CN101260026B - Purification method of preparing 1,2-propylene glycol by glycerine hydrogenation - Google Patents
Purification method of preparing 1,2-propylene glycol by glycerine hydrogenation Download PDFInfo
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- CN101260026B CN101260026B CN2008100360868A CN200810036086A CN101260026B CN 101260026 B CN101260026 B CN 101260026B CN 2008100360868 A CN2008100360868 A CN 2008100360868A CN 200810036086 A CN200810036086 A CN 200810036086A CN 101260026 B CN101260026 B CN 101260026B
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Abstract
The invention relates to a purification method for products of 1, 2-propylene glycol prepared through glycerol hydrogenation. A hydrogenation product contains water, a small amount of monohydric alcohol (methanol, ethanol and propanol), hydroxyacetone, glycol, unconverted glycerol and other compounds; after five steps of vacuum rectification, namely dehydration, light-removing component, heavy-removing component, glycol removal and product refining, are carried out to the reaction products of the composition, the purity of obtained 1, 2-propylene glycol products is greater than 99.9 percent, and the separation yield coefficient of the 1, 2-propylene glycol products is greater than 95 percent; unconverted glycerol and materials containing glycol are sent to a recycling treatment system; light components containing hydroxyacetone and other substances are returned to a reactor as raw material of hydrogenation.
Description
Technical field
The present invention relates to 1, the separation and refining method of 2-propylene glycol, specifically with 1 of glycerin catalytic hydrogenation preparing, the reaction product of 2-propylene glycol is that raw material is through rectification and purification production high purity 1, the method for 2-propylene glycol.
Background technology
1, the 2-propylene glycol is an important chemical material, is mainly used in the manufacturing unsaturated polyester, secondly also is used as softening agent, foodstuff additive, tobacco moistening agent and the antifreezing agent etc. of resin.Industry at present makes 1, the main method of 2-propylene glycol is with propylene oxide direct hydration under 150～160 ℃, residence time 30min, 1.2～1.4MPa pressure, generation contains 1, the aqueous solution of 2-propylene glycol about 16%, main side reaction is the glycol that generates dipropylene glycol (DIG) and tripropylene glycol (TPG) and a spot of more macromolecule, and reaction product obtains product through evaporation and rectifying.Though adopt propylene oxide and the direct uncatalyzed reaction hydration of water technology, avoid defective, theoretical atom utilization height with the sulfuric acid catalysis hydrolysis process, but side reaction is more, and separation process is also complicated, moreover the propylene oxide reaction transformation efficiency is low, the separating energy consumption height, the raw material propylene oxide costs an arm and a leg.Glycerine is more cheap relatively, by-product glycerol of biological diesel oil especially, and price is lower.Therefore, utilize glycerine hydrogenation to produce 1, the 2-propylene glycol not only has better economic, and produces 1 to enlarging, and the raw material sources of 2-propylene glycol and glycerine comprehensive utilization are all significant.
The present invention is to be raw material with the glycerine hydrogenation reaction product, contains 1 in this reaction product, 2-propylene glycol, water, methyl alcohol, ethanol, propyl alcohol, pyruvic alcohol, ethylene glycol and unconverted raw material glycerine etc.Because glycerine carries out hydrogenation reaction under higher temperature, easily dewater, side reaction such as cracking, so impurity is more in the reaction product.At the complicated ingredient of this reaction product, adopt which kind of separation method, seem particularly important.The objective of the invention is, guaranteeing 1, the purity of 2-propylene glycol is determined the rationally economic process for separating and purifying flow process and the operational condition of optimization greater than under 99.9% the condition.
The present invention after the reaction product of shortening is carried out detail analysis and experimental study, has determined five tower rectifying separation technical process to glycerine.The present invention had both considered rationality of technological process and economy, had optimized the operational condition that is complementary with it again, and product purity is reached more than 99.9%, and the product separation yield is greater than 95%, and refuse has almost reached zero release, was the environmental protection technical process.
