CN105017207A - 4,4-dimethyl-1,3-dioxane synthesis method - Google Patents
4,4-dimethyl-1,3-dioxane synthesis method Download PDFInfo
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- CN105017207A CN105017207A CN201510429235.7A CN201510429235A CN105017207A CN 105017207 A CN105017207 A CN 105017207A CN 201510429235 A CN201510429235 A CN 201510429235A CN 105017207 A CN105017207 A CN 105017207A
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- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
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Abstract
The invention relates to a 4,4-dimethyl-1,3-dioxane synthesis method. According to the 4,4-dimethyl-1,3-dioxane synthesis method, reaction monomers enter into a reactor respectively from different inlets, wherein an organic phase isobutene or isobutene-containing C4 fraction enters into the reactor from the lower part of the reactor and flows upward and a water phase phosphoric acid solution enters into the reactor from the upper part of the reactor and flows downward, the water phase material and the oil phase material contact in a counter current contact way in a multistage filling material zone and are fully dispersed so that a reaction is promoted, the reacted water phase is discharged from the bottom and the oil phase is discharged from the upper part. The 4,4-dimethyl-1,3-dioxane synthesis method has the advantages that a reaction conversion rate is high, reaction is thorough, formaldehyde-caused side reaction in the downstream process is greatly reduced, the reaction can be controlled easily, according to yield requirements, technical process conditions can be adjusted in the same reactor by adjustment of tertiary butanol and formaldehyde inlets so that the optimal reaction effects are obtained, and when the reaction occurs fluctuation, the reaction case can be improved and controlled by adjustment of the tertiary butanol and formaldehyde inlet positions.
Description
Technical field
The present invention relates to the synthesis of chemical intermediate, specifically refer to a kind of synthetic method of 4,4-dimethyl-1,3-dioxane.
Background technology
Isoprene is a kind of important industrial chemicals, can be separated and obtain, also obtain by chemosynthesis from cracked C 5 fraction.
To mainly contain two kinds: one be dehydriding to the method for synthesis isoprene, namely with iso-pentane or isopentene for raw material is by catalytic dehydrogenation Isoprene.There are iso-pentane two step method of dehydrogenating and a step dehydriding.Another is olefine aldehydr method, namely with iso-butylene or containing the C-4-fraction of iso-butylene or the trimethyl carbinol, formaldehyde for raw material, first synthetic intermediate 4,4-dimethyl-1,3-dioxane, is called for short DMD, and then DMD decomposes and obtains isoprene.Olefine aldehydr method divides again gas phase olefine aldehydr method and liquid phase olefine aldehydr method.The rare aldehyde method of gas phase adopts heteropolyacid catalyst, and gaseous state iso-butylene and formaldehyde generate intermediate DMD by catalyst bed reaction, are then separated by intermediate, decomposes and obtain isoprene.Liquid phase method is that C-4-fraction, the trimethyl carbinol and formaldehyde react and generates intermediate DMD in strong acid aqueous solution, is then decomposed in strong acid aqueous solution by intermediate DMD and obtains isoprene.
The reactor that liquid phase method uses mainly contains to be with in the tank reactor of stirring, shell and tube reactor and hollow and adds coil tube type; The common feature of these two kinds of forms is all following current operation, and namely each material coflow in the reactor, is normally flowed to top by reactor bottom, also have from top to flows.But, because the aqueous phase material in reactor is different from the density of oil phase material, two phase materials velocity of flow is in the reactor different: when flowing from bottom to top, and oil phase flowing is faster than aqueous phase, thus the oil phase actual residence time is in the reactor smaller than the aqueous phase residence time; Conversely, when from top to flows, aqueous phase flowing is faster than oil phase flowing, and the oil phase actual residence time in the reactor will be longer than the aqueous phase residence time.Further, this oil phase and the aqueous phase residence time in the reactor, be do not control by operation, cause reacting not exclusively, by-product is high, product yield is low, reaction result is undesirable.
Summary of the invention
Technical problem to be solved by this invention provides for the present situation of prior art the synthetic method that a kind of reaction conversion ratio is high, react more thoroughly isoprene intermediate 4,4-dimethyl-1,3-dioxane.
