CN108794300A - The Isolation method of raw material containing ethylene glycol and 1,2- butanediols and the preparation method of epoxy butane - Google Patents
The Isolation method of raw material containing ethylene glycol and 1,2- butanediols and the preparation method of epoxy butane Download PDFInfo
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
A kind of preparation method of epoxy butane, includes the following steps：Ethylene glycol and 1 will be contained, the raw material of 2- butanediols reactive distillation under esterification catalyst effect with esterifying agent, it respectively obtains and corresponds to the light component of reaction product and heavy constituent containing ethylene carbonate and butylene containing esterifying agent, by the heavy constituent rectifying containing ethylene carbonate and butylene, ethylene carbonate and butylene are respectively obtained；By butylene decarboxylation under decarboxylation catalyst effect, epoxy butane is obtained.The preparation method of above-mentioned epoxy butane, ethylene glycol and 1 will be contained, the raw material of 2- butanediols carries out ester exchange reaction with esterifying agent, make 1,2- butanediols are converted into not with the butylene of ethylene glycol azeotropic to purify ethylene glycol, 1,2- butanediol converts the butylene to be formed and then obtains the higher epoxy butane of added value by decarboxylation.
Description
Technical field
The present invention relates to chemosynthesis technical fields, containing ethylene glycol and 1 more particularly to one kind, the raw material of 2- butanediols
The preparation method of Isolation method and epoxy butane.
Background technology
Ended for the end of the year 2016, global ethylene glycol (EG) production capacity reaches 37,470,000 tons, and average annual production capacity growth rate reaches
5% or more.At present there are two types of the most important synthetic methods of ethylene glycol, respectively：Ethylene-ethylene oxide-ethylene glycol circuit and conjunction
At gas (hydrogen and carbon monoxide)-ethylene glycol route (being commonly called as coal-ethylene glycol circuit).
Since domestic coal resource is abundant, and when crude oil price is higher than 55 dollar/barrel, coal-ethylene glycol circuit shows bright
Aobvious cost advantage, therefore the technology receives pursuing for domestic enterprise in recent years.Coal-ethylene glycol circuit includes mainly synthesis gas
Dimethyl oxalate processed, Hydrogenation of Dimethyl Oxalate synthesize three units of thick ethylene glycol and thick purifying ethylene glycol.In dimethyl oxalate
In the reaction product of Hydrogenation ethylene glycol, other than containing the lower substance of the boiling points such as methanol, ethyl glycolate, also contain a small amount of 1,
2- propylene glycol, the substance that 1,2- butanediol (BG) etc. approaches with ethylene glycol boiling point, is difficult to detach by conventional distillation, wherein 1,2-
Butanediol and ethylene glycol boiling point are closest, and when rectifying easily forms azeotropic mixture, therefore is most difficult to detach.
Although also working out separation ethylene glycol and 1 in the prior art, the method for 2- butanediols, there are equipment throwings mostly
The problems such as money is big, technological process is long, and since 1,2- butanediols are industrially applied seldom, economic value is relatively low, therefore, indirectly
Limit the development of ethylene glycol and 1,2- butanediol isolation technics.
Epoxy butane (BO) is a kind of important industrial chemicals, is mainly used for synthesizing polyether, phosphate flame retardant and fourth
Glycol ethers solvent.Currently, the synthetic method of epoxy butane is mainly 1- butylene epoxidation process, typical process line was
Oxygen acid system, chlorohydrination, conjugated oxidation and hydrogen peroxide direct oxidation method.The wastewater flow rate of peroxide acid system and chlorohydrination due to generation
It is huge, is gradually limited and eliminated；The investment of conjugated oxidation production is larger；Hydrogen peroxide direct oxidation method needs to use methanol
Make solvent, since the boiling point of methanol and epoxy butane is sufficiently close to, has difficulties in product separation.
In conclusion finding one kind with ethylene glycol and 1, the mixture of 2- butanediols is raw material, without detaching ethylene glycol
Under the premise of 1,2- butanediols, the preparation method of the epoxy butane of ethylene glycol purification is become to the research hotspot of people.
Invention content
Based on this, it is necessary to provide one kind with ethylene glycol and 1, the mixture of 2- butanediols is raw material, without detaching second
Glycol and 1, under the premise of 2- butanediols purify, by the preparation method of the epoxy butane of ethylene glycol purification.
In addition, the application, which also provides one kind, containing ethylene glycol and 1, the Isolation method of the raw material of 2- butanediols.
One kind containing ethylene glycol and 1, and the Isolation method of the raw material of 2- butanediols includes the following steps：
It will contain ethylene glycol and 1, the raw materials of the 2- butanediols reactive distillation under esterification catalyst effect with esterifying agent, respectively
To the light component for corresponding to reaction product containing esterifying agent and the heavy constituent containing ethylene carbonate and butylene, the esterifying agent
General structure is as follows：
Wherein, X Cl, NH2Or the linear or branched alkyl group that OR, R are C1~C4；
By the heavy constituent rectifying containing ethylene carbonate and butylene, ethylene carbonate and carbonic acid fourth are respectively obtained
Enester.
