CN105481643B - The method that the pentanediol diisobutyrate of 2,2,4 trimethyl 1,3 is prepared by Qing Ye oxanes - Google Patents
The method that the pentanediol diisobutyrate of 2,2,4 trimethyl 1,3 is prepared by Qing Ye oxanes Download PDFInfo
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Abstract
2,2,4 trimethyls 1 are prepared the present invention relates to one kind, the method of the double isobutyrates of 3 pentanediols, and in particular to a kind of to prepare 2,2 by Qing Ye oxanes, 4 trimethyls 1, the method of the double isobutyrates of 3 pentanediols, the method is with Qing Ye oxanes (2,4 diisopropyls 5,5 dimethyl 1,3 dioxanes) and isobutyric acid be raw material, bed continuous catalysis cracking and an esterification are fixed using solid acid catalyst, the water of generation and isobutylaldehyde azeotropic distillation are removed；Lightness-removing column is removed and reclaims unreacted Qing Ye oxanes and isobutyric acid light component, and rectifying column rectifying obtains the double isobutyrates of the pentanediol of 2,2,4 trimethyl 1,3.The inventive method is realized by Qing Ye oxanes through acid-catalyzed cleavage and the continuous prodution of the double isobutyrates of esterification generation 2,2,4 trimethyl 1,3 pentanediol, and flow is simple, technique cleaning, high income, with very big large-scale industrial application value.
Description
Technical field
The invention belongs to field of fine chemical, it is related to a kind of preparation method of fatty group dibasic acid green plasticization agent, it is special
It is not to be related to a kind of synthetic method for preparing 2,2,4- trimethyl -1,3- pentanediol diisobutyrates.
Background technology
2,2,4 1 trimethyl -1,3- pentanediol diisobutyrates (TXIB) are that a kind of important green non-poisonous environment-friendly type increases
Modeling agent, it is this features such as with low viscosity, low-density, low-freezing, resistant to hydrolysis, water white transparency, high stability, safety non-toxic
Plasticizer meets the highest standard of laws and regulations requirement, and its non-toxic nature allows numerous toy manufacturers and consumer to feel to trust.The increasing
Modeling agent need not be configured again, be reduced because of the wind that the mistake of secondary configuration causes the product recall and Customer Complaint of costliness to produce
Danger.Due to viscosity stability and machinability with relatively low tack and brilliance, the plasticizer can meet the system of high speed
Mould production efficiency and cycle period requirement, and can guarantee that consistency of thickness.Therefore it is widely used in various polyvinyl chloride resin products, oil
In ink, pigment and EVA emulsions.It is the ideal substitute of existing carcinogenicity plasticizer phthalic acid diester (DEHP).
But the open report about TXIB preparation methods is less.United States Patent (USP) US4110539A discloses a kind of conjunction of TXIB
It is that, by 2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes is obtained through acid-catalyzed cleavage and esterification into method.
US5180847 discloses a kind of method of 2,2,4- trimethyls -1,3- pentanediol derivative cooperating manufactures.The method improves 2,2,
4- trimethyl -1, the conversion ratio and yield of 3- pentanediol mono isobutyrates obtain accessory substance TXIB by way of distillation, reach
The purpose of cooperating manufacture.But due to international technology block, it is difficult to meet demand of the China to TXIB.Chinese patent
CN102267896A has invented a kind of 2,2,4- trimethyls -1,3- pentanediol mono isobutyrates and isobutyric acid and has been prepared through esterification
The method of the pentanediol diisobutyrate TXIB of 2,2,4- trimethyls -1,3 one.But raw materials used 2,2,4- trimethyl -1 of the method,
Costly, cost of manufacture is high for 3- pentanediol mono isobutyrates.
The content of the invention
In order to break technical monopoly, to adapt to growing demand of the China to green plasticization agent.The purpose of the present invention
What is be directed to the deficiencies in the prior art and provide is a kind of by the isobutyric acid of Qing Ye oxanes preparation 2,2,4- trimethyl -1,3- pentanediols two
The process of ester.
In view of cracking esterification is the reversible reaction limited by thermodynamical equilibrium, to be conducive to cracking esterification to the phase
The direction of prestige is carried out, and after the water and isobutylaldehyde of first paragraph cracking esterification reaction product elimination reaction generation, then is carried out second segment and is split
Change esterification, to obtain conversion ratio higher.