The present invention solves the problems of the technologies described above adopted technical scheme: this temperature is that the phosphoric acid solution of 80-90 DEG C enters reactor from the upper entrance between upper packing area and the first intermediate filler district, flows through the first intermediate filler district, the second intermediate filler district and lower packing area in reactor from top to bottom successively;
Temperature is that the formaldehyde of 80-90 DEG C enters reactor from the first medial inlet between the first intermediate filler district and the second intermediate filler district; During formaldehyde is soluble in the aqueous phase, flow through the second intermediate filler district and lower packing area from top to bottom successively with aqueous phase;
Temperature is that the trimethyl carbinol of 80-90 DEG C enters reactor from the second medial inlet between the second intermediate filler district and lower packing area; Temperature is that the iso-butylene of 70-75 DEG C enters reactor from the lower entrances be positioned at below lower packing area, upwards flows from lower packing area;
The trimethyl carbinol can be soluble in the aqueous phase, and also can be dissolved in iso-butylene oil phase, and trimethyl carbinol part in reactor is soluble in the aqueous phase and flows from the top down with aqueous phase, and a part flows from bottom to top with oil phase;
Iso-butylene and phosphoric acid solution, the trimethyl carbinol and formaldehyde solution counter current contact in reactor, react in each packing area, generates 4,4-dimethyl-1,3-dioxane oil phase, namely first time product; First time product rising, the unreacting material carried secretly in uphill process enters buffering packing area, unreacted material reacts further in buffering packing area, generate 4,4-dimethyl-1,3-dioxane second time product, second time product rises together with first time product, enter the upper buffer zone be positioned at above packing area, oil phase is discharged from the material outlet in upper buffer zone;
In reaction process, the liquid product of generation is descending, enters the lower buffer zone be positioned at below lower packing area, discharges from the aqueous phase outlet of bottom;
Controlling reactor interior reaction temperature is 70 ~ 130 DEG C, reaction pressure is 1.7 ~ 2.3MPa, the mol ratio of iso-butylene and the trimethyl carbinol is 0.5 ~ 3, the mole number sum of iso-butylene and the trimethyl carbinol and the mol ratio of formaldehyde are 1 ~ 6, inorganics and organic weight ratio are 1-3, the per-cent that phosphoric acid quality accounts for raw material total mass is 2 ~ 8%, and the residence time of iso-butylene in reactor is 0.5 ~ 2 hour.The determination of the residence time is relevant with temperature of reaction, and temperature of reaction is high, then the residence time is short, and temperature of reaction is low, then the residence time is relatively long.
Or the synthetic method of this 4,4-dimethyl-1,3-dioxane, is characterized in that comprising the steps:
Temperature is that the phosphoric acid solution of 80-90 DEG C enters reactor from the upper entrance between upper packing area and the first intermediate filler district, flows through the first intermediate filler district, the second intermediate filler district and lower packing area in reactor from top to bottom successively;
To be the formaldehyde of 80-90 DEG C and temperature be temperature that the trimethyl carbinol of 80-90 DEG C enters reactor from the second medial inlet between the second intermediate filler district and lower packing area;
Temperature is that the iso-butylene of 70-75 DEG C enters reactor from the lower entrances be positioned at below lower packing area, upwards flows from lower packing area;
In reactor, phosphoric acid and formaldehyde flow from the top down with aqueous phase, flow through the packing area below corresponding opening for feed successively, and iso-butylene upwards flows from lower packing area in reactor, flow through each packing area of iso-butylene entrance top successively; Trimethyl carbinol part in reactor is soluble in the aqueous phase, and flow downward with aqueous phase, a part is dissolved in oil phase, upwards flows with oil phase;
Iso-butylene and phosphoric acid solution, the part trimethyl carbinol and formaldehyde solution counter current contact in reactor, react in each packing area, generates 4,4-dimethyl-1,3-dioxane oil phase, namely first time product; First time product rising, the unreacting material carried secretly in uphill process enters packing area, unreacted material reacts further in upper packing area, generate 4,4-dimethyl-1,3-dioxane second time product, second time product rises together with first time product, enter the upper buffer zone be positioned at above packing area, oil phase is discharged from the material outlet in upper buffer zone;
In reaction process, the water-phase product of generation is descending with aqueous phase, enters the lower buffer zone be positioned at below lower packing area, discharges from the aqueous phase outlet of bottom;
Controlling reactor interior reaction temperature is 70 ~ 130 DEG C, reaction pressure is 1.7 ~ 2.3MPa, the mol ratio of iso-butylene and the trimethyl carbinol is 0.5 ~ 3, the mole number sum of iso-butylene and the trimethyl carbinol and the mol ratio of formaldehyde are 1 ~ 6, inorganics and organic weight ratio are 1-3, the per-cent that phosphoric acid quality accounts for charging total mass is 2 ~ 8%, and the residence time of iso-butylene in reactor is 0.5 ~ 2 hour.
