CN110357763A - The method of separation of extractive distillation ethylene glycol and 1,2- butanediol - Google Patents
The method of separation of extractive distillation ethylene glycol and 1,2- butanediol Download PDFInfo
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- CN110357763A CN110357763A CN201910692001.XA CN201910692001A CN110357763A CN 110357763 A CN110357763 A CN 110357763A CN 201910692001 A CN201910692001 A CN 201910692001A CN 110357763 A CN110357763 A CN 110357763A
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 331
- 238000000895 extractive distillation Methods 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 40
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229940083957 1,2-butanediol Drugs 0.000 title claims abstract description 35
- 238000000926 separation method Methods 0.000 title claims abstract description 25
- 238000000605 extraction Methods 0.000 claims abstract description 61
- 238000011084 recovery Methods 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 20
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 37
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 12
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical group CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims description 12
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 229940057402 undecyl alcohol Drugs 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 4
- 229940043276 diisopropanolamine Drugs 0.000 claims description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 2
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 claims description 2
- LCEDQNDDFOCWGG-UHFFFAOYSA-N N-Formyl-Morpholine Natural products O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims 3
- BJXXCOMGRRCAGN-CLFAGFIQSA-N [2,2-bis(hydroxymethyl)-3-[(z)-octadec-9-enoyl]oxypropyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(CO)(CO)COC(=O)CCCCCCC\C=C/CCCCCCCC BJXXCOMGRRCAGN-CLFAGFIQSA-N 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- 230000001502 supplementing effect Effects 0.000 abstract description 2
- 238000010992 reflux Methods 0.000 description 9
- 150000001241 acetals Chemical class 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- -1 butantriol Chemical compound 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- 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
- C07C29/84—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is separation of extractive distillation ethylene glycol and 1, the method of 2- butanediol, the process flow of this method are as follows: the raw material ethylene glycol arbitrarily formed and 1,2- mixture of butanediols is fed in a certain position of extractive distillation column, while extractant is fed on the top of extractive distillation column, in extractive distillation column, 1,2- butanediol enters extractant recovery tower after tower reactor extraction from overhead extraction, ethylene glycol and extractant;In extractant recovery tower, ethylene glycol product is from overhead extraction, extractant exchanges heat after being produced by tower reactor through heat exchanger and raw material, extractive distillation column upper feed inlet is returned after cooler again, it is recycled, while supplementing the extractant lost from two the top of the distillation column in the upper feed inlet of extractive distillation column;Extractive distillation column and extractant recovery tower are negative-pressure operation, and tower top pressure is in 10kPa or less.This method separates the object system by using liquid phase higher boiling extractant, obtains 1,2- butanediol product and the ethylene glycol product that molar fraction is 99.9%, process is simple, and equipment investment is low, and low energy consumption, good separating effect.
Description
Technical field
The invention belongs to ethylene glycol and 1,2- butanediol separation technology field, be related to a kind of separation of extractive distillation ethylene glycol and
The method of 1,2- butanediol.
Background technique
During coal-ethylene glycol and biomass preparing ethylene glycol, by-product can be generated, in order to guarantee ethylene glycol product
Index, can produce the byproduct stream stock containing ethylene glycol during separating-purifying, flow in stock containing ethylene glycol, propylene glycol and
The products such as butanediol.In these products, ethylene glycol and 1,2- butanediol leads to 1, the 2- butanediol in raw material there are azeotropic point
Azeotropic mixture can be formed with ethylene glycol to steam from tower top, ethylene glycol yield is caused to decline.Therefore, how energy-efficiently by 1,
2- butanediol is separated from ethylene glycol product, be coal-ethylene glycol and biomass the preparing ethylene glycol technical problem that needs to solve it
One.
A kind of method that 102372598 A of patent CN proposes absorption, at least one in non-functional resin or molecular sieve
Kind is used as adsorbent, and butanediol is adsorbed, and inhales the ethylene glycol that extraction raffinate is 99.99% or 100% (mass fraction).But this method
It is restricted to the content of butanediol in processing raw material, it is desirable that butanediol content is not higher than 3%.