Summary of the invention
The objective of the invention is to separate 1 of purification glycerine hydrogenation preparation, 2-propylene glycol.Purification process is to become 15～85% water, 0.1～2% methyl alcohol, 0.1～2% ethanol, 0.1～2% propyl alcohol, 0.2～10% pyruvic alcohol, 0.5～5% ethylene glycol, 10～82%1 with quality group, the glycerine hydrogenation reaction product of 2-propylene glycol and 0.5～50% glycerine is the rectifying raw material, through dewatering, take off light constituent, take off heavy constituent, taking off ethylene glycol and five rectification under vacuum steps of product purification, obtain purity greater than 99.9% 1,2-propylene glycol product.Wherein, the mass concentration of the raw material glycerine of glycerine hydrogenation reaction is 20～100% the aqueous solution, and glycerine comes from industry glycerol or by-product glycerol of biological diesel oil.
Glycerin catalytic hydrogenation system 1 of the present invention, the separating technology of 2-propylene glycol reaction product is based upon on the basis of experimental, especially according to the character of the amount of each component in the product, compound and quality and definite technical process and operational condition.Specifically be to adopt dehydration, take off light constituent, take off heavy constituent, take off ethylene glycol and the product five tower rectification process of purifying and reach the present invention's purpose.Because five tower functions are different, its operational condition has bigger difference.The operational condition of dehydration tower is: 100～160 ℃ of column bottom temperatures, vacuum tightness 50～100kPa, reflux ratio 0～5; The operational condition of cut light tower is: 100～190 ℃ of column bottom temperatures, vacuum tightness 0.1～80kPa, reflux ratio 0～10; The operational condition of taking off heavies column is: 100～200 ℃ of column bottom temperatures, vacuum tightness 0.01～50kPa, reflux ratio 1～10; The operational condition of taking off the ethylene glycol tower is: 100～190 ℃ of column bottom temperatures, vacuum tightness 0.01～50kPa, reflux ratio 1～12; The operational condition of product purification tower is: 100～190 ℃ of column bottom temperatures, vacuum tightness 0.01～50kPa, reflux ratio 0.5～20.
Separate from the glycerine hydrogenation product and purify 1, the concrete operations flow process of 2-propylene glycol is as follows:
A, the glycerine hydrogenation reaction solution is removed water and a small amount of monohydroxy-alcohol (methyl alcohol, ethanol and propyl alcohol) through being pumped into dehydration tower.Dehydration tower top material part after condensation refluxes, and another part is made the thinner of hydrogenating materials glycerine or as waste water decontaminated water treatment system.
B. dehydration tower bottoms material enters cut light tower, removes the light constituent of less water and hydroxy acetone, and a part is back to cut light tower in the cat head material, and another part light constituent is made the hydrogenation reaction raw material.
C. cut light tower bottoms material enters and takes off heavies column and remove glycerine and high boiling component, and the cat head material partly returns and takes off heavies column, and another part is as the charging of taking off the ethylene glycol tower, and the bottoms material removes the glycerine recovery and processing system.
D. take off ethylene glycol column overhead material and partly reflux, another part enters the product purification tower, and the glycol recovery treatment system is gone in ethylene glycol and a small amount of heavy constituent at the bottom of the tower.
E. product purification tower cat head obtains highly purifiedly 1, and 2-propylene glycol, the material that contains ethylene glycol and product at the bottom of the tower return and take off the ethylene glycol tower and do charging.
Each rectifying tower in the aforesaid operations comprises dehydration tower, cut light tower, takes off heavies column, takes off ethylene glycol tower or 1, and the structure type of 2-propylene glycol purification tower is selected from a kind of in packing tower, sieve-tray tower, valve tray column, bubble-plate column or the membrane distillation tower respectively.
In the operation of dehydration tower, mainly be to tell most of water and lower boiling alcohols, vacuum tightness is that 100～75kPa gets final product, and vacuum tightness is too high, and condensate temperature requires lower, and normal recirculated water can not use, and causes the energy consumption height.Vacuum tightness is too low, and the water in the reaction product is difficult to take off and meets the demands; Reflux ratio is 1～2 better, if there is not backflow, easily product is taken in the light constituent that cat head contains certain water, and reflux ratio is the energy consumption height too greatly then.
Cut light tower mainly removes less water, low-boiling point alcohol and pyruvic alcohol, and this part light constituent is the key that influences product purity.Reflux ratio is 2, and vacuum tightness is that 5～15kPa is better.Reflux ratio is too big, and the energy consumption height is too little, will carry more products secretly in light constituent.Although this part light constituent returns hydrogenation, can increase the load of hydrogenation reaction if product content is too high, also increase energy consumption.Vacuum tightness can not be too high, faces the problem of condensation equally.
