CN102924271A - Method for producing tert-butyl ester compound by esterification, rectification and coupling of organic carboxylic acid and isobutene - Google Patents
Method for producing tert-butyl ester compound by esterification, rectification and coupling of organic carboxylic acid and isobutene Download PDFInfo
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- CN102924271A CN102924271A CN2012104724319A CN201210472431A CN102924271A CN 102924271 A CN102924271 A CN 102924271A CN 2012104724319 A CN2012104724319 A CN 2012104724319A CN 201210472431 A CN201210472431 A CN 201210472431A CN 102924271 A CN102924271 A CN 102924271A
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- rectifying tower
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 30
- 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
- 230000032050 esterification Effects 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 title claims abstract description 14
- 238000010168 coupling process Methods 0.000 title claims description 12
- 230000008878 coupling Effects 0.000 title claims description 10
- 238000005859 coupling reaction Methods 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title 1
- 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 23
- 238000004821 distillation Methods 0.000 claims abstract description 14
- 238000000066 reactive distillation Methods 0.000 claims abstract description 8
- 238000007086 side reaction Methods 0.000 claims description 97
- 239000002253 acid Substances 0.000 claims description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 241000282326 Felis catus Species 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 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
- 230000007306 turnover Effects 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 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 150000007524 organic acids Chemical class 0.000 abstract 2
- 208000012839 conversion disease Diseases 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
- 230000009466 transformation Effects 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
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-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
- 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
- 239000012071 phase Substances 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
- 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
- -1 iso-butane alkene Chemical class 0.000 description 2
- 230000003335 steric effect Effects 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
- 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
- 230000000295 complement effect Effects 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
- 238000005457 optimization Methods 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- 230000001105 regulatory effect 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
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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 a tert-butyl ester compound by esterification, rectification and reaction of organic acid and isobutene. Continuously introducing organic acid and isobutene into a reactive distillation device with a side reactor coupled with a distillation column according to a certain proportion, feeding the reacted materials into the distillation column, and then feeding the reacted materials into a next-stage side reactor for esterification reaction; under the continuous and stable operation condition, the operation pressure of the rectifying tower is controlled to be 0.002-0.1 MPa. The esterification reaction temperature is 20-80 ℃, and the reaction pressure is 0.1-1.0 MPa. The process has the advantages of short process flow, independent operation conditions of the side reactor and the rectifying tower and flexible control; the reaction conversion rate and the selectivity are high, and the mass fraction of the tert-butyl ester continuously discharged from the top of the tower reaches more than 99 percent.
Description
Technical field
The invention belongs to chemical field, relate to the method that tert-butyl ester compounds is produced in the coupling of a kind of organic carboxyl acid and iso-butylene esterification reaction rectification.
Background technology
Tert-butyl ester compound has some special propertys because containing the large tertiary butyl groups of steric effect, having excellent solubility property, suitable vaporator rate, medium flash-point and remarkable cleaning efficiency such as tert-butyl acetate, is a kind of hypotoxicity, eco-friendly solvent; Tert-butyl acrylate is owing to have uniqueness and active strong unsaturated double-bond and tertiary butyl groups, by autohemagglutination or the polymkeric substance that obtains with other monomer copolymerization, have good chemical property and the physicalies such as excellent light stability, weathering resistance, water-fast, oil resistant, chemicals-resistant, thereby have widely at aspects such as coating, leather, papermaking, tackiness agent, daily chemical products and to use.
Because trimethyl carbinol steric effect is large, adopting organic carboxyl acid and the trimethyl carbinol is that raw material is difficult to carry out by the synthetic tert-butyl ester of esterification, and iso-butylene has activated double bonds, can synthesize the tert-butyl ester with the esterification of organic carboxyl acid direct addition.US Patent No. 6194602 is used 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, 60 ℃ of temperature of reaction, acid/alkene ratio is 2: 1 o'clock, isobutene conversion is 60%, and the selectivity of tert-butyl acetate is 77.2%.
US Patent No. 6242640 uses the large pore zeolites such as Zeolite Y, Zeolite beta and Zeolite X as catalyzer, catalyzing iso-butane alkene and vinylformic acid reaction preparation tert-butyl acrylate, the control reaction pressure maintains 3.4MPa, 40 ℃ of temperature of reaction, acid/with the alkene ratio be 7: 1, air speed 23hr
-1, isobutene conversion reaches 84%.
