CN1050868A - Use the method for tubular reactor produced propylene glycol - Google Patents
Use the method for tubular reactor produced propylene glycol Download PDFInfo
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- CN1050868A CN1050868A CN 90109529 CN90109529A CN1050868A CN 1050868 A CN1050868 A CN 1050868A CN 90109529 CN90109529 CN 90109529 CN 90109529 A CN90109529 A CN 90109529A CN 1050868 A CN1050868 A CN 1050868A
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Abstract
Prepare in the technological process of propylene glycol in the propylene oxide hydration, use tubular reactor, reactant flow is had near plug flow character, can reach highly selective, prepare to high yield purity at the propylene glycol more than 99% as hydration reactor.
Description
The present invention relates to a kind of method of using the tubular reactor produced propylene glycol, particularly a kind of method of using static mixer formula reactor made propylene glycol belongs to the purposes invention.
It is the method that industry is at present used always that the propylene oxide hydration prepares propylene glycol.The chemical property of propylene oxide is relatively active, its hydration reaction is carried out under liquid state under the facile hydrolysis, pressurized conditions, and following two reactions mainly take place this reaction process:
Be the propylene oxide hydration reaction except the main reaction that generates purpose product propylene glycol, also have a parallel-series to pay reaction simultaneously, generate by product one propylene glycol that contracts.Because existing parallel-series pays reaction, the axial backmixing in the reactor will cause reaction preference to descend.And adopting back-mixing few, flow condition can make the selectivity of reaction process improve near the reactor assembly of piston flow.Existing technology hydration is reflected in the tower reactor (being added with the void tower or the packing tower of baffle plate) to be carried out, and mol ratio is that the mixture of 15～20 water and propylene oxide is preheated to 125 ℃ and enters the hydration tower, at 20kg/cm
2Carry out hydration reaction under the pressure, from the reaction solution that tower bottom flow goes out except that weight concentration is about 20% propylene glycol, also contain big water gaging and a small amount of unreacted propylene oxide and by product, this mixture is through concentrating, obtaining purity at the propylene glycol more than 99% after dehydration and the rectifying, this process choice is 85%, omnidistance yield 80.6%, unit consumption is 0.947 ton of PO/ ton PG, raw material cost accounts for direct operating cost 92.7%.The document of relevant propylene oxide hydration kinetics aspect does not propose the data of reaction rate constant, the curve (referring to Fig. 1 and Fig. 2) that only provides transformation efficiency to change with reaction times and temperature of reaction.Industrial reactor adopts above-mentioned curve data to design basically, and the residence time of reactor is more than half an hour.Because the required reaction times is longer, existing industrial reactor adopts tower reactor pattern (being added with the tower or the packing tower of baffle plate), because tower reactor exists the back-mixing of certain degree, makes selectivity descend.
The minimum theoretical unit consumption of propylene oxide hydration system propylene glycol process is 0.76 ton of PO/ ton PG, but because there is back-mixing in existing tower reactor, has increased parallel-series and paid reaction, and its selectivity has only 85%, and its unit consumption is 1.24 times of theoretical unit consumption.Propylene oxide hydration compressive reaction is a liquid phase reaction course, but propylene oxide and water and not exclusively dissolve each other, but partial miscibility, when reactant mixes, at first form two-phase, the initial ring Ethylene Oxide is from the process of organic phase to the water diffusion, until the organic phase completely dissolve then.Experimental result shows, and is bad in admixture, and under the less situation of phase interface, this will be a process slowly, become the controlled step of reaction.The kinetic curve that provides in the above-mentioned document has in fact only reflected apparent kinetics, the rule of inreal reflection hydration reaction itself.Experimental study shows that hydration reaction is a rapid reaction, and transformation efficiency reaches 90% in the time of 210 ℃, and the real reaction time only needs 0.25 minute, does not need 30 minutes.Why need 30 minutes, cause that like this, as long as solved mixed problem, reactor volume just can dwindle greatly because pre-mixing is bad.The objective of the invention is provides a kind of reactor according to the hydration reaction rule, makes the process of preparation propylene glycol have highly selective and high yield, and reduces unit consumption.
Fig. 1 process flow diagram of the present invention
Fig. 2 is reaction times (t) of providing of described document and the graph of relation of transformation efficiency (X).
Fig. 3 is the temperature of reaction (T) that provides of described document and the relation of transformation efficiency (X).
Fig. 4 is a convection current bump premixer synoptic diagram.