105622338 A of patent CN proposes separation method, technique and the device of a kind of reversible reaction conversion, by ethylene glycol
Corresponding acetal/ketone Product liquid mixture is formed by acetal or ketal reaction with 1,2- butanediol, then this liquid is mixed
It closes object to be separated by a series of rectifying columns, then hydrolysis of acetals/ketone product obtains ethylene glycol and 1 respectively, at the beginning of 2- butanediol
Product finally pass through rectification and purification respectively, obtain 1, the 2- butanediol product of 99.9% or more ethylene glycol and 98.5% or more.It should
For method by ethylene glycol and 1,2- butanediol separation problem becomes segregative acetal/ketone product separation problem, but separates stream
Journey is excessively complicated, needs raw material by reaction, rectifying, then react, then rectifying, just available ethylene glycol and 1, and 2- butanediol produces
Product.
Summary of the invention
Ethylene glycol and 1 is separated for current industrial production, when 2- butanediol, due to ethylene glycol and 1,2- butanediol exists most
Low azeotropic mixture needs high energy consumption and high equipment investment using conventional distillation and separating effect is bad, and the ethylene glycol rate of recovery is low to ask
Topic proposes a kind of separation of extractive distillation ethylene glycol and 1, the method for 2- butanediol.This method is extracted by using liquid phase higher boiling
Agent separates the object system, obtains 1,2- butanediol product and the ethylene glycol product that molar fraction is 99.9%.This method process is simple,
Equipment investment is low, and low energy consumption, good separating effect.
The present invention solve the technical problem the technical solution adopted is that:
The first scheme: a kind of separation of extractive distillation ethylene glycol and 1, the method for 2- butanediol, the process flow of this method
Are as follows: the raw material ethylene glycol arbitrarily formed and 1,2- mixture of butanediols are fed in a certain position of extractive distillation column, while extractant
It is fed on the top of extractive distillation column, in extractive distillation column, 1,2- butanediol is from overhead extraction, ethylene glycol and extractant from tower
Enter extractant recovery tower after kettle extraction;In extractant recovery tower, ethylene glycol product is adopted from overhead extraction, extractant by tower reactor
It exchanges heat after out through heat exchanger and raw material, then returns to extractive distillation column upper feed inlet after cooler, recycled,
The extractant lost from two the top of the distillation column is supplemented in the upper feed inlet of extractive distillation column simultaneously, it is final to realize azeotropic mixture object
It is the separation of ethylene glycol and 1,2- butanediol;
The extractant is polar organic solvent containing more than two hydroxyls or containing more organic molten of polar functional group
One or more of agent higher boiling liquid-phase extraction agent;
1, the 2- butanediol product that the extractive distillation column overhead extraction molar fraction is 99.9%, in extractant recovery tower
Overhead extraction molar fraction be 99.9% ethylene glycol product, tower reactor produce molar fraction be 99.99% extractant;
Second scheme: a kind of separation of extractive distillation ethylene glycol and 1, the method for 2- butanediol, the process flow of this method
Are as follows: the raw material ethylene glycol arbitrarily formed and 1,2- mixture of butanediols is fed in a certain position of extractive distillation column, while extractant
It is fed on the top of extractive distillation column, in extractive distillation column, ethylene glycol and partial extraction agent are after overhead extraction, into split-phase
Device carries out split-phase, and light phase is more containing extractant, returns to extracting rectifying column overhead;Heavy phase is more containing ethylene glycol, into purifying ethylene glycol
Tower, tower reactor produce ethylene glycol product, and tower top is the mixture of ethylene glycol and extractant, which returns after cooler is cooling
The same phase-splitter;
1,2- butanediol and extractant enter extractant recovery tower after the extraction of extractive distillation column tower reactor, recycle in extractant
In tower, 1,2- butanediol product is from overhead extraction, and extractant exchanges heat after being produced by tower reactor through heat exchanger and raw material, then through cold
But extractive distillation column upper feed inlet is returned to after device to recycle, while supplementing in the upper feed inlet of extractive distillation column from two
The extractant of rectifying column (purifying ethylene glycol tower tower reactor and extractant recycle column overhead) loss, it is final to realize azeotropic mixture object system second two
The separation of pure and mild 1,2- butanediol;
The extractant is higher boiling liquid phase long-chain alcohol;
The ethylene glycol product that the purifying ethylene glycol tower tower reactor extraction molar fraction is 99.9%, in extractant recovery tower
1, the 2- butanediol product that overhead extraction molar fraction is 99.9%, tower reactor produce the extractant that molar fraction is 99.99%;
Compared with prior art, the beneficial effects of the present invention are:
1) product purity of the ethylene glycol and 1 that the method for the present invention obtains, 2- butanediol is high, can reach 99.9% and (rub
That score), while ethylene glycol and 1, the high income of 2- butanediol can reach 99%.