The esterifying agent contains ethylene glycol and 1 with described in one of the embodiments, mixed alcohol in the raw material of 2- butanediols
Molar ratio be (1~5):1.
The esterification catalyst is selected from sodium alkoxide, titanate, alkali carbonate, organotin in one of the embodiments,
And at least one of anion exchange resin；In the esterification catalyst and the raw material containing ethylene glycol and 1,2- butanediols
The molar ratio of mixed alcohol is (0.001~0.1):1.
The top temperature of the reactive distillation is 10 DEG C~100 DEG C in one of the embodiments, and kettle temperature is 50 DEG C~200 DEG C,
The number of plates is 10~70, and absolute pressure is 0~10Bar.
Also contain esterifying agent in the light component for corresponding to reaction product containing esterifying agent in one of the embodiments,；
Further include the steps that detaching esterifying agent from the light component for corresponding to reaction product containing esterifying agent with recycled.
It is further comprising the steps of in one of the embodiments,：
By the ethylene carbonate and fatty alcohol reactive distillation, ethylene glycol is obtained, the fatty alcohol is the unitary of C1~C4
Primary alconol.
In one of the embodiments, when in the esterifying agent X be OR, R be C1~C4 straight chained alkyl when, the esterification
Agent corresponds to the unitary primary alconol that reaction product is C1~C4；
Further include detaching esterifying agent from the light component for corresponding to reaction product containing esterifying agent to correspond to reaction product with circulating sleeve
The step of using.
Also contain second two in the heavy constituent containing ethylene carbonate and butylene in one of the embodiments,
Alcohol；
Further include the steps that the separation ethylene glycol from the heavy constituent containing ethylene carbonate and butylene.
A kind of preparation method of epoxy butane, including ethylene glycol described in any one of the above embodiments and 1, the pre-separation of 2- butanediols
Step in method, it is further comprising the steps of：
By butylene decarboxylation under decarboxylation catalyst effect, epoxy butane is obtained.
The decarboxylation catalyst is selected from alkali metal sulfates, alkali metal villaumite, alkali metal nitre in one of the embodiments,
At least one of hydrochlorate, alkyl imidazole salt, ionic liquid, loading type alkali metal and carrying alkali metal oxide.
The absolute pressure of the decarboxylation is 0.1Bar~10Bar in one of the embodiments, and temperature is 60 DEG C~500
DEG C, mass space velocity 0.1h-1~5h-1。
The preparation method of above-mentioned epoxy butane, will contain ethylene glycol and 1, and raw material and the esterifying agent of 2- butanediols carry out transesterification
Reaction makes 1,2- butanediols be converted into not with the butylene of ethylene glycol azeotropic to purify ethylene glycol, 1,2- fourth
Glycol converts the butylene to be formed and then can be obtained the higher epoxy butane of added value by decarboxylation.
The preparation method of above-mentioned epoxy butane, without detaching ethylene glycol and 1, under the premise of 2- butanediols, by ethylene glycol
Epoxy butane is purified and obtains, compared with the preparation method of traditional epoxy butane, operation letter low with equipment investment cost
The advantages that single, safe.
Figure of description
Fig. 1 is the flow diagram of the preparation method of the epoxy butane of an embodiment.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below to the specific reality of the present invention
The mode of applying is described in detail.Many details are elaborated in the following description in order to fully understand the present invention.But
The invention can be embodied in many other ways as described herein, and those skilled in the art can be without prejudice to this hair
Similar improvement is done in the case of bright intension, therefore the present invention is not limited to the specific embodiments disclosed below.
One embodiment contain ethylene glycol and 1, the Isolation method of the raw material of 2- butanediols, include the following steps S110~
S160：
S110, ethylene glycol and 1 will be contained, the raw materials of the 2- butanediols reactive distillation under esterification catalyst effect with esterifying agent,
It respectively obtains and corresponds to the light component of reaction product containing esterifying agent and containing the recombination of ethylene carbonate (EC) and butylene (BC)
Point.
In the present embodiment, above-mentioned to contain ethylene glycol and 1, the raw material of 2- butanediols is preparing ethylene glycol by using dimethyl oxalate plus hydrogen
Reaction product.
Further, above-mentioned to contain ethylene glycol and 1, the raw material of 2- butanediols is containing 95%~99.5% ethylene glycol and 0.5%
The reaction product of the not purified preparing ethylene glycol by using dimethyl oxalate plus hydrogen of~5%1,2- butanediols；Or for containing 38%~90%
The reaction product of preparing ethylene glycol by using dimethyl oxalate plus hydrogen after the purification of ethylene glycol and 10%~62%1,2- butanediols.