The technical scheme is that：
With Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) and isobutyric acid for raw material, using solid
Acid catalyst carries out two-part fixed bed continuous catalysis cracking and esterification, 100-180 DEG C of reaction temperature, the water of generation successively
With isobutylaldehyde azeotropic distillation, the azeotropic mixture of water and isobutylaldehyde is steamed into layering tank, layering Guan Zhong lower floors water from overhead
A part of azeotropic again that is back in destilling tower steams the isobutylaldehyde generated in reaction in phase, and another part is arranged from layering pot bottom
Go out, organic phase isobutylaldehyde draws collection to layering tank at the middle and upper levels, and the leftover materials in destilling tower are removed and reclaimed not into lightness-removing column
The Qing Ye oxanes and isobutyric acid light component of reaction are returned in second segment fixed bed reactors, and unrecovered material then enters in lightness-removing column
Enter rectifying column rectifying and obtain 2,2,4- trimethyl -1,3- pentanediol diisobutyrates.
Two-part fixed bed continuous catalysis cracking esterification of the present invention, refers to be filled with solid acid at two
The two-part cracking esterification being carried out continuously in the fixed bed reactors of catalyst, the removing of first paragraph cracking esterification reaction product
Second segment cracking esterification is carried out after the water for reacting generation.
Comprise the following steps that：
A) raw material Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) and isobutyric acid are by required mole
Than mixing, it is preheated after continuously enter from top and carry out cracking ester equipped with the first paragraph fixed bed reactors of solid acid catalyst
Change reaction, gained product is dehydrated into destilling tower；Material after dehydration is continuously withdrawn in destilling tower stripping pars infrasegmentalis,
Unreacted Qing Ye oxanes and isobutyric acid light component are removed and reclaimed into lightness-removing column, as the thing of second segment cracking esterification
Material is sent to from top charging and proceeds cracking esterification in second segment fixed bed reactors；First paragraph and second segment cracking ester
The product for changing reaction enters from destilling tower top, carries out azeotropic distillation, and water present in product and isobutylaldehyde are steaming
Evaporate and removed in the way of azeotropic distillation in tower, without water entrainer is added, water steams with the azeotropic mixture of isobutylaldehyde from overhead
Go out, after condensed device condensation, into layering tank, and be divided into organic phase and water phase, upper organic phase isobutylaldehyde in tank is layered
Draw and collect, a part is back to the interior azeotropic again of destilling tower and steams the isobutylaldehyde generated in reaction, another portion in lower floor's water phase
Divide from layering pot bottom discharge；
B) unreacted Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes), isobutyric acid and purpose are produced
Thing 2,2,4- trimethyl -1,3- pentanediol diisobutyrates are discharged by destilling tower bottom, and into lightness-removing column rectifying, tower top is steamed
Light fraction be Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) and isobutyric acid, the condensation of condensed device,
Reclaimed in condensation storage tank, the Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) and isobutyric acid of recovery
During second segment fixed bed reactors can be returned to as reaction raw materials cycling and reutilization, lightness-removing column materials at bottom of tower is 2,2,4- tri-
Methyl isophthalic acid, 3- pentanediol diisobutyrate crude products；
C) through the 2,2,4- trimethyl -1,3- pentanediol diisobutyrates crude products obtained by the above method through lightness-removing column bottom of towe
Product rectifying column rectifying is sent to, tower top steams a small amount of 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate impurity, bottom of towe discharging
2,2,4- trimethyl -1,3- pentanediol diisobutyrate sterlings can be obtained.
Raw material Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) of the present invention and isobutyric acid
The temperature preheated after mixing can be identical or different with the temperature that first paragraph fixed bed reactors are set.
Into the raw material Qing Ye oxanes of first paragraph fixed bed reactors, (2,4- diisopropyl -5,5- dimethyl -1,3- two is disliked
Alkane) with isobutyric mol ratio be 0.1-0.5:1, preferred scope 0.2-0.3:1；
The mass flow for entering into second segment fixed bed reactors is 1-5 times of first paragraph fixed bed reactors inlet amount,
2-3 times of preferred scope；
Two-part fixed bed continuous catalysis cracking esterification reaction temperature is 100-180 DEG C, and preferred scope is 120-160 DEG C；
The cracking esterification air speed of two sections of described fixed bed reactors is 1-10h-1, preferred scope is 3-8h-1。
Solid acid catalyst of the present invention is support type solid-carrying heteropolyacid PW12/SiO2Or the polystyrene resin of sulfonation
Amberlyst-15；
The consumption of the solid acid catalyst is：The 0.1%~2% of Qing Ye oxanes and isobutyric acid gross mass；
Solid heteropoly acid PW in the solid acid catalyst12(12- phosphotungstic acids) is in Nano-meter SiO_22Quality on carrier is supported
Measure is 10%~60%.
