is rich in epoxy chloropropane and chlorallylene is benchmark, and the content of methyl alcohol is below 0.1 % by weight, is preferably below 0.01 % by weight.
Described the first extraction phase can be sent into from the bottom of described the second extraction tower, thereby be carried out the second counter current contact with the 3rd extraction agent that comes from described the second extraction tower top.
According to extracting process of the present invention, the temperature of described the first counter current contact and the second counter current contact can be that the routine of this area is selected, can realize the effect of extracting and separating, the probability of epoxy chloropropane generation side reaction in extraction separation process can be reduced to minimum being as the criterion again.Usually, described the first counter current contact and described the second counter current contact can be carried out separately at the temperature of-10 ℃ to 50 ℃.From easy to operate and angle economy, described the first counter current contact and the second counter current contact can be carried out separately at the temperature of 0-40 ℃.The residence time of material in the first extraction tower and the second extraction tower can be that the routine of this area is selected, and no longer describes in detail herein.
Extracting process according to the present invention is not particularly limited for all the other conditions of extraction, can be that the routine of this area is selected.Particularly, described the first extraction tower and the second extraction tower can be the common various equipment that can realize extraction function in this area, as sieve-tray tower, packing tower, rotating disc contactor or valve tray column, are preferably the void tower that does not add member.
According to extracting process of the present invention, be not particularly limited for the source of the described solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water, the method that can prepare epoxy chloropropane by various routines obtains.For example, can, under the existence of HTS, under epoxidation reaction condition, hydrogen peroxide be contacted in methyl alcohol with chlorallylene, thereby obtain the described solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water.
The composition of the described solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water is not particularly limited, and can be conventional composition.Usually, take the total amount of the described solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water as benchmark, the content of epoxy chloropropane can be 8-20 % by weight, and the content of methyl alcohol can be 45-60 % by weight, the content of chlorallylene can be 4-20 % by weight, and the content of water can be 10-24 % by weight.
According to extracting process of the present invention, the second extraction phase obtaining from the second extraction tower can discharge after purifying.Because the second extraction phase mainly contains water, therefore preferably described the first extraction agent comes from described the second extraction phase at least partly, can reduce like this water consumption of the inventive method.Described the second extraction phase can be sent in described the first extraction tower as the first extraction agent after purifying treatment.Preferably the second extraction phase is directly sent in described the first extraction tower, as at least part of the first extraction agent, can further reclaim like this epoxy chloropropane, methyl alcohol and the chlorallylene in the second extraction phase, thereby further improve the percentage extraction of epoxy chloropropane, and alleviate the burden of follow-up purifying treatment.Send into the second extraction phase in the first extraction tower amount so that in the first extraction tower the weight ratio of the first extraction agent and the second extraction agent can meet previously described requirement and be as the criterion.Because the second extraction phase is take water as main, therefore in the time that the first extraction agent comes from the second extraction phase at least partly, can disregard the content of the component beyond dewatering in the second extraction phase.
According to extracting process of the present invention, can adopt the ordinary method of this area to distill described the second extracting phase, thereby isolate epoxy chloropropane and chlorallylene.Isolated chlorallylene can be sent in epoxy reaction unit, as the raw material of epoxidation reaction, also can send in the first extraction tower as the second extraction agent; Isolated epoxy chloropropane can directly be exported, or sends in refined unit and carry out exporting after further refining.The present invention is not particularly limited for the condition that described the second extracting phase is distilled, and can be that the routine of this area is selected, and repeats no more herein.
According to extracting process of the present invention, the first extracting phase that is rich in first alcohol and water obtaining from described the first extraction tower can distill under the conventional distillation condition in this area, thereby isolates methyl alcohol.Isolated methyl alcohol can be sent in epoxidation reaction unit, as the solvent of epoxidation reaction again.Described the first extracting phase that is rich in first alcohol and water being distilled, be not particularly limited with the condition of isolating methyl alcohol, can be that the routine of this area is selected, and repeats no more herein.
