CN102826956B - Method for separating methyl propionate-methanol-water system by integration of salt-effect extraction and rectification - Google Patents
Method for separating methyl propionate-methanol-water system by integration of salt-effect extraction and rectification Download PDFInfo
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- CN102826956B CN102826956B CN201210379282.1A CN201210379282A CN102826956B CN 102826956 B CN102826956 B CN 102826956B CN 201210379282 A CN201210379282 A CN 201210379282A CN 102826956 B CN102826956 B CN 102826956B
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Abstract
The invention relates to a method for separating a methyl propionate-methanol-water system by integration of salt-effect extraction and rectification, which comprises the following steps: carrying out salt-effect extraction on a methyl propionate-methanol-water system by using saturated brine as an extractant; after the extraction separation, sending the water phase on the tower bottom of an extraction tower T1 to a methanol recovery tower T3, obtaining methanol of which the mass percent is higher than 99.98% from the T3 tower top and a salt concentrated solution from the T3 tower bottom, and returning the concentrated solution to the extraction tower T1 to be mixed with the extractant for cyclic use; and sending the organic phase from the tower top of the extraction tower T1 to a methyl propionate concentrating tower T2 for further methyl propionate concentration, obtaining a mixture of methyl propionate, methanol and water from the T2 tower top, sending the mixture to the extraction tower T2 to be mixed with the raw material solution for re-extraction, and obtaining methyl propionate of which the mass percent is higher than 99.97% from the T2 tower bottom, wherein the total yield is up to more than 89%. The invention has the advantages of simple technique, high separation efficiency, low production cost, environment friendliness, basically no discharge in the whole process, and the like.
Description
Technical field
The present invention relates to chemical separation technology, particularly a kind of salt is imitated the method extracting with the integrated separated methyl propionate-methanol-water system of rectifying.
Background technology
Methyl propionate can be used as the solvent of nitrocellulose, seasonings and spices, also for nitro spray paint, among the production process of coating.At present, the synthetic of methyl propionate mainly be take the vitriol oil as catalyzer, by propionic acid and methyl alcohol direct reaction, made, and in reaction after product, contains the impurity such as free acid, alcohol and water; In the waste liquid producing, also contain a large amount of methyl propionates in methyl methacrylate production process.No matter be all to contain methyl propionate, methyl alcohol, water mixed solution in the waste liquid producing in esterification or methyl methacrylate production process.In above-mentioned mixing solutions methyl propionate easily with methyl alcohol, water formation binary, ternary azeotrope, adopt traditional rectification method to be difficult to obtain highly purified methyl propionate, and energy consumption is higher.
In traditional industry, methyl propionate refining adopts sodium bicarbonate or saturated solution of sodium carbonate washing conventionally, then with rectifying after sodium carbonate or dried over sodium sulfate; Or with saturated sodium-chloride water solution washing, then with distilling under Vanadium Pentoxide in FLAKES exists after dried over anhydrous sodium carbonate, this process is complicated, and equipment is perishable, and alkali and salt cycle process energy consumption are high, and a large amount of " three wastes " discharge, easily forms series of environmental problems.
Chinese patent CN 102584525 A disclose a kind of with ethylene glycol, 1,2-propylene glycol, glycerol, methyl-phenoxide, toluene or chlorobenzene are extraction agent, under normal pressure or reduced pressure, adopt the method for batch extracting rectified separation of methanol-methyl propionate azeotropic mixture, by controlling extractive distillation column tower top temperature and different reflux ratio, can obtain in batches the variant productions such as methyl alcohol, methyl alcohol-methyl propionate, methyl propionate and methyl propionate-extraction agent.This patent is separation of methanol-methyl propionate azeotropic system effectively, but owing to adopting periodical operation, its process cost and energy consumption are higher, unstable product quality, and adopt toluene or chlorobenzene as extraction agent, its toxicity is larger, is unfavorable for workers with long time operation.