During rectifying column rectifying, the material of discharge is respectively 2,2,4- trimethyl -1, the isobutyric acid of 3- pentanediols two in rectifying column
Ester sterling, bottom heavy oil component, heavy oil component is impurity, trimethyl -1 of kettle top 2,2,4-, 3- pentanediol mono isobutyrate impurity.
Advantageous Effects
1st, azeotropic distillation is the isobutylaldehyde of reaction generation, without adding water entrainer；
2nd, using two-part fixed bed continuous catalysis cracking and esterification reaction tech, realize by Qing Ye oxanes through acid catalysis
2,2,4- trimethyl -1 of cracking and esterification generation, the continuous prodution of the double isobutyrates of 3- pentanediols, flow is simple, and technique is clear
It is clean, high income, with good economic benefit and environmental benefit.
Brief description of the drawings
Fig. 1 is that two-part fixed bed continuous cracking esterification prepares the isobutyric acid of 2,2,4- trimethyl -1,3- pentanediols two
The flow chart of ester technique.
1 is first paragraph fixed bed reactors, equipped with solid acid catalyst；
2 is second segment fixed bed reactors, equipped with solid acid catalyst；
3 is destilling tower；
4 is lightness-removing column；
5 is rectifying column；
6th, 7,8 it is condenser；
9 is layering tank；10th, 11 is condensation storage tank；
12 is first paragraph fixed bed reactors feeding pipe position；
13 is second segment fixed bed reactors feeding pipe position；
14 enter destilling tower conduit positions for cracking esterification material；
15 flow back into destilling tower conduit positions for part water；
L6 sends to lightness-removing column pipeline for destilling tower kettle material；
17 is that lightness-removing column reclaims unreacted Qing Ye oxanes and isobutyric acid sends to second segment fixed bed reactors feeding pipe
Position；
18 send to rectifying column pipeline for lightness-removing column kettle material；
19 is water；
20 is isobutylaldehyde；
21 is bottom heavy oil component；
22 is the trimethyl -1,3- pentanediol diisobutyrate sterlings of product 2,2,4 1；
23 is a small amount of 2,2,4 1 trimethyl -1,3- pentanediol mono isobutyrate impurity by condensing.
Fig. 2 is the infrared spectrum of 2,2,4 1 trimethyl -1,3- pentanediol diisobutyrates (TXIB).
Fig. 3 is 2,2,4 1 trimethyl -1,3- pentanediol diisobutyrate (TXIB) nuclear magnetic spectrograms1H NMR。
Fig. 4 is 2,2,4 1 trimethyl -1,3- pentanediol diisobutyrate (TXIB) nuclear magnetic spectrograms13C NMR。
Specific embodiment
By the after blue or green leaf oxane (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) and isobutyl acid starting material are preheated
One section of fixed bed reactors feeding pipe 12 enters on the first paragraph fixed bed reactors equipped with solid acid catalyst, in catalyst
There is cracking esterification in lower Qing Ye oxane (2,4- diisopropyl -5,5- dimethyl -1, the 3- dioxanes) isobutyric acid of effect, to have
Carried out beneficial to cracking esterification, improve conversion ratio, the reaction mass of first paragraph fixed bed reactors entered by material and is distilled
The pipeline 14 of tower is sent into destilling tower 3 and is dehydrated.In destilling tower 3, because the water and isobutylaldehyde of the generation of cracking esterification can be in 60-
61 DEG C form azeotropic mixture and are constantly separated from tower top.Cracking esterification material by after dehydration in destilling tower stripping
Pars infrasegmentalis is continuously extracted, and being sent to second segment fixed bed reactors 2 by second segment fixed bed reactors feeding pipe 13 continues
Carry out cracking esterification.It is the to extract out and be input to the mass flow of second segment fixed bed reactors in the stripping section of destilling tower 3
One section 1-5 times of fixed bed reactors inlet amount, preferred scope is 2-3 times.By the thing that second segment fixed bed reactors react
The same pipeline 14 for entering destilling tower by material of material enters the azeotropic of destilling tower 3 removing water and isobutylaldehyde.The tower top steaming thing of destilling tower 3
After condensed device 6 is condensed, organic phase and water phase are divided into layering tank 9, upper organic phase is drawn, and lower floor's aqueous portion is returned