Fig. 1 shows a kind of preferred implementation of extracting process of the present invention, in this embodiment, to mix with the second extraction phase 9 obtaining at the second extraction tower 2 containing the solution 3 of epoxy chloropropane, methyl alcohol, chlorallylene and water, the mixture obtaining is sent into from the bottom of the first extraction tower 1, carry out counter current contact with the chlorallylene 4 of conduct the second extraction agent of sending into from the top of the first extraction tower 1, obtain as first extracting phase 6 that is rich in methyl alcohol of light liquid phase and as first extraction phase 8 that is rich in epoxy chloropropane of heavy-fluid phase.The first extraction phase 8 is sent into from the bottom of the second extraction tower 2, carry out counter current contact with the water 5 of conduct the 3rd extraction agent of sending into from the top of the second extraction tower 2, obtain as second extracting phase 7 that is rich in epoxy chloropropane and chlorallylene of light liquid phase and as second extraction phase 9 that contains methyl alcohol of heavy-fluid phase, and after the second extraction phase 9 is mixed with the described solution 3 containing epoxy chloropropane, methyl alcohol, chlorallylene and water, send in the first extraction tower 1.The second extracting phase 7 is sent in follow-up distillation unit and distilled, to obtain epoxy chloropropane.
Describe the present invention in detail below in conjunction with embodiment.
In following examples and comparative example, adopt chromatogram analysis method to measure the composition as the second extracting phase that is rich in epoxy chloropropane and chlorallylene for the treatment of the solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water of extraction liquid and obtain from the second extraction tower.
In following examples and comparative example, adopt following formula to calculate the percentage extraction of epoxy chloropropane:
The percentage extraction (%) of epoxy chloropropane=(weight of the epoxy chloropropane in the second extracting phase/containing the weight of contained epoxy chloropropane in the solution of epoxy chloropropane, methyl alcohol, chlorallylene and water) × 100%.
In following examples and comparative example, if not otherwise specified, adopt following formula to calculate the methanol content extracting in the epoxy chloropropane obtaining:
Methanol content (%)=(in the second extracting phase in weight/the second extracting phase of methyl alcohol the weight of epoxy chloropropane) × 100%.
In following examples, adopt the method shown in Fig. 1 to separate, wherein, the first extraction tower and the second extraction tower are the void tower that does not load filler.
Embodiment 1-6 is for illustrating the extracting process of epoxy chloropropane of the present invention.
Under room temperature (25 ℃) and normal pressure (1 standard atmospheric pressure), 100 weight parts are contained to epoxy chloropropane, methyl alcohol, after the solution of chlorallylene and water mixes as the water of the first extraction agent with 65 weight parts, send into from the bottom of the first extraction tower, by 65 weight part chlorallylene (technical grades, purchased from Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 97 % by weight) add from the top of the first extraction tower as the second extraction agent, make two bursts of logistics at the temperature of 12 ℃, carry out counter current contact, at the bottom of the tower of described the first extraction tower, obtain the first extraction phase that is rich in epoxy chloropropane as heavy-fluid phase, obtain the first extracting phase that is rich in methyl alcohol as light liquid phase from the tower top of described the first extraction tower.
Described the first extraction phase is sent into from the bottom of the second extraction tower, 47 weight parts waters are sent into from the top of the second extraction tower as the 3rd extraction agent, make two bursts of logistics at the temperature of 12 ℃, carry out counter current contact, at the bottom of the tower of described the second extraction tower, obtain the second extraction phase that contains methyl alcohol as heavy-fluid phase, obtain the second extracting phase that is rich in epoxy chloropropane and chlorallylene as light liquid phase at the tower top of described the second extraction tower.
In the described solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water, the content of epoxy chloropropane is 11.6 % by weight, and the content of methyl alcohol is 56.4 % by weight, and the content of chlorallylene is 17.9 % by weight, and the content of water is 13.1 % by weight, and surplus is impurity.
The composition of the second extracting phase that detection obtains, and calculate percentage extraction and the methanol content of epoxy chloropropane, result is listed in table 1.
Adopt the method separation epoxy chloropropane identical with embodiment 1, different is, the second extraction phase that the second extraction tower is obtained replaces the water as the first extraction agent in embodiment 1, and wherein, the consumption of the second extraction phase is identical with the consumption as the water of the first extraction agent in embodiment 1.
The composition of the second extracting phase that detection obtains, and calculate percentage extraction and the methanol content of epoxy chloropropane, result is listed in table 1.