Summary of the invention
The object of the invention is in order to overcome above deficiency, provide a kind of technique simple, separation efficiency is high, be easy to obtain highly purified methyl propionate, and process energy consumption reduces greatly, save production cost, environmental friendliness, whole process realizes the salt effect extraction of zero release and the method for the integrated separated methyl propionate-methanol-water system of rectifying substantially.
The present invention is achieved through the following technical solutions: a kind of salt effect extracts the method with the integrated separated methyl propionate-methanol-water system of rectifying, comprise the following steps: take saturated brine as extraction agent, in extraction tower T1, methyl propionate-methanol-water system is carried out to the extraction of salt effect, after extracting and separating, water at the bottom of extraction tower T1 tower is delivered to methanol distillation column T3, it is more than 99.98% methyl alcohol that methanol distillation column T3 tower top obtains massfraction, methanol distillation column T3 tower reactor obtains the concentrated solution of salt, after again this concentrated solution being turned back to extraction tower T1 and new extraction agent mixing, recycle, it is 97.57% methyl propionate that extraction tower T1 tower top organic phase obtains massfraction, this organic phase is delivered to the further concentrate methyl propionate of methyl propionate upgrading tower T2, it is 75.92% methyl propionate mixture that methyl propionate upgrading tower T2 tower top obtains massfraction, again this methyl propionate mixture is delivered to after extraction tower T1 mixes with stock liquid and re-started extraction, it is more than 99.97% methyl propionate that methyl propionate upgrading tower T2 tower reactor obtains massfraction.
Further improvement of the present invention is, comprises the following steps:
A, stock liquid enter in tower from the bottom of described extraction tower T1, with reverse contact of saturated brine from inflow extraction tower T1 inside, stock liquid top, carry out counter-current extraction, and the mass ratio of stock liquid and saturated brine is 1～5:1;
The organic phase of B, described extraction tower T1 and the water standing residence time in extraction tower T1 is 20 minutes, then organic phase and water are delivered to respectively to methyl propionate upgrading tower T2 and methanol distillation column T3, further reclaims methyl propionate and methyl alcohol;
C, described organic phase are after methyl propionate upgrading tower T2 processes, it is 75.92% methyl propionate mixture that methyl propionate upgrading tower T2 tower top obtains massfraction, again this methyl propionate mixture is delivered to after extraction tower T1 mixes with stock liquid and re-started extraction, it is more than 99.97% methyl propionate that described methyl propionate upgrading tower T2 tower reactor obtains massfraction.
D, described water are after methanol distillation column T3 processes, it is more than 99.98% methyl alcohol that described methanol distillation column T3 tower top obtains massfraction, described methanol distillation column T3 tower reactor obtains the concentrated solution of salt, then recycles after this concentrated solution is turned back to extraction tower T1 and new extraction agent mixes.
Further improvement of the present invention is: described extraction agent is KCl or LiCl or NaCl or NH
4cl or CaCl
2or MgCl
2or AlCl
3or NaNO
3or NH
4nO
3or Na
2sO
4or K
2sO
4or MgSO
4or Al
2(SO
4)
3or Na
3pO
4or NH
4h
2pO
4or NaH
2pO
4or K
2hPO
4or (NH
4)
2hPO
4or Na
2c
2o
4or K
2c
2o
4or CaC
2o
4or Na
2cO
3or K
2cO
3or NaHSO
4or KHSO
4or KF or any two kinds or any two or more mixture.
Further improvement of the present invention is: the mass ratio of the stock liquid described in steps A and described saturated brine is 1:1.
Further improvement of the present invention is: organic phase described in step C is when methyl propionate upgrading tower T2 processes, and described methyl propionate upgrading tower T2 tower top temperature is 64.1～65.3 ℃, and tower reactor temperature is 79.7～80.6 ℃, and reflux ratio is 3～5.
Further improvement of the present invention is: water described in step D is when methanol distillation column T3 processes, and described methanol distillation column T3 tower top temperature is 64.5～65.3 ℃, and tower reactor temperature is 98.3～100.8 ℃, and reflux ratio is 1～3.
Further improvement of the present invention is: described extraction agent is NH
4h
2pO
4or Al
2(SO
4)
3or NaHSO
4or any two kinds or any two or more mixture.