Flow to destilling tower 3.2,2,4- trimethyl -1,3- the pentanediol diisobutyrates and unreacted leafiness of cracking esterification generation
Oxane (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) and isobutyric acid, by the discharging of the bottom of destilling tower 3 through destilling tower tower
The pipeline 16 that kettle material sends to lightness-removing column enters lightness-removing column rectifying, Qing Ye oxanes that lightness-removing column tower top is steamed (2,4- diisopropyls-
5,5- dimethyl -1,3- dioxanes) and isobutyric acid reclaims unreacted Qing Ye oxanes through lightness-removing column and isobutyric acid sends to second segment
Fixed bed reactors feeding pipe 17 enters second segment fixed bed reactors 2 and reclaims Recycling, the 2,2,4- of lightness-removing column bottom
Trimethyl -1,3- pentanediol diisobutyrates crude product sends to rectifying column pipeline 18 and is sent to product rectifying through lightness-removing column kettle material
Tower rectifying, tower top steams a small amount of 2, and 2,4- trimethyl -1,3- pentanediol mono isobutyrates impurity 23, bottom excludes heavy oil component
21, obtain 2,2,4- trimethyl -1,3- pentanediol diisobutyrates sterling 22.
Embodiment 1
The Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) that 110 DEG C will be preheated to are pressed with isobutyric acid
Mol ratio 0.3:1st, continuously it is input into 20L/h in the first paragraph fixed bed reactors equipped with 5L solid acid catalysts, cracking esterification
Reaction temperature is 110 DEG C, and air speed is 4h-1, the reaction mass of first paragraph fixed bed reactors is entered the pipe of destilling tower by material
Road 14 is dehydrated into destilling tower 3.In destilling tower 3, because the water and isobutylaldehyde of the generation of cracking esterification are formed altogether at 60-61 DEG C
Boiling thing is constantly separated from tower top.It is continuous with 40L/h in the stripping pars infrasegmentalis of destilling tower 3 by the reaction mass after dehydration
Be extracted, be transported to by second segment fixed bed reactors feeding pipe 13 anti-equipped with 5L solid acid catalyst second segment fixed beds
Answering device 2 carries out cracking esterification, 140 DEG C of reaction temperature, and air speed is 8h-1.Extracted out in the stripping section of destilling tower 3 and be input to second
The mass flow of section fixed bed reactors is 2 times of first paragraph fixed bed reactors inlet amount.By second segment fixed bed reaction
The same pipeline 14 for entering destilling tower by material of material of device reaction enters the azeotropic of destilling tower 3 removing water and isobutylaldehyde.Destilling tower 3
After the condensed device 6 of tower top steaming thing is condensed, organic phase and water phase are divided into layering tank 9, upper organic phase is drawn, lower floor
Aqueous portion is back to destilling tower 3.The discharging of the tower reactor of destilling tower 3 constitutes mass ratio：2,2,4- trimethyl -1,3- pentanediols two are different
Butyrate crude product 22.62%, isobutyric acid 51.29%, Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes)
26.09%.The pipeline of lightness-removing column is sent in the discharging of (conversion ratio 38%, yield 92%) destilling tower 3 tower reactor through destilling tower kettle material
16 enter lightness-removing column rectifying, the Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) that lightness-removing column tower top is steamed
With isobutyric acid second segment fixed bed reactors feeding pipe 17 is sent to through the unreacted Qing Ye oxanes of lightness-removing column recovery and isobutyric acid
Recycling, the 2 of lightness-removing column bottom, 2,4- trimethyl -1, the isobutyl of 3- pentanediols two are reclaimed into second segment fixed bed reactors 2
Acid esters crude product sends to rectifying column pipeline 18 and is input to rectifying column rectifying through lightness-removing column kettle material, and tower top steams a small amount of 2,2,4-
Trimethyl -1,3- pentanediol mono isobutyrates impurity 23, bottom excludes heavy oil component 21, obtains 2 of quality purity more than 98%,
2,4- trimethyl -1,3- pentanediol diisobutyrates sterling 22.