Comparative example 1
Adopt the following methods pair solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water identical with the composition of embodiment 1 to extract:
Under room temperature (25 ℃) and normal pressure (1 standard atmospheric pressure), 100 weight parts are first mixed with 65 weight parts waters containing the solution of epoxy chloropropane, methyl alcohol, chlorallylene and water, then add the chlorallylene (with embodiment 1) of 65 weight parts, standing separation after fully mixing, obtains being rich in the liquid phase (heavy-fluid phase) of epoxy chloropropane and is rich in the liquid phase (light liquid phase) of methyl alcohol.
What detection obtained is rich in the composition of the liquid phase of epoxy chloropropane, and calculates percentage extraction and the methanol content of epoxy chloropropane, and result is listed in table 1.Wherein, methanol content adopts following formula to calculate:
Methanol content (%)=(being rich in the weight of epoxy chloropropane in the liquid phase of the weight of methyl alcohol in the liquid phase of epoxy chloropropane/be rich in epoxy chloropropane) × 100%.
Comparative example 2
Adopt the method identical with embodiment 1 to extract, different, the second extraction tower is not set.
What detection obtained is rich in the composition of the extraction phase of epoxy chloropropane, and calculates percentage extraction and the methanol content of epoxy chloropropane, and result is listed in table 1.Wherein, methanol content adopts following formula to calculate:
Methanol content (%)=(in the first extraction phase in weight/the first extraction phase of methyl alcohol the weight of epoxy chloropropane) × 100%.
Comparative example 3
Adopt the method identical with embodiment 1 to extract, different, in the first extraction tower, do not use the first extraction agent.What detection obtained is rich in the composition of the extracting phase of epoxy chloropropane, and calculates percentage extraction and the methanol content of epoxy chloropropane, and result is listed in table 1.
Comparative example 4
Adopt the method identical with embodiment 1 to extract, different, the second extraction agent is glyceryl trichloride.What detection obtained is rich in the composition of the extracting phase of epoxy chloropropane, and calculates percentage extraction and the methanol content of epoxy chloropropane, and result is listed in table 1.
Under room temperature (25 ℃) and normal pressure (1 standard atmospheric pressure), 100 weight parts are contained to epoxy chloropropane, methyl alcohol, after the solution of chlorallylene and water mixes as the second extraction phase of the first extraction agent with 100 weight parts, send into from the bottom of the first extraction tower, by 50 weight part chlorallylene (technical grades, purchased from Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 97 % by weight) add from the top of the first extraction tower as the second extraction agent, make two bursts of logistics at the temperature of 35 ℃, carry out counter current contact, at the bottom of the tower of described the first extraction tower, obtain the first extraction phase that is rich in epoxy chloropropane as heavy-fluid phase, obtain the first extracting phase that is rich in methyl alcohol as light liquid phase from the tower top of described the first extraction tower.
Described the first extraction phase is sent into from the bottom of the second extraction tower, 50 weight parts waters are sent into from the top of the second extraction tower as the 3rd extraction agent, make two bursts of logistics at the temperature of 35 ℃, carry out counter current contact, at the bottom of the tower of described the second extraction tower, obtain the second extraction phase containing methyl alcohol as heavy-fluid phase, obtain the second extracting phase that is rich in epoxy chloropropane and chlorallylene as light liquid phase at the tower top of described the second extraction tower.
In the described solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water, the content of epoxy chloropropane is 18.31 % by weight, and the content of chlorallylene is 18.83 % by weight, and the content of methyl alcohol is 49.92 % by weight, and the content of water is 11.52 % by weight, and surplus is impurity.
What detection obtained is rich in the composition of the second extracting phase of epoxy chloropropane, and calculates percentage extraction and the methanol content of epoxy chloropropane, and result is listed in table 1.
Comparative example 5
Adopt the method identical with embodiment 3 to extract, different, in the first extraction tower, be 120 weight parts as the consumption of the second extraction phase of the first extraction agent, be 50 weight parts as the consumption of the chlorallylene of the second extraction agent.What detection obtained is rich in the composition of the extracting phase of epoxy chloropropane, and calculates percentage extraction and the methanol content of epoxy chloropropane, and result is listed in table 1.