Wherein, the general structure of esterifying agent is as follows：
In the structural formula, X Cl, NH2Or the linear or branched alkyl group that OR, R are C1~C4.
That is, esterifying agent is phosgene, urea, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate etc., this
In be not listed one by one, as long as meeting above-mentioned general formula.
Further, esterifying agent contains ethylene glycol and 1 with above-mentioned, in the raw material of 2- butanediols the molar ratio of mixed alcohol be (1~
5):1。
Further, esterification catalyst is selected from sodium alkoxide, titanate esters, alkali carbonate, organotin and anion exchange tree
At least one of fat.
Further, sodium alkoxide is sodium methoxide, sodium ethoxide etc.；Titanate esters are butyl titanate etc.；Alkali carbonate is carbon
Sour sodium, potassium carbonate, cesium carbonate, rubidium carbonate etc.；Organotin is stannous oxalate etc.；Anion exchange resin is handed over for weakly-basic anion
Change resin etc..
Further, esterification catalyst with contain ethylene glycol and 1, the molar ratio of mixed alcohol is in the raw material of 2- butanediols
(0.001~0.1):1.
Further, the top temperature of reactive distillation be 10 DEG C~100 DEG C, kettle temperature be 50 DEG C~200 DEG C, the number of plates be 10~
70, absolute pressure is 0~10Bar.
S120, by the above-mentioned heavy constituent rectifying containing ethylene carbonate and butylene, respectively obtain ethylene carbonate and
Butylene.
It should be noted that in the above-mentioned heavy constituent containing ethylene carbonate and butylene, also contain esterification catalyst.
Further, since the reactivity of 1,2- butanediol and esterifying agent is better than the reactivity of ethylene glycol and esterifying agent, because
This, in the above-mentioned heavy constituent containing ethylene carbonate and butylene, it is also possible to contain ethylene glycol.
When it is above-mentioned containing the heavy constituent of ethylene carbonate and butylene in also contain ethylene glycol when, above-mentioned Isolation method
Further include the steps that ethylene glycol (being denoted as step S130) is detached from the heavy constituent containing ethylene carbonate and butylene.
In the present embodiment, the method for detaching ethylene carbonate, butylene, esterification catalyst and ethylene glycol is three
Grade rectifying.
Specifically, level-one rectifying will be carried out containing the heavy constituent of ethylene carbonate and butylene, it is high-purity from overhead extraction
The ethylene glycol of degree, tower reactor produce ethylene carbonate, butylene and esterification catalyst mixture, above-mentioned ethylene carbonate,
The mixture of butylene and esterification catalyst carries out two-stage rectification again, from the butylene of overhead extraction high-purity, tower
The mixture of the mixture of kettle extraction ethylene carbonate and esterification catalyst, ethylene carbonate and esterification catalyst carries out three-level again
Rectifying produces esterification catalyst recycled from the ethylene carbonate of overhead extraction high-purity from tower reactor.
Wherein, the top temperature of level-one rectifying is 50 DEG C~200 DEG C, and kettle temperature is 70 DEG C~300 DEG C, and the number of plates is 30~80, into
Material position is set to the position of the number of plates 15~45,0~1Bar of absolute pressure position.
The top temperature of two-stage rectification is 130 DEG C~250 DEG C, and kettle temperature is 150 DEG C~270 DEG C, and the number of plates is 60~200, charging
Position is the position of the number of plates 40~100, and absolute pressure is 0~1Bar.
The top temperature of three-level rectifying is 100~260, and kettle temperature is 160~300 DEG C, and the number of plates is 1~30, and feed entrance point is tower
The position that plate number is 1~29, absolute pressure are 0~1Bar.
It is appreciated that the rectificating method of the above-mentioned heavy constituent containing ethylene glycol, ethylene carbonate and butylene is not limited to
Procedure described above, if ethylene glycol, ethylene carbonate, butylene and esterification catalyst can be detached, such as
Step S120 and step S130 are carried out at the same time, i.e., are simultaneously divided ethylene glycol, ethylene carbonate, butylene and esterifying agent
From.
It should be noted that if ethylene glycol is completely converted into ethylene carbonate, as long as then above-mentioned rectificating method can be by carbonic acid
Vinyl acetate, butylene and esterification catalyst separation, i.e., step S130 can be omitted.
In addition, the above-mentioned light component for corresponding to reaction product containing esterifying agent is also possible to containing the complete esterifying agent of unreacted.When containing
When esterifying agent is corresponded in the light component of reaction product containing esterifying agent, then above-mentioned Isolation method further includes being corresponded to from containing esterifying agent
Esterifying agent is detached in the light component of reaction product, and step S140 (is denoted as) with the step of recycled.
