CN110437201A - A kind of composite absorber and its method for ethylene oxide absorption conversion coupled cogeneration ethylene carbonate - Google Patents
A kind of composite absorber and its method for ethylene oxide absorption conversion coupled cogeneration ethylene carbonate Download PDFInfo
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- CN110437201A CN110437201A CN201910785196.2A CN201910785196A CN110437201A CN 110437201 A CN110437201 A CN 110437201A CN 201910785196 A CN201910785196 A CN 201910785196A CN 110437201 A CN110437201 A CN 110437201A
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- ethylene oxide
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- ethylene carbonate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
Abstract
The present invention provides a kind of composite absorber and its for the method for ethylene oxide absorption conversion coupled cogeneration ethylene carbonate.The composite absorber includes ionic liquid and ethylene carbonate, and the structure of the ionic liquid is as shown in Formulas I, formula II or formula III.Above-mentioned composite absorber is used to absorb ethylene oxide and carbon dioxide by the present invention, ionic liquid is also used as catalyst during absorption, and ethylene oxide and carbon dioxide reaction are produced ethylene carbonate, and absorption while realizes pre-inversion, energy consumption is reduced, there is preferable industrial application value.Above-mentioned composite absorber is also used for ethylene oxide absorption conversion coupled cogeneration ethylene carbonate by the present invention, it will absorb and convert direct-coupling, realize step production ethylene carbonate, it is not only easy to operate, equipment manufacturing cost is low, and reduce stripping process, energy consumption is reduced, economical and efficient and energy-saving and environment-friendly requirement are realized.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of composite absorber and its convert for ethylene oxide absorption
The method of coupled cogeneration ethylene carbonate.
Background technique
The ethylene carbonate of referred to as 21 century green chemical industry raw material be it is a kind of using very extensive chemical intermediate and
Fine solvent.One of raw material of synthesizing ethylene carbonate ethylene oxide mainly utilizes ethylene to aoxidize life under silver-containing catalyst effect
At ethylene oxide, during preparing ethylene oxide while there can be the foreign gases such as methane, ethane.It refines in order to obtain
Ethylene oxide is industrially usually absorbed ethylene oxide using absorption process from gaseous mixture, then by stripping, concentration etc.
Process is refining to obtain the ethylene oxide of high-purity；The ethylene oxide and carbon dioxide of purification catalyze and synthesize carbonic acid second in a kettle
Enester.
In the technique for producing ethylene carbonate, absorbent is industrially often used water as, absorbent is used water as, selected
Selecting property is low and gasification latent heat will also result in greatly a large amount of energy consumption, therefore some patents make certain change to this both at home and abroad
Into.US4221727A1 discloses a kind of method using organic solvent ethylene carbonate as absorbent, and US5559255A is disclosed
A method of using organic solvent propene carbonate as absorbent, CN109422708A discloses one kind with triethylene glycol dimethyl ether
It is the method etc. of absorbent with ionic liquid.These absorbents improve the absorbability and selectivity to ethylene oxide, still
In the whole process flow, the process for stripping ethylene oxide still consumes big energy, and process flow is complicated, equipment manufacturing cost
Height, one-time investment are big.
Therefore, in order to the absorption of the gaseous mixture ethylene oxide after ethylene and the life of ethylene carbonate is better achieved
Produce, it is still necessary to New Absorbent and technique, be allowed to can either efficient absorption ethylene oxide, and be able to solve energy consumption in stripping process
Big problem.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of composite absorber and its for ethylene oxide
The method of sorption enhanced coupled cogeneration ethylene carbonate.The present invention using ionic liquid and ethylene carbonate composite absorber into
The absorption of row ethylene oxide and carbon dioxide, ionic liquid is also used as catalyst during absorption, and absorption is obtained
Ethylene oxide and carbon dioxide reaction produce ethylene carbonate, both improved the assimilation effect of ethylene oxide in this way, also reduced
The process of ethylene oxide desorption purification, absorption while, realize pre-inversion, reduce energy consumption, have preferable industrial application valence
Value.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of composite absorber, the composite absorber includes ionic liquid and carbonic acid second
Enester, the structure of the ionic liquid is as shown in Formulas I, formula II or formula III:
Wherein, the R in Formulas I1And R2It is each independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted
C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-
Any one in C30 heteroaryl or substituted or unsubstituted C1-C6 alkoxy；
R in formula II3、R4、R5And R6It is each independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted
C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted
Any one in C3-C30 heteroaryl or substituted or unsubstituted C1-C6 alkoxy；
R in formula III7、R8、R9And R10It is each independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted
C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted
Any one in C3-C30 heteroaryl or substituted or unsubstituted C1-C6 alkoxy；
Anion X in Formulas I, formula II and formula III-It is each independently selected from Cl-、Br-Or I-In any one.