Under room temperature (25 ℃) and normal pressure (1 standard atmospheric pressure), 100 weight parts are contained to epoxy chloropropane, methyl alcohol, after the solution of chlorallylene and water mixes as the second extraction phase of the first extraction agent with 25 weight parts, send into from the bottom of the first extraction tower, by 50 weight part chlorallylene (technical grades, purchased from Ba Ling petrochemical complex limited liability company, the content of chlorallylene is 97 % by weight) add from the top of the first extraction tower as the second extraction agent, make two bursts of logistics at the temperature of 25 ℃, carry out counter current contact, at the bottom of the tower of described the first extraction tower, obtain the first extraction phase that is rich in epoxy chloropropane as heavy-fluid phase, obtain the first extracting phase that is rich in methyl alcohol as light liquid phase from the tower top of described the first extraction tower.
Described the first extraction phase is sent into from the bottom of the second extraction tower, 50 weight parts waters are sent into from the top of the second extraction tower as the 3rd extraction agent, make two bursts of logistics at the temperature of 25 ℃, carry out counter current contact, at the bottom of the tower of described the second extraction tower, obtain the second extraction phase containing methyl alcohol as heavy-fluid phase, obtain the second extracting phase that is rich in epoxy chloropropane and chlorallylene as light liquid phase at the tower top of described the second extraction tower.
In the described solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water, the content of epoxy chloropropane is 11.7 % by weight, and the content of chlorallylene is 17.5 % by weight, and the content of methyl alcohol is 56 % by weight, and the content of water is 13.4 % by weight, and surplus is impurity.
What detection obtained is rich in the composition of the second extracting phase of epoxy chloropropane, and calculates percentage extraction and the methanol content of epoxy chloropropane, and result is listed in table 1.
Comparative example 6
Adopt the method identical with embodiment 4 to extract, different, in the first extraction tower, be 20 weight parts as the consumption of the second extraction phase of the first extraction agent, be 50 weight parts as the consumption of the chlorallylene of the second extraction agent.What detection obtained is rich in the composition of the extracting phase of epoxy chloropropane, and calculates percentage extraction and the methanol content of epoxy chloropropane, and result is listed in table 1.
Adopt the method identical with embodiment 3 to extract, different, in the first extraction tower, be 80 weight parts as the consumption of the second extraction phase of the first extraction agent, be 50 weight parts as the consumption of the chlorallylene of the second extraction agent.What detection obtained is rich in the composition of the second extracting phase of epoxy chloropropane, and calculates percentage extraction and the methanol content of epoxy chloropropane, and result is listed in table 1.
Adopt the method identical with embodiment 4 to extract, different, in the first extraction tower, be 30 weight parts as the consumption of the second extraction phase of the first extraction agent, be 50 weight parts as the consumption of the chlorallylene of the second extraction agent.What detection obtained is rich in the composition of the second extracting phase of epoxy chloropropane, and calculates percentage extraction and the methanol content of epoxy chloropropane, and result is listed in table 1.
Table 1
In table 1, < 50ppm represents that methanol content is less than 50ppm; < 100ppm represents that methanol content is less than 100ppm and is not less than 50ppm.
As can be seen from Table 1, adopt the liquid phase that is rich in epoxy chloropropane that extracting process of the present invention obtains not containing or substantially containing methyl alcohol, thereby can effectively avoid in follow-up still-process, because methyl alcohol exists the epoxy chloropropane yield decline causing; And, adopt method of the present invention can also obtain higher epoxy chloropropane percentage extraction.
Claims (10)
1. an extracting process for epoxy chloropropane, the method comprises the following steps:
(1) the second extraction agent is flowed in the first extraction tower from top to bottom, with contain the first extraction agent and treat that the logistics of extraction liquid carries out the first counter current contact, obtain as first extraction phase that is rich in epoxy chloropropane of heavy-fluid phase and as first extracting phase that is rich in methyl alcohol of light liquid phase, describedly treat that extraction liquid is the solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water
Described the first extraction agent is water, and described the second extraction agent is chlorallylene, and the weight ratio of described the first extraction agent and the second extraction agent is 1:0.5-2;
(2) described the first extraction phase is flowed in the second extraction tower from bottom to top, carry out the second counter current contact with the 3rd extraction agent, obtain as second extracting phase that is rich in epoxy chloropropane and chlorallylene of light liquid phase and as second extraction phase that contains methyl alcohol of heavy-fluid phase, described the 3rd extraction agent is water.