Or the synthetic method of this 4,4-dimethyl-1,3-dioxane, is characterized in that comprising the steps:
To be the phosphoric acid solution of 80-90 DEG C and temperature be temperature that the formaldehyde solution of 80-90 DEG C enters reactor from the upper entrance between upper packing area and the first intermediate filler district, flows through the first intermediate filler district, the second intermediate filler district and lower packing area in reactor from top to bottom successively;
Temperature is that the trimethyl carbinol of 80-90 DEG C enters reactor from the second medial inlet being positioned at the first intermediate filler district and the second intermediate filler district;
Temperature is that the iso-butylene of 70-75 DEG C enters reactor from the lower entrances be positioned at below lower packing area;
Phosphoric acid solution and formaldehyde from up to down flow in reactor; Trimethyl carbinol part in reactor is soluble in the aqueous phase and flows from the top down with aqueous phase, and a part is dissolved in oil phase and flows from bottom to top with oil phase; Iso-butylene is bottom-up flowing in reactor, with phosphoric acid solution, the trimethyl carbinol and formaldehyde solution counter current contact in reactor, reacts in each packing area, generates 4,4-dimethyl-1,3-dioxane oil phase, namely first time product; First time product rising, the unreacting material carried secretly in uphill process enters buffering packing area, unreacted material reacts further in buffering packing area, generate 4,4-dimethyl-1,3-dioxane second time product, second time product rises together with first time product, enter the upper buffer zone be positioned at above packing area, oil phase is discharged from the oil phase outlet in upper buffer zone;
In reaction process, the water-phase product of generation is descending, enters the lower buffer zone be positioned at below lower packing area, discharges from the aqueous phase outlet of reactor bottom;
Upper buffer zone is positioned at the top of reactor, and lower buffer zone is positioned at the bottom of reactor;
Controlling temperature of reaction is 70 ~ 130 DEG C, and reaction pressure is 1.7 ~ 2.3MPa;
In reactor, the mol ratio of iso-butylene and the trimethyl carbinol is 0.5 ~ 3, the mole number sum of iso-butylene and the trimethyl carbinol and the mol ratio of formaldehyde are 1 ~ 6, inorganics and organic weight ratio are 1-3, the per-cent that phosphoric acid quality accounts for charging total mass is 2 ~ 8%, and the residence time of iso-butylene in reactor is 0.5 ~ 2 hour.
Preferably, the height of described upper packing area accounts for 5 ~ 20% of total filler height, the height in described first intermediate filler district accounts for 3 ~ 7% of total filler height, the height in described second intermediate filler district accounts for 3 ~ 7% of total filler height, and the height of described lower packing area accounts for 66 ~ 89% of total filler district height; The height sum of each packing area is total filler height, and described total filler height stops with iso-butylene material and is as the criterion for 0.5 ~ 2 hour in reactor.
The mol ratio of preferred described iso-butylene and the trimethyl carbinol is 1 ~ 2, and the mole number sum of iso-butylene and the trimethyl carbinol and the mol ratio of formaldehyde are 1.5 ~ 3.5, and inorganics and organic weight ratio are 1-2, and the per-cent that phosphoric acid accounts for raw material gross weight is 3 ~ 5%;
Controlling temperature of reaction is 80 ~ 100 DEG C, and reaction pressure is 1.9 ~ 2.1MPa.
In order to control temperature of reaction more accurately, described lower packing area can be divided into two sections, and be provided with First Heat Exchanger between two sections.
Inorganics in above-mentioned each scheme is phosphoric acid and water, and organism is other material except phosphoric acid and water, comprises iso-butylene, formaldehyde and the trimethyl carbinol.
Or, corresponding to described upper packing area, the first intermediate filler district, the second intermediate filler district and lower packing area, the outer wall of described reactor is respectively equipped with jacket heat-exchanger.
Further, described second intermediate filler district also can be divided into two sections, is namely positioned at the second intermediate filler district epimere and the second intermediate filler district hypomere of top, and the jacket heat-exchanger corresponding to two sections is independent separately.
The present invention utilizes the dissolving partition ratio of formaldehyde in aqueous phase much larger than the dissolving partition ratio in organic phase, to flow downward from its charging mouth of pipe along with aqueous phase in the reactor, iso-butylene is then flow from bottom to top in the reactor, the reverse contact of reactant of two react withs, all contact with another reactant of maximum concentration before leaving reactor, reaction is carried out more thorough, and reaction conversion ratio improves greatly; Packing area more than the formaldehyde charging mouth of pipe, the iso-butylene dissolving formaldehyde and the excessive concentrations be distributed in organic phase on a small quantity can be reacted, thus greatly reduce the content leaving formaldehyde the oil phase of reactor from reactor head, greatly reduce the side reaction that in the decomposition process of lower procedure and intermediate DMD, unreacting acetal causes more and occur.