Term used herein " C1-C6 alkyl " refers to the linear chain or branched chain alkane with 1,2,3,4,5 or 6 carbon atom
Base, without limitation include methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-pentyl,
Isopentyl, n-hexyl etc..Term " C2-C6 alkenyl " refers to the linear chain or branched chain alkenyl with 2,3,4,5 or 6 carbon atoms,
A double bond is included at least in strand, without limitation includes-CH=CH (CH3) ,-CH=C (CH3)2、-C(CH3)=CH2、-
C(CH3)=CH (CH3)、-C(CH2CH3)=CH2, butadienyl, pentadienyl or hexadienyl etc..Term " C2-C6 alkynyl " is
Refer to the linear chain or branched chain alkynyl with 2,3,4,5 or 6 carbon atoms, without limitation includes-C ≡ CH ,-C ≡ C (CH3)、-C≡
C(CH2CH3)、-CH2C≡CH、-CH2C≡C(CH3) or-CH2C≡C(CH2CH3) etc..Term " C6-C30 aryl " is with 6-30
The aryl of a carbon atom, such as may include 6,12 or 18 carbon atoms etc., it without limitation include phenyl, naphthalene or connection
Phenyl etc..Term " C3-C30 heteroaryl " refer to monocyclic, bicyclic or tricyclic etc. have 3,4,5,6,7,8,9,10,11,12,
13, the aromatic ring system of 14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29 or 30 etc. annular atoms,
And it contains at least one hetero atom that can be identical or different, and the hetero atom is such as oxygen, nitrogen or sulphur, and is furthermore existed
Can be in each situation it is benzo-fused, without limitation include thienyl, furyl, pyrrole radicals, oxazolyl, thiazolyl,
Imidazole radicals, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazoles base, triazolyl, benzofuranyl, benzothienyl, benzo are disliked
Oxazolyl, benzo isoxazolyl, benzimidazolyl, benzotriazole base, indazolyl, indyl, isoindolyl, pyridyl group, pyridazinyl,
Pyrimidine radicals, pyrazinyl, triazine radical, quinolyl, quinazolyl, isoquinolyl etc..Term " C1-C6 alkoxy " refers to 1,2,
3, the straight or branched alkoxyl of 4,5 or 6 carbon atoms includes methoxyl group, ethyoxyl, positive propoxy, isopropyl without limitation
Oxygroup or tert-butoxy etc..
The present invention carries out the suction of ethylene oxide and carbon dioxide using the composite absorber of ionic liquid and ethylene carbonate
It receives, ionic liquid is also used as catalyst during absorption, the ethylene oxide and carbon dioxide reaction that absorption is obtained
Ethylene carbonate is produced, had both improved the assimilation effect of ethylene oxide in this way, decreases the process of ethylene oxide desorption purification,
Pre-inversion is realized while absorption, reduces energy consumption, and there is preferable industrial application value.
The anion of composite absorber intermediate ion liquid of the present invention is selected from specific Cl-、Br-Or I-In it is any one
Kind, this is because the cation of ionic liquid can result in the polarization of ethylene oxide C-O key, the ring of halide ion attack at the same time
The lesser beta carbon of steric hindrance in oxygen ring, two kinds of effects simultaneously cause the easy open loop of ethylene oxide and carbon dioxide
Reaction generates ethylene carbonate.
Preferably, in Formulas I, formula II and formula III, the substituted group is each independently selected from hydroxyl, amino, nitro, aldehyde
Any one in base, ester group, carboxyl, nitroso, amide groups or carbonyl.
Preferably, the ionic liquid and ethylene carbonate mass ratio are 1:(1-10), such as can be 1:1,1:2,1:
3,1:4,1:5,1:6,1:7,1:8,1:9 or 1:10 etc..
