CN203238195U - Manufacturing device of 1,3-propylene glycol - Google Patents
Manufacturing device of 1,3-propylene glycol Download PDFInfo
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- CN203238195U CN203238195U CN2012205504665U CN201220550466U CN203238195U CN 203238195 U CN203238195 U CN 203238195U CN 2012205504665 U CN2012205504665 U CN 2012205504665U CN 201220550466 U CN201220550466 U CN 201220550466U CN 203238195 U CN203238195 U CN 203238195U
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Abstract
The utility model discloses a manufacturing device of 1,3-propylene glycol, and the manufacturing device can be used for effectively removing byproducts when manufacturing 1,3-propylene glycol through glycerol to prepare high-purity 1,3-propylene glycol. The manufacturing device comprises a supercritical reactor used for reacting the glycerol with supercritical water and acid to produce acrolein; a hydration reaction distiller used for generating a hydration reaction on the acrolein generated in the supercritical reactor under the conditions that allyl alcohol exists at a gaseous state and 3-hydroxypropionaldehyde exists at a liquid state and for separating the 3-hydroxypropionaldehyde from the allyl alcohol of the byproducts; a control mechanism used for controlling the allyl alcohol in the hydration reaction distiller to exist at the gaseous state and controlling the 3-hydroxypropionaldehyde to exist at the liquid state; a hydrogenation reactor used for performing a hydrogenation reaction on the separated 3-hydroxypropionaldehyde in the hydration reaction distiller to generate 1,3-propylene glycol; a distillation tower used for removing the 1,2-propylene glycol of byproducts from the 1,3-propylene glycol generated by the hydrogenation reactor.
Description
Technical field
The utility model relates to the method and apparatus of making 1,3-PD from glycerine.
Background technology
1,3-PD is that demand in recent years increases with the raw material of the high-quality trevira headed by the Poly(Trimethylene Terephthalate) (PTT).As one of synthetic method of 1,3-PD, non-patent literature 1 disclosed acrolein hydration hydrogenation method is known.The method is to make under the condition that catalyzer exists as the propylene atmospheric oxidation of petroleum and synthesis of acrolein, it is carried out the method for hydration hydrogenation reaction again, and the method is established as industrially preparing process.But crude oil price is surging in recent years, so, wish to develop the method from the synthetic 1,3-PD of biological raw material.
Although be not reported from the method for biological raw material chemosynthesis 1,3-PD,, the technology that synthetic its predecessor is propenal exists, and as one of them non-patent literature 2 is for example arranged.Non-patent literature 2 discloses biological raw material is glycerine as initial substance, comes the method for synthesis of acrolein with 40 ℃, the supercritical water of 35MPa.The effect of promotor of the dehydration reaction of glycerine is accelerated in the proton performance that it is characterized in that making indium addition to produce to the sulfuric acid in the supercritical water.
The prior art document
Patent documentation
Patent documentation 1: No. 3486195 communique of Japan's special permission
Patent documentation 2: No. 2735717 communique of Japan's special permission
Non-patent literature
Non-patent literature 1:1,3-PDO, PTT System make purposes お I び Longitude Economic (strain) シ-エ system シ-プ ラ ネ ッ ト division department in August, 2000
Non-patent literature 2:Acrolein synthesis from glycerol in hot-compressed water, Bioresource Technology98 (2007) 1285-1290
The utility model content
The problem that utility model will solve
The method of non-patent literature 2 records except generating propenal, has also generated the vinyl carbinol as secondary resultant.For example disclose the method that propenal is changed into 1,3-PD in the patent documentation 1 and 2, still, when with these methods the propenal that contains vinyl carbinol having been changed into 1,3-PD, vinyl carbinol changes into 1,2-PD.When the 1,3-PD that contains 1,2-PD is come polymerization PTT as raw material, exist the problem of the physical property such as the crystallinity deterioration reduction of the polymkeric substance that obtains.
For this reason, the purpose of this utility model is to produce highly purified 1,3-PD by effectively removing secondary resultant when making 1,3-PD from glycerine.
Be used for solving the means of problem
To achieve these goals, the application's utility model people found that through with keen determination research, making 1 from glycerine, in the technique of ammediol, make propenal carry out hydration reaction and after having generated 3-HPA (3-HPA), remove vinyl carbinol, make again 3-HPA carry out hydrogenation reaction and generated 1, behind the ammediol, remove 1,2-PD, just can produce highly purified 1,3-PD.
That is, the utility model comprises following content.
(1) a kind of manufacturing installation of 1,3-PD possesses: supercritical reaction device, hydration reaction distiller, controlling organization, hydrogenator and distillation tower,
Above-mentioned supercritical reaction device reacts glycerine and supercritical water and acid, generates propenal;
In above-mentioned hydration reaction distiller, under the condition that vinyl carbinol exists with gaseous phase and 3-HPA exists with liquid state, make the propenal generation hydration reaction that in the supercritical reaction device, generates, generate 3-HPA, and, this 3-HPA is separated from the vinyl carbinol that exists as secondary resultant;
Above-mentioned controlling organization becomes the condition that vinyl carbinol exists with gaseous phase and 3-HPA exists with liquid state with control in the hydration reaction distiller;
In above-mentioned hydrogenator, make the 3-HPA after the hydration reaction distiller separates carry out hydrogenation reaction, generate 1,3-PD;
Above-mentioned distillation tower is removed the 1,2-PD that exists as secondary resultant from the 1,3-PD that generates hydrogenator.