Compared with prior art, reaction mass is counter current contact in the reactor, and reaction conversion ratio is high, reaction is more thorough, greatly reduce the side reaction that formaldehyde in lower procedure causes, and reaction easily controls; And can according to output demand, by regulating the entrance of the trimethyl carbinol and formaldehyde to carry out technological operation optimization condition in same reactor, reaction is made to reach best effect, especially, when reacting generation fluctuation, improving by regulating the entry position of isopropylcarbinol and formaldehyde and controlling response situation preferably.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of reactor in the embodiment of the present invention;
Fig. 2 is the schematic top plan view of material sparger in the embodiment of the present invention;
Fig. 3 is the front view of Fig. 2;
Fig. 4 and Fig. 5 is the schematic diagram of other two kinds of reactors.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
The structure of reactor used in the synthetic method of this 4,4-dimethyl-1,3-dioxane is described below:
As shown in Figure 1 to Figure 3, the synthesizer of this 4,4-dimethyl-1,3-dioxane comprises:
Reactor 1 is vertical structure, and its top is provided with gaseous phase outlet 11 and two pressure detection mouths 12, and the bottom of reactor is provided with aqueous phase outlet 13.Gaseous phase outlet 11 connects the surge tank 14 being used for constant reactor pressure.Also can not arrange gaseous phase outlet and surge tank, the gas accumulated by the top in upper buffer zone controls reactor pressure.
Buffer zone 2, packing area and lower buffer zone 4 is provided with from top to bottom successively in reactor; Wherein, packing area comprises packing area 31, intermediate filler district and lower packing area 33; And intermediate filler district is divided into two sections, comprise the first intermediate filler district 321 being positioned at top and the second intermediate filler district 322 being positioned at below, wherein in first below the first intermediate filler district, feed distributor connects formaldehyde entrance, and the feed distributor below the second intermediate filler district connects trimethyl carbinol entrance.
Interval, each packing area is arranged, the filler including upper backup pad and lower supporting plate and be filled between upper and lower back up pad, and upper and lower back up pad is engraved structure and is connected on the inwall of described vertical reactor; To facilitate the flowing of material and to avoid logistics to the impact of filler in packing area.Filler can select any one rectifying tower filler in prior art, can be structured packing, and can be also random packing, the present embodiment be random packing.
Thereunder feed distributor is equipped with corresponding to each packing area; Upper feeding sparger 51 wherein near upper packing area connects phosphoric acid aqueous phase entrance 61, upper feeding sparger go out mouth down; The lower feed distributor 53 being positioned at below connects iso-butylene entrance 63, and the outlet of lower feed distributor upward; In below first intermediate filler district 321 first, feed distributor 521 connects opening for feed 621 i.e. formaldehyde entrance in first, and in first, feed distributor 521 goes out mouth down; In below second intermediate filler district 322 second, feed distributor 522 connects opening for feed 622 i.e. trimethyl carbinol entrance in second, and in second, feed distributor goes out mouth down.That is, in the present invention, each feed distributor is except being positioned at the outlet of the lower feed distributor of below towards upper outside, and remaining all exports packing area downward.The outer wall of reactor is provided with the jacket heat-exchanger 15 corresponding with each packing area.
The reactor shown in Fig. 4 can also be adopted, lower packing area is divided into two sections, namely be provided with First Heat Exchanger 333 between first time packing section 331 and second time packing section 332, two sections.Second intermediate filler is divided between the second intermediate filler district epimere 3221 and the second intermediate filler district hypomere 3222, two sections and is also provided with the second interchanger 3223.This structure of reactor also can control temperature of reaction well.
Reactor shown in Fig. 5 lower packing area is divided into first time packing section 331 and second time packing section 332; Second intermediate filler divides into the second intermediate filler district epimere 3221 and the second intermediate filler district hypomere 3222; Corresponding jacket heat-exchanger is also divided into independently two portions.This reactor also can control temperature of reaction well.
Two filler sections are divided into spaced two portions by the present embodiment, and arrange interchanger between two sections, can remove reaction heat in time, and reaction more easily controls.
Each material sparger includes the ring pipe 63 being positioned at reactor, the entrance of ring pipe connects feed-pipe 64, the many pipe connectings be connected with ring pipe 65 are provided with in the centre hole of ring pipe, each pipe connecting in the present embodiment is arranged as cross-shaped configuration, and ring pipe and each pipe connecting are evenly equipped with multiple material outlet 66.Each pipe connecting also can be arranged to star as required or radially arrange.
