CN102924271B - Method for producing tert-butyl ester compound by performing esterification reaction, rectification and coupling to organic carboxylic acid and isobutene - Google Patents
Method for producing tert-butyl ester compound by performing esterification reaction, rectification and coupling to organic carboxylic acid and isobutene Download PDFInfo
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 29
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 title claims abstract description 14
- 238000010168 coupling process Methods 0.000 title claims abstract description 14
- 230000008878 coupling Effects 0.000 title claims abstract description 13
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000007086 side reaction Methods 0.000 claims description 99
- 239000002253 acid Substances 0.000 claims description 30
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000004821 distillation Methods 0.000 claims description 13
- 230000032050 esterification Effects 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000066 reactive distillation Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 230000007306 turnover Effects 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 abstract 1
- 150000007524 organic acids Chemical class 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- -1 iso-butane alkene Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KUYMVWXKHQSIAS-UHFFFAOYSA-N tert-butyl 2-chloroacetate Chemical compound CC(C)(C)OC(=O)CCl KUYMVWXKHQSIAS-UHFFFAOYSA-N 0.000 description 2
- JAELLLITIZHOGQ-UHFFFAOYSA-N tert-butyl propanoate Chemical compound CCC(=O)OC(C)(C)C JAELLLITIZHOGQ-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N trimethylmethane Natural products CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for producing tert-butyl ester compound by performing esterification reaction, rectification and coupling to organic carboxylic acid and isobutene. The method comprises the steps that organic acid and isobutene are continuously fed into a reaction and rectification device according to certain ratio, which is formed by coupling a side reactor and a rectification column; material enters the rectification column after reaction and then enters a side reactor at the nest stage to be conducted to esterification reaction; and the operation pressure of the rectification column is controlled to be 0.002 to 0.1 MPa in a continuous and stable operation condition. The esterification reaction temperature is 20 to 80 DEG C, and the reaction pressure is 0.1 to 1.0 MPa. The method has the advantages that the process is short, operation conditions of the side reactor and the rectification column are separated, the side reactor and the rectification column are flexible to control, the reaction conversion rate and the selectivity are high, and the mass fraction of tert-butyl ester continuously discharged from the top of the rectification column is more than 99 percent.
Description
Technical field
The invention belongs to chemical field, relate to a kind of method of organic carboxyl acid and iso-butylene esterification reaction rectification coupling production tert-butyl ester compound.
Background technology
Tert-butyl ester compound is because having some special propertys containing the large tertiary butyl groups of steric effect, as tert-butyl acetate has the cleaning efficiency of excellent solubility property, suitable vaporator rate, medium flash-point and brilliance, be a kind of hypotoxicity, eco-friendly solvent; Tert-butyl acrylate is owing to having uniqueness and active strong unsaturated double-bond and tertiary butyl groups, by autohemagglutination or the polymkeric substance that obtains with other monomer copolymerization, there is good chemical property and the physicals such as excellent light stability, weathering resistance, water-fast, oil resistant, chemicals-resistant, thus have a wide range of applications in coating, leather, papermaking, tackiness agent, daily chemical product etc.
Because trimethyl carbinol steric effect is large, adopt organic carboxyl acid and the trimethyl carbinol to be that raw material synthesizes the tert-butyl ester by esterification and is difficult to carry out, and iso-butylene has activated double bonds, can with the organic carboxyl acid direct addition lactate synthesis tert-butyl ester.US Patent No. 6194602 uses macro-porous zeolite catalyst catalyzing iso-butane alkene and the acetic acid synthesized tert-butyl esters of acetic acidreaction such as Zeolite Y, the trimethyl carbinol is as improving optionally improving agent, temperature of reaction 60 DEG C, when acid/alkene ratio is 2: 1, isobutene conversion is 60%, and the selectivity of tert-butyl acetate is 77.2%.
US Patent No. 6242640 uses the large pore zeolite such as Zeolite Y, Zeolite beta and Zeolite X as catalyzer, tert-butyl acrylate is prepared in catalyzing iso-butane alkene and vinylformic acid reaction, controls reaction pressure and maintains 3.4MPa, temperature of reaction 40 DEG C, acid/be 7: 1, air speed 23hr with alkene ratio
-1, isobutene conversion reaches 84%.
