CN105017207B - The synthetic method of one kind 4,4- dimethyl-1,3-dioxanes - Google Patents
The synthetic method of one kind 4,4- dimethyl-1,3-dioxanes Download PDFInfo
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- CN105017207B CN105017207B CN201510429235.7A CN201510429235A CN105017207B CN 105017207 B CN105017207 B CN 105017207B CN 201510429235 A CN201510429235 A CN 201510429235A CN 105017207 B CN105017207 B CN 105017207B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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 present invention relates to one kind 4,4 dimethyl 1, the synthetic method of 3 dioxane, reaction monomers enter reactor from different entrances respectively, and wherein organic phase isobutene or the C-4-fraction containing isobutene enters from reactor lower part, flow up, water phase phosphoric acid solution enters from reactor top, flows downward, aqueous-phase material material and oil phase material counter current contacting in multistage packing area, it is fully dispersed, promote reaction；The water obtained after reaction is mutually discharged from bottom, and oil phase is discharged from top.Reaction conversion ratio is high, reaction is more thorough, greatly reduces the side reaction caused by formaldehyde in lower procedure, and reaction is easy to control；And can also be according to output demand, by adjusting the entrance of the tert-butyl alcohol and formaldehyde come technological operation optimization condition in same reactor, reaction is set to reach optimum efficiency, especially when reaction is fluctuated, it can improve and preferably control response situation by adjusting the entry position of isobutanol and formaldehyde.
Description
Technical field
The present invention relates to the synthesis of chemical intermediate, refers specifically to the synthesis of one kind 4,4- dimethyl-1,3-dioxanes
Method.
Background technology
Isoprene is a kind of important industrial chemicals, can be isolated from cracked C 5 fraction, can also pass through chemistry
Synthesis obtains.
The method of synthesis isoprene mainly has two kinds：First, dehydriding, i.e., passed through using isopentane or iso-amylene as raw material
Catalytic dehydrogenation generates isoprene.There are two step method of dehydrogenating of isopentane and a step dehydriding.Another is olefine aldehydr method, i.e., with isobutene
Or C-4-fraction containing isobutene or the tert-butyl alcohol, formaldehyde are raw material, first synthetic intermediate 4,4- dimethyl -1,3- dioxy six
Ring, abbreviation DMD, then DMD, which is decomposed, obtains isoprene.Olefine aldehydr method divides gas phase olefine aldehydr method and liquid phase olefine aldehydr method again.The dilute aldehyde of gas phase
Method is to use heteropolyacid catalyst, and gaseous state isobutene generates intermediate DMD with formaldehyde by catalyst bed reaction, then by
Mesosome is separated, and is decomposed and is obtained isoprene.Liquid phase method is that C-4-fraction, the tert-butyl alcohol and formaldehyde react in strong acid aqueous solution
Intermediate DMD is generated, then intermediate DMD is decomposed in strong acid aqueous solution and obtains isoprene.
Reactor used in liquid phase method mainly has the tank reactor with stirring, shell and tube reactor and hollow interior plus disk
Tubular type；The characteristics of both forms institute is common is all forward flow operation, i.e., each material co-flow in the reactor, typically by anti-
Device bottom is answered to be flowed to top, also some is from top to flows.However, due to aqueous-phase material material and oil phase thing in reactor
The density of material is different, and the flowing velocity of two phase materials in the reactor is different：When being flowed from bottom to top, oil phase stream
It is dynamic mutually faster than water, thus the actual residence time of oil phase in the reactor be smaller than the water phase residence time；In turn, when from top
During to flows, aqueous phase stream is moved than oil phase flowing soon, and the actual residence time of oil phase in the reactor will be longer than water and mutually stop
Time.Also, the residence time of this oil phase and water mutually in the reactor, is controlled from operation, cause reaction not exclusively,
By-product is high, product yield is low, and reaction result is undesirable.
The content of the invention
The technical problems to be solved by the invention are that the present situation for being directed to the prior art provides a kind of reaction conversion ratio height, reaction
More thorough isoprene intermediate 4, the synthetic method of 4- dimethyl-1,3-dioxanes.