The present invention preferably controls the mass ratio of ionic liquid and ethylene carbonate in above range, is due to working as ionic liquid
The viscosity of body too high levels, composite absorber increases, and can not come into full contact with ethylene oxide, may reduce the suction of ethylene oxide
It produces effects rate, and if ionic liquid content is too low, the selection absorbability of composite absorber weakens, and will affect ethylene oxide
Assimilation effect, while ionic liquid content is too low, absorbs the pre-reaction stage, and ethylene oxide and carbon dioxide cycloaddition reaction are urged
Changing efficiency can be substantially reduced.
Second aspect, the present invention also provides a kind of ethylene oxide absorption conversion coupled cogeneration ethylene carbonate method,
The method uses composite absorber as described in relation to the first aspect.
The present invention creatively uses ionic liquid and the compound conduct absorbent of ethylene carbonate to inhale ethylene oxide
Conversion coupling is received, a step sorption enhanced ethylene oxide is realized, effectively reduces the energy consumption and expense of device.
Preferably, described method includes following steps: the composite absorber and the unstripped gas containing ethylene oxide are connect
Touching, obtained rich ethylene oxide absorption liquid enter in main reactor, obtain ethylene carbonate.
The component and its molar content of unstripped gas of the present invention are respectively as follows: ethylene oxide 2.6%, methane
52.77%, ethylene 32.53%, oxygen 4.9%, carbon dioxide 1.5%, argon gas 4.18%, nitrogen 1% and 0.52% group of ethane
At.Unstripped gas of the present invention is the gaseous mixture after ethylene, exists simultaneously ethylene oxide and carbon dioxide, In in unstripped gas
In absorption process, ionic liquid can not only effectively absorb ethylene oxide and carbon dioxide, additionally it is possible to which both catalysis reaction generates
Ethylene carbonate realizes the pre-reaction for preparing ethylene carbonate while absorbing, reduces energy consumption, also reduction back segment carbonyl
Change main reaction unit ethylene oxide tail gas content, guarantee safety, there is preferable industrial application value.
The ethylene oxide conversion ratio of heretofore described pre-reaction is 2-35%, for example, can be 2%, 5%, 8%,
10%, 12%, 15%, 20%, 23%, 27%, 30% or 35% etc..
The conversion ratio of pre-reaction stage ethylene oxide of the present invention is only 2-35%, is since the pre-reaction stage can not mention
For excessive carbon dioxide, and catalyst pre-reaction at a temperature of be unable to reach optimal conversion, cause pre-reaction rank
The conversion ratio of section ethylene oxide is lower.
Preferably, described method includes following steps: the composite absorber is being inhaled with containing ethylene oxide unstripped gas
It receives adverse current in tower to come into full contact with, the weak mixture after tower top decylization oxidative ethane returns to ethylene stage, tower reactor after treatment
Rich ethylene oxide absorption liquid enters main reactor after exchanging heat, and reaction obtains reaction solution, anti-comprising ionic liquid by what is obtained
Liquid a part is answered to recycle as absorbing liquid, another part obtains the ethylene carbonate of high-purity after treatment.
It should be noted that carbon dioxide can be added into main reactor in the stage of reaction, make the amount of carbon dioxide
Be relative to ethylene oxide it is sufficient, that is, be able to satisfy the reacting ethylene oxide that enough carbon dioxide and absorption obtain and generate
Ethylene carbonate.
It is ionic liquid-catalyzed to absorb obtained ethylene oxide and carbon dioxide reaction production in main reactor of the present invention
Ethylene carbonate.For the tail gas treatment process after ethylene, ethylene oxide absorption is got off using absorption tower at present, is passed through
Enter reactor after stripping, purification and generates ethylene carbonate.And creativeness uses ethylene carbonate and ionic liquid to the present invention for the first time
The composite absorber of body carrys out sorption enhanced coupled cogeneration ethylene carbonate, not only has higher absorption performance to ethylene oxide, and
And ionic liquid also have steam force down with the small equal excellent performances of specific heat capacity, after complete reaction, product can be used as absorbent again
Secondary be recycled in absorption tower is recycled, and simplifies separation cyclic process.For process flow, the method for the invention will absorb
With conversion direct-coupling, realize that a step produces ethylene carbonate, not only workload is small, and equipment manufacturing cost is low, and reduces and stripped
Journey reduces energy consumption, realizes economical and efficient and energy-saving and environment-friendly requirement.