2) extractant used in this application is higher boiling liquid-phase extraction agent, not volatile, and extractant is produced from tower reactor.Two
Kind separation scheme improves separating effect with respect to conventional distillation separation, reduces energy consumption.Long-chain alcohols is directed in second scheme
Extractant uses continuous extraction rectifying mode, realizes the requirement of above-mentioned high-purity and high-recovery.The first scheme is being realized
While the requirement of above-mentioned high-purity and high-recovery, energy-saving effect is significant, and treating capacity is 10kmol/h, charging in embodiment 2
When molar fraction is 1,2- butanediol 90% and ethylene glycol 10%, energy consumption can be reduced to 259.94kW, energy-saving effect and economy
Remarkable benefit.
3) it exchanges heat after extractant is produced by tower reactor through heat exchanger and raw material, then is returned on extractive distillation column through cooler
Portion's feed inlet, energy consumption accordingly consider cycling extraction agent and the heat exchange of raw material, and energy consumption accordingly considers cycling extraction agent and raw material
Heat exchange, further reduce energy consumption.
Detailed description of the invention
Fig. 1 be separation of extractive distillation ethylene glycol of the present invention and 1, the first scheme of the method for 2- butanediol, embodiment 1-3's
Process flow chart.
Fig. 2 is separation of extractive distillation ethylene glycol of the present invention and 1, the method second scheme of 2- butanediol, the work of embodiment 4
Skill flow chart.
Specific embodiment
The present invention is explained further below with reference to examples and drawings, but not in this, as to the application protection scope
It limits.
As shown in Figure 1, raw material ethylene glycol and 1,2- mixture of butanediols (any than) a certain position of extractive distillation column into
Material, while extractant is fed on the top of extractive distillation column, in extractive distillation column, 1,2- butanediol is from overhead extraction, second two
Pure and mild extractant enters extractant recovery tower after tower reactor extraction, in extractant recovery tower, ethylene glycol product from overhead extraction,
Extractant exchanges heat after being produced by tower reactor through heat exchanger and raw material, then the charging of extractive distillation column top is returned after cooler
Mouthful, it is recycled, while the upper feed inlet appropriate in extractive distillation column supplements extractant, it is final to realize azeotropic mixture object
It is the separation of ethylene glycol and 1,2- butanediol.The 1,2- butanediol that the extractive distillation column overhead extraction molar fraction is 99.9%
Product, the ethylene glycol product for being 99.9% in the overhead extraction molar fraction of extractant recovery tower, tower reactor extraction molar fraction are
99.99% extractant.Extractant only requires supplementation with the extractant lost from two the top of the distillation column.