Technical solution is used by the present invention solves above-mentioned technical problem：The temperature be 80-90 DEG C phosphoric acid solution from
Upper entrance between upper packing area and the first intermediate filler area enters reactor, is flowed successively from top to bottom in reactor
Through the first intermediate filler area, the second intermediate filler area and lower packing area；
Temperature is 80-90 DEG C of formaldehyde among first between the first intermediate filler area and the second intermediate filler area
Entrance enters reactor；During formaldehyde is soluble in the aqueous phase, mutually filled out from top to bottom followed by the second intermediate filler area with water
Expect area；
Temperature is 80-90 DEG C of the tert-butyl alcohol from the second medial inlet between the second intermediate filler area and lower packing area
Into reactor；Temperature is that 70-75 DEG C of isobutene enters reactor from the lower entrances below lower packing area, is filled out under
Material area flows up；
The tert-butyl alcohol can be soluble in the aqueous phase, and can also be dissolved in isobutene oil phase, and tert-butyl alcohol part in reactor is soluble in the aqueous phase
Mutually flowed from the top to the bottom with water, a part flows from bottom to top with oil phase；
Isobutene and phosphoric acid solution, the tert-butyl alcohol and the formalin counter current contacting in reactor, occur in each packing area
Reaction, generates 4,4- dimethyl-1,3-dioxane oil phases, i.e. first time product；First time product rises, and is pressed from both sides in uphill process
The unreacting material of band enters buffering packing area, and unreacted material further reacts in buffering packing area, 4, the 4- bis- of generation
Methyl isophthalic acid, second of product of 3- dioxane, second of product rise together with first time product, on upper packing area
The upper buffering area of side, material outlet discharge of the oil phase out of upper buffering area；
In reaction process, the liquid product downlink of generation, into the lower buffering area below lower packing area, from bottom
Water mutually export discharge；
It is 70~130 DEG C to control reactor interior reaction temperature, and reaction pressure is 1.7~2.3MPa, isobutene and the tert-butyl alcohol
Molar ratio be 0.5~3, the molar ratio of the sum of molal quantity of isobutene and the tert-butyl alcohol and formaldehyde is 1~6, inorganic matter with it is organic
The weight ratio of thing is 1-3, and the percentage that phosphoric acid quality accounts for raw material gross mass is 2~8%, during stop of the isobutene in reactor
Between for 0.5~2 it is small when.Determining for residence time is related with reaction temperature, and reaction temperature is high, then the residence time is short, reaction temperature
Low, then the residence time is relatively long.
Alternatively, the synthetic method of 4, the 4- dimethyl-1,3-dioxanes, it is characterised in that comprise the following steps：
Temperature be 80-90 DEG C phosphoric acid solution from the upper entrance between upper packing area and the first intermediate filler area into
Enter reactor, from top to bottom followed by the first intermediate filler area, the second intermediate filler area and lower packing area in reactor；
The tert-butyl alcohol that the formaldehyde and temperature that temperature is 80-90 DEG C are 80-90 DEG C is filled out from positioned at the second intermediate filler area with
The second medial inlet between material area enters reactor；
Temperature is that 70-75 DEG C of isobutene enters reactor from the lower entrances below lower packing area, from lower filler
Area flows up；
In reactor, phosphoric acid is mutually flowed from the top to the bottom with formaldehyde with water, followed by the packing area below corresponding feed inlet,
Isobutene flows up in reactor from lower packing area, followed by each packing area of isobutene entrance top；The tert-butyl alcohol exists
A part is soluble in the aqueous phase in reactor, is mutually flowed downwardly together with water, a part is dissolved in oil phase, is flowed up with oil phase；
Isobutene and phosphoric acid solution, the part tert-butyl alcohol and the formalin counter current contacting in reactor, in each packing area
React, generate 4,4- dimethyl-1,3-dioxane oil phases, i.e. first time product；First time product rises, uphill process
The unreacting material of middle entrainment enters upper packing area, and unreacted material further reacts in upper packing area, 4, the 4- bis- of generation
Methyl isophthalic acid, second of product of 3- dioxane, second of product rise together with first time product, on upper packing area
The upper buffering area of side, material outlet discharge of the oil phase out of upper buffering area；
In reaction process, the water-phase product of generation is with water phase downlink, into the lower buffering area below lower packing area,
Discharge is mutually exported from the water of bottom；
It is 70~130 DEG C to control reactor interior reaction temperature, and reaction pressure is 1.7~2.3MPa, isobutene and the tert-butyl alcohol
Molar ratio be 0.5~3, the molar ratio of the sum of molal quantity of isobutene and the tert-butyl alcohol and formaldehyde is 1~6, inorganic matter with it is organic
The weight ratio of thing is 1-3, and the percentage that phosphoric acid quality accounts for charging gross mass is 2~8%, during stop of the isobutene in reactor
Between for 0.5~2 it is small when.