2. method according to claim 1, wherein, the weight ratio of described the first extraction agent and the second extraction agent is 1:0.6-1.8.
3. method according to claim 1 and 2, wherein, with respect to the solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water described in 100 weight parts, the consumption of described the second extraction agent is 10-200 weight part.
4. method according to claim 3, wherein, with respect to the solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water described in 100 weight parts, the consumption of described the second extraction agent is 40-100 weight part.
5. method according to claim 1, wherein, with respect to the solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water described in 100 weight parts, the consumption of described the 3rd extraction agent is 10-100 weight part.
6. method according to claim 5, wherein, with respect to the solution that contains epoxy chloropropane, methyl alcohol, chlorallylene and water described in 100 weight parts, the consumption of described the 3rd extraction agent is 30-80 weight part.
7. method according to claim 1, wherein, described the first counter current contact and the each comfortable temperature of described the second counter current contact are to carry out under the condition of-10 ℃ to 50 ℃.
8. method according to claim 1, wherein, described the first extraction agent comes from described the second extraction phase at least partly.
9. method according to claim 8, wherein, described the second extraction phase is sent in described the first extraction tower at least partly, so that described the first extraction agent to be provided.
10. method according to claim 1, wherein, take the total amount of the described solution containing epoxy chloropropane, methyl alcohol, chlorallylene and water as benchmark, the content of epoxy chloropropane is 8-20 % by weight, the content of methyl alcohol is 45-60 % by weight, the content of chlorallylene is 4-20 % by weight, and the content of water is 10-24 % by weight.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062737A (en) * | 2020-09-18 | 2020-12-11 | 江苏扬农化工集团有限公司 | Method for extracting epichlorohydrin |
| CN113248459A (en) * | 2021-06-04 | 2021-08-13 | 江苏扬农化工集团有限公司 | Extraction method of water phase containing epoxy chloropropane |
| CN114478442A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Method and system for removing hydrogen peroxide from epoxidation reaction product of 3-chloropropene and hydrogen peroxide |
| CN115745920A (en) * | 2022-12-08 | 2023-03-07 | 万华化学集团股份有限公司 | Method for recovering effective components in waste liquid in epoxy chloropropane production |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200837063A (en) * | 2006-12-22 | 2008-09-16 | Hanwha Chemical Corp | Process for preparation of an oxirane |
| CN101293882A (en) * | 2007-04-24 | 2008-10-29 | 中国石油化工股份有限公司 | Process for the separation of epoxychloropropane |
-
2012
- 2012-10-25 CN CN201210413367.7A patent/CN103772327B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200837063A (en) * | 2006-12-22 | 2008-09-16 | Hanwha Chemical Corp | Process for preparation of an oxirane |
| CN101293882A (en) * | 2007-04-24 | 2008-10-29 | 中国石油化工股份有限公司 | Process for the separation of epoxychloropropane |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062737A (en) * | 2020-09-18 | 2020-12-11 | 江苏扬农化工集团有限公司 | Method for extracting epichlorohydrin |
| CN112062737B (en) * | 2020-09-18 | 2023-03-14 | 江苏扬农化工集团有限公司 | Method for extracting epichlorohydrin |
| CN114478442A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Method and system for removing hydrogen peroxide from epoxidation reaction product of 3-chloropropene and hydrogen peroxide |
| CN113248459A (en) * | 2021-06-04 | 2021-08-13 | 江苏扬农化工集团有限公司 | Extraction method of water phase containing epoxy chloropropane |
| CN115745920A (en) * | 2022-12-08 | 2023-03-07 | 万华化学集团股份有限公司 | Method for recovering effective components in waste liquid in epoxy chloropropane production |
| CN115745920B (en) * | 2022-12-08 | 2024-05-03 | 万华化学集团股份有限公司 | Method for recovering effective components of waste liquid in epichlorohydrin production |
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