Fig. 5 is the preferred kenics static mixing element that uses in the inventive method, and its width is identical with internal diameter of the pipeline.
Further specify the method for application tubular reactor produced propylene glycol of the present invention below in conjunction with accompanying drawing.
The present invention is a kind of processing method of using the tubular reactor produced propylene glycol, sees accompanying drawing 1: the reverse premixer (IA) that enters of (6) two bursts of logistics of propylene oxide (5) and water, mixture (8) enters tubular hydration reactor (1).Reacted material (9) contains outside the propylene glycol, also contain big water gaging and a small amount of unreacted propylene oxide and by product and enter evaporator tower (2), enriched material (11) enters further dehydration of dehydration tower (3), after entering rectifying tower (4) rectifying, thick material (14) obtains purity in the propylene glycol more than 99% (15), raffinate (16) is by discharge at the bottom of the rectifying tower, and water and a small amount of unreacted propylene oxide that discharge at evaporator tower (2) and dehydration tower (3) top enter premixer (IA) by circular route (17).
Key of the present invention is to have used tubular reactor as hydration reactor when water and propylene oxide hydration prepare propylene glycol, water and propylene oxide mix in premixer earlier, premixer is by the water inlet of reverse setting and propylene oxide inlet, and mixture outlet constitutes, premixer can make water and two bursts of logistics of propylene oxide produce the adverse current bump, making mixture reach sufficient microcosmic in moment (＜0.1 second) mixes, enter tubular hydration reactor again and prepare propylene glycol, 170～220 ℃ of hydration reaction temperature, reaction pressure 25～35kg/cm
2, the reaction times is 0.5～3 minute, and the mol ratio of water and propylene oxide is 15～40, and the length-to-diameter ratio of tubular hydration reactor is greater than 20.Turbulent flows is made with the holding tube inner fluid in Re＞2300 at the tubular reactor inner fluid, reduces axial backmixing.In order to make hydration reaction reach preferable effect, the kenics static mixing element is set in tubular reactor, because the guiding of hybrid element, material is cut and twists, displacement and distortion separate and merge, and make material reach thorough mixing; On the other hand, the mobile centrifugal force that is produced of ring rotation is made in logistics in static mixing element will make a part of material flow to tube wall from tube hub, part material flows to tube hub from tube wall, make the logistics micelle from the center to the tube wall, from the tube wall to the center, make radial flow repeatedly again, fully radially mix.Simultaneously, logistics group changes sense of rotation repeatedly, is subjected to bigger shear action, has strengthened less turbulence.Therefore, material is radially obtaining thorough mixing on static mixing element, have good mixed performance, and axial backmixing is very little, and flowing near piston flow of material can make and pay the reaction minimizing, and selectivity improves.Static mixing element is set in tubular reactor, and tubular reactor both can play the plug flow reactor effect, can play mixing tank again, so can omit premixer.If adopt the blank pipe reactor, then should mix premixer, and under turbulence state, operate, to reduce axial backmixing.
The blank pipe reactor that adopts the present invention to propose, the propylene oxide hydration reaction can reach technico-economical comparison and list in table-1, has listed file names with the PEP report data on the table, contrasts.
| The project reactor | The water ratio | Selectivity | Total recovery | Unit consumption | Steam consumption | Cooling-water consumption |
| Tubular type (reactor) PEP report | 30 15 | 93％ 85％ | 88.7％ 80.6％ | 0.86 0.94 | 4.98 3.87 | 383 tons 175 tons |
Can see that by table-1 though the steam consumption of tubular reactor and cooling-water consumption are higher than the PEP report, leading indicators such as selectivity, total recovery and unit consumption obviously surpass external present advanced level.If the propylene oxide unit price is with 40 yuan/ton of 5000 yuan/ton, steam unit price, the water coolant unit price is in 0.05 yuan/ton, and one ton of propylene glycol of every production can reduce production costs 357 yuan, and the propylene glycol device for producing 5000 tons per year can increase by 1,870,000 yuan of profits.
Following example is to further specify of the present invention, rather than limits the scope of the invention.
Embodiment 1
Use the tubular reactor of kenics static mixer element, inside diameter D 8mm, long 102.5cm.The feed flow rates propylene oxide is 5.4g/min, and water is 34g/min, and the mole of water ratio is 20.3, and isothermal operation, temperature of reaction are 188 ℃, reaction pressure 30kg/cm
2, the transformation efficiency of reactor outlet propylene oxide is 94.8%, the selectivity of propylene glycol is 93.1%.