Alternatively, the synthetic method of 4, the 4- dimethyl-1,3-dioxanes, it is characterised in that comprise the following steps：
The formalin that the phosphoric acid solution and temperature that temperature is 80-90 DEG C are 80-90 DEG C is from positioned at upper packing area and first
Upper entrance between intermediate filler area enters reactor, in reactor from top to bottom followed by the first intermediate filler area,
Second intermediate filler area and lower packing area；
Temperature is that 80-90 DEG C of the tert-butyl alcohol enters among the second of the first intermediate filler area and the second intermediate filler area
Mouth enters reactor；
Temperature is that 70-75 DEG C of isobutene enters reactor from the lower entrances below lower packing area；
Phosphoric acid solution and formaldehyde flow from up to down in reactor；Tert-butyl alcohol part in reactor be soluble in the aqueous phase with
Water mutually flows from the top to the bottom together, and a part is dissolved in oil phase and is flowed from bottom to top with oil phase；Isobutene in reactor from
Under flow up, with phosphoric acid solution, the tert-butyl alcohol and formalin in reactor counter current contacting, occur in each packing area anti-
Should, generate 4,4- dimethyl-1,3-dioxane oil phases, i.e. first time product；First time product rises, and is carried secretly in uphill process
Unreacting material enter buffering packing area, unreacted material buffering packing area in further react, 4, the 4- diformazans of generation
Second of product of base -1,3- dioxane, second of product rise together with first time product, into above upper packing area
Upper buffering area, oil phase out of upper buffering area oil phase outlet discharge；
In reaction process, the water-phase product downlink of generation, into the lower buffering area below lower packing area, from reactor
The water of bottom mutually exports discharge；
Upper buffering area is located at the top of reactor, and lower buffering area is located at the bottom of reactor；
Controlling reaction temperature is 70~130 DEG C, and reaction pressure is 1.7~2.3MPa；
In reactor, the molar ratio of isobutene and the tert-butyl alcohol is 0.5~3, the sum of molal quantity of isobutene and the tert-butyl alcohol with
The molar ratio of formaldehyde is 1~6, and the weight ratio of inorganic matter and organic matter is 1-3, and the percentage that phosphoric acid quality accounts for charging gross mass is
2~8%, when residence time of the isobutene in reactor is 0.5~2 small.
Preferably, the height of the upper packing area accounts for the 5~20% of total filler height, the height in the first intermediate filler area
Degree accounts for the 3~7% of total filler height, and the height in the second intermediate filler area accounts for the 3~7% of total filler height, is filled out under described
The height in material area accounts for the 66~89% of total filler area height；The sum of height of each packing area is total filler height, described always to fill out
Material height be subject to isobutene material stopped in reactor 0.5~2 it is small when.
It is preferred that the molar ratio of the isobutene and the tert-butyl alcohol is 1~2, the sum of molal quantity of isobutene and the tert-butyl alcohol and formaldehyde
Molar ratio be 1.5~3.5, the weight ratio of inorganic matter and organic matter be 1-2, the percentage that phosphoric acid accounts for raw material gross weight is 3~
5%；
Controlling reaction temperature is 80~100 DEG C, and reaction pressure is 1.9~2.1MPa.
For more accurately controlling reaction temperature, the lower filler can be divided into two sections, and be equipped between two sections
First Heat Exchanger.
Inorganic matter in above-mentioned each scheme is phosphoric acid and water, and organic matter is the other materials in addition to phosphoric acid and water, including different
Butylene, formaldehyde and the tert-butyl alcohol.
Alternatively, correspond to the upper packing area, the first intermediate filler area, the second intermediate filler area and lower packing area, in institute
State and jacket heat-exchanger is respectively equipped with the outer wall of reactor.
Further, the second intermediate filler area can also be divided into two sections, i.e., the second intermediate filler area above
Epimere and the second intermediate filler area hypomere, the jacket heat-exchanger corresponding to two sections are each independent.
The present invention is much larger than the dissolving distribution coefficient in organic phase using dissolving distribution coefficient of the formaldehyde in water phase, anti-
Answer mutually feed from it with dampening in device and flow downward at the mouth of pipe, isobutene is then to flow from bottom to top in the reactor, two
The reactant of chemically reactive inversely contacts, and is all to be contacted before reactor is left with another reactant of maximum concentration, reaction
Carry out more thorough, reaction conversion ratio greatly improves；Packing area more than the formaldehyde charging mouth of pipe, will can on a small quantity dissolve distribution
The isobutene of formaldehyde and excessive concentrations in organic phase is reacted, and reactor is left so as to substantially reduce from reactor head
Oil phase in formaldehyde content, how caused greatly reduce unreacting acetal in the lower procedure i.e. decomposition process of intermediate DMD
Side reaction occurs.