(2) in the manufacturing installation of (1) record, also possess feeler mechanism and storing mechanism; Feeler mechanism is for detection of the condition in the hydration reactor; Storing mechanism stores the condition that vinyl carbinol exists with gaseous phase and 3-HPA exists with liquid state;
Above-mentioned controlling organization is obtained the detected condition by above-mentioned feeler mechanism, and the condition that obtains and the condition that is stored in the above-mentioned storing mechanism are compared, and the condition in the control hydration reactor is so that itself and the term harmonization of storing.
The utility model effect
According to the utility model, can make highly purified 1,3-PD from glycerine.
Description of drawings
Fig. 1 represents an embodiment of the manufacturing installation of 1,3-PD.
Fig. 2 represents an embodiment of hydration reaction distiller.
Fig. 3 represents an embodiment of hydration reaction distiller.
Fig. 4 represents to possess an embodiment of the 1,3-PD manufacturing installation of hydration reaction distiller.
Fig. 5 represents to possess an embodiment of the 1,3-PD manufacturing installation of hydration reaction distiller.
Fig. 6 represents to possess an embodiment of the 1,3-PD manufacturing installation of hydration reaction distiller.
Fig. 7 represents to possess an embodiment of the 1,3-PD manufacturing installation of hydration reaction distiller.
Fig. 8 represents to possess controlling organization 46, the hydration reaction distiller of feeler mechanism 47 and storing mechanism 48.
Fig. 9 represents the flow process of the manufacture method of 1,3-PD.
Figure 10 represents the flow process of the manufacture method of 1,3-PD.
Nomenclature
1,2 ... pump, 3,4,5 ... well heater, 6 ... strainer, 7,9,10 ... water cooler, 8,11 ... reducing valve, 12,14,17,22,25,28,41 ... distillation tower, 13,24,27,29,35,36,37,38,40,42,43 ... heat exchanger, 15,18,23,26,30,39 ... reboiler, 16 ... hydration reactor, 19 ... hydrogenator, 20 ... hydrogen separator, 21 ... vaporizer, 31 ... the solid composition is removed device, 32 ... organic composition is removed device, and 33 ... ion exchange tower, 34 ... water tank, 44 ... add the water decomposition reactor, 45 ... the hydration reaction distiller, 46 ... controlling organization, 47 ... feeler mechanism, 48 ... storing mechanism, 49 ... flow control device, 50 ... heating arrangements, 51 ... cooling body
Embodiment
Below, describe the utility model in detail.
(1) manufacture method of 1,3-PD
The manufacture method of 1,3-PD of the present utility model comprises that supercritical reaction operation, hydration reaction operation, first are removed operation, hydrogenation reaction operation and second is removed operation;
In above-mentioned supercritical reaction operation, glycerine and supercritical water and acid are reacted, generate propenal;
In above-mentioned hydration reaction operation, make the propenal that in the supercritical reaction operation, generates carry out hydration reaction, generate 3-HPA;
Remove in the operation above-mentioned first, from the 3-HPA that the hydration reaction operation, generates, remove the vinyl carbinol that exists as secondary resultant;
In above-mentioned hydrogenation reaction operation, make the first 3-HPA of removing after the operation carry out hydrogenation reaction, generate 1,3-PD;
Remove in the operation above-mentioned second, from the 1,3-PD that the hydrogenation reaction operation, generates, remove the 1,2-PD (Fig. 9) that exists as secondary resultant.
Manufacture method of the present utility model is not limited to above-mentioned operation, also can comprise arbitrarily operation again.For example, also can suitably implement refrigerating work procedure, decompression operation, heating process, throw out and remove operation etc.
The supercritical reaction operation
In the supercritical reaction operation, make glycerine and supercritical water and acid-respons and convert propenal to.
The condition of supercritical reaction operation so long as be under the condition of supercritical state at water, then is not particularly limited.The stagnation point of water is 374 ℃, 22.1MPa, so temperature of reaction is more than 374 ℃, is preferably more than 400 ℃, and more preferably more than 453 ℃, reaction pressure is more than the 22.1MPa, to be preferably more than the 34.5MPa.The upper limit of temperature of reaction is not particularly limited, but preferably below 600 ℃, more preferably below 500 ℃.The upper limit of reaction pressure is not particularly limited, but preferably below 50MPa.
Preferably the two all is to implement the supercritical reaction operation under the reaction conditions of supercritical state at water and glycerine.Under this condition, glycerine increases to the solubleness of water, can make glycerine reaction under high density.Like this, can reduce the energy of per unit raw material, reduce manufacturing cost.The stagnation point of glycerine is 453 ℃, 6.68MPa.
The reaction times of supercritical reaction operation is so long as in the scope that the propenal that generates does not decompose, then be not particularly limited.For example, be 0.1 second～60 seconds, preferably 0.5 second～30 seconds, be more preferably 1～10 second.
The amount of glycerine accounts for more than 14 % by weight with respect to the mixture of glycerine, water and acid, preferably accounts for more than 20 % by weight, more preferably accounts for more than 50 % by weight, and preferably accounts for below 70 % by weight.
The kind of acid is not particularly limited.For example can be mineral acid, organic acid, specifically, can be sulfuric acid, hydrochloric acid, nitric acid, methylsulfonic acid, Phenylsulfonic acid etc.
The amount of acid is scaled hydrogen ion concentration, and preferably 6.3 * 10 of glycerine mol concentration
-3～1.8 * 10
-1Doubly.Specifically, preferably, the sulfuric acid concentration when glycerol concentration is 14 % by weight (1.57mol/L) is 0.005～0.142mol/L, and the sulfuric acid concentration when glycerol concentration is 50 % by weight (6.11mol/L) is 0.0193～0.549mmol/L.