In the present embodiment, esterifying agent is detached from the light component for corresponding to reaction product containing esterifying agent with recycled
Step is specially：
By the above-mentioned light component variable-pressure rectification for corresponding to reaction product containing esterifying agent, obtained esterifying agent is with recycled.
It should be noted that if not considering the recycling of esterifying agent, above-mentioned steps S140 can be omitted.
It is appreciated that when esterifying agent is esterifying agent (i.e. esterifying agent is phosgene) that X is Cl in general structure, correspond to anti-
It is HCl to answer product, when esterifying agent is that X is NH in general structure2Esterifying agent (i.e. esterifying agent be urea) when, correspond to reaction production
Object is NH3, when esterifying agent is esterifying agent (i.e. esterifying agent is dialkyl carbonate alcohol) that X is OR in general structure, correspond to anti-
It is ROH to answer product, and R is the linear or branched alkyl group of C1~C4.
In the present embodiment, the further comprising the steps of S150 of above-mentioned Isolation method：
By ethylene carbonate and fatty alcohol reactive distillation, ethylene glycol is obtained.
Wherein, fatty alcohol is the unitary primary alconol of C1~C4.
It should be noted that if not considering ethylene carbonate being further converted to ethylene glycol, then step S150 can be omitted.
It is appreciated that when if esterifying agent is X is OR in general structure esterifying agent (i.e. esterifying agent is dialkyl carbonate),
And R be C1~C4 straight chained alkyl when, then its correspond to reaction product be C1~C4 unitary primary alconol, at this time can be by the esterifying agent pair
Answer reaction product recycled.I.e. above-mentioned Isolation method further includes being detached from the light component for corresponding to reaction product containing esterifying agent
Esterifying agent corresponds to reaction product and (is denoted as step S160) with the step of recycled.
It should be noted that if not considering that esterifying agent corresponds to the recycling of reaction product, then step S160 can be omitted.
In addition it is also necessary to explanation, step S140 and step S150 can be carried out at the same time, such as：By above-mentioned containing esterification
Agent corresponds to the light component variable-pressure rectification of reaction product, respectively obtains the correspondence reaction product of esterifying agent and esterifying agent.
Above-mentioned to contain ethylene glycol and 1, the Isolation method of the raw material of 2- butanediols will contain ethylene glycol and 1, the original of 2- butanediols
Material carries out reactive distillation with esterifying agent, by the way that by ethylene glycol and 1,2- butanediols are separately converted to ethylene carbonate and butylene carbonate
Ester, then according to the boiling point difference of ethylene carbonate and butylene, so that it may to divide ethylene carbonate and butylene
It leaves and, avoid to easily forming the ethylene glycol and 1 that azeotropic mixture is difficult separation, 2- butanediols are directly separated, and there is equipment to throw
Provide at low cost, safe operation, it is simple the advantages that.
Referring to Fig. 1, the preparation method flow diagram of the epoxy butane for an embodiment, corresponding epoxy butane
Preparation method include the following steps S210~S260：
S210, ethylene glycol and 1 will be contained, the raw materials of 2- butanediols and esterification esterifying agent reactive distillation under the action of catalyst,
It respectively obtains and corresponds to the light component of reaction product and heavy constituent containing ethylene carbonate and butylene containing esterifying agent.
Wherein, the general structure of esterifying agent is as follows：
In the structural formula, X Cl, NH2Or the linear or branched alkyl group that OR, R are C1~C4.
That is, esterifying agent is phosgene, urea, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate etc., this
In be not listed one by one, as long as meeting above-mentioned general formula.
In the present embodiment, above-mentioned esterifying agent is that X is OR in structure, and R is the straight chained alkyl of C1~C4.
Further, esterifying agent contains ethylene glycol and 1 with above-mentioned, in the raw material of 2- butanediols the molar ratio of mixed alcohol be (1~
5):1。
Further, esterification catalyst is selected from sodium alkoxide, titanate esters, alkali carbonate, organotin and anion exchange tree
At least one of fat.
Further, sodium alkoxide is sodium methoxide, sodium ethoxide etc.；Titanate esters are butyl titanate etc.；Alkali carbonate is carbon
Sour sodium, potassium carbonate, cesium carbonate, rubidium carbonate etc..
Further, esterification catalyst with contain ethylene glycol and 1, the molar ratio of mixed alcohol is in the raw material of 2- butanediols
(0.001~0.1):1.
Further, the top temperature of reactive distillation be 10 DEG C~100 DEG C, kettle temperature be 50 DEG C~200 DEG C, the number of plates be 10~
70, absolute pressure is 0~10Bar.
S220, by the above-mentioned heavy constituent rectifying containing ethylene carbonate and butylene, respectively obtain ethylene carbonate and
Butylene.
It should be noted that in the above-mentioned heavy constituent containing ethylene carbonate and butylene, also contain esterification catalyst.