Compared with prior art, reaction mass counter current contacting in the reactor, reaction conversion ratio is high, reaction is more thorough,
The side reaction caused by formaldehyde in lower procedure is greatly reduced, and reaction is easy to control；And can also according to output demand,
By adjusting the entrance of the tert-butyl alcohol and formaldehyde come technological operation optimization condition in same reactor, reaction is set to reach optimum efficiency,
Especially when reaction is fluctuated, it can be reacted by adjusting the entry position of isobutanol and formaldehyde to improve and preferably control
Situation.
Brief description of the drawings
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 distributor 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
The present invention is described in further detail below in conjunction with attached drawing embodiment.
Structure of reactor used in the synthetic method of 4, the 4- dimethyl-1,3-dioxanes is described as follows：
As shown in Figure 1 to Figure 3, the synthesizer of 4, the 4- dimethyl-1,3-dioxanes includes：
Reactor 1, is vertical structure, its top is equipped with gaseous phase outlet 11 and two pressure detecting mouths 12, the bottom of reactor
Portion mutually exports 13 equipped with water.Gaseous phase outlet 11 is connected to the surge tank 14 of constant reactor pressure.Gas can not also be set
Mutually outlet and surge tank, reactor pressure is controlled by the gas of the top accumulation in upper buffering area.
It is equipped with upper buffering area 2, packing area and lower buffering area 4 in reactor successively from top to bottom；Wherein, packing area includes upper
Packing area 31, intermediate filler area and lower packing area 33；And intermediate filler area is divided among two sections, including above first
Packing area 321 and underlying second intermediate filler area 322, wherein below the first intermediate filler area first in feed distribution
Device connects formaldehyde entrance, the feed distributor connection tert-butyl alcohol entrance below the second intermediate filler area.
Each packing area is arranged at intervals, and including upper backup pad and lower supporting plate and is filled between upper and lower support plate
Filler, upper and lower support plate are engraved structure and are connected on the inner wall of the vertical reactor；To facilitate the flowing of material simultaneously
Avoid impact of the logistics to filler in packing area.Filler can select any one rectifying tower packing in the prior art, Ke Yiwei
Structured packing, or random packing, the present embodiment are random packing.
Feed distributor is equipped with thereunder corresponding to each packing area；Wherein close to the upper feeding distributor of upper packing area
51 connection phosphoric acid water phase entrances 61, upper feeding distributor goes out mouth down；Underlying lower feed distributor 53 connects isobutyl
Alkene entrance 63, the outlet of lower feed distributor is upward；Feed distributor 521 connects in the first of the lower section of first intermediate filler area 321
Connect the first middle charging aperture 621 i.e. formaldehyde entrance, feed distributor 521 goes out mouth down in first；Under second intermediate filler area 322
It is tert-butyl alcohol entrance that feed distributor 522, which connects the second middle charging aperture 622, in the second of side, the outlet of feed distributor in second
Downward.That is, in the present invention each feed distributor in addition to the outlet upward of underlying lower feed distributor, remaining
The packing area all exported downward.The outer wall of reactor is equipped with and the corresponding jacket heat-exchanger in each packing area
15。
The reactor shown in Fig. 4 can also be used, lower filler is divided into two sections, i.e. first time packing section 331 and second
Lower packing section 332, is equipped with First Heat Exchanger 333 between two sections.Second intermediate filler divides into the second intermediate filler area epimere
3221 and the second intermediate filler area hypomere 3222, the second heat exchanger 3223 also is provided between two sections.The structure of reactor also can
Controlling reaction temperature well.
Reactor shown in Fig. 5 is that lower filler is divided into first time packing section 331 and second time packing section 332；Second
Intermediate filler divides into the second intermediate filler area epimere 3221 and the second intermediate filler area hypomere 3222；Corresponding jacket heat-exchanger
It is also classified into independent two parts.The reactor also being capable of controlling reaction temperature well.
Two filler sections are divided into spaced two parts by the present embodiment, and set heat exchanger between two sections,
Reaction heat can be removed in time, and reaction is easier to control.
Each material distributor includes the ring pipe 63 in reactor, the entrance connection feed pipe 64 of ring pipe, ring
It is equipped with the more connecting tubes 65 being connected with ring pipe in the centre bore of shape pipe, each connecting tube in the present embodiment is arranged as cross
Multiple material outlets 66 are evenly equipped with type structure, ring pipe and each connecting tube.Each connecting tube can also be arranged to star as needed
Shape or radial arrangement.