The hydration reaction operation
In the hydration reaction operation, the propenal that obtains in the supercritical reaction operation is converted to 3-HPA (3-HPA).
Hydration reaction available metal catalyzer is implemented.As the metal kind of metal catalyst, such as mercury, iridium, platinum, palladium, rhodium, nickel, cobalt, chromium, vanadium, molybdenum etc. are arranged.Metal catalyst can be only to contain above-mentioned a kind of metal, also can contain above-mentioned multiple combination.In addition, also can adopt ion exchange resin to implement hydration reaction.
The condition of hydration reaction is not particularly limited, and for example can be 30～120 ℃, the condition of 0.1～0.2MPa.The weight ratio of propenal and water is not particularly limited, and for example can be the scope of 1:2～1:20.
The hydration reaction operation is preferably implemented under the condition that propenal exists with gaseous phase and 3-HPA exists with liquid state.Under this condition, the 3-HPA that hydration reaction generates becomes liquid and falls, and separates with the propenal of gaseous phase.Because hydration reaction is balanced reaction, so the 3-HPA of generation is separated continuously, can promotes reaction, and then can suppress the generation of secondary resultant.
Boiling point changes because of pressure, and under normal pressure, the boiling point of propenal is lower than the boiling point of 3-HPA.Those of ordinary skill in the art can by suitably regulating pressure and temperature, set required condition.
First removes operation
Remove in the operation first, from the 3-HPA that obtains in the hydration reaction operation, remove the vinyl carbinol of secondary resultant.
The method of removing vinyl carbinol is not particularly limited, but preferred utilization distillation is removed.Because the boiling point of vinyl carbinol is lower than the boiling point of 3-HPA, so, can only make vinyl carbinol gasify to separate.
First removes operation also can implement with the hydration reaction operation (Figure 10) simultaneously.For example, under the condition that vinyl carbinol exists with gaseous phase and 3-HPA exists with liquid state, more particularly, under the condition that water exists with gaseous phase and 3-HPA exists with liquid state, carry out hydration reaction, thus, make the 3-HPA of generation become liquid and fall, can from the vinyl carbinol of gaseous phase, separate.In addition, under these conditions, owing to propenal also exists as gas, so, can from propenal, separate 3-HPA.
Therefore, as mentioned above, can promote the generation of hydration reaction, the secondary resultant of inhibition.In addition, the reactor and first that the hydration reaction operation uses needn't be set respectively remove the distiller that operation is used, can reduce equipment cost.
Boiling point changes because of pressure, and the boiling point under the normal pressure is propenal, vinyl carbinol, water, 3-HPA from low to high successively.Those of ordinary skill in the art can by suitably regulating pressure and temperature, set required condition.
The hydrogenation reaction operation
In the hydrogenation reaction operation, the first 3-HPA of removing after the operation is converted into 1,3-PD.
Hydrogenation reaction can under the hydrogen environment, be implemented with catalyzer.As catalyzer, such as adopting heterogeneous series catalysts (outstanding turbid series catalysts, fixed bed catalyst etc.), homogeneous phase series catalysts etc.
The condition of hydrogenation reaction operation is not particularly limited, for example, and preferred 30～150 ℃, more preferably 60～130 ℃, in addition, preferred 2～20MPa, more preferably 5～16MPa.
Second removes operation
Remove in the operation second, from the 1,3-PD that the hydrogenation reaction operation, generates, remove the 1,2-PD of secondary resultant.
The method of removing 1,2-PD is not particularly limited, but preferred utilization distillation is removed.Because the boiling point of 1,2-PD is lower than the boiling point of 1,3-PD, so, can only make 1,2-PD gasify to separate.
Remove and remove secondary resultant in the operation by removing operation and second first, can produce highly purified 1,3-PD.Can make high-quality polymkeric substance by making highly purified 1,3-PD polymerization." polymerization " described in the utility model comprised any of homopolymerization and copolymerization.
As the preferred polymers of using highly purified 1,3-PD to make, the multipolymer that for example is 1,3-PD and terephthalic acid is Poly(Trimethylene Terephthalate) (PTT).
(2) manufacturing installation of 1,3-PD
The manufacturing installation of 1,3-PD of the present utility model possesses supercritical reaction device (for example pipe arrangement), hydration reaction distiller, controlling organization, hydrogenator and distillation tower.
In above-mentioned supercritical reaction device, make glycerine and supercritical water and acid-respons, generate propenal;
In above-mentioned hydration reaction distiller, under the condition (condition that preferably water exists with gaseous phase and 3-HPA exists with liquid state) that vinyl carbinol exists with gaseous phase and 3-HPA exists with liquid state, make the acrolein hydration reaction that in the supercritical reaction device, generates, generate 3-HPA, and, this 3-HPA is separated from the vinyl carbinol that exists as secondary resultant;
Above-mentioned controlling organization becomes the condition that vinyl carbinol exists with gaseous phase and 3-HPA exists with liquid state (condition that preferably water exists with gaseous phase and 3-HPA exists with liquid state) to control in the hydration reaction distiller;
In above-mentioned hydrogenator, make the 3-HPA that in the hydration reaction distiller, has separated carry out hydrogenation reaction, generate 1,3-PD;
In above-mentioned distillation tower, from the 1,3-PD that hydrogenator, generates, remove the 1,2-PD that exists as secondary resultant.