In addition, in the present embodiment, in the above-mentioned heavy constituent containing ethylene carbonate and butylene, also containing second two
Alcohol.
Further, the method for rectifying is three-level rectifying.
Specifically, by above-mentioned, the heavy constituent containing ethylene glycol, ethylene carbonate and butylene carries out level-one rectifying, from tower
Top extraction high-purity ethylene glycol, tower reactor produce ethylene carbonate, butylene and esterification catalyst mixture, above-mentioned carbon
The mixture of vinyl acetate, butylene and esterification catalyst carries out two-stage rectification again, from the carbonic acid of overhead extraction high-purity
Butene esters, tower reactor produce the mixture of ethylene carbonate and esterification catalyst, the mixture of ethylene carbonate and esterification catalyst
Three-level rectifying is carried out again, and from the ethylene carbonate of overhead extraction high-purity, esterification catalyst recycled is produced from tower reactor.
Wherein, the top temperature of level-one rectifying is 50 DEG C~200 DEG C, and kettle temperature is 70 DEG C~300 DEG C, and the number of plates is 30~80, into
Material position is set to the position of the number of plates 15~45,0~1Bar of absolute pressure position.
The top temperature of two-stage rectification is 130 DEG C~250 DEG C, and kettle temperature is 150 DEG C~270 DEG C, and the number of plates is 60~200, charging
Position is the position of the number of plates 40~100, and absolute pressure is 0~1Bar.
The top temperature of three-level rectifying is 100~260, and kettle temperature is 160~300 DEG C, and the number of plates is 1~30, and feed entrance point is tower
The position that plate number is 1~29, absolute pressure are 0~1Bar.
It is appreciated that the rectificating method of the above-mentioned heavy constituent containing ethylene glycol, ethylene carbonate and butylene is not limited to
Procedure described above, as long as ethylene glycol, ethylene carbonate, butylene and esterification catalyst can be detached.
S230, by butylene decarboxylation catalyst effect under decarboxylation, obtain epoxy butane.
Wherein, decarboxylation catalyst be selected from alkali metal sulfates, alkali metal villaumite, alkali nitrates, alkyl imidazole salt, from
At least one of sub- liquid, loading type alkali metal and carrying alkali metal oxide.
Further, alkali metal sulfates are sodium sulphate, zinc sulfate, STANNOUS SULPHATE CRYSTALLINE, magnesium sulfate, aluminum sulfate etc.；Alkali metal chlorine
Salt is sodium chloride, greening zinc, stannic chloride, magnesium chloride etc.；Alkali nitrates be sodium nitrate, zinc nitrate, nitric acid tin, magnesium nitrate,
Aluminum nitrate etc..
Further, loading type alkali metal is using silica, X-type molecular sieve or Y type molecular sieve as the support type alkali of carrier
Metal, wherein alkali metal are sodium, zinc, tin, magnesium, aluminium etc.；Carrying alkali metal oxide is with silica, X-type molecular sieve or Y types point
Son sieve be carrier carrying alkali metal oxide, wherein alkali metal be oxidized to oxidation receive, zinc oxide, tin oxide, magnesia, oxidation
Aluminium etc..
Further, the absolute pressure of decarboxylation is 0.1Bar~10Bar, and temperature is 60 DEG C~500 DEG C, and mass space velocity is
0.1h-1~5h-1。
In addition, it is complete also to contain unreacted in the present embodiment, in the above-mentioned light component for corresponding to reaction product containing esterifying agent
Esterifying agent.When containing esterifying agent in the light component for corresponding to reaction product containing esterifying agent, then above-mentioned Isolation method further includes
Following steps：
S240, by the above-mentioned light component variable-pressure rectification for corresponding to reaction product containing esterifying agent, respectively obtain esterifying agent and esterification
Agent corresponds to reaction product.
Wherein, the esterifying agent that variable-pressure rectification obtains can be with recycled.
It should be noted that if not considering the recycling of esterifying agent, then step S240 can be omitted.
In the present embodiment, above-mentioned Isolation method is further comprising the steps of：
S250, by ethylene carbonate and fatty alcohol reactive distillation, obtain ethylene glycol.
Wherein, fatty alcohol is the unitary primary alconol of C1~C4.
Due in the present embodiment, esterifying agent is that (i.e. esterifying agent is dialkyl carbonate for X is OR in general structure esterifying agent
Base ester), and therefore the straight chained alkyl that R is C1~C4 corresponds to the unitary primary alconol that reaction product is C1~C4, it at this time can should
Esterifying agent corresponds to reaction product recycled.
It should be noted that if not considering ethylene carbonate being further converted to ethylene glycol, then step S250 can be omitted.
I.e. in the present embodiment, above-mentioned Isolation method is further comprising the steps of：
S260, the esterifying agent that variable-pressure rectification obtains is corresponded into reaction product recycled.