The synthetic method of 4, the 4- dimethyl-1,3-dioxanes comprises the following steps：
Phosphate aqueous solution enters reactor from the upper entrance between upper packing area and the first intermediate filler area；
Formalin enters reaction from positioned at first medial inlet in the first intermediate filler area and the second intermediate filler area
Device；
Tertiary butanol aqueous solution enters reaction from the second medial inlet between the second intermediate filler area and lower packing area
Device；
Isobutene enters reactor from the lower entrances below lower packing area；
Flowed from up to down in reactor in phosphoric acid solution and formaldehyde；The tert-butyl alcohol in reactor a part with water mutually from upper
Flow downward, a part flows from bottom to top with oil phase；Isobutene bottom-up flowing in reactor, with phosphoric acid solution, uncle
Butanol and the formalin counter current contacting in reactor, react in each packing area, generate 4,4- dimethyl -1,3- dioxies
Six ring oil phases, i.e. first time product；First time product rises, and the unreacting material carried secretly in uphill process enters upper packing area,
Unreacted material further reacts in upper packing area, 4,4- dimethyl-1,3-dioxanes, second of product of generation, and second
Secondary product rises together with first time product, into the upper buffering area above upper packing area, thing of the oil phase out of buffering area
Material outlet discharge；
In reaction process, the liquid product downlink of generation, into the lower buffering area below intermediate filler area, from reaction
The water of device bottom mutually exports discharge；
Upper buffering area is located at the top of reactor, and lower buffering area is located at the bottom of reactor.
In reactor, the molar ratio of isobutene and the tert-butyl alcohol is 0.5~3, the sum of molal quantity of isobutene and the tert-butyl alcohol with
The molar ratio of formaldehyde is 1~6, and the percentage that phosphoric acid quality accounts for raw material gross mass is 2~8%.
Embodiment 1
In the present embodiment, lower packing area packed height is 8m, and the second intermediate filler area packed height is 1m, is filled out among first
Material area's packed height is 0.5m, and upper packing area packed height is 0.5m；Filler isWhat glass fiber was coiled into
Glass spring, dissipates and piles up in each packing area；Reactor inside diameter is
Isobutene：Purity 99.9%；Fed from lower material distributor, flow 184g/h, 70 DEG C of feeding temperature；
Tertiary butanol aqueous solution：T butanol content 85.1%, feeds, flow 220g/h from the first intermediate material distributor, into
85 DEG C of material temperature degree；
Formalin：Content of formaldehyde 36.5%, methanol content 1.0%；86 DEG C of flow 165g/h, feeding temperature；
Phosphate aqueous solution：Phosphorus acid content 7.5%；Flow 381g/h, 86 DEG C of feeding temperature；
Formalin and phosphate aqueous solution are fed from upper feeding distributor.
Second intermediate feed mouth is closed.
It is 85 ± 5 DEG C to control reactor interior reaction temperature, and reaction pressure is 2.0 ± 0.1MPa.
411g/h oil phases are exported from reactor top oil phase and discharged, and 539g/h water mutually mutually exports out from reactor bottom water
Material.
Oil phase and water phase composition are detected, testing result is shown as shown in table 1.
Embodiment 2
Isobutene：Purity 99.9%, feeds, flow 188g/h, 71 DEG C of feeding temperature from lower feed distributor；
Tertiary butanol aqueous solution：T butanol content 85.1%, feeds, flow 220g/h from the second intermediate feed distributor, into
88 DEG C of material temperature degree；
Formalin：Content of formaldehyde 36.5%, methanol content 1.0%, feeds, flow 140g/ from upper feeding distributor
H, 85 DEG C of feeding temperature；
Phosphate aqueous solution：Phosphorus acid content 7.2%, feeds, flow 369g/h, 85 DEG C of feeding temperature from upper feeding distributor.
First intermediate feed mouth is closed.
It is 85 ± 5 DEG C to control reactor interior reaction temperature, and reaction pressure is 2.0 ± 0.1MPa.
Oil phase rate of discharge 392g/h, water phase rate of discharge 500g/h.
Oil phase, water phase testing result are as shown in table 1.