In a preferred implementation, the manufacturing installation of 1,3-PD as shown in Figure 8, also possesses feeler mechanism 47 and storing mechanism 48.Feeler mechanism 47 is for detection of the condition in the hydration reactor.Storing mechanism 48 is being stored the condition that vinyl carbinol exists with gaseous phase and 3-HPA is deposited with liquid state (for example temperature and pressure) and/or water exists with gaseous phase and 3-HPA exists with liquid state condition.
Controlling organization 46 is obtained the condition that is detected by feeler mechanism 47, and the condition that obtains and the condition that is stored in the storing mechanism 48 are compared, and the condition in the control hydration reactor is so that itself and the term harmonization of storing.
Condition in the hydration reactor for example can be controlled for example valve of flow control device 49(by controlling organization) regulate the feed rate of propenal, water, thus change.In addition, also can heating arrangements 50, cooling body 51 be set with respect to hydration reactor, by controlling organization these mechanisms be controlled, and the condition in the hydration reactor is changed.
As controlling organization 46, it for example can be computer.Utilization is stored in the program among RAM, ROM, the HDD of computer etc., realizes the function of controlling organization.
As feeler mechanism 47, such as being the thermometer commonly used, pressure warning unit etc.
As storing mechanism 47, such as being RAM, ROM, HDD etc.
Below, with reference to Fig. 1, describe an embodiment of 1,3-PD manufacturing installation in detail.Among Fig. 1, do not use hydration reaction distiller 45, but be provided with hydration reactor 16 and distillation tower 17.On the other hand, the 1,3-PD manufacturing installation of Fig. 4～7 possesses hydration reaction distiller 45.
Manufacturing installation, from the response path upstream side, configuring successively pump 1, pump 2, well heater 3, well heater 4, well heater 5, strainer 6, water cooler 7, reducing valve 8, water cooler 9, water cooler 10, reducing valve 11, distillation tower 12, heat exchanger 13, distillation tower 14, reboiler 15, hydration reactor 16, distillation tower 17, reboiler 18, hydrogenator 19, hydrogen separator 20, vaporizer 21, distillation tower 22, reboiler 23, heat exchanger 24, distillation tower 25, reboiler 26, heat exchanger 27, distillation tower 28, heat exchanger 29.
Make be pressurized to the supercritical water of 22～50MPa and acid and act on glycerine by pump 1 and pump 2 after, implement several times cooling.
Make supercritical water and acid act on glycerine and obtain reaction solution, inject reaction quenching water coolant, this reaction solution is cooled to the fully low temperature (first cools off) of viscosity of the high viscosity composition of tar contained in temperature that main reaction stops and the reaction solution etc.Like this, can reduce the generation of secondary resultant, and suppress the viscosity of the high viscosity compositions such as tar and the rising of tack, can keep the UA states of solid composition such as carbon particles.Under UA state, the particle diameter of solid composition is several μ m～tens of μ m, and tack is minimum, so, can not stop up pipe arrangement.In addition, when the operation of solid substance is removed in separation, also can reduce to be attached to the effect that pressure reduction rises on the surface of separation because of solid substance.Therefore, can significantly reduce the frequency of maintenance of tripping device of the switching, strainer back washing operation etc. of equipment operation system, reduce and follow the power loss that stops and restarting, so, operating cost can be reduced.In addition, owing to being the separation of after the reaction solution cooling that 400 ℃ is waited high temperature, carrying out the solid composition, so, can prevent the thermal degradation when of tripping device.
The viscosity of the first cooled reaction solution preferably below 0.1Pas, can realize that the low viscous temperature of this degree is specifically preferably more than 100 ℃.On the other hand, stop fully in order to make building-up reactions, pyrolysis, preferably the temperature below 200 ℃.Therefore, the first cooling temperature is preferably 100～200 ℃.As the method for the first cooling, be that water coolant directly is mixed in the reaction solution, to compare with the heat exchange from the pipe arrangement periphery of adopting sleeve pipe etc., temperature variation is fast.Like this, can stop at high speed pyrolysis, the propenal that can stop to generate changes the secondary resultant that becomes tar, carbon particles etc., therefore, can improve the raw material yield.In addition, because the minimizing of secondary resultant generation, so, can help to suppress the obstruction of pipe arrangement and machine, the generation of corrosion, help accurate pressure-controlling.
Then, from reaction solution, separate removed the solid composition after, with water cooler 7 reaction solution is cooled to below the boiling point of water and the tar ingredients in the reaction solution is not bonded to temperature (second cools off) on the machine.Then, with reducing valve 8 decompressions, avoid pipe arrangement, valve to be stopped up by the solid composition, simultaneously, also can reduce adhering to of tar ingredients, so the pressure controling precision of reducing valve 8 improves.Especially because the opening (Inter mouth of reducing valve) minimum, so, not only suppressed adhering to but also suppressing adhering to of tar ingredients of solid composition, so the opening and closing operations that can very effectively make valve is easily and stabilization.In addition, by cooling temperature being set in below the boiling point of water, the afterreaction liquid that can suppress to reduce pressure gasification, volume sharply expand, so, the security that can improve reaction unit.
The viscosity of the second cooled reaction solution preferably below 10Pas, can realize the low viscous temperature of this degree, specifically more than 53 ℃, preferably more than 80 ℃.On the other hand, consider from the gasification that suppresses decompression afterreaction liquid, the viewpoint that sharply expands, temperature is preferably below 100 ℃.Therefore, consider that at least more than the boiling point of propenal, the second cooling temperature is 53～100 ℃, preferably 80～100 ℃.