It should be noted that if not considering that esterifying agent corresponds to the recycling of reaction product, then step S260 can be omitted.
The preparation method of above-mentioned epoxy butane, will contain ethylene glycol and 1, and raw material and the esterifying agent of 2- butanediols carry out reacting essence
It evaporates, since the reactivity of 1,2- butanediols and esterifying agent is better than the reactivity of ethylene glycol and esterifying agent, therefore, 1,2- fourth two
Alcohol almost all is converted into butylene, and ethylene glycol then may only be partially converted into ethylene carbonate, then according to second two
The boiling point difference of alcohol, ethylene carbonate and butylene, so that it may the higher ethylene glycol of added value to be purified, carbonic acid fourth
Enester then obtains the higher epoxy butane of added value by decarboxylation.
Compared to the preparation method of traditional epoxy butane, above-mentioned to contain ethylene glycol and 1,2- butanediols are the epoxy fourth of raw material
The preparation method of alkane, product separation is simple, and cost of investment is low, do not generate the three wastes, safety and environmental protection, and epoxy butane selectivity and
Purity is all higher.
It is specific embodiment below
Embodiment 1
Raw material containing 95% ethylene glycol and 5%1,2- butanediols is reacted with dimethyl carbonate under sodium methoxide effect
Rectifying obtains the light component containing methanol and dimethyl carbonate and the heavy constituent containing ethylene carbonate and butylene, wherein instead
Answer 100 DEG C of 64 DEG C of top temperature, the kettle temperature, the number of plates 50, absolute pressure 1Bar of rectifying, dimethyl carbonate rubs with mixed alcohol in raw material
You are than being 1.3:1, the molar ratio of mixed alcohol is 0.01 in sodium methoxide and raw material:1.
By the heavy constituent containing ethylene carbonate and butylene by level-one rectifying after, from the second of overhead extraction high-purity
Glycol, tower reactor produce ethylene carbonate, butylene and sodium methoxide mixture, above-mentioned ethylene carbonate, butylene
Mixture with sodium methoxide is again by two-stage rectification, and from the butylene of overhead extraction high-purity, tower reactor produces ethylene carbonate
The mixture of the mixture of ester and sodium methoxide, ethylene carbonate and sodium methoxide is again by three-level rectifying, from overhead extraction high-purity
Ethylene carbonate, produce sodium methoxide recycled, wherein 80 DEG C of the top temperature of level-one rectifying, 160 DEG C of kettle temperature, the number of plates from tower reactor
35, absolute pressure 0.1Bar, 201 DEG C of 145 DEG C of top temperature, the kettle temperature of two-stage rectification, the number of plates 130, absolute pressure 0.1Bar, three-level
165 DEG C of 160 DEG C of top temperature, the kettle temperature of rectifying, the number of plates 1, absolute pressure 0.1Bar.
By butylene decarboxylation under the action of zinc nitrate, epoxy butane is obtained, the absolute pressure of wherein decarboxylation is
0.4Bar, temperature be 230 DEG C, mass space velocity 1.1h-1。
By ethylene carbonate and methanol reactive distillation, ethylene glycol is obtained.
By the above-mentioned light component variable-pressure rectification containing methanol and dimethyl carbonate, dimethyl carbonate and methanol are respectively obtained, it will
Dimethyl carbonate recycled, methanol loop is applied mechanically.
After testing, it be 97.2%, EG purity is that 98.4%, BO purity is that BC conversion ratios, which are 99.0%, BO selectivity,
96.1%.
Embodiment 2
By raw material and diethyl carbonate containing 40% ethylene glycol and 60%1,2- butanediols under butyl titanate effect into
Row reactive distillation obtains the light component containing ethyl alcohol and diethyl carbonate and the heavy constituent containing ethylene carbonate and butylene,
Wherein 90 DEG C of the top temperature of reactive distillation, 130 DEG C of kettle temperature, the number of plates 69, absolute pressure 1Bar, diethyl carbonate are mixed with raw material
The molar ratio of alcohol is 4:1, the molar ratio of mixed alcohol is 0.05 in butyl titanate and raw material:1.
By the heavy constituent containing ethylene carbonate and butylene by level-one rectifying after, from the second of overhead extraction high-purity
Glycol, tower reactor produce ethylene carbonate, butylene and butyl titanate mixture, above-mentioned ethylene carbonate, carbonic acid fourth
The mixture of enester and butyl titanate is again by two-stage rectification, from the butylene of overhead extraction high-purity, tower reactor extraction
The mixture of the mixture of ethylene carbonate and butyl titanate, ethylene carbonate and butyl titanate again by three-level rectifying,
From the ethylene carbonate of overhead extraction high-purity, butyl titanate recycled, wherein the top temperature of level-one rectifying are produced from tower reactor
134 DEG C, 198 DEG C of kettle temperature, the number of plates 56, absolute pressure 0.4Bar, 249 DEG C of 241 DEG C of top temperature, kettle temperature, the number of plates of two-stage rectification
155, absolute pressure 0.9Bar, 165 DEG C of 160 DEG C of top temperature, the kettle temperature of three-level rectifying, the number of plates 5, absolute pressure 0.1Bar.