The present invention compared with prior art has the following advantages: the effective separated methyl propionate-methanol-water system of energy, and separated rear methyl propionate massfraction reaches more than 99.97%, and total recovery reaches more than 89%; Methanol quality mark reaches more than 99.98%, and salts solution recycles after concentrated.The present invention not only technique is simple, and separation efficiency is high, is easy to obtain highly purified methyl propionate, and process energy consumption reduces greatly, save production cost, and environmental friendliness, whole process realizes zero release substantially.
accompanying drawing explanation:
Fig. 1 is process flow sheet of the present invention;
Number in the figure: 1. saturated brine, 2. stock liquid, 3. organic phase, 4. water, 5. 75.95% methyl propionate mixture, 6. methyl propionate, 7. methyl alcohol, 8. salt concentrated solution, T1-extraction tower T1, T2-methyl propionate upgrading tower T2, T3-methanol distillation column T3.
embodiment:
in order to deepen the understanding of the present invention, below in conjunction with embodiment and accompanying drawing, the invention will be further described, and this embodiment only, for explaining the present invention, does not form limiting the scope of the present invention.
As Fig. 1 shows the embodiment of the extraction of a kind of salt of the present invention effect and the method for the integrated separated methyl propionate-methanol-water system of rectifying, comprise the following steps: 1. the saturated brine of take is extraction agent, in extraction tower T1, methyl propionate-methanol-water system is carried out to the extraction of salt effect, after extracting and separating, 4. water at the bottom of extraction tower T1 tower is delivered to methanol distillation column T3, T3 tower top obtain massfraction be more than 99.98% methyl alcohol 7., the concentrated solution that T3 tower reactor obtains salt 8., after more 8. this concentrated solution being turned back to extraction tower T1 and 1. new extraction agent mixing, recycle, 3. extraction tower T1 tower top organic phase obtains massfraction is 97.57% methyl propionate, 3. this organic phase is delivered to the further concentrate methyl propionate of methyl propionate upgrading tower T2, T2 tower top obtain massfraction be 75.92% methyl propionate mixture 5., again 5. this mixture is delivered to after 2. extraction tower T1 mixes with stock liquid and re-started extraction, T2 tower reactor obtain massfraction be more than 99.97% methyl propionate 6..
Further optimization step of the present invention comprises:
2. A, stock liquid enter in tower from extraction tower T1 bottom, and from 1. reverse contact of the stock liquid saturated brine that 2. top flows into extraction tower T1 inside, carry out counter-current extraction, and 2. stock liquid is 1～5:1 with described saturated brine mass ratio 1.;
B, extraction tower T1 organic phase 3. with water 4. the standing residence time in extraction tower T1 be 20 minutes, then 4. 3. this organic phase delivered to respectively to methyl propionate upgrading tower T2 and methanol distillation column T3 with water, further reclaim methyl propionate and methyl alcohol;
C, organic phase are 3. after methyl propionate upgrading tower T2 processes, T2 tower top obtain massfraction be 75.92% methyl propionate mixture 5., again 5. this mixture is delivered to after 2. extraction tower T1 mixes with stock liquid and is re-started extraction, T2 tower reactor obtain massfraction be more than 99.97% methyl propionate 6.;
D, described water are 4. after methanol distillation column T3 processes, described T3 tower top obtain massfraction be more than 99.98% methyl alcohol 7., 8. the concentrated solution that described T3 tower reactor obtains salt, then recycles after 8. this concentrated solution is turned back to extraction tower T1 and 1. new extraction agent mixes.
Extraction agent described in the present invention is KCl or LiCl or NaCl or NH
4cl or CaCl
2or MgCl
2or AlCl
3or NaNO
3or NH
4nO
3or Na
2sO
4or K
2sO
4or MgSO
4or Al
2(SO
4)
3or Na
3pO
4or NH
4h
2pO
4or NaH
2pO
4or K
2hPO
4or (NH
4)
2hPO
4or Na
2c
2o
4or K
2c
2o
4or CaC
2o
4or Na
2cO
3or K
2cO
3or NaHSO
4or KHSO
4or KF, as visible in table 1, salt can reduce the mutual solubility of system, and the massfraction of water and methyl alcohol in organic phase is lowered, and reaches the object of dehydration and dealcoholysis, reclaims the factors such as difficulty or ease, preferred NH in conjunction with salt
4h
2pO
4or Al
2(SO
4)
3or NaHSO
4for optimum extractant.