After the decompression, with water cooler 9 and water cooler 10, reaction solution is cooled to the boiling point (the 3rd cooling) of desired substance.In other words, the temperature of the 3rd refrigerating work procedure is remained on more than the boiling point of desired substance.Like this, the easily reaction solution gasification from discharging of desired substance.Therefore, can improve energy efficiency when in follow-up distillation process, reheating.Consider that more than the boiling point of propenal, the 3rd cooling temperature is in the scope of the 53 ℃～second cooling temperature.Cooled reaction solution is sent to distillation tower 12 after reducing valve 11 decompressions.
Removing the solid composition from the supercritical reaction to the separation is to implement in the vertical pipe arrangement of being separated by valve, like this, contains the reaction solution of secondary resultant, under action of gravity, flows down equably with respect to the Zhou Fangxiang of pipe arrangement.If implement in horizontal pipe arrangement, the solid composition in the secondary resultant that then produces is deposited in the pipe arrangement bottom, under the effect along with the friction of flowing, produces corrosion in the bottom of pipe arrangement, reducing valve etc.And flow down equably by the Zhou Fangxiang with respect to pipe arrangement so that with the smoothing that contacts of the solid substance particle of pipe arrangement inner face, can further be reduced the effect of corrosion.In addition, 6 reaction unit and solid ingredient separating device from well heater 3 to strainer have been prepared 2 more than the system, can alternate-running, alternately discharge secondary resultant particle.Like this, when certain system implementation upkeep operation, other above system can keep running condition at least, so, will not stop by whole equipment, improve continuous operation.At this moment, the well heater 3 of reaction unit leading portion is compared with the well heater 5 of reaction pipe arrangement, and the residence time is long, and equipment scale is large.In addition, in well heater 3, because not as the organism of the glycerine of raw material etc., so, do not produce secondary resultant.This shows, in whole operation, the usage ratio of energy is large in well heater 3, compares with its downstream side operation, causes the worry of trouble minimum to secondary resultant.Therefore, considered the mode of a plurality of systems, each system shares well heater 3, is branched off into a plurality of systems from the reaction pipe arrangement, and like this, in the operation of downstream side, even the system that carries out upkeep operation is arranged, well heater 3 also can continuous operation.Like this, can make to stop/restarting the Minimal energy loss that causes, so, equipment cost, operating cost can be reduced.
The reaction solution that flow into distillation tower 12 separates by distillation, discharges the reaction solution that contains propenal, water, acetaldehyde, formaldehyde, vinyl carbinol etc. from the top, discharges the waste water that contains water, sulfuric acid, tar etc. from the bottom.Reaction solution flows into distillation tower 14 after heat exchanger 13 is cooled.The reaction solution that flow into distillation tower 14 separates by distillation, discharges the waste liquid that contains acetaldehyde and formaldehyde etc. from the top, discharges the reaction solution that contains propenal, water and vinyl carbinol etc. from the bottom.The reaction solution of discharging from distillation tower 14 flows into reboiler 15, in order to make the acrolein hydration reaction, is warmed up near 40～110 ℃ the temperature of reaction of hydration reaction, preferably is warmed up to 50～70 ℃.
After adding entry, flow into the reaction solution of hydration reactor 16 by hydration reaction, mainly convert 3-HPA (3-HPA) to.Hydration reaction can adopt catalyzer or the ion exchange resin that comprises one or more metals, for example mercury, iridium, platinum, palladium, rhodium, nickel, cobalt, chromium, vanadium, molybdenum, is that the scope of 1:2～1:20 is carried out in the weight ratio of 30～120 ℃ of temperature of reaction, pressure 0.1～0.2MPa, propenal and water.The reaction solution of discharging from hydration reactor flows into distillation tower 17, separates by distillation, discharges the waste liquid that contains propenal, water, vinyl carbinol etc. from the top, discharges the reaction solution that contains 3-HPA, water etc. from the bottom.Waste liquid is after heat exchanger 36 is cooled, and a part is back to hydration reactor.In order to make the 3-HPA hydrogenation reaction, reaction solution is raised near 30～150 ℃ the temperature of reaction of hydrogenation reaction at reboiler 18, preferably be warmed up to 60～130 ℃.
After adding entry as required, flow into the reaction solution of hydrogenator 19, by catalyzer and hydrogenation.Catalyzer is heterogeneous system, itself or hold at carrier and be used, fixed bed catalyst preferably, but also can use the catalyzer of homogeneous phase system.When using outstanding turbid series catalysts, the preferred use drawn Buddhist nun's nickel catalyzator, little noble metal catalyst that holds dispersedly on carrier.When using fixed bed catalyst, preferred use the precious metals such as platinum, palladium, rhodium, nickel, copper, chromium, zinc, etc. metal is little holds dispersedly at zeolites such as the supported catalyst such as titanium oxide, aluminum oxide, silica, zeolite or ZSM-5.Temperature of reaction is 30～150 ℃, and especially preferably 60～130 ℃, pressure is 2～20MPa, especially preferably 5～16MPa.