As shown in Fig. 2, raw material ethylene glycol and 1,2- mixture of butanediols (any than) a certain position of extractive distillation column into
Material, while extractant is fed on the top of extractive distillation column, in extractive distillation column, ethylene glycol and partial extraction agent are adopted from tower top
After out, split-phase is carried out into phase-splitter, light phase is more containing extractant, returns to extracting rectifying column overhead;Heavy phase is more containing ethylene glycol, into
Enter purifying ethylene glycol tower, tower reactor produces ethylene glycol product, and tower top is the mixture of ethylene glycol and extractant, and the mixture is through cooling
The same phase-splitter is returned after device is cooling;1,2- butanediol and extractant return after the extraction of extractive distillation column tower reactor into extractant
Receive tower, in extractant recovery tower, 1,2- butanediol product from overhead extraction, extractant produced by tower reactor after through heat exchanger and former
Material exchanges heat, then returns to extractive distillation column upper feed inlet after cooler and recycle, final to realize azeotropic mixture object system second
The separation of two pure and mild 1,2- butanediols.The ethylene glycol product that the tower reactor extraction molar fraction of purifying ethylene glycol tower is 99.9%,
1, the 2- butanediol product that the overhead extraction molar fraction of extractant recovery tower is 99.9%, tower reactor extraction molar fraction are
99.99% extractant.Extractant is only required supplementation with from two rectifying columns (purifying ethylene glycol tower tower reactor and extractant recovery tower towers
Top) loss extractant.
Each rectifying column (extractive distillation column, extractant recovery tower, purifying ethylene glycol tower) is negative-pressure operation, tower among the above
Pressure on top surface is in 10kPa or less.
The extractant is higher boiling, low volatility liquid-phase extraction agent, is had for the polarity of hydroxyl more (two or more)
Solvent or when containing more one or more of the organic solvent of polar functional group, such as glycerine, butantriol, triethylene glycol,
Tetraethylene glycol, trimethylolpropane, sulfolane, triethanolamine, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, diisopropanolamine (DIPA) are right
Hydroxyanisol, N- N-formyl morpholine N etc., process flow are shown in Fig. 1;Extractant is undecyl alcohol, tridecanol, tetradecyl alchohol, 15
When one or more of long-chain alcohols such as alcohol, heptadecanol, process flow is shown in Fig. 2.
Embodiment 1
Such as Fig. 1, extractive distillation column has 52 pieces of theoretical plates, and reflux ratio 1.75, extractant is sulfolane, from the 19th piece of theory
Plate (from tower top toward tower bottom number) charging, flow 20.5kmol/h;Ethylene glycol and 1, the mixture of 2- butanediol, molar fraction are
1,2- butanediol 50% and ethylene glycol 50% are fed, flow 10kmol/h from the 38th piece of theoretical plate.Extracting rectifying column overhead pressure
Power 10kPa, 132.2 DEG C of tower top temperature, 169.8 DEG C of bottom temperature, 1, the 2- butanediol of overhead extraction 99.9mol%, produced quantity
For 5kmol/h;Tower reactor obtains the mixture of ethylene glycol and sulfolane, enters extractant recovery tower, extractant from the 8th piece of theoretical plate
Recovery tower has 15 pieces of theoretical plates, reflux ratio 0.62, tower top pressure 10kPa, and 132.7 DEG C of tower top temperature, bottom temperature 200.1
DEG C, in the ethylene glycol product of overhead extraction 99.9mol%, produced quantity 5kmol/h;Extractant recovery tower tower reactor obtains extractant
Sulfolane, purity can reach 99.99mol%.1,2- butanediol product recovery rate is 99.95%, and the ethylene glycol product rate of recovery is
99.87%.
Embodiment 2
Such as Fig. 1, extractive distillation column has 62 pieces of theoretical plates, and reflux ratio 0.43, extractant is trimethylolpropane, from the 5th
The charging of block theoretical plate, flow 11kmol/h;Ethylene glycol and 1, the mixture of 2- butanediol, molar fraction 1,2- butanediol
90% and ethylene glycol 10%, it is fed from the 20th piece of theoretical plate, flow 10kmol/h.Extractive distillation column tower top pressure 6kPa, tower
120.9 DEG C of temperature of top, 199.5 DEG C of bottom temperature, overhead extraction amount is 9kmol/h, in 1, the 2- fourth of overhead extraction 99.9mol%
Glycol;Tower reactor obtains the mixture of ethylene glycol and trimethylolpropane, enters extractant recovery tower from the 6th piece of theoretical plate, extraction
Agent recovery tower has 9 pieces of theoretical plates, reflux ratio 1.21, tower top pressure 6kPa, and 121.3 DEG C of tower top temperature, bottom temperature 211.9
DEG C, overhead extraction amount is 1kmol/h, in the ethylene glycol of overhead extraction 99.9mol%;Tower reactor obtains extractant trihydroxy methyl third
Alkane, purity can reach 99.99mol%.1, the 2- butanediol rate of recovery is 99.99%, and the ethylene glycol rate of recovery is 99.00%.