Because the esterification of organic carboxyl acid and iso-butylene limits by thermodynamic(al)equilibrium, when proportioning raw materials is reacted according to stoichiometric coefficient ratio, the transformation efficiency of reaction is not high.Iso-butylene contains active double bond, also easily dimerization occurs or poly reacts when reacting with organic carboxyl acid esterification, causes the selectivity of organic ester product low.Although adopt the greatly excessive isobutene polymerisation that can make of organic carboxyl acid to react the little of generation, in order to reclaim a large amount of organic carboxyl acids, need to adopt the methods such as rectifying to be separated, energy consumption is higher.Adopt reactive distillation process can break chemical reaction equilibrium restriction, improve transformation efficiency and selectivity.Reactive distillation generally carries out in a rectifying tower equipment, and reacting must be consistent with the working condition (as temperature, pressure) of rectifying.For organic carboxyl acid and the reaction of the iso-butylene direct esterification synthesis tert-butyl ester, temperature of reaction is generally within the scope of 25 ~ 60 DEG C, and the boiling point of the raw material of esterification and product is all higher, as acetic acid boiling point 118 DEG C, tert.-butyl acetate boiling point 98 DEG C, carry out rectifying separation at ambient pressure, in tower, temperature is between 98 ~ 118 DEG C, and the temperature of reaction and rectifying does not match.In addition, the esterification of iso-butylene and part organic carboxyl acid also needs to carry out under an increased pressure, and rectifying is carried out under normal pressure or reduced pressure, and the pressure of reaction and rectifying does not also mate.Therefore, the reactive distillation process carried out in a rectifying tower is not suitable for organic carboxyl acid and iso-butylene esterification production tert-butyl ester compound.
Summary of the invention
The object of the present invention is to provide a kind of in the reaction and rectification device primarily of rectifying tower and side reaction device coupling composition, produced the reactive distillation process of tert-butyl ester compound by organic carboxyl acid and isobutene reaction.
Object of the present invention can be reached by following measures:
A kind of method of organic carboxyl acid and iso-butylene esterification reaction rectification coupling production tert-butyl ester compound, the method adopts the reaction and rectification device primarily of rectifying tower and side reaction device coupling composition, described rectifying tower is divided into distillation column reactor rectification zone and rectifying tower rectification zone from the bottom to top, described distillation column reactor rectification zone is passed through into and out of material pipe and each side reaction device butt coupling, thus forms reactive distillation district; Iso-butylene passes into each the side reaction device be connected with rectifying tower continuously, kettle material and organic carboxyl acid enter First side reaction device, after iso-butylene generation esterification, return distillation column reactor rectification zone, in each side reaction device, catalyzer is housed, kettle material enters each side reaction device successively and carries out esterification, returns distillation column reactor rectification zone after reaction; Esterification reaction product carries out rectifying in rectifying tower rectification zone, and gained tert-butyl ester compound is discharged by tower top; Described rectifying tower working pressure is at 0.002 ~ 0.1MPa; Temperature in each side reaction device is at 20 ~ 80 DEG C, and esterification reaction pressure controls at 0.1 ~ 1.0Mpa, and reaction time controls at 1 ~ 15hr.
Wherein, the mol ratio preferably 1.0 ~ 1.5:1 of described iso-butylene total amount and described organic carboxyl acid, further preferred 0.95 ~ 1.1:1.
Described organic carboxyl acid is preferably containing the saturated or unsaturated fatty acids of 1 ~ 4 carbon atom, or the lipid acid of halogen substituent; Further preferable formic acid, acetic acid, propionic acid, vinylformic acid, butyric acid, isopropylformic acid, Mono Chloro Acetic Acid or bromoacetic acid.
Organic carboxyl acid can continuously feeding, also can intermittent feeding, iso-butylene continuously feeding.
The turnover material of described side reaction device is all connected with rectifying tower, side reaction device number of units 1 ~ 10, preferably 3 ~ 4.
When side reaction device number of units is multiple stage, it is 1 ~ 99% that the iso-butylene passing into each side reaction device accounts for the ratio always passing into total amount, preferably 20 ~ 80%.
Organic carboxyl acid can continuously feeding, also can intermittent feeding, iso-butylene continuously feeding.
Described side reaction device can be tank reactor, also can at fixed-bed reactor.For the custom catalysts of esterification, as homogeneous phase or heterogeneous catalyst such as the vitriol oil, tosic acid, ion exchange resin, molecular sieves, all may be used for the present invention.Catalyst levels in each side reaction device is add fresh organic carboxyl acid quality 1 ~ 50%, preferably 3 ~ 20%.
The described preferred 5-50 block of rectifying tower rectification zone stage number, further preferred 10-30 block.
The described preferred 2-20 block of distillation column reactor rectification zone stage number, further preferred 3-10 block.
The stage number at interval preferably 1 ~ 5 piece between sides adjacent reactor.