The impact of salt on system mutual solubility at 25 ℃, table 1
Note: I, II, III represent respectively water, methyl alcohol, methyl propionate.
The present invention adopts technique shown in Fig. 1 and selected salt, the effective separated methyl propionate-methanol-water system of energy, and separated rear methyl propionate massfraction reaches more than 99.97%, and total recovery reaches more than 89%; Methanol quality mark reaches more than 99.98%, and salts solution recycles after concentrated.
2. stock liquid described in preferred steps A of the present invention is 1:1 with described saturated brine mass ratio 1., in step C, organic phase is 3. when methyl propionate upgrading tower T2 processes, T2 tower top temperature is 64.1～65.3 ℃, tower reactor temperature is 79.7～80.6 ℃, reflux ratio is 3～5, and in step D, water is 4. when methanol distillation column T3 processes, and T3 tower top temperature is 64.5～65.3 ℃, tower reactor temperature is 98.3～100.8 ℃, and reflux ratio is 1～3.
Embodiment mono-: a kind of salt effect extracts the method with the integrated separated methyl propionate-Methanol-water system of rectifying, and its concrete separation method comprises the following steps:
Under A, normal temperature, stock liquid is (containing methyl propionate 59.45%, methyl alcohol 25.35%, water 15.20%, is massfraction) and NH 2.
4h
2pO
4saturated brine mass rate is 1. 20 kg/h, and 2. stock liquid enters from extraction tower T1 bottom, with the NH flowing into from extraction tower T1 top
4h
2pO
4saturated brine is reverse contact extracting and separating 1.;
4. 3. B, organic phase all reach balance with water in every grade of extractor of multiple stage continuous adverse current extraction tower, through 4 stage countercurrent extractions, 3. 4. the standing residence time in extraction tower T1 is 20 minutes to organic phase with water, again 4. 3. organic phase delivered to respectively to methyl propionate upgrading tower T2 and methanol distillation column T3 with water, further reclaim methyl propionate and methyl alcohol;
C, 3. organic phase is sent into methyl propionate recovery tower T2, control inlet amount is 12.13kg/h, tower top load is 1.5kg/h, control tower top and tower reactor temperature and be respectively 65.3 ℃ and 79.7 ℃, reflux ratio is 3, number of theoretical plate is 30, organic phase feed entrance point is 3. at the 15th column plate, T2 tower top obtain massfraction be 75.92% methyl propionate mixture 5., again 5. this mixture is delivered to after 2. extraction tower T1 mixes with stock liquid and is re-started extraction, T2 tower reactor obtain massfraction be more than 99.97% methyl propionate 6.;
D, more 4. water is sent into methanol distillation column T3 by impeller pump, control inlet amount is 27.87kg/h, tower top load is 19.5 kg/h, control tower top, tower reactor temperature are respectively 64.5 ℃, 98.3 ℃, reflux ratio 1, number of theoretical plate 44, water feed entrance point is 4. at the 25th block of column plate, 7. T3 tower top obtains more than 99.98% methyl alcohol of massfraction, and 8. the concentrated solution that T3 tower reactor obtains salt, then recycles after 8. this concentrated solution is turned back to extraction tower T1 and 1. new extraction agent mixes.
In aforesaid method, the operating parameters of each tower and separating resulting are as shown in table 2 and table 3:
Table 2 tower operating parameters
Composition and the content (wt%) of each stream thigh in table 3 sepn process
Embodiment bis-: a kind of salt effect extracts the method with the integrated separated methyl propionate-Methanol-water system of rectifying, and its concrete separation method comprises the following steps:
Under A, normal temperature, stock liquid is (containing methyl propionate 59.45%, methyl alcohol 25.35%, water 15.20%, is massfraction) and Al 2.