The major function of taking off heavies column is to remove glycerine and heavy constituent, and the top goes out ethylene glycol and product.Therefore vacuum tightness is higher relatively, and reflux ratio is unsuitable excessive.If vacuum tightness is lower, product and ethylene glycol all be extracted out, necessary rising tower still temperature, so not only energy consumption increases, and might increase the generation of dehydrating glycerin reaction.The excessive energy consumption of reflux ratio is big.So vacuum tightness is 1.5～5kPa, reflux ratio is 1.5～2 better.
The operational condition of taking off ethylene glycol tower and product purification tower is more or less the same.The former does not contain product at the bottom of guaranteeing tower, the latter is guaranteeing that cat head does not contain under the situation of ethylene glycol, and gas clean-up reduces tower still material temperature as far as possible, cuts down the consumption of energy and reduces the polycondensation that ethylene glycol may exist.
Through above-mentioned separation process and operational condition Combinatorial Optimization, product purity can reach more than 99.9%, and product yield the water discharging that contains monohydroxy-alcohol of minute quantity is only arranged, and chemical oxygen demand is very low greater than 95%.
Description of drawings
Accompanying drawing 1 is a glycerine hydrogenation system 1, the separation and purification schema of 2-propanediol product.
Drawing reference numeral is represented: 1-glycerine hydrogenation reaction solution, 2-dehydration tower, 3-waste water, the 4-cut light tower, 5-light constituent receiving tank, the 6-light constituent, 7-takes off heavies column, 8-bottoms material, 9-takes off the ethylene glycol tower, ethylene glycol and a small amount of heavy constituent at the bottom of the 10-tower, 11-product purification tower, 12-1,2-propylene glycol product.
Embodiment
To be illustrated with specific embodiment below, but content of the present invention is not limited to embodiment.
Embodiment 1
With 80% (quality) aqueous glycerin solution is raw material, carries out catalytic hydrogenation reaction on pilot plant, and the reaction product composition sees Table 1.Analyze and use the gas-chromatography capillary separation column, fid detector, mark in propyl carbinol is done.
The quality of table 1 glycerine hydrogenation reaction product is formed (%)
| Water | Methyl alcohol | Ethanol | Propyl alcohol | Pyruvic alcohol | 1, the 2-propylene glycol | Ethylene glycol | Glycerine |
| 36.31? | 0.26? | 0.23? | 0.11? | 0.86? | 51.33? | 2.30? | 9.60? |
According to five tower flow process separating technologies of the present invention, at first will send into dehydration tower [2] with feedstock pump and deviate from water and monohydroxy-alcohol from the reaction solution [1] of hydrogenator 20kg/h.In 130 ℃ of column bottom temperatures, vacuum tightness is under the condition of 75kPa and reflux ratio 1, and cat head discharging 6.5kg/h removes condenser, and a part is as refluxing, and a part of water (about 4.0kg/h) is as the thinner of hydrogenating materials glycerine.The waste water 3 decontaminated water treatment plants of containing a small amount of lower boiling monohydroxy-alcohol.Its composition sees Table 2.The bottoms material is sent to cut light tower [4].
The quality of table 2 dehydration tower top material is formed (%)
| Water | Methyl alcohol | Ethanol | Propyl alcohol | Pyruvic alcohol | 1, the 2-propylene glycol | Ethylene glycol |
| 98.60? | 0.54? | 0.47? | 0.13? | 0.01? | 0.08? | 0.01? |
Cut light tower [4] mainly removes less water, lower boiling monohydroxy-alcohol and pyruvic alcohol, but wherein be entrained with a large amount of 1, the 2-propylene glycol, this part material goes condenser condenses on the cut light tower top through pipeline, flow is 2.8kg/h.Wherein a part is as refluxing, and another part enters light constituent receiving tank [5].A part is returned cut light tower [4] and is done charging in the receiving tank [5], and another part [6] returns hydrogenator and makes raw material.Its composition sees Table 3.The operational condition of cut light tower [4] is: 148 ℃ of column bottom temperatures, vacuum tightness 10kPa, reflux ratio 3.The bottoms material is sent to and takes off heavies column [7].