The reaction solution of discharging from hydrogenator flows into hydrogen separator 20, and reaction solution separates with hydrogen.Hydrogen after the separation is back in the hydrogenator.Reaction solution flows into vaporizer 21, with portion of water from.Water after the separation is back to hydration reactor or hydrogenator.Reaction solution flows into distillation tower 22, separates by distillation, discharges the waste liquid that contains water etc. from the top, discharge from the bottom contain 1,3-PD (1,3-PDO), 1,2-PD (1,2PDO), the reaction solution of 4-oxygen-1,7 heptanediol etc.Waste liquid is after heat exchanger 37 is cooled, and a part is back to hydration reactor 16, hydrogenator 19.Reaction solution flows into distillation tower 25 through reboiler 23 and heat exchanger 24, separates by distillation, discharges the waste liquid that contains 1,2-PD from the top, discharges the reaction solution that contains 1,3-PD, 4-oxygen-1,7 heptanediol etc. from the bottom.Reaction solution flows into distillation tower 28 through reboiler 26 and heat exchanger 27, separates by distillation, discharges 1,3-PD from the top, discharges the waste liquid that contains 4-oxygen-1,7 heptanediol etc. from the bottom.
Waste liquid flows into distillation tower 41 through reboiler 39 and heat exchanger 40, separates by distillation, discharges 4-oxygen-1,7 heptanediol from the top, discharges heavy ingredient from the bottom.4-oxygen-1,7 heptanediol is added water decomposition by catalyzer through over-heat-exchanger 42,43 in adding water decomposition reactor 44, become 1,3-PD.Catalyzer is heterogeneous system, itself or hold at carrier and be used, fixed bed catalyst preferably, but also can use the homogeneous phase series catalysts.When using outstanding turbid series catalysts, preferably use little noble metal catalyst that holds dispersedly on carrier.When using fixed bed catalyst, preferred adopt the precious metals such as platinum, palladium, rhodium, nickel, copper, chromium, zinc, etc. metal is little holds dispersedly at zeolites such as the supported catalyst such as titanium oxide, aluminum oxide, silica, zeolite or ZSM-5.Temperature of reaction is 30～300 ℃, and preferably 60～260 ℃, pressure is 0.1～10MPa, preferably 1～6MPa.
By the waste water that contains tar and sulfuric acid etc. that reboiler 30 is incubated, flow into the solid composition and remove device 31, the solid composition is removed.Because being maintained at, waste water can keep namely 50～100 ℃, preferably 80～100 ℃ of mobile temperature ranges, so, remove in the device at the solid composition, capture the solid substances such as carbon particles, suppress adhering to of the high viscosity composition such as tar.Removing of solid composition can be used strainer, cyclonic separator, settling bath etc.
Remove the waste water inflow organism of device 31 discharges from the solid composition and remove device 32, the organism in the waste water is removed.Organic removing can be carried out with the mode of absorption, can adopt activated carbon, zeolite etc. as sorbing material.Like this, contained tar, other organism is removed in the waste water.
Remove the waste water inflow ion exchange tower 33 that device 32 is discharged from organism, by ion exchange resin, the acid such as sulfuric acid contained in the waste water are removed.
Remove the water that device 31 is made with extra care till the ion exchange tower 33 from the solid composition, flow into water tank 34, the water coolant of using as raw water or reaction quenching is reused.Like this, can reduce the usage quantity of water, but the suppression equipment operating cost.In addition, do not need to be equipped with the waste water of the chemical substance that contains the so poisonous appointment of propenal, formaldehyde is discharged required waste water disposal facility outside the system, so, cost of equipment and running expense can be reduced.
Remove device 31 till the ion exchange tower 33 from the solid composition, prepared the system more than 2, can alternate-running, alternately discharge impurity.Like this, when certain system implementation upkeep operation, other more than one system can keep running condition at least, so, will not stop by whole equipment, improve continuous operation.
In hydration reaction, can adopt hydration reaction distiller as shown in Figure 2.Propenal and water are entered in the hydration reaction distillation device as gas stream, and the 3-HPA that generates by carrying out hydration reaction because boiling point is higher than water and propenal, so become liquid, falls hydration reaction distiller bottom.Because hydration reaction is balanced reaction, so 3-HPA becomes liquid and is removed continuously from environment and promoted reaction, the residence time, comparable device before shortened.In addition, by shortening the residence time, can suppress the generation of secondary resultant.In addition, owing in the hydration reaction distiller, 3-HPA is separated with water and propenal, so, can dispense the distillation tower in the such hydration reaction downstream side of distillation tower 17 among Fig. 1, can reduce equipment cost.In addition, also can dispense the distillation tower of the such hydration reaction upstream side of distillation tower 14 among Fig. 1.
In hydration reaction, more than the boiling point of propenal, when the boiling point that is lower than water reacts, can use hydration reaction distiller as shown in Figure 3.Propenal flows into from hydration reaction distiller bottom as gas, and water flows into from hydration reaction distiller top as liquid.For water is evenly distributed in the environment, can adopt water-jet etc. to be sprayed onto in the hydration reaction distiller.The 3-HPA that hydration reaction generates becomes liquid, falls hydration reaction distiller bottom with water.Because hydration reaction is balanced reaction, so 3-HPA becomes liquid and is removed continuously from environment and promoted reaction, the residence time, comparable device before shortened.In addition, by shortening the residence time, can suppress the generation of secondary resultant.In addition, owing in reactor, 3-HPA and water are separated with propenal, so, can dispense the distillation tower in the such hydration reaction downstream side of distillation tower 17 among Fig. 1, can reduce equipment cost.In addition, also can dispense the distillation tower of the such hydration reaction upstream side of distillation tower 14 among Fig. 1.Because water is essential in the hydrogenation reaction in downstream, so it is no problem that water is sneaked into 3-PHA.
Below, illustrate in greater detail the utility model with embodiment and comparative example, but scope of the present utility model is not limited to this.