Embodiment 3
Lower packing area packed height is 8m, and the second intermediate filler area packed height is 1m, and the first intermediate filler area filler is high
It is 0.5m to spend for 0.5m, upper packing area packed height；Filler isWhat glass fiber was coiled intoGlass spring,
Dissipate and pile up in each packing area；Reactor inside diameter is
Isobutene：Purity 99.9%, feeds, flow 165g/h, 72 DEG C of feeding temperature from lower feed distributor；
Tertiary butanol aqueous solution：T butanol content 85.1%, feeds, flow 214g/h from the second intermediate feed distributor, into
90 DEG C of material temperature degree；
Formalin：Content of formaldehyde 36.5%, methanol content 1.0%, feeds, flow from the first intermediate feed distributor
132g/h, 80 DEG C of feeding temperature；
Phosphate aqueous solution：Phosphorus acid content 7.2%, feeds, flow 359g/h, 88 DEG C of feeding temperature from upper feeding distributor.
It is 85 ± 5 DEG C to control reactor interior reaction temperature, and reaction pressure is 2.0 ± 0.1MPa.
Oil phase rate of discharge 378g/h, water phase rate of discharge 492g/h.The testing result of oil phase and water phase is as shown in table 1.
Embodiment 4
Lower packing area packed height is 8m, and the second intermediate filler area packed height is 1m, and the first intermediate filler area filler is high
It is 0.5m to spend for 0.5m, upper packing area packed height；Filler isWhat glass fiber was coiled intoGlass spring,
Dissipate and pile up in each packing area；Reactor inside diameter is
Isobutene：Purity 99.9%, feeds, flow 180g/h, 71 DEG C of feeding temperature from lower feed distributor；
Tertiary butanol aqueous solution：T butanol content 85.1%, feeds, flow 200g/h from the first intermediate feed distributor, into
85 DEG C of material temperature degree；
Formalin：Content of formaldehyde 36.5%, methanol content 1.0%, feeds, flow from the first intermediate feed distributor
151g/h, 85 DEG C of feeding temperature；
Phosphate aqueous solution：Phosphorus acid content 7.2%, feeds, flow 362g/h, 86 DEG C of feeding temperature from upper feeding distributor.
Second intermediate feed mouth is closed.
It is 85 ± 5 DEG C to control reactor interior reaction temperature, and reaction pressure is 2.0 ± 0.1MPa.
Oil phase rate of discharge 388g/h, water phase rate of discharge 504g/h.
Water phase and the testing result of oil phase are as shown in table 1.
Comparative example
Lower packing area packed height is 8m, and the second intermediate filler area packed height is 1m, and the first intermediate filler area filler is high
It is 0.5m to spend for 0.5m, upper packing area packed height；Filler isWhat glass fiber was coiled intoGlass spring,
Dissipate and pile up in each packing area；Reactor inside diameter is
Isobutene：Purity 99.9%, flow 182g/h, 72 DEG C of feeding temperature；
Tertiary butanol aqueous solution：T butanol content 85.1%, flow 218g/h, 85 DEG C of feeding temperature；
Formalin：Content of formaldehyde 36.5%, methanol content 1.0%, flow 153g/h, 85 DEG C of feeding temperature；
Phosphate aqueous solution：Phosphorus acid content 7.2%, feeds, flow 379g/h, 86 DEG C of feeding temperature from upper feeding distributor.
Each raw material enters after merging from reactor bottom water phase discharge port, and reactor, row are discharged from top oil phase discharge port
Except material enters a reception container, portion excludes oil phase from container, and water is mutually excluded from oil phase lower part, respectively metering and sampling point
Analysis, is contrasted with each embodiment data.
It is 85 ± 5 DEG C to control reactor interior reaction temperature, and reaction pressure is 2.0 ± 0.1MPa.
Oil phase rate of discharge 400g/h, water phase rate of discharge 532g/h.
Water phase and the testing result of oil phase are as shown in table 1.
1 each embodiment of table feed intake and product amount, product detection tables of data
Note：MBD is 3- methyl isophthalic acids in table, 3- butanediols；Methyl butenol includes 3- methyl-3-butene-1-alcohols, 3- first
Base -2- butene-1-ols, three kinds of 2- methyl-3-butene-1-alcohols.
Each embodiment data in table 1 are averaged, and compared with comparative example, such as table 2.
Table 2：Embodiment and comparative example comparison sheet
As seen from Table 2：
The embodiment of the present invention average value has following more marked difference compared with comparative example average value：
(1) main intermediate DMD contents increase by 3 percentage points in oil phase, are about 18% with respect to raising amount；
(2) content of formaldehyde in oil phase and water phase is lower than in comparative example, relative reduction amount about 50%；
(3) oil phase is that other (accessory substances) are reduced than comparative example, relative reduction amount about 33%.