Embodiment 2
The Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) that 130 DEG C will be preheated to are pressed with isobutyric acid
Mol ratio 0.2:1st, continuously it is input into 15L/h in the first paragraph fixed bed reactors equipped with 5L solid acid catalysts, cracking esterification
Reaction temperature is 130 DEG C, and air speed is 3h-1, the reaction mass of first paragraph fixed bed reactors is entered the pipe of destilling tower by material
Road 14 is dehydrated into destilling tower 3.In destilling tower 3, because the water and isobutylaldehyde of the generation of cracking esterification are formed altogether at 60-61 DEG C
Boiling thing is constantly separated from tower top.It is continuous with 30L/h in the stripping pars infrasegmentalis of destilling tower 3 by the reaction mass after dehydration
Be extracted, be transported to by second segment fixed bed reactors feeding pipe 13 anti-equipped with 5L solid acid catalyst second segment fixed beds
Answering device 2 carries out cracking esterification, 150 DEG C of reaction temperature, and air speed is 6h-1.Extracted out in the stripping section of destilling tower 3 and be input to second
The mass flow of section fixed bed reactors is 2 times of first paragraph fixed bed reactors inlet amount.By second segment fixed bed reaction
The same pipeline 14 for entering destilling tower by material of material of device reaction enters the azeotropic of destilling tower 3 removing water and isobutylaldehyde.Destilling tower 3
After the condensed device 6 of tower top steaming thing is condensed, organic phase and water phase are divided into layering tank 9, upper organic phase is drawn, lower floor
Aqueous portion is back to destilling tower 3.The discharging of the tower reactor of destilling tower 3 constitutes mass ratio：2,2,4- trimethyl -1,3- pentanediols two are different
Butyrate crude product 27.27%, isobutyric acid 59.94%, Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes)
12.79%.The pipeline of lightness-removing column is sent in the discharging of (conversion ratio 62%, yield 85%) destilling tower 3 tower reactor through destilling tower kettle material
16 enter lightness-removing column rectifying, the Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) that lightness-removing column tower top is steamed
With isobutyric acid second segment fixed bed reactors feeding pipe 17 is sent to through the unreacted Qing Ye oxanes of lightness-removing column recovery and isobutyric acid
Recycling, the 2 of lightness-removing column bottom, 2,4- trimethyl -1, the isobutyl of 3- pentanediols two are reclaimed into second segment fixed bed reactors 2
Acid esters crude product sends to rectifying column pipeline 18 and is input to rectifying column rectifying through lightness-removing column kettle material, and tower top steams a small amount of 2,2,4-
Trimethyl -1,3- pentanediol mono isobutyrates impurity 23, bottom excludes heavy oil component 21, obtains 2 of quality purity more than 98%,
2,4- trimethyl -1,3- pentanediol diisobutyrates sterling 22.
Claims (6)
1. one kind prepares 2,2,4- trimethyl -1, the method for the double isobutyrates of 3- pentanediols by Qing Ye oxanes, it is characterised in that：Tool
Body step is as follows：
A) mol ratio needed for raw material Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) and isobutyric acid are pressed is mixed
Close, into first paragraph fixed bed reactors raw material Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) with
Isobutyric mol ratio is 0.1-0.5:1, it is preheated after continuously from top enter equipped with solid acid catalyst first paragraph consolidate
Fixed bed reactor (1) carries out cracking esterification, and gained product is dehydrated into destilling tower (3)；Material after dehydration is steaming
Evaporate tower (3) stripping pars infrasegmentalis to be continuously withdrawn, unreacted blue or green leaf oxane and isobutyric acid are removed and reclaimed into lightness-removing column (4)
Light component, is sent in second segment fixed bed reactors (2) from top charging as the material of second segment cracking esterification and continues
Carry out cracking esterification；First paragraph enters with the product of second segment cracking esterification from destilling tower top, is total to
Boiling distillation, water present in product and isobutylaldehyde are removed in the way of azeotropic distillation in a distillation column, without adding band
Aqua, water is steamed with the azeotropic mixture of isobutylaldehyde from overhead, after condensed device (6) condensation, into layering tank (9), and
It is divided into organic phase and water phase in layering tank, upper organic phase isobutylaldehyde is drawn and collected, and a part is back to steaming in lower floor's water phase
Evaporate the interior azeotropic again of tower and steam the isobutylaldehyde generated in reaction, another part is discharged from layering pot bottom；
B) unreacted Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes), isobutyric acid and purpose product 2,
2,4- trimethyl -1,3- pentanediol diisobutyrates are discharged by destilling tower (3) bottom, and into lightness-removing column (4) rectifying, tower top steams
The light fraction for going out is Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) and isobutyric acid, condensed device (7)
Condensation, in being reclaimed in condensation storage tank (10), (2,4- diisopropyl -5,5- dimethyl -1,3- bis- is disliked the Qing Ye oxanes of recovery
Alkane) and during isobutyric acid can return to second segment fixed bed reactors (2) as reaction raw materials cycling and reutilization, lightness-removing column (4) tower
Substrate material is 2,2,4- trimethyl -1,3- pentanediol diisobutyrate crude products；
C) through the 2,2,4- trimethyls -1,3- pentanediol diisobutyrates crude product obtained by the above method through lightness-removing column (4) bottom of towe
It is sent to product rectifying column (5) rectifying, tower top steams a small amount of 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates impurity (23),
Bottom of towe discharging can obtain 2,2,4- trimethyls -1,3- pentanediol diisobutyrates sterling (22).