And the interval stage number of the turnover material that side reaction device is connected on rectifying tower preferably 1 ~ 5 piece.
The continuous extraction material of tower top of reaction and rectification device of the present invention, the massfraction of tert-butyl ester compound wherein can reach more than 99%, and the massfraction of organic carboxyl acid is lower than 0.5%, and the massfraction of diisobutylene is lower than 1%.Crude product can obtain the tert-butyl ester finished product of massfraction more than 99.5% after rectification and purification.
Advantage of the present invention is:
Side reaction device is placed in the outside of rectifying tower by the present invention, and the feed material in side reaction device comes from rectifying tower, enters the column plate above it, not only connect each other but also relatively independent between side reaction device and rectifying tower after reaction.The operational condition of side reaction device and rectifying tower can unanimously also can be different, even need to regulate arbitrarily according to technique.The volume of side reaction device can regulate arbitrarily, achieves the optimum matching of response capacity and separating power.It is short that this coupling technique has technical process, and operation is easy to control, and tert-butyl ester compound selective is high, and production cost is low, the advantage of high financial profit.
Accompanying drawing explanation
Fig. 1 is the brief process flow diagram that tert-butyl ester compound is produced in reactive distillation coupling.
Number in the figure is: 1-distillation column reactor rectification zone, 2-rectifying tower rectification zone, 3-rectifying tower overhead vapor phase pipeline, 4-rectifying tower overhead condenser, 5-rectifying tower connects vacuum system line, 6-rectifying column top return pipeline, 7-rectifying tower tower top tert-butyl ester extraction pipeline, 8-returns the liquid phase pipeline of rectifying tower from n-th side reaction device, the liquid phase feeding pipeline that 9-returns from rectifying tower to n-th side reaction device, 10-n-th side reaction device, the isobutylene feed pipeline of 11-n-th side reaction device, 12-returns the liquid phase pipeline of rectifying tower from the 2nd side reaction device, the liquid phase feeding pipeline that 13-returns from rectifying tower to the 2nd side reaction device, 14-the 2nd side reaction device, the isobutylene feed pipeline of 15-the 2nd side reaction device, 16-returns the liquid phase pipeline of rectifying tower from the 1st side reaction device, esterification reaction product and unreacted reactant return to distillation column reactor rectification zone by this pipeline, the liquid phase feeding pipeline that 17-returns from tower bottom of rectifying tower to the 1st side reaction device, kettle material enters the 1st side reaction device by this pipeline, 18-the 1st side reaction device, the organic carboxyl acid feeding line of 19-the 1st side reaction device, the isobutylene feed pipeline of 20-the 1st side reaction device, 21-tower bottom of rectifying tower reboiler liquid phase circulation pipeline, 22-tower bottom of rectifying tower reboiler, 23-tower reactor reboiler vapour phase circulation line.
Embodiment
For further illustrating the present invention, be illustrated below by embodiment.
According to accompanying drawing, the technical process of following examples all illustrates that the technical process shown in described Fig. 1 is carried out.
Embodiment 1:
At internal diameter 1.0m, stage number is in the rectifying tower of 30 blocks of column plates, amasss 5m with 2 stage bodies
3tank reactor be connected, wherein kettle material enters First side reaction device, and side reaction device outlet material enters the 5th piece of column plate (stage number counts from bottom to top); Enter the 2nd reactor from the 6th piece of rectifiying plate material out, side reaction device outlet material enters the 11st block of column plate, and the material between rectifying tower and side reaction device passes through pump delivery.
The in-built 150kg ion-exchange resin catalyst of every platform side reaction device (the D006 type that Hebei Kairui Chemical LLC produces).Acetic acid is 5kmol/h to the feed flow rates of the 1st side reaction device, and iso-butylene is respectively 3.5 to the feed flow rates of the 1st, 2 side reaction device, 1.5kmol/h.Esterification reaction temperature 35 DEG C, each side reaction device pressure is 0.15MPa, and rectifying tower working pressure is 0.1MPa.Rectifying tower operating reflux ratio is 1.5, and rectifying quantity of reflux is 10kmol/h, and overhead extraction amount is 5kmol/h, is 3kmol/h from rectifying tower to the flow rate being attached thereto the side reaction device charging connect.After reaction and rectification device is stable, rectifying tower tower top temperature 97.5 DEG C, bottom temperature 118 DEG C, the massfraction of overhead extraction liquid phase component is: iso-butylene 0.22%, tert.-butyl acetate 99.22%, diisobutylene 0.21%, acetic acid 0.35%.Acetic acid conversion is 99.32%, the selectivity 99.78% of tert.-butyl acetate.