Preferably, the composite absorber is with the mass ratio (liquid gas mass ratio) containing ethylene oxide unstripped gas
(1-5): 1, such as can be 1:1,1.5:1,2:1,2.3:1,3:1,3.5:1,4:1 or 5:1 etc., preferably (2-3): 1.
Preferably, the operating pressure on the absorption tower be 1-5MPa, such as can be 1MPa, 1.5MPa, 2MPa,
2.3MPa, 3MPa, 3.5MPa, 4MPa, 4.6MPa or 5Mpa etc., preferably 1.5-2.5MPa.
Preferably, the operation temperature on the absorption tower be 50-100 DEG C, such as can be 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C,
90 DEG C or 100 DEG C etc., preferably 60-80 DEG C.
Preferably, the reaction pressure of the main reactor be 1-5MPa, such as can be 1MPa, 1.2MPa, 2MPa,
2.5MPa, 3MPa, 3.4MPa, 4MPa, 4.5MPa or 5Mpa etc., preferably 2-3MPa.
Preferably, the reaction temperature of the main reactor is 80-300 DEG C, such as can be 80 DEG C, 90 DEG C, 100 DEG C, 110
℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、
240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C or 300 DEG C etc., preferably 100-200 DEG C.
Preferably, the time of the reaction be 0.5-5h, such as can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h,
4h, 4.5h or 5h etc., preferably 1-3h.
Preferably, the rich ethylene oxide absorption liquid exchanges heat to entering main reactor after 100-200 DEG C, such as can be
100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C etc..
Preferably, a part of the reaction solution is cooled to 60-80 DEG C before entering absorption tower, such as can be 60 DEG C, 62
DEG C, 65 DEG C, 68 DEG C, 70 DEG C, 73 DEG C, 76 DEG C or 80 DEG C etc..
Compared with the existing technology, the invention has the following advantages:
(1) present invention utilizes the composite absorber of ionic liquid and ethylene carbonate progress ethylene oxide and carbon dioxide
It absorbs, ionic liquid is also used as catalyst during absorption, will absorb obtained ethylene oxide and carbon dioxide is anti-
Ethylene carbonate should be produced, had both improved the assimilation effect of ethylene oxide in this way, decreases the mistake of ethylene oxide desorption purification
Journey, absorption while, realize pre-inversion, reduce energy consumption, have preferable industrial application value；
(2) the creative composite absorber using ethylene carbonate and ionic liquid carrys out sorption enhanced coupling to the present invention for the first time
Coproduction ethylene carbonate not only has higher absorption performance to ethylene oxide, but also also there is ionic liquid steam to force down and compare
The small equal excellent performances of thermal capacitance, after complete reaction, product can be used as absorbent and be re-circulated to recycling in absorption tower, simplify
Separation cyclic process.For process flow, the method for the invention will absorb and conversion direct-coupling, realizes that a step produces carbon
Vinyl acetate, not only workload is small, and equipment manufacturing cost is low, and reduces stripping process, reduces energy consumption, realizes economical and efficient and section
The requirement of energy environmental protection；
(3) composite absorber of the present invention is in the process for ethylene oxide absorption conversion coupled cogeneration ethylene carbonate
In, in the absorption stage, the absorptivity of ethylene oxide can reach 98.5% or more, in the main reaction stage, the conversion of ethylene oxide
Rate reaches as high as 99.2%, and selectivity is also 92% or more.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
It present embodiments provides a kind of composite absorber and its converts coupled cogeneration ethylene carbonate for ethylene oxide absorption
The method of ester, specific steps are as follows:
The unstripped gas of 80 DEG C of ethylene oxide containing 2.26mol% is entered into absorption tower, composite absorber ionic liquid by tower bottom
1- (2- ethoxy) -3- methylimidazole bromine ([Hemim] Br) and ethylene carbonate are with the mass ratio of 1:10 after mixing from suction
It receives tower (T1) tower top to enter, unstripped gas and absorbent counter current contacting, absorbing temperature is 80 DEG C, operating pressure 2MPa, liquid makings
Amount than be 3, absorb pre-inversion section ethylene oxide conversion ratio be 28.8%, the concentration 69ppm of absorbing tower apical ring oxidative ethane, this
When absorptivity be 99.9%.