2. in accordance with the method for claim 1, it is characterised in that：Raw material Qing Ye oxanes (2,4- diisopropyl -5,5- diformazans
Base -1,3- dioxanes) and isobutyric acid mixing after preheat temperature can with first paragraph fixed bed reactors (1) set temperature it is identical
Or it is different.
3. in accordance with the method for claim 1, it is characterised in that：
Into the raw material Qing Ye oxanes (2,4- diisopropyl -5,5- dimethyl -1,3- dioxanes) of first paragraph fixed bed reactors
It is 0.2-0.3 with isobutyric mol ratio:1；
The mass flow for entering into second segment fixed bed reactors is 1-5 times of first paragraph fixed bed reactors inlet amount；
Two-part fixed bed continuous catalysis cracking esterification reaction temperature is 100-180 DEG C；
The cracking esterification air speed of two sections of described fixed bed reactors is 1-10h-1。
4. in accordance with the method for claim 1, it is characterised in that：
The mass flow for entering into second segment fixed bed reactors is 2-3 times of first paragraph fixed bed reactors inlet amount；
Two-part fixed bed continuous catalysis cracking esterification reaction temperature is 120-160 DEG C；
The cracking esterification air speed of two sections of described fixed bed reactors is 3-8h-1。
5. in accordance with the method for claim 1, it is characterised in that：
The solid acid catalyst is support type solid-carrying heteropolyacid PW12/SiO2Or the polystyrene resin Amberlyst- of sulfonation
15；
The consumption of the solid acid catalyst is：The 0.1%~2% of Qing Ye oxanes and isobutyric acid gross mass；
Solid heteropoly acid PW in the solid acid catalyst12(12- phosphotungstic acids) is in Nano-meter SiO_22Quality loading on carrier is
10%~60%.
6. in accordance with the method for claim 1, it is characterised in that：During rectifying column (5) rectifying, the material point of discharge in rectifying column
Not Wei 2,2,4- trimethyl -1,3- pentanediol diisobutyrates sterling (22), bottom heavy oil component (21), heavy oil component is for miscellaneous
Matter, trimethyl -1 of kettle top 2,2,4-, 3- pentanediol mono isobutyrates impurity (23).
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| US4110539A (en) * | 1977-07-13 | 1978-08-29 | Eastman Kodak Company | Process for the preparation of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate |
| CN101337885A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Method for preparing 1-Methoxy-2-propyl acetate by continuous esterification reaction |
| CN101337884A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Method for preparing 2-Butoxyethyl acetate by continuous esterification reaction |
| CN102267896A (en) * | 2011-06-09 | 2011-12-07 | 江苏天音化工有限公司 | Method for preparing 2,2,4-trimethyl-1,3-pentanediol diisobutyrate |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4110539A (en) * | 1977-07-13 | 1978-08-29 | Eastman Kodak Company | Process for the preparation of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate |
| CN101337885A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Method for preparing 1-Methoxy-2-propyl acetate by continuous esterification reaction |
| CN101337884A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Method for preparing 2-Butoxyethyl acetate by continuous esterification reaction |
| CN102267896A (en) * | 2011-06-09 | 2011-12-07 | 江苏天音化工有限公司 | Method for preparing 2,2,4-trimethyl-1,3-pentanediol diisobutyrate |
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