Table 3 cut light tower top material quality is formed (%)
| Water | Methyl alcohol | Ethanol | Pyruvic alcohol | 1, the 2-propylene glycol | Ethylene glycol |
| 26.35? | 0.05? | 0.06? | 2.12? | 70.45? | 0.20? |
In taking off heavies column [7], column bottom temperature is controlled at 147 ℃, and vacuum tightness is 1.5kPa, and reflux ratio is 2.5.Top material at this tower mainly contains 1,2-propylene glycol, ethylene glycol and a spot of glycerine, enter condenser condenses after, a part of material is as backflow, most of material (12.2kg/h) is as the charging of taking off ethylene glycol tower [9], forms to see Table 4.The bottoms material [8] that contains 95% glycerine is sent to the glycerine recovery system.
Table 4 takes off heavies column top material quality and forms (%)
| Water | Pyruvic alcohol | 1, the 2-propylene glycol | Ethylene glycol | Glycerine |
| 0.003? | 0.05? | 94.10? | 5.20? | 0.53? |
In taking off ethylene glycol tower [9], column bottom temperature is controlled at 144 ℃, and vacuum tightness is 3kPa, and reflux ratio is 3.The cat head material goes condenser condenses, and flow is 11kg/h, and a part refluxes, and another part is sent to product rectifying tower [11], and its composition sees Table 5.The bottoms material [10] that contains 98% ethylene glycol goes to the glycol recovery system.
Table 5 takes off ethylene glycol top of tower quality of material and forms (%)
| Water | Pyruvic alcohol | 1, the 2-propylene glycol | Ethylene glycol |
| 0.005? | 0.05? | 98.69? | 1.20? |
In product rectifying tower [11], column bottom temperature is controlled at 144 ℃, and vacuum tightness is 3kPa, and reflux ratio is 5.The cat head material goes condenser condenses, and part goes out 1 outside doing to reflux, 2-propylene glycol product 9.75kg/h, and composition sees Table 6.The bottoms material that contains product and ethylene glycol returns and takes off ethylene glycol tower [9] and do charging.
Table 6 product purification tower top material quality is formed (%)
| Water | Pyruvic alcohol | 1, the 2-propylene glycol | Ethylene glycol |
| 0.006? | 0.05? | 99.92? | 0.02? |
By above-mentioned separating technology, 1,2-propylene glycol purity can reach 99.9%, and product yield reaches 95%.
Embodiment 2
With 70% (quality) biological glycerol is raw material, uses water as thinner, and through catalytic hydrogenation reaction, the reaction product composition sees Table 7.Analyze and use the gas-chromatography capillary separation column, fid detector, mark in propyl carbinol is done.
The quality of table 7 biological glycerol hydrogenation reaction product is formed (%)
| Water | Methyl alcohol | Ethanol | Propyl alcohol | Pyruvic alcohol | 1, the 2-propylene glycol | Ethylene glycol | Glycerine |
| 42.56? | 0.26? | 0.54? | 0.28? | 1.03? | 40.28? | 1.70? | 13.30? |
Other condition is undertaken by embodiment 1 method.Separating purifies the results are shown in Table 8.