2(SO
4)
3saturated brine mass rate is 1. 20 kg/h, and 2. stock liquid enters from extraction tower T1 bottom, with the Al flowing into from extraction tower T1 top
2(SO
4)
3saturated brine is reverse contact extracting and separating 1.;
4. 3. B, organic phase all reach balance with water in every grade of extractor of multiple stage continuous adverse current extraction tower, through 4 stage countercurrent extractions, 3. 4. the standing residence time in extraction tower T1 is 20 minutes to organic phase with water, again 4. 3. organic phase delivered to respectively to methyl propionate upgrading tower T2 and methanol distillation column T3 with water, further reclaim methyl propionate and methyl alcohol;
C, 3. organic phase is sent into methyl propionate recovery tower T2, control inlet amount is 12.13kg/h, tower top load is 1.5kg/h, control tower top and tower reactor temperature and be respectively 64.8 ℃ and 80.2 ℃, reflux ratio is 3, number of theoretical plate is 30, organic phase feed entrance point is 3. at the 15th column plate, T2 tower top obtain massfraction be 76.83% methyl propionate mixture 5., again 5. this mixture is delivered to after 2. extraction tower T1 mixes with stock liquid and is re-started extraction, T2 tower reactor obtain massfraction be more than 99.93% methyl propionate 6.;
D, more 4. water is sent into methanol distillation column T3 by impeller pump, control inlet amount is 27.87kg/h, tower top load is 19.5 kg/h, control tower top, tower reactor temperature are respectively 64.9 ℃, 98.7 ℃, reflux ratio 1, number of theoretical plate 44, water feed entrance point is 4. at the 25th block of column plate, 7. T3 tower top obtains more than 99.86% methyl alcohol of massfraction, and 8. the concentrated solution that T3 tower reactor obtains salt, then recycles after 8. this concentrated solution is turned back to extraction tower T1 and 1. new extraction agent mixes.
Embodiment tri-: a kind of salt effect extracts the method with the integrated separated methyl propionate-Methanol-water system of rectifying, and its concrete separation method comprises the following steps:
Under A, normal temperature, stock liquid is (containing methyl propionate 59.45%, methyl alcohol 25.35%, water 15.20%, is massfraction) and NaHSO 2.
4saturated brine mass rate is 1. 20 kg/h, and 2. stock liquid enters from extraction tower T1 bottom, with the NaHSO flowing into from extraction tower T1 top
4saturated brine is reverse contact extracting and separating 1.;
4. 3. B, organic phase all reach balance with water in every grade of extractor of multiple stage continuous adverse current extraction tower, through 4 stage countercurrent extractions, 3. 4. the standing residence time in extraction tower T1 is 20 minutes to organic phase with water, again 4. 3. organic phase delivered to respectively to methyl propionate upgrading tower T2 and methanol distillation column T3 with water, further reclaim methyl propionate and methyl alcohol.
C, 3. organic phase is sent into methyl propionate recovery tower T2, control inlet amount is 12.13kg/h, tower top load is 1.5kg/h, control tower top and tower reactor temperature and be respectively 65.1 ℃ and 79.8.2 ℃, reflux ratio is 3, and number of theoretical plate is 30, and organic phase feed entrance point is 3. at the 15th column plate, T2 tower top obtain massfraction be 76.83% methyl propionate mixture 5., more 5. this mixture is delivered to after 2. extraction tower T1 mixes with stock liquid and is re-started extraction; T2 tower reactor obtain massfraction be more than 99.87% methyl propionate 6..
D, more 4. water is sent into methanol distillation column T3 by impeller pump, control inlet amount is 27.87kg/h, tower top load is 19.5 kg/h, control tower top, tower reactor temperature are respectively 65.1 ℃, 99.6 ℃, reflux ratio 1, number of theoretical plate 44, water feed entrance point is 4. at the 25th block of column plate, 7. T3 tower top obtains more than 99.91% methyl alcohol of massfraction, and 8. the concentrated solution that T3 tower reactor obtains salt, then recycles after 8. this concentrated solution is turned back to extraction tower T1 and 1. new extraction agent mixes.