The synthetic method of this 4,4-dimethyl-1,3-dioxane comprises the steps:
Phosphate aqueous solution enters reactor from the upper entrance between upper packing area and the first intermediate filler district;
Formalin enters reactor from the first medial inlet being positioned at the first intermediate filler district and the second intermediate filler district;
Tertiary butanol aqueous solution enters reactor from the second medial inlet between the second intermediate filler district and lower packing area;
Iso-butylene enters reactor from the lower entrances be positioned at below lower packing area;
From up to down flow in reactor in phosphoric acid solution and formaldehyde; Trimethyl carbinol part in reactor flows from the top down with aqueous phase, and a part flows from bottom to top with oil phase; Iso-butylene is bottom-up flowing in reactor, with phosphoric acid solution, the trimethyl carbinol and formaldehyde solution counter current contact in reactor, reacts in each packing area, generates 4,4-dimethyl-1,3-dioxane oil phase, namely first time product; First time product rising, the unreacting material carried secretly in uphill process enters packing area, unreacted material reacts further in upper packing area, generate 4,4-dimethyl-1,3-dioxane second time product, second time product rises together with first time product, enter the upper buffer zone be positioned at above packing area, oil phase is discharged from the material outlet in buffer zone;
In reaction process, the liquid product of generation is descending, enters the lower buffer zone be positioned at below intermediate filler district, discharges from the aqueous phase outlet of reactor bottom;
Upper buffer zone is positioned at the top of reactor, and lower buffer zone is positioned at the bottom of reactor.
In reactor, the mol ratio of iso-butylene and the trimethyl carbinol is 0.5 ~ 3, and the mole number sum of iso-butylene and the trimethyl carbinol and the mol ratio of formaldehyde are 1 ~ 6, and the per-cent that phosphoric acid quality accounts for raw material total mass is 2 ~ 8%.
Embodiment 1
In the present embodiment, lower packing area packed height is 8m, and the second intermediate filler district packed height is 1m, and the first intermediate filler district packed height is 0.5m, and upper packing area packed height is 0.5m; Filler is
glass yarn is coiled into
glass spring, falls apart and piles up in each packing area; Reactor inside diameter is
Iso-butylene: purity 99.9%; From the charging of lower material sparger, flow 184g/h, feeding temperature 70 DEG C;
Tertiary butanol aqueous solution: t butanol content 85.1%, from the first intermediate material sparger charging, flow 220g/h, feeding temperature 85 DEG C;
Formalin: formaldehyde content 36.5%, methanol content 1.0%; Flow 165g/h, feeding temperature 86 DEG C;
Phosphate aqueous solution: phosphorus acid content 7.5%; Flow 381g/h, feeding temperature 86 DEG C;
Formalin and phosphate aqueous solution are from the charging of upper feeding sparger.
Second intermediate feed mouth is closed.
Controlling reactor interior reaction temperature is 85 ± 5 DEG C, and reaction pressure is 2.0 ± 0.1MPa.
411g/h oil phase is from reactor top oil phase outlet discharging, and 539g/h aqueous phase is from reactor bottom aqueous phase outlet discharging.
Oil phase and aqueous phase composition are detected, shown in detected result is as shown in table 1.
Embodiment 2
Iso-butylene: purity 99.9%, from lower feed distributor charging, flow 188g/h, feeding temperature 71 DEG C;
Tertiary butanol aqueous solution: t butanol content 85.1%, from the second intermediate feed sparger charging, flow 220g/h, feeding temperature 88 DEG C;
Formalin: formaldehyde content 36.5%, methanol content 1.0%, from the charging of upper feeding sparger, flow 140g/h, feeding temperature 85 DEG C;
Phosphate aqueous solution: phosphorus acid content 7.2%, from the charging of upper feeding sparger, flow 369g/h, feeding temperature 85 DEG C.
First intermediate feed mouth is closed.
Controlling reactor interior reaction temperature is 85 ± 5 DEG C, and reaction pressure is 2.0 ± 0.1MPa.
Oil phase rate of discharge 392g/h, aqueous phase rate of discharge 500g/h.
Oil phase, aqueous phase detected result are as shown in table 1.