By butylene decarboxylation under the action of sodium chloride, epoxy butane is obtained, the absolute pressure of wherein decarboxylation is
3Bar, temperature be 270 DEG C, mass space velocity 3.2h-1。
By ethylene carbonate and ethanol synthesis rectifying, ethylene glycol is obtained.
By the above-mentioned light component variable-pressure rectification containing ethyl alcohol and diethyl carbonate, diethyl carbonate and ethyl alcohol are respectively obtained, it will
Diethyl carbonate recycled, by ethyl alcohol recycled.
After testing, it be 99.8%, EG purity is that 99.1%, BO purity is that BC conversion ratios, which are 99.5%, BO selectivity,
99.5%.
Embodiment 3
By the raw material containing 85% ethylene glycol and 15%1,2- butanediols with urea under the effect of amide anion exchanger resin
Reactive distillation is carried out, the light component containing ammonia and urea and the heavy constituent containing ethylene carbonate and butylene are obtained, wherein
72 DEG C of 30 DEG C of top temperature, the kettle temperature of reactive distillation, the number of plates 34, absolute pressure 1Bar, the molar ratio of urea and mixed alcohol in raw material
It is 2.6:1, the molar ratio of mixed alcohol is 0.1 in amide anion exchanger resin and raw material:1.
By the heavy constituent containing ethylene carbonate and butylene by level-one rectifying after, from the second of overhead extraction high-purity
Glycol, tower reactor produce ethylene carbonate, butylene and amide anion exchanger resin mixture, above-mentioned ethylene carbonate
The mixture of ester, butylene and amide anion exchanger resin is again by two-stage rectification, from the carbon of overhead extraction high-purity
Sour butene esters, tower reactor produce the mixture of ethylene carbonate and amide anion exchanger resin, ethylene carbonate and amino the moon from
The mixture of sub-exchange resin, from the ethylene carbonate of overhead extraction high-purity, amino is produced from tower reactor again by three-level rectifying
Anion exchange resin recycled, wherein 158 DEG C of the top temperature of level-one rectifying, 199 DEG C of kettle temperature, the number of plates 75, absolute pressure
0.8Bar, 234 DEG C of 167 DEG C of top temperature, the kettle temperature of two-stage rectification, the number of plates 200, absolute pressure 0.3Bar, the top temperature of three-level rectifying
192 DEG C, 195 DEG C of kettle temperature, the number of plates 20, absolute pressure 0.4Bar.
By butylene decarboxylation under the action of hexadecyl imidazoles, epoxy butane is obtained, wherein decarboxylation is exhausted
It is 7.1Bar to pressure, temperature is 350 DEG C, mass space velocity 4.0h-1。
By ethylene carbonate and methanol reactive distillation, ethylene glycol is obtained.
By the above-mentioned light component variable-pressure rectification containing ammonia and urea, urea and ammonia are respectively obtained, urea cycle is applied mechanically.
After testing, it be 99.3%, EG purity is that 99.5%, BO purity is that BC conversion ratios, which are 99.9%, BO selectivity,
99.3%.
Embodiment 4
56% ethylene glycol and 44%1 will be contained, the raw material of 2- butanediols carries out reactive distillation with phosgene under sodium carbonate effect,
Respectively obtain the light component of containing hydrogen chloride and phosgene and the heavy constituent containing ethylene carbonate and butylene, wherein reactive distillation
5 DEG C of top temperature, 26 DEG C of kettle temperature, the number of plates 5, absolute pressure 8Bar, the molar ratio of mixed alcohol is 1 in phosgene and raw material:1, carbonic acid
The molar ratio of sodium and mixed alcohol in raw material is 0.002:1.
By the heavy constituent containing ethylene carbonate and butylene by level-one rectifying after, from the second of overhead extraction high-purity
Glycol, tower reactor produce ethylene carbonate, butylene and sodium carbonate mixture, above-mentioned ethylene carbonate, butylene
Mixture with sodium carbonate is again by two-stage rectification, and from the butylene of overhead extraction high-purity, tower reactor produces ethylene carbonate
The mixture of the mixture of ester and sodium carbonate, ethylene carbonate and sodium carbonate is again by three-level rectifying, from overhead extraction high-purity
Ethylene carbonate, produce sodium carbonate recycled, wherein 115 DEG C of the top temperature of level-one rectifying, 172 DEG C of kettle temperature, column plate from tower reactor
Number 80, absolute pressure 0.3Bar, 241 DEG C of 225 DEG C of top temperature, the kettle temperature of two-stage rectification, the number of plates 189, absolute pressure 0.6Bar, three
255 DEG C of 251 DEG C of top temperature, the kettle temperature of grade rectifying, the number of plates 10, absolute pressure 0.9Bar.