Claims (8)
1. one kind 4, the synthetic method of 4- dimethyl-1,3-dioxanes, it is characterised in that comprise the following steps：
The phosphoric acid solution that temperature is 80-90 DEG C enters anti-from the upper entrance between upper packing area and the first intermediate filler area
Device is answered, from top to bottom followed by the first intermediate filler area, the second intermediate filler area and lower packing area in reactor；
Temperature is 80-90 DEG C of formaldehyde from the first medial inlet between the first intermediate filler area and the second intermediate filler area
Into reactor；During formaldehyde is soluble in the aqueous phase, with water mutually from top to bottom followed by the second intermediate filler area and lower packing area；
The tert-butyl alcohol that temperature is 80-90 DEG C enters from the second medial inlet between the second intermediate filler area and lower packing area
Reactor；Temperature is that 70-75 DEG C of isobutene enters reactor from the lower entrances below lower packing area, from lower packing area
Flow up；
The tert-butyl alcohol can be soluble in the aqueous phase, and can also be dissolved in isobutene oil phase, and tert-butyl alcohol part in reactor is soluble in the aqueous phase with water
Mutually flow from the top to the bottom, a part flows from bottom to top with oil phase；
Isobutene and phosphoric acid solution, the tert-butyl alcohol and the formalin counter current contacting in reactor, react in each packing area,
Generate 4,4- dimethyl-1,3-dioxane oil phases, i.e. first time product；First time product rises, and is carried secretly in uphill process
Unreacting material enters upper packing area, and unreacted material further reacts in upper packing area, 4,4- of generation dimethyl -1,3- bis-
Oxygen six rings, second of product, second of product rise together with first time product, into the upper buffering above upper packing area
Area, material outlet discharge of the oil phase out of buffering area；
In reaction process, the liquid product downlink of generation, into the lower buffering area below lower packing area, the water from bottom
Mutually outlet discharge；
It is 70~130 DEG C to control reactor interior reaction temperature, and reaction pressure is 1.7~2.3MPa, and isobutene and the tert-butyl alcohol rub
, than being 0.5~3, the molar ratio of the sum of molal quantity of isobutene and the tert-butyl alcohol and formaldehyde is 1~6 for you, inorganic matter and organic matter
Weight ratio is 1-3, and the percentage that phosphoric acid quality accounts for charging gross mass is 2~8%, and residence time of the isobutene in reactor be
0.5~2 it is small when.
2. one kind 4, the synthetic method of 4- dimethyl-1,3-dioxanes, it is characterised in that comprise the following steps：
The phosphoric acid solution that temperature is 80-90 DEG C enters anti-from the upper entrance between upper packing area and the first intermediate filler area
Device is answered, from top to bottom followed by the first intermediate filler area, the second intermediate filler area and lower packing area in reactor；
The tert-butyl alcohol that the formaldehyde and temperature that temperature is 80-90 DEG C are 80-90 DEG C is from positioned at the second intermediate filler area and lower packing area
Between the second medial inlet enter reactor；
Temperature is that 70-75 DEG C of isobutene enters reactor from the lower entrances below lower packing area, from lower packing area to
Upper flowing；
In reactor, phosphoric acid is mutually flowed from the top to the bottom with formaldehyde with water, followed by the packing area below corresponding feed inlet, isobutyl
Alkene flows up in reactor from lower packing area, followed by each packing area of isobutene entrance top；The tert-butyl alcohol is reacting
A part is soluble in the aqueous phase in device, is mutually flowed downwardly together with water, a part is dissolved in oil phase, is flowed up with oil phase；
Isobutene and phosphoric acid solution, the part tert-butyl alcohol and the formalin counter current contacting in reactor, occur in each packing area
Reaction, generates 4,4- dimethyl-1,3-dioxane oil phases, i.e. first time product；First time product rises, and is pressed from both sides in uphill process
The unreacting material of band enters upper packing area, and unreacted material further reacts in upper packing area, 4,4- of generation dimethyl -1,
Second of product of 3- dioxane, second of product rise together with first time product, into upper above upper packing area
Buffering area, material outlet discharge of the oil phase out of buffering area；
In reaction process, the liquid product downlink of generation, into the lower buffering area below lower packing area, the water from bottom
Mutually outlet discharge；
It is 70~130 DEG C to control reactor interior reaction temperature, and reaction pressure is 1.7~2.3MPa, and isobutene and the tert-butyl alcohol rub
, than being 0.5~3, the molar ratio of the sum of molal quantity of isobutene and the tert-butyl alcohol and formaldehyde is 1~6 for you, inorganic matter and organic matter
Weight ratio is 1-3, and the percentage that phosphoric acid quality accounts for charging gross mass is 2~8%, and residence time of the isobutene in reactor be
0.5~2 it is small when.