Embodiment 3
Such as Fig. 1, extractive distillation column has 70 pieces of theoretical plates, reflux ratio 11.90, and extractant is the mixed of butantriol and glycerine
Object is closed, wherein glycerine accounts for 90mol%, feeds from the 5th piece of theoretical plate, flow 28kmol/h;Ethylene glycol and 1,2- butanediol
Mixture, molar fraction 1,2- butanediol 20% and ethylene glycol 80% feeds from the 43rd piece of theoretical plate, and flow is
10kmol/h.Extractive distillation column tower top pressure 1kPa, 86.9 DEG C of tower top temperature, 155.3 DEG C of bottom temperature, overhead extraction amount is
2kmol/h, in 1, the 2- butanediol of overhead extraction 99.9mol%;Tower reactor obtains the mixture of ethylene glycol, glycerine and butantriol
Enter extractant recovery tower from the 11st block of plate, extractant recovery tower has 20 pieces of theoretical plates, reflux ratio 0.31, tower top pressure
1kPa, 86.6 DEG C of tower top temperature, 175.7 DEG C of bottom temperature, overhead extraction amount is 8kmol/h, overhead extraction 99.9mol%'s
Ethylene glycol;Tower reactor obtains the mixture of extractant glycerine and butantriol, and total purity can reach 99.99mol%.1,2- butanediol
The rate of recovery is 99.90%, and the ethylene glycol rate of recovery is 99.94%.
Embodiment 4
Such as Fig. 2, extractive distillation column has 102 pieces of theoretical plates, and reflux ratio 3, extractant is undecyl alcohol, from the 2nd piece of theoretical plate
Charging, flow 21.5kmol/h;Ethylene glycol and 1, the mixture of 2- butanediol, molar fraction 1,2- butanediol 50% and second
Glycol 50% is fed, flow 10kmol/h from the 67th piece of theoretical plate.Extractive distillation column tower top pressure 10kPa, tower top temperature
130.6 DEG C, 202.9 DEG C of bottom temperature, the mixture of overhead extraction ethylene glycol and undecyl alcohol, light phase returns to extracting rectifying after split-phase
Tower, heavy phase enter purifying ethylene glycol tower from the 4th piece of theoretical plate, and purifying ethylene glycol tower has 14 pieces of theoretical plates, reflux ratio 0.22, tower
Pressure on top surface 10kPa, 130.6 DEG C of tower top temperature, 146.6 DEG C of bottom temperature, in the ethylene glycol of tower reactor extraction 99.9mol%.Extraction
Tower bottom of rectifying tower obtains the mixture of ethylene glycol and undecyl alcohol, enters extractant recovery tower, extractant recovery tower from the 40th block of plate
There are 44 pieces of theoretical plates, reflux ratio 3.62, tower top pressure 10kPa, 132.3 DEG C of tower top temperature, 207.6 DEG C of bottom temperature, tower top
Produced quantity is 5kmol/h, in 1, the 2- butanediol of overhead extraction 99.9mol%;Tower reactor obtains extractant undecyl alcohol, and purity is
99.99mol%.1, the 2- butanediol rate of recovery is 99.86%, and the ethylene glycol rate of recovery is 99.94%.
All reboiler energy consumptions of entire technique of each embodiment of table 1
Embodiment | 1 | 2 | 3 | 4 |
Energy consumption (kW) | 371.41 | 259.94 | 636.55 | 1132.91 |
Feed composition no requirement (NR) of the method for the present invention to raw material, obtained ethylene glycol and 1, the purity and recycling of 2- butanediol
Rate is all very high, although and the scheme in embodiment 4 with respect to embodiment 1-3 energy consumption it is higher, be able to achieve ethylene glycol from extracting rectifying
Column overhead re-refines to obtain ethylene glycol product (different from embodiment 1-3, ethylene glycol is obtained from extractive distillation column tower reactor after obtaining
To), relatively existing distillation and separation method cost is relatively low.