(cat head material quality group becomes table 8 biological glycerol hydrogenation reaction product purification result, %)
| Rectifying tower | Water | Methyl alcohol | Ethanol | Propyl alcohol | Pyruvic alcohol | 1, the 2-propylene glycol | Ethylene glycol | Glycerine |
| Dehydration tower | 99.02? | 0.41? | 0.33? | 0.12? | 0.01? | 0.07? | 0.01? | 0? |
| Cut light tower | 25.98? | 0.07? | 0.05? | 0.01? | 2.35? | 72.01? | 0.24? | 0.05? |
| Take off heavies column | 0.002? | 0? | 0? | 0? | 0.04? | 94.38? | 4.93? | 0.46? |
| Take off the ethylene glycol tower | 0.005? | 0? | 0? | 0? | 0.03? | 98.54? | 1.18? | 0? |
| The product rectifying tower | 0.008? | 0? | 0? | 0? | 0.06? | 99.90? | 0.03? | 0? |
Claims (2)
1. glycerine hydrogenation system 1, the method of purification of 2-propanediol product, it is characterized in that this method of purification is is the rectifying raw material with the glycerine hydrogenation reaction product, its quality group becomes: 15～85% water, 0.1～2% methyl alcohol, 0.1～2% ethanol, 0.1～2% propyl alcohol, 0.2～10% pyruvic alcohol, 0.5～5% ethylene glycol, 10～82%1,2-propylene glycol and 0.5～50% glycerine, through dewatering, take off light constituent, take off heavy constituent, taking off ethylene glycol and five rectification under vacuum steps of product purification, obtain purity greater than 1 of 99.9 quality %, 2-propylene glycol product; Wherein, the raw material qualities of glycerin concentration of glycerine hydrogenation reaction is 20～100% the aqueous solution, and glycerine comes from industry glycerol or by-product glycerol of biological diesel oil;
The rectification and purification process of glycerine hydrogenation reaction product comprises the steps:
A. the water in the hydrogenation reaction product [1] and methyl alcohol, ethanol and propyl alcohol be at first in dehydration tower [2] removed overhead, and a part refluxes, and another part is made the thinner of hydrogenating materials glycerine or as waste water decontaminated water treatment system;
B. dehydration tower [2] bottoms material enters cut light tower [4], removes the light constituent of less water and hydroxy acetone, and a part is back to cut light tower [4] in the cat head material, and another part light constituent [6] is made the hydrogenation reaction raw material;
C. cut light tower [4] bottoms material enters and takes off heavies column [7], and the cat head material partly returns and takes off heavies column [7], and another part is as the charging of taking off ethylene glycol tower [9], and bottoms material [8] removes the glycerine recovery and processing system;
D. take off ethylene glycol tower [9] cat head material and partly reflux, another part enters product purification tower [11], and the glycol recovery treatment system is gone in ethylene glycol and a small amount of heavy constituent [10] at the bottom of the tower;
E. product purification tower [11] cat head obtains highly purifiedly 1, and 2-propylene glycol [12], the material that contains ethylene glycol and product at the bottom of the tower return and take off ethylene glycol tower [9] and do charging;
The operational condition of dehydration tower [2] is: 100～160 ℃ of column bottom temperatures, vacuum tightness 50～100kPa, reflux ratio 0～5; The operational condition of cut light tower [4] is: 100～190 ℃ of column bottom temperatures, vacuum tightness 0.1～80kPa, reflux ratio 0～10; The operational condition of taking off heavies column [7] is: 100～200 ℃ of column bottom temperatures, vacuum tightness 0.01～50kPa, reflux ratio 1～10; The operational condition of taking off ethylene glycol tower [9] is: 100～190 ℃ of column bottom temperatures, vacuum tightness 0.01～50kPa, reflux ratio 1～12; The operational condition of product purification tower [11] is: 100～190 ℃ of column bottom temperatures, vacuum tightness 0.01～50kPa, reflux ratio 0.5～20.
2. according to the described method of claim 1, it is characterized in that dehydration tower [2], cut light tower [4], take off heavies column [7], take off ethylene glycol tower [9] or 1, the structure type of 2-propylene glycol purification tower [11] is selected from a kind of in packing tower, sieve-tray tower, valve tray column, bubble-plate column or the membrane distillation tower respectively.
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| CN2008100360868A CN101260026B (en) | 2008-04-16 | 2008-04-16 | Purification method of preparing 1,2-propylene glycol by glycerine hydrogenation |
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| CN2008100360868A CN101260026B (en) | 2008-04-16 | 2008-04-16 | Purification method of preparing 1,2-propylene glycol by glycerine hydrogenation |
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| CN101260026B true CN101260026B (en) | 2011-03-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| BRPI0902818A2 (en) * | 2009-03-09 | 2010-11-23 | Petroleo Brasileiro Sa | Propylene glycol production process from biodiesel glycerine |
| CN105777492A (en) * | 2016-04-19 | 2016-07-20 | 中石化上海工程有限公司 | Method for rectifying and concentrating 1,3-propylene glycol |
| CN105732321A (en) * | 2016-04-19 | 2016-07-06 | 中石化上海工程有限公司 | Rectification enriching device for 1, 3-propylene glycol |
| CN112723991A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | System and method for preparing 1, 2-propylene glycol from glycerol |
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