Above-mentioned absorbing liquid is added in reactor, increasing reaction temperature is 125 DEG C, and pressure is to react 1h under 2MPa, is passed through
Detection gained is crossed, the conversion ratio of residual epoxide ethane is 95.2%, and selectivity is 99.8%.
Embodiment 2
It present embodiments provides a kind of composite absorber and its converts coupled cogeneration ethylene carbonate for ethylene oxide absorption
The method of ester, specific steps are as follows:
The unstripped gas of 80 DEG C of ethylene oxide containing 2.26mol% is entered into absorption tower, composite absorber ionic liquid by tower bottom
1- hexyl -3- methylimidazole bromine ([Hmim] Br) and ethylene carbonate are with the mass ratio of 1:10 after mixing from absorption tower (T1)
Tower top enters, unstripped gas and absorbent counter current contacting, and absorbing temperature is 80 DEG C, operating pressure 2MPa, and liquid gas mass ratio is 3,
The conversion ratio for absorbing pre-inversion section ethylene oxide is 15.8%, and the concentration 227ppm of absorbing tower apical ring oxidative ethane absorbs at this time
Rate is 99.5%.
Above-mentioned absorbing liquid is added in reactor, increasing reaction temperature is 120 DEG C, and pressure is to react 3h under 2MPa, is passed through
Detection gained is crossed, the conversion ratio of residual epoxide ethane is 52.5%, and selectivity is 99.8%.
Embodiment 3
It present embodiments provides a kind of composite absorber and its converts coupled cogeneration ethylene carbonate for ethylene oxide absorption
The method of ester, specific steps are as follows:
The unstripped gas of 80 DEG C of ethylene oxide containing 2.26mol% is entered into absorption tower, composite absorber ionic liquid by tower bottom
1- (2- ethoxy) -3- methylimidazole bromine ([Hemim] Br) and ethylene carbonate are with the mass ratio of 1:9 after mixing from absorption
Tower (T1) tower top enters, unstripped gas and absorbent counter current contacting, and absorbing temperature is 80 DEG C, operating pressure 2MPa, liquid makings amount
Than being 3, the conversion ratio of pre-inversion section ethylene oxide is absorbed for 32.2%, the concentration 44ppm of absorbing tower apical ring oxidative ethane, at this time
Absorptivity is 99.9%.
Above-mentioned absorbing liquid is added in reactor, increasing reaction temperature is 120 DEG C, and pressure is to react 1h under 2MPa, is passed through
Detection gained is crossed, the conversion ratio of residual epoxide ethane is 99.2%, and selectivity is 99.8%.
Embodiment 4
It present embodiments provides a kind of composite absorber and its converts coupled cogeneration ethylene carbonate for ethylene oxide absorption
The method of ester, specific steps are as follows:
The unstripped gas of 80 DEG C of ethylene oxide containing 2.26mol% is entered into absorption tower, composite absorber ionic liquid by tower bottom
2- ethoxy tributyl ammonium bromide (HETBAB) and ethylene carbonate are with the mass ratio of 1:10 after mixing from absorption tower (T1)
Tower top enters, unstripped gas and absorbent counter current contacting, and absorbing temperature is 80 DEG C, operating pressure 2MPa, and liquid gas mass ratio is 3,
The conversion ratio for absorbing pre-inversion section ethylene oxide is 29.2%, the concentration 55ppm of absorbing tower apical ring oxidative ethane, at this time absorptivity
It is 99.9%.
Above-mentioned absorbing liquid is added in reactor, increasing reaction temperature is 125 DEG C, and pressure is to react 1h under 2MPa, is passed through
Detection gained is crossed, the conversion ratio of residual epoxide ethane is 95.8%, and selectivity is 99.8%.
Embodiment 5
It present embodiments provides a kind of composite absorber and its converts coupled cogeneration ethylene carbonate for ethylene oxide absorption
The method of ester, specific steps are as follows:
The unstripped gas of 80 DEG C of ethylene oxide containing 2.26mol% is entered into absorption tower, composite absorber ionic liquid by tower bottom
Ethylenebis (tri-phenyl-phosphorus bromide) (E [TPB]) and ethylene carbonate are with the mass ratio of 1:10 after mixing from absorption tower
(T1) tower top enters, unstripped gas and absorbent counter current contacting, and absorbing temperature is 80 DEG C, operating pressure 3MPa, liquid gas mass ratio
It is 3, the conversion ratio for absorbing pre-inversion section ethylene oxide is 25.6%, and the concentration 95ppm of absorbing tower apical ring oxidative ethane inhales at this time
Yield is 99.8%.