[embodiment]
(embodiment 1)
Adopt device shown in Figure 1, after having implemented supercritical reaction under the condition of raw material glycerol concentration 15wt%, 400 ℃ of temperature of reaction, reaction pressure 35MPa, reaction times 2s, by injecting the quenching of water coolant, be cooled to 200 ℃, be cooled to 125 ℃ with water cooler 7 from 200 ℃, from the 35MPa 0.35MPa that reduces pressure, be cooled to 95 ℃ with water cooler 9 from 125 ℃ with reducing valve 8, be cooled to 60 ℃ with water cooler 10 from 95 ℃, with reducing valve 11 decompressions to normal atmosphere.After having implemented hydration reaction under the condition of 60 ℃ of temperature of reaction, reaction pressure 0.1MPa, reaction times 1h, under the condition of 60～120 ℃ of temperature of reaction, reaction pressure 15MPa, reaction times 1h, implement hydrogenation reaction, carried out the synthetic of 1,3-PD.As a result, in the reaction solution that obtains, the yield of 1,3-PD is 52%, does not detect 1,2-PD.
(embodiment 2)
Adopt the device that contains hydration reaction distiller 45 shown in Figure 4, after having implemented supercritical reaction under the condition of raw material glycerol concentration 15wt%, 400 ℃ of temperature of reaction, reaction pressure 35MPa, reaction times 2s, by injecting the quenching of water coolant, be cooled to 200 ℃, be cooled to 125 ℃ with water cooler 7 from 200 ℃, from the 35MPa 0.35MPa that reduces pressure, be cooled to 95 ℃ with water cooler 9 from 125 ℃ with reducing valve 8, be cooled to 60 ℃ with water cooler 10 from 95 ℃, with reducing valve 11 decompressions to normal atmosphere.After having implemented hydration reaction under the condition of 60 ℃ of temperature of reaction, reaction pressure 0.1MPa, reaction times 1h, under the condition of 60～120 ℃ of temperature of reaction, reaction pressure 15MPa, reaction times 1h, implement hydrogenation reaction, carried out the synthetic of 1,3-PD.As a result, in the reaction solution that obtains, the yield of 1,3-PD is 55%, does not detect 1,2-PD.
(embodiment 3)
Adopt the device that contains hydration reaction distiller 45 shown in Figure 5, after having implemented supercritical reaction under the condition of raw material glycerol concentration 15wt%, 400 ℃ of temperature of reaction, reaction pressure 35MPa, reaction times 2s, by injecting the quenching of water coolant, be cooled to 200 ℃, be cooled to 125 ℃ with water cooler 7 from 200 ℃, from the 35MPa 0.35MPa that reduces pressure, be cooled to 95 ℃ with water cooler 9 from 125 ℃ with reducing valve 8, be cooled to 60 ℃ with water cooler 10 from 95 ℃, with reducing valve 11 decompressions to normal atmosphere.After having implemented hydration reaction under the condition of 60 ℃ of temperature of reaction, reaction pressure 0.1MPa, reaction times 1h, under the condition of 60～120 ℃ of temperature of reaction, reaction pressure 15MPa, reaction times 1h, implement hydrogenation reaction, carried out the synthetic of 1,3-PD.As a result, in the reaction solution that obtains, the yield of 1,3-PD is 57%, does not detect 1,2-PD.
(embodiment 4)
Adopt the device that contains hydration reaction distiller 45 shown in Figure 6, after having implemented supercritical reaction under the condition of raw material glycerol concentration 15wt%, 400 ℃ of temperature of reaction, reaction pressure 35MPa, reaction times 2s, by injecting the quenching of water coolant, be cooled to 200 ℃, be cooled to 125 ℃ with water cooler 7 from 200 ℃, from the 35MPa 0.35MPa that reduces pressure, be cooled to 95 ℃ with water cooler 9 from 125 ℃ with reducing valve 8, be cooled to 60 ℃ with water cooler 10 from 95 ℃, with reducing valve 11 decompressions to normal atmosphere.After having implemented hydration reaction under the condition of 60 ℃ of temperature of reaction, reaction pressure 0.1MPa, reaction times 1h, under the condition of 60～120 ℃ of temperature of reaction, reaction pressure 15MPa, reaction times 1h, implement hydrogenation reaction, carried out the synthetic of 1,3-PD.As a result, in the reaction solution that obtains, the yield of 1,3-PD is 55%, does not detect 1,2-PD.
(embodiment 5)
Adopt the device that contains hydration reaction distiller 45 shown in Figure 7, after having implemented supercritical reaction under the condition of raw material glycerol concentration 15wt%, 400 ℃ of temperature of reaction, reaction pressure 35MPa, reaction times 2s, by injecting the quenching of water coolant, be cooled to 200 ℃, be cooled to 125 ℃ with water cooler 7 from 200 ℃, from the 35MPa 0.35MPa that reduces pressure, be cooled to 95 ℃ with water cooler 9 from 125 ℃ with reducing valve 8, be cooled to 60 ℃ with water cooler 10 from 95 ℃, with reducing valve 11 decompressions to normal atmosphere.After having implemented hydration reaction under the condition of 60 ℃ of temperature of reaction, reaction pressure 0.1MPa, reaction times 1h, under the condition of 60～120 ℃ of temperature of reaction, reaction pressure 15MPa, reaction times 1h, implement hydrogenation reaction, carried out the synthetic of 1,3-PD.As a result, in the reaction solution that obtains, the yield of 1,3-PD is 57%, does not detect 1,2-PD.