Embodiment 3
Lower packing area packed height is 8m, and the second intermediate filler district packed height is 1m, and the first intermediate filler district packed height is 0.5m, and upper packing area packed height is 0.5m; Filler is
glass yarn is coiled into
glass spring, falls apart and piles up in each packing area; Reactor inside diameter is
Iso-butylene: purity 99.9%, from lower feed distributor charging, flow 165g/h, feeding temperature 72 DEG C;
Tertiary butanol aqueous solution: t butanol content 85.1%, from the second intermediate feed sparger charging, flow 214g/h, feeding temperature 90 DEG C;
Formalin: formaldehyde content 36.5%, methanol content 1.0%, from the first intermediate feed sparger charging, flow 132g/h, feeding temperature 80 DEG C;
Phosphate aqueous solution: phosphorus acid content 7.2%, from the charging of upper feeding sparger, flow 359g/h, feeding temperature 88 DEG C.
Controlling reactor interior reaction temperature is 85 ± 5 DEG C, and reaction pressure is 2.0 ± 0.1MPa.
Oil phase rate of discharge 378g/h, aqueous phase rate of discharge 492g/h.The detected result of oil phase and aqueous phase is as shown in table 1.
Embodiment 4
Lower packing area packed height is 8m, and the second intermediate filler district packed height is 1m, and the first intermediate filler district packed height is 0.5m, and upper packing area packed height is 0.5m; Filler is
glass yarn is coiled into
glass spring, falls apart and piles up in each packing area; Reactor inside diameter is
Iso-butylene: purity 99.9%, from lower feed distributor charging, flow 180g/h, feeding temperature 71 DEG C;
Tertiary butanol aqueous solution: t butanol content 85.1%, from the first intermediate feed sparger charging, flow 200g/h, feeding temperature 85 DEG C;
Formalin: formaldehyde content 36.5%, methanol content 1.0%, from the first intermediate feed sparger charging, flow 151g/h, feeding temperature 85 DEG C;
Phosphate aqueous solution: phosphorus acid content 7.2%, from the charging of upper feeding sparger, flow 362g/h, feeding temperature 86 DEG C.
Second intermediate feed mouth is closed.
Controlling reactor interior reaction temperature is 85 ± 5 DEG C, and reaction pressure is 2.0 ± 0.1MPa.
Oil phase rate of discharge 388g/h, aqueous phase rate of discharge 504g/h.
The detected result of aqueous phase and oil phase is as shown in table 1.
Comparative example
Lower packing area packed height is 8m, and the second intermediate filler district packed height is 1m, and the first intermediate filler district packed height is 0.5m, and upper packing area packed height is 0.5m; Filler is
glass yarn is coiled into
glass spring, falls apart and piles up in each packing area; Reactor inside diameter is
Iso-butylene: purity 99.9%, flow 182g/h, feeding temperature 72 DEG C;
Tertiary butanol aqueous solution: t butanol content 85.1%, flow 218g/h, feeding temperature 85 DEG C;
Formalin: formaldehyde content 36.5%, methanol content 1.0%, flow 153g/h, feeding temperature 85 DEG C;
Phosphate aqueous solution: phosphorus acid content 7.2%, from the charging of upper feeding sparger, flow 379g/h, feeding temperature 86 DEG C.
Each raw material enters from reactor bottom aqueous phase discharge port after merging, and discharges reactor from top oil phase discharge port, gets rid of material and enters a receiving vessel, oil phase from container portion is got rid of, aqueous phase is got rid of from oil phase bottom, and metering and sampling analysis, contrast with each embodiment data respectively.
Controlling reactor interior reaction temperature is 85 ± 5 DEG C, and reaction pressure is 2.0 ± 0.1MPa.
Oil phase rate of discharge 400g/h, aqueous phase rate of discharge 532g/h.
The detected result of aqueous phase and oil phase is as shown in table 1.
Feeding intake and product amount, product detection data sheet of each embodiment of table 1
Note: in table, MBD is 3-methyl isophthalic acid, 3-butyleneglycol; Methyl butenol comprises 3-methyl-3-butene-1-alcohol, 3-M2BOL, 2-methyl-3-butene-1-alcohol three kinds.
Embodiment data each in table 1 are average, and compare with comparative example, as table 2.
Table 2: embodiment and comparative example comparison sheet
As seen from Table 2:
Embodiments of the invention mean value, compared with comparative example mean value, has following comparatively marked difference:
(1) in oil phase, main intermediate DMD content increases by 3 percentage points, and relative increasing amount is about 18%;
(2) formaldehyde content in oil phase and aqueous phase all than low in comparative example, relative reducing amount about 50%;
(3) oil phase is that other (by products) reduce than comparative example, relative reducing amount about 33%.