Above-mentioned absorbing liquid is added in reactor, increasing reaction temperature is 160 DEG C, and pressure is to react 3h under 3MPa, is passed through
Detection gained is crossed, the conversion ratio of residual epoxide ethane is 92.9%, and selectivity is 99%.
Embodiment 6
It present embodiments provides a kind of composite absorber and its converts coupled cogeneration ethylene carbonate for ethylene oxide absorption
The method of ester, specific steps are as follows:
The unstripped gas of 60 DEG C of ethylene oxide containing 2.26mol% is entered into absorption tower, composite absorber ionic liquid by tower bottom
1- (2- ethoxy) -3- methylimidazole bromine ([Hemim] Br) and ethylene carbonate are with the mass ratio of 1:1 after mixing from absorption
Tower (T1) tower top enters, unstripped gas and absorbent counter current contacting, and absorbing temperature is 60 DEG C, operating pressure 2MPa, liquid makings amount
Than being 2, wherein the conversion ratio for absorbing pre-inversion section ethylene oxide is 18.2%, the concentration of 2 tower top ethylene oxide of absorption tower
152ppm, absorptivity is 99.4% at this time.
Above-mentioned absorbing liquid is added in reactor, increasing reaction temperature is 80 DEG C, and pressure is to react 0.5h under 5MPa, is passed through
Detection gained is crossed, the conversion ratio of residual epoxide ethane is 65.5%, and selectivity is 98.2%.
Embodiment 7
It present embodiments provides a kind of composite absorber and its converts coupled cogeneration ethylene carbonate for ethylene oxide absorption
The method of ester, specific steps are as follows:
The unstripped gas of 100 DEG C of ethylene oxide containing 2.26mol% is entered into absorption tower, composite absorber ionic liquid by tower bottom
1- (2- ethoxy) -3- methylimidazole bromine ([Hemim] Br) and ethylene carbonate are with the mass ratio of 1:5 after mixing from absorption
Tower (T1) tower top enters, unstripped gas and absorbent counter current contacting, and absorbing temperature is 100 DEG C, operating pressure 2MPa, liquid makings amount
Than being 3, the conversion ratio for absorbing pre-inversion section ethylene oxide is 30.1%, the concentration 395ppm of absorbing tower apical ring oxidative ethane, this
When absorptivity be 98.5%.
Above-mentioned absorbing liquid is added in reactor, increasing reaction temperature is 300 DEG C, and pressure is to react 5h under 2MPa, is passed through
Detection gained is crossed, the conversion ratio of residual epoxide ethane is 95.2%, and selectivity is 98.2%.
Embodiment 8
It present embodiments provides a kind of composite absorber and its converts coupled cogeneration ethylene carbonate for ethylene oxide absorption
The method of ester, specific steps are as follows:
The unstripped gas of 60 DEG C of ethylene oxide containing 2.26mol% is entered into absorption tower, composite absorber ionic liquid by tower bottom
2- ethoxy tributyl ammonium bromide (HETBAB) and ethylene carbonate are with the mass ratio of 1:7 after mixing from absorption tower (T1) tower
Jacking enters, unstripped gas and absorbent counter current contacting, and absorbing temperature is 60 DEG C, operating pressure 2MPa, and liquid gas mass ratio is 2,
In, the conversion ratio for absorbing pre-inversion section ethylene oxide is 17.2%, and the concentration 108ppm of absorbing tower apical ring oxidative ethane inhales at this time
Yield is 99.5%.
Above-mentioned absorbing liquid is added in reactor, increasing reaction temperature is 200 DEG C, and pressure is to react 2h under 1.5MPa,
Gained after testing, the conversion ratio of residual epoxide ethane are 85.1%, and selectivity is 92%.
Embodiment 9
It present embodiments provides a kind of composite absorber and its converts coupled cogeneration ethylene carbonate for ethylene oxide absorption
The method of ester, the difference with embodiment 1 are only that: 1- (2- ethoxy) -3- methylimidazole bromine ([Hemim] Br) and ethylene carbonate
The mass ratio of ester is 1:12.