3. one kind 4, the synthetic method of 4- dimethyl-1,3-dioxanes, it is characterised in that comprise the following steps：
The formalin that the phosphoric acid solution and temperature that temperature is 80-90 DEG C are 80-90 DEG C is among upper packing area and first
Upper entrance between packing area enters reactor, from top to bottom followed by the first intermediate filler area, second in reactor
Intermediate filler area and lower packing area；
The tert-butyl alcohol that temperature is 80-90 DEG C enters from the second medial inlet between the second intermediate filler area and lower packing area
Reactor；
Temperature is that 70-75 DEG C of isobutene enters reactor from the lower entrances below lower packing area；
Phosphoric acid solution and formaldehyde flow from up to down in reactor；Tert-butyl alcohol part in reactor is soluble in the aqueous phase with water phase
Flow from the top to the bottom together, a part is dissolved in oil phase and is flowed from bottom to top with oil phase；Isobutene in reactor from it is lower to
Upper flowing, with phosphoric acid solution, the tert-butyl alcohol and formalin in reactor counter current contacting, react in each packing area, it is raw
Into 4,4- dimethyl-1,3-dioxane oil phases, i.e. first time product；First time product rises, and is carried secretly not in uphill process
Reaction raw materials enter upper packing area, and unreacted material further reacts in upper packing area, generate 4,4- dimethyl -1,3- dioxies
Six second of ring products, second of product rise together with first time product, into the upper buffering area above upper packing area,
Material outlet discharge of the oil phase out of buffering area；
In reaction process, the liquid product downlink of generation, into the lower buffering area below lower packing area, from reactor bottom
Water mutually export discharge；
Upper buffering area is located at the top of reactor, and lower buffering area is located at the bottom of reactor；
Controlling reaction temperature is 70~130 DEG C, and reaction pressure is 1.7~2.3MPa；
In reactor, the molar ratio of isobutene and the tert-butyl alcohol is 0.5~3, the sum of molal quantity of isobutene and the tert-butyl alcohol and formaldehyde
Molar ratio be 1~6, the weight ratio of inorganic matter and organic matter be 1-3, the percentage that phosphoric acid quality accounts for charging gross mass is 2~
8%, when residence time of the isobutene in reactor is 0.5~2 small.
4. according to the synthetic method described in claim 1,2 or 3, it is characterised in that the height of the upper packing area accounts for total filler height
The 5~20% of degree, the height in the first intermediate filler area accounts for the 3~7% of total filler height, the second intermediate filler area
The 3~7% of total filler height are highly accounted for, the height of the lower packing area accounts for the 66~89% of total filler area height；Each packing area
The sum of height be total filler height, the total filler height stopped using isobutene material in reactor 0.5~2 it is small when as
It is accurate.
5. synthetic method according to claim 4, it is characterised in that the molar ratio of the isobutene and the tert-butyl alcohol is 1~2,
For isobutene with being 1.5~3.5 with the molar ratio of the sum of the molal quantity of tert-butyl alcohol formaldehyde, the weight ratio of inorganic matter and organic matter is 1-
2, the percentage that phosphoric acid quality accounts for charging gross mass is 3~5%；
Controlling reaction temperature is 80~100 DEG C, and reaction pressure is 1.9~2.1MPa.
6. synthetic method according to claim 5, it is characterised in that the lower filler divides into two sections, and between two sections
Equipped with First Heat Exchanger.
7. synthetic method according to claim 5, it is characterised in that corresponding to the upper packing area, the first intermediate filler
Area, the second intermediate filler area and lower packing area, jacket heat-exchanger is respectively equipped with the outer wall of the reactor.
8. synthetic method according to claim 7, it is characterised in that second intermediate filler divides into two sections, that is, is located at
Second intermediate filler area epimere of top and the second intermediate filler area hypomere, the jacket heat-exchanger corresponding to two sections are each independent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| RU2764519C1 (en) * | 2021-03-16 | 2022-01-18 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Use of carbon nanotubes to increase selectivity in the production of 4,4-dimethyl-1,3-dioxane |
| 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) |
| 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 |
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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 |
| RU2764519C1 (en) * | 2021-03-16 | 2022-01-18 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Use of carbon nanotubes to increase selectivity in the production of 4,4-dimethyl-1,3-dioxane |
| 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) |
| 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 |
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