Claims (8)
1. the synthetic method of a dimethyl-1,3-dioxane, is characterized in that comprising the steps:
Temperature is that the phosphoric acid solution of 80-90 DEG C enters reactor from the upper entrance between upper packing area and the first intermediate filler district, flows through the first intermediate filler district, the second intermediate filler district and lower packing area in reactor from top to bottom successively;
Temperature is that the formaldehyde of 80-90 DEG C enters reactor from the first medial inlet between the first intermediate filler district and the second intermediate filler district; During formaldehyde is soluble in the aqueous phase, flow through the second intermediate filler district and lower packing area from top to bottom successively with aqueous phase;
Temperature is that the trimethyl carbinol of 80-90 DEG C enters reactor from the second medial inlet between the second intermediate filler district and lower packing area; Temperature is that the iso-butylene of 70-75 DEG C enters reactor from the lower entrances be positioned at below lower packing area, upwards flows from lower packing area;
The trimethyl carbinol can be soluble in the aqueous phase, and also can be dissolved in iso-butylene oil phase, and trimethyl carbinol part in reactor is soluble in the aqueous phase and flows from the top down with aqueous phase, and a part flows from bottom to top with oil phase;
Iso-butylene and phosphoric acid solution, the trimethyl carbinol and formaldehyde solution counter current contact in reactor, react in each packing area, generates 4,4-dimethyl-1,3-dioxane oil phase, namely first time product; First time product rising, the unreacting material carried secretly in uphill process enters packing area, unreacted material reacts further in upper packing area, generate 4,4-dimethyl-1,3-dioxane second time product, second time product rises together with first time product, enter the upper buffer zone be positioned at above packing area, oil phase is discharged from the material outlet in buffer zone;
In reaction process, the liquid product of generation is descending, enters the lower buffer zone be positioned at below lower packing area, discharges from the aqueous phase outlet of bottom;
Controlling reactor interior reaction temperature is 70 ~ 130 DEG C, reaction pressure is 1.7 ~ 2.3MPa, the mol ratio of iso-butylene and the trimethyl carbinol is 0.5 ~ 3, the mole number sum of iso-butylene and the trimethyl carbinol and the mol ratio of formaldehyde are 1 ~ 6, inorganics and organic weight ratio are 1-3, the percentage ratio that phosphoric acid quality accounts for charging total mass is 2 ~ 8%, and the residence time of iso-butylene in reactor is 0.5 ~ 2 hour.
2. the synthetic method of a dimethyl-1,3-dioxane, is characterized in that comprising the steps:
Temperature is that the phosphoric acid solution of 80-90 DEG C enters reactor from the upper entrance between upper packing area and the first intermediate filler district, flows through the first intermediate filler district, the second intermediate filler district and lower packing area in reactor from top to bottom successively;
To be the formaldehyde of 80-90 DEG C and temperature be temperature that the trimethyl carbinol of 80-90 DEG C enters reactor from the second medial inlet between the second intermediate filler district and lower packing area;
Temperature is that the iso-butylene of 70-75 DEG C enters reactor from the lower entrances be positioned at below lower packing area, upwards flows from lower packing area;
In reactor, phosphoric acid and formaldehyde flow from the top down with aqueous phase, flow through the packing area below corresponding opening for feed successively, and iso-butylene upwards flows from lower packing area in reactor, flow through each packing area of iso-butylene entrance top successively; Trimethyl carbinol part in reactor is soluble in the aqueous phase, and flow downward with aqueous phase, a part is dissolved in oil phase, upwards flows with oil phase;
Iso-butylene and phosphoric acid solution, the part trimethyl carbinol and formaldehyde solution counter current contact in reactor, react in each packing area, generates 4,4-dimethyl-1,3-dioxane oil phase, namely first time product; First time product rising, the unreacting material carried secretly in uphill process enters packing area, unreacted material reacts further in upper packing area, generate 4,4-dimethyl-1,3-dioxane second time product, second time product rises together with first time product, enter the upper buffer zone be positioned at above packing area, oil phase is discharged from the material outlet in buffer zone;
In reaction process, the liquid product of generation is descending, enters the lower buffer zone be positioned at below lower packing area, discharges from the aqueous phase outlet of bottom;
Controlling reactor interior reaction temperature is 70 ~ 130 DEG C, reaction pressure is 1.7 ~ 2.3MPa, the mol ratio of iso-butylene and the trimethyl carbinol is 0.5 ~ 3, the mole number sum of iso-butylene and the trimethyl carbinol and the mol ratio of formaldehyde are 1 ~ 6, inorganics and organic weight ratio are 1-3, the percentage ratio that phosphoric acid quality accounts for charging total mass is 2 ~ 8%, and the residence time of iso-butylene in reactor is 0.5 ~ 2 hour.