The present invention does not address place and is suitable for the prior art.
Claims (6)
1. a kind of separation of extractive distillation ethylene glycol and 1, the method for 2- butanediol, the process flow of this method are as follows: arbitrarily form
Raw material ethylene glycol and 1,2- mixture of butanediols are fed in a certain position of extractive distillation column, while extractant is in extractive distillation column
Top charging, in extractive distillation column, 1,2- butanediol from overhead extraction, ethylene glycol and extractant from tower reactor extraction after enter
Extractant recovery tower;In extractant recovery tower, ethylene glycol product from overhead extraction, extractant produced by tower reactor after through heat exchanger
It exchanges heat with raw material, then returns to extractive distillation column upper feed inlet after cooler, recycled, while in extraction essence
The upper feed inlet for evaporating tower supplements the extractant lost from two the top of the distillation column, final to realize azeotropic mixture object system's ethylene glycol and 1,
The separation of 2- butanediol;
Extractive distillation column and extractant recovery tower are negative-pressure operation, and tower top pressure is in 10kPa or less;
The extractant is for the polar organic solvent containing more than two hydroxyls or containing in the more organic solvent of polar functional group
One or more of higher boiling liquid-phase extraction agent.
2. the method according to claim 1, wherein the extractive distillation column overhead extraction molar fraction is
99.9% 1,2- butanediol product, the ethylene glycol product for being 99.9% in the overhead extraction molar fraction of extractant recovery tower,
Tower reactor produces the extractant that molar fraction is 99.99%.
3. the method according to claim 1, wherein the extractant is glycerine, butantriol, triethylene glycol, four
Glycol, trimethylolpropane, sulfolane, triethanolamine, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, diisopropanolamine (DIPA), to hydroxyl
One or more of base methyl phenyl ethers anisole or N- N-formyl morpholine N.
4. a kind of separation of extractive distillation ethylene glycol and 1, the method for 2- butanediol, the process flow of this method are as follows: arbitrarily form
Raw material ethylene glycol and 1,2- mixture of butanediols is fed in a certain position of extractive distillation column, while extractant is in extractive distillation column
Top charging, in extractive distillation column, ethylene glycol and partial extraction agent carry out split-phase after overhead extraction, into phase-splitter, gently
It is mutually more containing extractant, return to extracting rectifying column overhead;Heavy phase is more containing ethylene glycol, and into purifying ethylene glycol tower, tower reactor produces second
Glycol product, tower top are the mixture of ethylene glycol and extractant, which returns to the same phase-splitter after cooler is cooling;
1,2- butanediol and extractant enter extractant recovery tower after the extraction of extractive distillation column tower reactor, in extractant recovery tower
In, 1,2- butanediol product is from overhead extraction, and extractant exchanges heat after being produced by tower reactor through heat exchanger and raw material, then through cooling
Extractive distillation column upper feed inlet is returned after device to recycle, while being supplemented in the upper feed inlet of extractive distillation column from ethylene glycol
The extractant for the treatment of column tower reactor and extractant recovery tower overhead loss, it is final to realize azeotropic mixture object system's ethylene glycol and 1,2- butanediol
Separation;
Extractive distillation column, purifying ethylene glycol tower and extractant recovery tower are negative-pressure operation, and tower top pressure is in 10kPa or less;
The extractant is higher boiling liquid phase long-chain alcohol.
5. according to the method described in claim 4, it is characterized in that, the tower reactor extraction molar fraction of purifying ethylene glycol tower is
99.9% ethylene glycol product, 1, the 2- butanediol product for being 99.9% in the overhead extraction molar fraction of extractant recovery tower,
It is 99.99% extractant that tower reactor, which produces molar fraction,.
6. according to the method described in claim 4, it is characterized in that, the extractant is undecyl alcohol, tridecanol, tetradecyl alchohol, ten
One or more of pentol, heptadecanol.
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