By butylene decarboxylation under the action of magnesium sulfate, epoxy butane is obtained, the absolute pressure of wherein decarboxylation is
10Bar, temperature be 470 DEG C, mass space velocity 0.6h-1。
By ethylene carbonate and methanol reactive distillation, ethylene glycol is obtained.
By the above-mentioned light component variable-pressure rectification containing phosgene and hydrogen chloride, phosgene and hydrogen chloride are respectively obtained, phosgene is recycled
It applies mechanically.
After testing, it be 95.0%, EG purity is that 99.6%, BO purity is that BC conversion ratios, which are 98.2%, BO selectivity,
93.2%.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (11)
1. one kind containing ethylene glycol and 1, the Isolation method of the raw material of 2- butanediols, which is characterized in that include the following steps：
Ethylene glycol and 1 will be contained, the raw materials of the 2- butanediols reactive distillation under esterification catalyst effect with esterifying agent respectively obtains and contains
Esterifying agent corresponds to the light component of reaction product and the heavy constituent containing ethylene carbonate and butylene, the structure of the esterifying agent
General formula is as follows：
Wherein, X Cl, NH2Or the linear or branched alkyl group that OR, R are C1~C4；
By the heavy constituent rectifying containing ethylene carbonate and butylene, ethylene carbonate and butylene carbonate are respectively obtained
Ester.
2. according to claim 1 contain ethylene glycol and 1, the Isolation method of the raw material of 2- butanediols, which is characterized in that institute
The molar ratio for stating esterifying agent and mixed alcohol in the raw material containing ethylene glycol and 1,2- butanediols is (1~5):1.
3. according to claim 1 contain ethylene glycol and 1, the Isolation method of the raw material of 2- butanediols, which is characterized in that institute
It states esterification catalyst and is selected from least one of sodium alkoxide, titanate esters, alkali carbonate, organotin and anion exchange resin；
The molar ratio of the esterification catalyst and mixed alcohol in the raw material containing ethylene glycol and 1,2- butanediols is (0.001~0.1):
1。
4. according to claim 1 contain ethylene glycol and 1, the Isolation method of the raw material of 2- butanediols, which is characterized in that institute
State reactive distillation top temperature be 10 DEG C~100 DEG C, kettle temperature be 50 DEG C~200 DEG C, the number of plates be 10~70, absolute pressure be 0~
10Bar。
5. containing ethylene glycol and 1 according to Claims 1 to 4 any one of them, the Isolation method of the raw material of 2- butanediols is special
Sign is, also contains esterifying agent in the light component that reaction product is corresponded to containing esterifying agent；
Further include the steps that esterifying agent is detached from the light component for corresponding to reaction product containing esterifying agent with recycled.
6. according to claim 5 contain ethylene glycol and 1, the Isolation method of the raw material of 2- butanediols, which is characterized in that also
Include the following steps：
By the ethylene carbonate and fatty alcohol reactive distillation, ethylene glycol is obtained, the fatty alcohol is the unitary primary alconol of C1~C4.
7. according to claim 6 contain ethylene glycol and 1, the Isolation method of the raw material of 2- butanediols, which is characterized in that when
X is OR in the esterifying agent, and when R is the straight chained alkyl of C1~C4, the esterifying agent corresponds to the unitary that reaction product is C1~C4
Primary alconol；
Further include detaching esterifying agent from the light component for corresponding to reaction product containing esterifying agent to correspond to reaction product with recycled
Step.
8. containing ethylene glycol and 1 according to Claims 1 to 4 any one of them, the Isolation method of the raw material of 2- butanediols is special
Sign is, also contains ethylene glycol in the heavy constituent containing ethylene carbonate and butylene；
Further include the steps that the separation ethylene glycol from the heavy constituent containing ethylene carbonate and butylene.
9. a kind of preparation method of epoxy butane, which is characterized in that comprising claim 1~8 any one of them ethylene glycol and
Step in the Isolation method of 1,2- butanediol, it is further comprising the steps of：
By butylene decarboxylation under decarboxylation catalyst effect, epoxy butane is obtained.
10. the preparation method of epoxy butane according to claim 9, which is characterized in that the decarboxylation catalyst is selected from alkali
Metal sulfate, alkali metal villaumite, alkali nitrates, alkyl imidazole salt, ionic liquid, loading type alkali metal and load alkali gold
Belong at least one of oxide.
11. the preparation method of epoxy butane according to claim 9, which is characterized in that the absolute pressure of the decarboxylation is
0.1Bar~10Bar, temperature are 60 DEG C~500 DEG C, mass space velocity 0.1h-1~5h-1。
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