(comparative example)
With parameter similarly to Example 1, carried out the synthetic of 1,3-PD.But, do not carry out that vinyl carbinol in the distillation tower 17 reclaims and distillation tower 25 in 1,2-PD reclaim.As a result, from reaction solution, detected 1% 1,2-PD.
Claims (2)
1. the manufacturing installation of a 1,3-PD is characterized in that, this manufacturing installation possesses: supercritical reaction device, hydration reaction distiller, controlling organization, hydrogenator and distillation tower,
Above-mentioned supercritical reaction device reacts glycerine and supercritical water and acid, generates propenal;
Above-mentioned hydration reaction distiller is arranged at the downstream of above-mentioned supercritical reaction device, in above-mentioned hydration reaction distiller, under the condition that vinyl carbinol exists with gaseous phase and 3-HPA exists with liquid state, make the propenal generation hydration reaction that in the supercritical reaction device, generates, generate 3-HPA, and, this 3-HPA is separated from the vinyl carbinol that exists as secondary resultant;
Above-mentioned controlling organization is controlled the hydration reaction distiller, and the control of hydration reaction distiller is become the condition that vinyl carbinol exists with gaseous phase and 3-HPA exists with liquid state;
Above-mentioned hydrogenator is arranged at the downstream of above-mentioned hydration reaction distiller, in above-mentioned hydrogenator, makes the 3-HPA after the hydration reaction distiller separates carry out hydrogenation reaction, generates 1,3-PD;
Above-mentioned distillation tower is arranged at the downstream of above-mentioned hydrogenator, and above-mentioned distillation tower is removed the 1,2-PD that exists as secondary resultant from the 1,3-PD that generates hydrogenator.
2. manufacturing installation as claimed in claim 1 is characterized in that, also possesses feeler mechanism and storing mechanism; Above-mentioned feeler mechanism is for detection of the condition in the hydration reactor; Above-mentioned storing mechanism stores the condition that vinyl carbinol exists with gaseous phase and 3-HPA exists with liquid state;
Above-mentioned controlling organization is obtained the detected condition by above-mentioned feeler mechanism, and the condition that obtains and the condition that is stored in the above-mentioned storing mechanism are compared, and the condition in the control hydration reactor is so that itself and the term harmonization of storing.
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| JP2011234545A JP5755995B2 (en) | 2011-10-26 | 2011-10-26 | Reaction process using supercritical water |
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| CN2012205504665U Expired - Fee Related CN203238195U (en) | 2011-10-26 | 2012-10-25 | Manufacturing device of 1,3-propylene glycol |
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| CN111957062A (en) * | 2020-09-11 | 2020-11-20 | 赵汇川 | Reduced pressure distillation device and process for continuous desalting of crude glycerol |
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| JP2014097956A (en) * | 2012-11-14 | 2014-05-29 | Hitachi Ltd | Method and apparatus for producing 1,3-propanediol |
| CN111116884B (en) * | 2019-12-23 | 2022-01-21 | 上海炼升化工股份有限公司 | Polyester polyol production system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3926136A1 (en) * | 1989-08-08 | 1991-02-14 | Degussa | METHOD FOR PRODUCING 1,3-PROPANDIOL |
| DE4038192A1 (en) * | 1990-11-30 | 1992-06-04 | Degussa | PROCESS FOR PREPARING 1,3-PROPANDIOL |
| DE4132663C2 (en) * | 1991-10-01 | 1993-10-14 | Degussa | Process for producing 1,3-propanediol by hydrogenating hydroxypropionaldehyde |
| DE4238492C2 (en) * | 1992-11-14 | 1995-06-14 | Degussa | Process for the preparation of 1,2- and 1,3-propanediol |
| DE4238493C1 (en) * | 1992-11-14 | 1994-04-21 | Degussa | Process for the production of acrolein and its use |
| US6342646B1 (en) * | 1999-07-30 | 2002-01-29 | E. I. Du Pont De Nemours And Company | Catalytic hydrogenation of 3-hydroxypropanal to 1,3-propanediol |
| MY140801A (en) * | 2002-10-03 | 2010-01-15 | Shell Int Research | Reduction of the viscosity of reactive heavy byproducts during the production of 1,3-propanediol |
| CA2516639A1 (en) * | 2003-02-24 | 2004-09-10 | Shell Internationale Research Maatschappij B.V. | Purification of 1,3-propanediol by distillation |
| CA2522928C (en) * | 2003-05-06 | 2013-09-24 | E.I. Du Pont De Nemours And Company | Purification of biologically-produced 1,3-propanediol |
| JP2008280349A (en) * | 2008-06-02 | 2008-11-20 | Nippon Shokubai Co Ltd | Method for producing acrylic acid, apparatus for producing acrylic acid, and composition for producing acrylic acid |
| JP4687754B2 (en) * | 2008-07-01 | 2011-05-25 | 株式会社日立プラントテクノロジー | Method for producing acrolein using supercritical water |
| JP5478132B2 (en) * | 2009-07-01 | 2014-04-23 | 株式会社日立製作所 | Acrolein synthesis method and apparatus |
| WO2011099112A1 (en) * | 2010-02-09 | 2011-08-18 | 株式会社日立プラントテクノロジー | Process for synthesis of acrolein |
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| CN111957062A (en) * | 2020-09-11 | 2020-11-20 | 赵汇川 | Reduced pressure distillation device and process for continuous desalting of crude glycerol |
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| CN103073389A (en) | 2013-05-01 |
| JP2013091621A (en) | 2013-05-16 |
| JP5755995B2 (en) | 2015-07-29 |
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