The present invention passes through technique and selected salt as shown in Figure 1, salt can carry out two or more arbitrary combination, meet actual treatment requirement, or corresponding conversion is adjusted or implemented to relevant parameters, also can amplify accordingly in proportion according to the size of stock liquid treatment capacity the effective separated methyl propionate-methanol-water system of energy, after separated, methyl propionate massfraction reaches more than 99.97%, and total recovery reaches more than 89%; Methanol quality mark reaches more than 99.98%, and salts solution recycles after concentrated.The present invention not only technique is simple, and separation efficiency is high, is easy to obtain highly purified methyl propionate, and process energy consumption reduces greatly, save production cost, and environmental friendliness, whole process realizes zero release substantially.
Claims (4)
1. salt is imitated the method extracting with the integrated separated methyl propionate-methanol-water system of rectifying, it is characterized in that: comprise following concrete steps:
A, stock liquid enter in tower from extraction tower (T1) bottom, with reverse contact of saturated brine from stock liquid top inflow extraction tower (T1) inside, carry out counter-current extraction, and the mass ratio of stock liquid and described saturated brine is 1～5:1;
B, extraction tower (T1) organic phase and the standing residence time of water in extraction tower (T1) are 20 minutes, then this organic phase and water are delivered to respectively to methyl propionate upgrading tower (T2) and methanol distillation column (T3), further reclaim methyl propionate and methyl alcohol;
C, organic phase are after methyl propionate upgrading tower (T2) is processed, it is 75.92% methyl propionate mixture that methyl propionate upgrading tower (T2) tower top obtains massfraction, this mixture is delivered to after extraction tower (T1) mixes with stock liquid again and re-started extraction, it is more than 99.97% methyl propionate that described methyl propionate upgrading tower (T2) tower reactor obtains massfraction;
D, described water are after methanol distillation column (T3) is processed, it is more than 99.98% methyl alcohol that described methanol distillation column (T3) tower top obtains massfraction, described methanol distillation column (T3) tower reactor obtains the concentrated solution of salt, then recycles after this concentrated solution is turned back to extraction tower (T1) and new extraction agent mixes;
Described salt is Al
2(SO
4)
3, NH
4h
2pO
4or NaHSO
4.
2. salt is imitated the method extracting with the integrated separated methyl propionate-methanol-water system of rectifying according to claim 1, it is characterized in that: the mass ratio of the stock liquid described in steps A and described saturated brine is 1:1.
3. salt is imitated the method extracting with the integrated separated methyl propionate-methanol-water system of rectifying according to claim 1, it is characterized in that: when organic phase described in step C is processed through methyl propionate upgrading tower (T2), described methyl propionate upgrading tower (T2) tower top temperature is 64.1～65.3 ℃, tower reactor temperature is 79.7～80.6 ℃, and reflux ratio is 3～5.
4. salt is imitated the method extracting with the integrated separated methyl propionate-methanol-water system of rectifying according to claim 1, it is characterized in that: when water described in step D is processed through methanol distillation column (T3), described methanol distillation column (T3) tower top temperature is 64.5～65.3 ℃, tower reactor temperature is 98.3～100.8 ℃, and reflux ratio is 1～3.
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| CN105218293B (en) * | 2015-09-01 | 2017-07-14 | 烟台大学 | A kind of method and device of separation of methylbenzene and alcohol mixture |
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Inventor after: Tian Shu Inventor after: Cao Yufeng Inventor after: Shi Yujun Inventor after: Jing Xiaohui Inventor after: Jiu Qinhua Inventor before: Cao Yufeng Inventor before: Shi Yujun Inventor before: Jing Xiaohui Inventor before: Jiu Qinhua |
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Free format text: CORRECT: INVENTOR; FROM: CAO YUFENG SHI YUJUN JING XIAOHUI MIAO QINHUA TO: TIAN SHU CAO YUFENG SHI YUJUN JING XIAOHUI MIAO QINHUA |
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Granted publication date: 20140910 Termination date: 20151009 |
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