3. the synthetic method of a dimethyl-1,3-dioxane, is characterized in that comprising the steps:
To be the phosphoric acid solution of 80-90 DEG C and temperature be temperature that the formaldehyde solution of 80-90 DEG C enters reactor from the upper entrance between upper packing area and the first intermediate filler district, flows through packing area, the first intermediate filler district, the second intermediate filler district and lower packing area in reactor from top to bottom successively;
Temperature is that the trimethyl carbinol of 80-90 DEG C enters reactor from the second medial inlet being positioned at the first intermediate filler district and the second intermediate filler district;
Temperature is that the iso-butylene of 70-75 DEG C enters reactor from the lower entrances be positioned at below lower packing area;
Phosphoric acid solution and formaldehyde from up to down flow in reactor; Trimethyl carbinol part in reactor is soluble in the aqueous phase and flows from the top down with aqueous phase, and a part is dissolved in oil phase and flows from bottom to top with oil phase; Iso-butylene is bottom-up flowing in reactor, with phosphoric acid solution, the trimethyl carbinol and formaldehyde solution counter current contact in reactor, reacts in each packing area, generates 4,4-dimethyl-1,3-dioxane oil phase, namely first time product; First time product rising, the unreacting material carried secretly in uphill process enters packing area, unreacted material reacts further in upper packing area, generate 4,4-dimethyl-1,3-dioxane second time product, second time product rises together with first time product, enter the upper buffer zone be positioned at above packing area, oil phase is discharged from the material outlet in buffer zone;
In reaction process, the liquid product of generation is descending, enters the lower buffer zone be positioned at below lower packing area, discharges from the aqueous phase outlet of reactor bottom;
Upper buffer zone is positioned at the top of reactor, and lower buffer zone is positioned at the bottom of reactor;
Controlling temperature of reaction is 70 ~ 130 DEG C, and reaction pressure is 1.7 ~ 2.3MPa;
In reactor, the mol ratio of iso-butylene and the trimethyl carbinol is 0.5 ~ 3, the mole number sum of iso-butylene and the trimethyl carbinol and the mol ratio of formaldehyde are 1 ~ 6, inorganics and organic weight ratio are 1-3, the percentage ratio that phosphoric acid quality accounts for charging total mass is 2 ~ 8%, and the residence time of iso-butylene in reactor is 0.5 ~ 2 hour.
4. the synthetic method according to claim 1,2 or 3, it is characterized in that the height of described upper packing area accounts for 5 ~ 20% of total filler height, the height in described first intermediate filler district accounts for 3 ~ 7% of total filler height, the height in described second intermediate filler district accounts for 3 ~ 7% of total filler height, and the height of described lower packing area accounts for 66 ~ 89% of total filler district height; The height sum of each packing area is total filler height, and described total filler height stops with iso-butylene material and is as the criterion for 0.5 ~ 2 hour in reactor.
5. synthetic method according to claim 4, it is characterized in that the mol ratio of described iso-butylene and the trimethyl carbinol is 1 ~ 2, iso-butylene be 1.5 ~ 3.5 with the mol ratio of the mole number sum formaldehyde of the trimethyl carbinol, inorganics and organic weight ratio are 1-2, and the percentage ratio that phosphoric acid quality accounts for charging total mass is 3 ~ 5%;
Controlling temperature of reaction is 80 ~ 100 DEG C, and reaction pressure is 1.9 ~ 2.1MPa.
6. synthetic method according to claim 5, is characterized in that described lower packing area is divided into two sections, and is provided with First Heat Exchanger between two sections.
7. synthetic method according to claim 5, is characterized in that corresponding to described upper packing area, the first intermediate filler district, the second intermediate filler district and lower packing area, the outer wall of described reactor is respectively equipped with jacket heat-exchanger.
8. synthetic method according to claim 7, is characterized in that described second intermediate filler divides into two sections, is namely positioned at the second intermediate filler district epimere and the second intermediate filler district hypomere of top, and the jacket heat-exchanger corresponding to two sections is independent separately.
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| RU2764518C1 (en) * | 2021-03-16 | 2022-01-18 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Method for producing 4,4-dimethyl-1,3-dioxane using polyarylene phthalide |
| RU2764517C1 (en) * | 2021-03-16 | 2022-01-18 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Method for producing 4,4-dimethyl-1,3-dioxane using carbon nanotubes |
| RU2764520C1 (en) * | 2021-03-16 | 2022-01-18 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Method for obtaining 4,4-dimethyl-1,3-dioxane (variants) |
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