Embodiment 2:
At internal diameter 0.8m, stage number is in the rectifying tower of 30 blocks of column plates, amasss 3m with 4 stage bodies
3tank reactor be connected, wherein kettle material enters First side reaction device, and side reaction device outlet material enters the 1st piece of column plate (stage number counts from bottom to top); Enter the 2nd side reaction device from the 2nd piece of rectifiying plate material out, side reaction device outlet material enters the 3rd block of column plate; Enter the 3rd side reaction device from the 4th piece of rectifiying plate material out, side reaction device outlet material enters the 5th block of column plate; Enter the 4th side reaction device from the 6th piece of rectifiying plate material out, side reaction device outlet material enters the 7th block of column plate; Material between rectifying tower and side reaction device passes through pump delivery.
The in-built 80kgY molecular sieve catalyst of every platform side reaction device (Y molecular sieve that Lanzhou Petrochemical catalyst plant is produced).Vinylformic acid is 5kmol/h to the feed flow rates of the 1st side reaction device, iso-butylene is respectively 2.0 to the feed flow rates of the 1st, 2,3,4 side reaction device, 1.5,1.0,0.5kmol/h.Esterification reaction temperature 20 DEG C, side reaction device pressure 0.2MPa, rectifying tower working pressure is 0.01MPa.Rectifying tower operating reflux ratio is 1.5, and rectifying quantity of reflux is 7.5kmol/h, and overhead extraction amount is 5kmol/h, is 3kmol/h from rectifying tower to the flow rate being attached thereto the side reaction device charging connect.After reaction and rectification device is stable, rectifying tower tower top temperature 62 DEG C, bottom temperature 98 DEG C, the massfraction of overhead extraction component is: iso-butylene 0.20%, tert-butyl acrylate 98.80%, diisobutylene 0.45%, vinylformic acid 0.55%.Vinylformic acid transformation efficiency is 99.02%, the selectivity 99.48% of tert-butyl acrylate.
Embodiment 3:
At internal diameter 0.8m, stage number is in the rectifying tower of 25 blocks of column plates, amasss 3m with 3 stage bodies
3tank reactor be connected, wherein kettle material enters First side reaction device, and side reaction device outlet material enters the 2nd piece of column plate (stage number counts from bottom to top); Enter the 2nd side reaction device from the 3rd piece of rectifiying plate material out, side reaction device outlet material enters the 5th block of column plate; Enter the 3rd side reaction device from the 6th piece of rectifiying plate material out, side reaction device outlet material enters the 8th block of column plate, and the material between rectifying tower and side reaction device passes through pump delivery.
Every platform side reaction device in-built 100kg HZSM-5 molecular sieve catalyst (the HZSM-5 molecular sieve that Chemical Plant of Nankai Univ. produces, silica alumina ratio is 38).Mono Chloro Acetic Acid is 5kmol/h to the feed flow rates of the 1st side reaction device, iso-butylene is respectively 3.75 to the feed flow rates of the 1st, 2,3 side reaction device, 2.25,1.5kmol/h.Esterification reaction temperature 80 DEG C, side reaction device pressure 1.0MPa, rectifying tower working pressure is 0.005MPa.Rectifying tower operating reflux ratio is 1.5, and rectifying quantity of reflux is 7.5kmol/h, and overhead extraction amount is 5kmol/h, is 5kmol/h from rectifying tower to the flow rate being attached thereto the side reaction device charging connect.After reaction and rectification device is stable, rectifying tower tower top temperature 67.6 DEG C, bottom temperature 106.2 DEG C, the massfraction of overhead extraction component is: iso-butylene 45.65%, chloroacetic acid tert-butyl ester 84.05%, diisobutylene 0.18%, Mono Chloro Acetic Acid 0.12%.Mono Chloro Acetic Acid transformation efficiency is 99.77%, the selectivity 99.71% of chloroacetic acid tert-butyl ester.
Embodiment 4:
At internal diameter 1.0m, stage number is in the rectifying tower of 50 blocks of column plates, amasss 3m with 10 stage bodies
3tank reactor be connected, wherein kettle material enters First side reaction device, and side reaction device outlet material enters the 1st piece of column plate (stage number counts from bottom to top); Enter the 2nd side reaction device from the 2nd piece of rectifiying plate material out, side reaction device outlet material enters the 3rd block of column plate; The 3rd side reaction device is entered from the 4th piece of rectifiying plate material out, side reaction device outlet material enters the 5th block of column plate, kth platform side reaction device is entered according to this from kth+1 piece of rectifiying plate material out, side reaction device outlet material enters kth block column plate, the 10th side reaction device is entered from the 11st piece of rectifiying plate material out, side reaction device outlet material enters the 10th block of column plate, and the material between rectifying tower and side reaction device passes through pump delivery.