Absorb pre-inversion section ethylene oxide conversion ratio be 17%, the concentration 158ppm of absorbing tower apical ring oxidative ethane, this
When absorptivity 99.4%；Above-mentioned absorbing liquid is added in reactor, gained, residual epoxide ethane turn after testing after reaction
Rate is 95.2%, and selectivity is 99.8%.
Comparative example 1
It present embodiments provides a kind of composite absorber and its converts coupled cogeneration ethylene carbonate for ethylene oxide absorption
The method of ester, specific steps are as follows:
The unstripped gas of 80 DEG C of ethylene oxide containing 2.26mol% is entered into absorption tower by tower bottom, absorbent ethylene carbonate from
Absorption tower (T1) tower top enters, unstripped gas and absorbent counter current contacting, and absorbing temperature is 80 DEG C, operating pressure 2MPa, liquid gas
Mass ratio is 3, the concentration 450ppm of absorbing tower apical ring oxidative ethane, and absorptivity is 98.2% at this time.
Above-mentioned absorbing liquid is added in main reactor, is added catalyst 1- butyl -3- methylimidazole bromine ([bmim] Br),
Increasing reaction temperature is 120 DEG C, and pressure is to react 3h under 2MPa, and gained, the conversion ratio of residual epoxide ethane are after testing
51.6%, selectivity is 99.9%.
Composite absorber of the present invention is converted for ethylene oxide absorption it can be seen from embodiment and testing result
During coupled cogeneration ethylene carbonate, in the absorption stage, the absorptivity of ethylene oxide can reach 98.5% or more, this says
The bright composite absorber using ionic liquid and ethylene carbonate, has higher absorption capacity ethylene oxide, also, due to
Ionic liquid have steam force down with the small equal excellent performances of specific heat capacity, product can be used as absorbent and recycle again after complete reaction
It is recycled in absorption tower, simplifies separation cyclic process.In the absorption stage, the conversion ratio of ethylene oxide is in 15.8-
32.2%, in the main reaction stage, the conversion ratio of ethylene oxide reaches as high as 99.2%, and selectivity is also 99% or more.For
Entire process flow, the present invention will absorb and convert ethylene oxide direct-coupling, realize that a step produces ethylene carbonate, not only subtract
Workload is lacked, has reduced equipment manufacturing cost, and also reduce stripping process, reduce energy consumption, realize economical and efficient and section
The requirement of energy environmental protection.
Compared to embodiment 1, comparative example 1 ethylene oxide absorption stage only with ethylene carbonate, then by
The main reaction stage adds catalyst to realize the esterification of ethylene oxide and carbon dioxide, as can be seen that inhaling from data
Receipts stage, the absorptivity of 1 ethylene oxide of comparative example are lower than the suction using the composite absorber containing ionic liquid to ethylene oxide
It produces effects rate, in the main reaction stage, the conversion of the conversion ratio of ethylene oxide also below 1 intermediate ion liquid catalyst main reaction of embodiment
Rate.This explanation adds ionic liquid in ethylene oxide absorption conversion process, can not only enhance the selection to ethylene oxide and absorb
Property, also there is higher catalytic efficiency to the esterification of ethylene oxide and carbon dioxide.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of composite absorber, which is characterized in that the composite absorber includes ionic liquid and ethylene carbonate, it is described from
The structure of sub- liquid is as shown in Formulas I, formula II or formula III:
Wherein, the R in Formulas I1And R2It is each independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-
C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30
Any one in heteroaryl or substituted or unsubstituted C1-C6 alkoxy；
R in formula II3、R4、R5And R6It is each independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-
C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30
Any one in heteroaryl or substituted or unsubstituted C1-C6 alkoxy；
R in formula III7、R8、R9And R10It is each independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted
C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-
Any one in C30 heteroaryl or substituted or unsubstituted C1-C6 alkoxy；
Anion X in Formulas I, formula II and formula III-It is each independently selected from Cl-、Br-Or I-In any one.
2. composite absorber according to claim 1, which is characterized in that in Formulas I, formula II and formula III, the substituted base
Group is each independently selected from any one in hydroxyl, amino, nitro, aldehyde radical, ester group, carboxyl, nitroso, amide groups or carbonyl
Kind.