Reactor is with embodiment 1, but pipe range is 156Cm.The feed flow rates propylene oxide is 3.9g/min, and water is 38.4g/min, and the mole of water ratio is 31.8.Adiabatic operation, reactor inlet temperatures are 195 ℃, reaction pressure 30kg/cm
2, the transformation efficiency of reactor outlet propylene oxide is greater than 99.9%, and the selectivity of propylene glycol is 94.7%.
Embodiment 3
Use the tubular reactor of kenics static mixing element.Inside diameter D 150mm, pipe range 4.5m.The feed flow rates propylene oxide is 0.53T/h, and water is 3.3T/h, and mole of water is than 20.Adiabatic operation, reactor inlet temperatures are 180 ℃, operation pressure 30kg/cm
2, the transformation efficiency of reactor outlet propylene oxide is 90%, selectivity is 93.2%.
Embodiment 4
Reactor is with embodiment 3, but pipe range is 4.6M.The feed flow rates propylene oxide is 0.53T/h, and water is 4.9T/h, and mole of water is than 30, adiabatic operation, and reactor inlet temperatures is 195 ℃, working pressure 30kg/cm
2, reactor outlet propylene oxide transformation efficiency is 95%, selectivity 95%.
The blank pipe reactor, bore D15mm, pipe range 156cm, feed flow rates propylene oxide are 9.5g/min, and water is 115g/min, and mole of water is than 39.4, and isothermal operation, temperature of reaction are 181 ℃, working pressure 30kg/cm
2, the transformation efficiency of reactor outlet propylene oxide is 93%, selectivity is 96%.
Embodiment 6
The blank pipe reactor, bore D160mm, pipe range 320cm.The feed flow rates propylene oxide is 0.53T/h, and water is 4.1T/h, and mole of water is than 25.Adiabatic operation, 190 ℃ of reactor inlet temperatures, working pressure 30kg/cm
2, the transformation efficiency of reactor outlet propylene oxide is 95%, selectivity is 95%.
Claims (3)
1, a kind of method of using the tubular reactor produced propylene glycol, it is characterized in that water and propylene oxide mix earlier in premixer, and then enter tubular hydration reactor and prepare propylene glycol, the temperature of hydration reaction is 170～220 ℃, reaction pressure 25～35kg/cm
2, the reaction times is 0.5～3 minute, and the mol ratio of water and propylene oxide is 15～40, and the length-to-diameter ratio of tubular hydration reactor is greater than 20.
2, the method for application tubular reactor produced propylene glycol according to claim 1, it is characterized in that premixer is water inlet and the propylene oxide inlet by reverse setting, and mixture outlet constitutes, it can make water and two bursts of logistics of propylene oxide produce the adverse current bump, after mixture reaches sufficient microcosmic mixing, enter tubular hydration reactor again.
3, the method for application tubular reactor produced propylene glycol according to claim 1 is characterized in that in the above-mentioned method placing kenics type static mixing element under the situation that premixer is arranged can make the hydration reaction of water and propylene oxide reach best effect in described tubular hydration reactor having or do not have.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90109529 CN1026102C (en) | 1990-12-05 | 1990-12-05 | 1, 2-propanediol made method using pipe reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90109529 CN1026102C (en) | 1990-12-05 | 1990-12-05 | 1, 2-propanediol made method using pipe reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1050868A true CN1050868A (en) | 1991-04-24 |
| CN1026102C CN1026102C (en) | 1994-10-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90109529 Expired - Fee Related CN1026102C (en) | 1990-12-05 | 1990-12-05 | 1, 2-propanediol made method using pipe reactor |
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| Country | Link |
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| CN (1) | CN1026102C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311316A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol through hydratation of cyclopentene |
| CN108602041A (en) * | 2015-12-09 | 2018-09-28 | 国际壳牌研究有限公司 | The method for being used to prepare glycol |
-
1990
- 1990-12-05 CN CN 90109529 patent/CN1026102C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311316A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol through hydratation of cyclopentene |
| CN102311316B (en) * | 2010-07-07 | 2014-07-23 | 中国石油化工股份有限公司 | Method for preparing cyclopentanol through hydratation of cyclopentene |
| CN108602041A (en) * | 2015-12-09 | 2018-09-28 | 国际壳牌研究有限公司 | The method for being used to prepare glycol |
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| Publication number | Publication date |
|---|---|
| CN1026102C (en) | 1994-10-05 |
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