The in-built 40kg ion-exchange resin catalyst of every platform side reaction device (the D006 type that Hebei Kairui Chemical LLC produces).Propionic acid is 5kmol/h to the feed flow rates of the 1st side reaction device, and iso-butylene is 0.5kmol/h to the feed flow rates of every platform side reaction device.Esterification reaction temperature 40 DEG C, side reaction device pressure 0.3MPa, rectifying tower working pressure is 0.01MPa.Rectifying tower operating reflux ratio is 2, and rectifying quantity of reflux is 10kmol/h, and overhead extraction amount is 5kmol/h, is 2kmol/h from rectifying tower to the flow rate being attached thereto the side reaction device charging connect.After reaction and rectification device is stable, rectifying tower tower top temperature 61 DEG C, bottom temperature 94 DEG C, the massfraction of overhead extraction component is: iso-butylene 0.15%, propanoic acid tert-butyl ester 99.34%, diisobutylene 0.16%, propionic acid 0.35%.Propionic acid rate is 99.38%, the selectivity 99.81% of propanoic acid tert-butyl ester.
Claims (8)
1. the method for an organic carboxyl acid and iso-butylene esterification reaction rectification coupling production tert-butyl ester compound, it is characterized in that the method adopts the reaction and rectification device primarily of rectifying tower and side reaction device coupling composition, described rectifying tower is divided into distillation column reactor rectification zone and rectifying tower rectification zone from the bottom to top, described distillation column reactor rectification zone is passed through into and out of material pipe and each side reaction device butt coupling, thus forms reactive distillation district; Iso-butylene passes into each the side reaction device be connected with rectifying tower continuously, kettle material and organic carboxyl acid enter First side reaction device, after iso-butylene generation esterification, return the column plate of distillation column reactor rectification zone above it, and the interval stage number of turnover material on rectifying tower that side reaction device is connected is 1 ~ 5 piece; In each side reaction device, catalyzer is housed, kettle material enters each side reaction device successively and carries out esterification, returns distillation column reactor rectification zone after reaction; Between sides adjacent reactor, the stage number at interval is 1 ~ 5 piece; Esterification reaction product carries out rectifying in rectifying tower rectification zone, and gained tert-butyl ester compound is discharged by tower top; Described rectifying tower working pressure is at 0.002 ~ 0.1 MPa; Temperature in each side reaction device is at 20 ~ 80 DEG C, and esterification reaction pressure controls at 0.1 ~ 1.0 MPa; Wherein said iso-butylene total amount and the mol ratio of described organic carboxyl acid are 1.0 ~ 1.5:1; Described organic carboxyl acid is the saturated or unsaturated fatty acids containing 1 ~ 4 carbon atom, or the lipid acid of halogen substituent; The turnover material of side reaction device is all connected with rectifying tower, side reaction device number of units 2 ~ 10; Rectifying tower rectification zone stage number is at 5 ~ 50 pieces; Distillation column reactor rectification zone stage number is at 2 ~ 20 pieces.
2. method according to claim 1, is characterized in that the mol ratio of described iso-butylene total amount and described organic carboxyl acid is 0.95 ~ 1.1:1.
3. method according to claim 1, is characterized in that described organic carboxyl acid is formic acid, acetic acid, propionic acid, vinylformic acid, butyric acid, isopropylformic acid, Mono Chloro Acetic Acid or bromoacetic acid.
4. method according to claim 1, is characterized in that the turnover material of side reaction device is all connected with rectifying tower, side reaction device number of units 3 ~ 4.
5. method according to claim 4, it is 1 ~ 99% that the iso-butylene that it is characterized in that passing into each side reaction device accounts for the ratio always passing into total amount.
6. method according to claim 5, it is 20 ~ 80% that the iso-butylene that it is characterized in that passing into each side reaction device accounts for the ratio always passing into total amount.
7. method according to claim 1, is characterized in that rectifying tower rectification zone stage number is at 10 ~ 30 pieces.
8. method according to claim 1, is characterized in that distillation column reactor rectification zone stage number is at 3 ~ 10 pieces.
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| CN101070265A (en) * | 2007-06-18 | 2007-11-14 | 南京工业大学 | Process for producing benzyl chlorides chemical compound |
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| CN101402566A (en) * | 2008-07-16 | 2009-04-08 | 彭鸽威 | Method for producing high-purity low-class fatty acid ester |
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