3. composite absorber according to claim 1 or 2, which is characterized in that the ionic liquid and ethylene carbonate matter
Amount is than being 1:(1-10).
4. a kind of method of ethylene oxide absorption conversion coupled cogeneration ethylene carbonate, which is characterized in that the method is using such as
The described in any item composite absorbers of claim 1-3.
5. according to the method described in claim 4, it is characterized in that, described method includes following steps: by the composite absorption
Agent and the feed gas containing ethylene oxide, obtained rich ethylene oxide absorption liquid enter in main reactor, obtain carbonic acid second
Enester.
6. method according to claim 4 or 5, which is characterized in that described method includes following steps: by the compound suction
It receives agent countercurrently to come into full contact in absorption tower with containing ethylene oxide unstripped gas, the weak mixture after tower top decylization oxidative ethane passes through
The ethylene stage is returned to after processing, tower reactor richness ethylene oxide absorption liquid enters main reactor after exchanging heat, and reaction is reacted
Liquid, recycles obtained reaction solution a part comprising ionic liquid as absorbing liquid, and another part obtains height after treatment
The ethylene carbonate of purity.
7. according to the method described in claim 6, it is characterized in that, the composite absorber contains ethylene oxide raw material with described
The mass ratio of gas is (1-5): 1, preferably (2-3): 1.
8. method according to claim 6 or 7, which is characterized in that the operating pressure on the absorption tower is 1-5MPa, preferably
1.5-2.5MPa；
Preferably, the operation temperature on the absorption tower is 50-100 DEG C, preferably 60-80 DEG C；
Preferably, the reaction pressure of the main reactor is 1-5MPa, preferably 2-3MPa；
Preferably, the reaction temperature of the main reactor is 80-300 DEG C, preferably 100-200 DEG C；
Preferably, the time of the reaction is 0.5-5h, preferably 1-3h.
9. according to the described in any item methods of claim 6-8, which is characterized in that it is described richness ethylene oxide absorption liquid exchange heat to
Enter main reactor after 100-200 DEG C.
10. the method according to claim 6, which is characterized in that a part of the reaction solution, which enters, to be absorbed
60-80 DEG C is cooled to before tower.
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|---|---|---|---|
| CN201910785196.2A CN110437201B (en) | 2019-08-23 | 2019-08-23 | Composite absorbent and method for ethylene oxide absorption, conversion and coupling co-production of ethylene carbonate by using same |
| US17/637,241 US20220274944A1 (en) | 2019-08-23 | 2020-03-23 | Composite absorbent and use thereof |
| PCT/CN2020/080560 WO2021036238A1 (en) | 2019-08-23 | 2020-03-23 | Composite absorbent and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910785196.2A CN110437201B (en) | 2019-08-23 | 2019-08-23 | Composite absorbent and method for ethylene oxide absorption, conversion and coupling co-production of ethylene carbonate by using same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471033A (en) * | 2020-04-29 | 2020-07-31 | 中国科学院过程工程研究所 | Device and method for preparing cyclic carbonate by integrating absorption separation and catalytic reaction |
| WO2021036238A1 (en) * | 2019-08-23 | 2021-03-04 | 中国科学院过程工程研究所 | Composite absorbent and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4221727A (en) * | 1979-08-17 | 1980-09-09 | The Dow Chemical Company | Ethylene oxide recovery |
| CN105732566A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Method of producing ethylene carbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4221727A (en) * | 1979-08-17 | 1980-09-09 | The Dow Chemical Company | Ethylene oxide recovery |
| CN105732566A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Method of producing ethylene carbonate |
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| 程牧曦等: "环氧乙烷和二氧化碳酯化制备碳酸乙烯酯反应催化剂", 《化工进展》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021036238A1 (en) * | 2019-08-23 | 2021-03-04 | 中国科学院过程工程研究所 | Composite absorbent and use thereof |
| CN111471033A (en) * | 2020-04-29 | 2020-07-31 | 中国科学院过程工程研究所 | Device and method for preparing cyclic carbonate by integrating absorption separation and catalytic reaction |
| CN111471033B (en) * | 2020-04-29 | 2021-04-20 | 中国科学院过程工程研究所 | Device and method for preparing cyclic carbonate by integrating absorption separation and catalytic reaction |
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