Because the esterification of organic carboxyl acid and iso-butylene is subjected to thermodynamics equilibrium limit, when proportioning raw materials was reacted according to the stoichiometric coefficient ratio, the transformation efficiency of reaction was not high.Iso-butylene contains active two keys, and the reaction of dimerization or poly also easily occurs when reacting with the organic carboxyl acid esterification, causes the selectivity of organic ester product low.Organic carboxyl acid is greatly excessive can to make the isobutene polymerisation reaction occur seldom although adopt, and in order to reclaim a large amount of organic carboxyl acids, needs to adopt the method such as rectifying to separate, and energy consumption is higher.Adopt reactive distillation process can break the chemical reaction equilibrium restriction, improve transformation efficiency and selectivity.Reactive distillation generally carries out in a rectifying tower equipment, and reaction must be consistent with the working condition (such as temperature, pressure) of rectifying.For organic carboxyl acid and the synthetic tert-butyl ester reaction of iso-butylene direct esterification, temperature of reaction is generally in 25～60 ℃ of scopes, and the boiling point of the raw material of esterification and product is all higher, such as 118 ℃ of acetic acid boiling points, 98 ℃ of tert.-butyl acetate boiling points, under normal pressure, carry out rectifying separation, temperature is between 98～118 ℃ in the tower, and the temperature of reaction and rectifying is not complementary.In addition, the esterification of iso-butylene and part organic carboxyl acid also need to be carried out under pressurized conditions, and rectifying is carried out under normal pressure or reduced pressure, and the pressure of reaction and rectifying does not mate yet.Therefore, the reactive distillation process that carries out in a rectifying tower is not suitable for organic carboxyl acid and tert-butyl ester compounds is produced in the iso-butylene esterification.
Summary of the invention
The object of the present invention is to provide in a kind of reaction and rectification device mainly being formed by rectifying tower and the coupling of side reaction device, produced the reactive distillation process of tert-butyl ester compound by organic carboxyl acid and isobutene reaction.
Purpose of the present invention can reach by following measures:
The method that tert-butyl ester compounds is produced in a kind of organic carboxyl acid and the coupling of iso-butylene esterification reaction rectification, the method adopts the reaction and rectification device that mainly is comprised of rectifying tower and the coupling of side reaction device, 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, thereby consists of the reactive distillation district; Iso-butylene passes into each the side reaction device that is connected with rectifying tower continuously, tower reactor material and organic carboxyl acid enter First side reaction device, after iso-butylene generation esterification, return the distillation column reactor rectification zone, in each side reaction device catalyzer is housed, the tower reactor material enters successively each side reaction device and carries out esterification, returns the distillation column reactor rectification zone after the reaction; Esterification reaction product carries out rectifying in the rectifying tower rectification zone, and gained tert-butyl ester compounds is discharged by cat head; Described rectifying tower working pressure is at 0.002～0.1MPa; Temperature in each side reaction device is at 20～80 ℃, and esterification reaction pressure is controlled at 0.1～1.0Mpa, and reaction time is controlled at 1～15hr.
Wherein, the mole proportion optimization 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 preferably contains the saturated or unsaturated fatty acids of 1～4 carbon atom, the perhaps 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, and the iso-butylene continuously feeding.
The turnover material of described side reaction device all links to each other with rectifying tower, 1 ~ 10 of side reaction device number of units, preferred 3～4.
When side reaction device number of units was many, it was 1～99% that the iso-butylene that passes into each side reaction device accounts for the ratio that always passes into total amount, preferred 20 ~ 80%.
Organic carboxyl acid can continuously feeding, also can intermittent feeding, and the iso-butylene continuously feeding.
Described side reaction device can be tank reactor, also can be at fixed-bed reactor.Be used for the custom catalysts of esterification, such as homogeneous phase or heterogeneous catalyst such as the vitriol oil, tosic acid, ion exchange resin, molecular sieves, all can be used for the present invention.Catalyst levels in each side reaction device is for adding 1 ~ 50%, preferred 3 ~ 20% of fresh organic carboxyl acid quality.
The preferred 5-50 piece of described rectifying tower rectification zone stage number, further preferred 10-30 piece.
The preferred 2-20 piece of described distillation column reactor rectification zone stage number, further preferred 3-10 piece.
The stage number at interval is preferred 1～5 between the sides adjacent reactor.
Preferred 1～5 of the interval stage number of the turnover material that is connected with the side reaction device on rectifying tower.
The continuous extraction material of the cat head 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% through after the rectification and purification.
Advantage of the present invention is:
The present invention places the outside of rectifying tower with the side reaction device, and the feed material in the side reaction device comes from rectifying tower, enters the column plate of its top after reaction, not only connects each other but also relatively independent between side reaction device and the rectifying tower.The operational condition of side reaction device and rectifying tower can unanimously also can be different, even regulate arbitrarily according to arts demand.The volume of side reaction device can be regulated arbitrarily, has realized the optimum matching of response capacity and separating power.This coupling technique has the technical process weak point, and operation is easy to control, and tert-butyl ester compound selective is high, and production cost is low, the advantage that economic benefit is high.
Description of drawings
Fig. 1 is the brief process flow diagram that tert-butyl ester compound is produced in the reactive distillation coupling.
Number in the figure is: 1-distillation column reactor rectification zone, 2-rectifying tower rectification zone, 3-rectifying tower cat head vapour phase pipeline, 4-rectifying tower cat head condenser, the 5-rectifying tower connects vacuum system line, 6-rectifying column top return pipeline, 7-rectifying tower cat head tert-butyl ester extraction pipeline, 8-returns the liquid phase pipeline of rectifying tower from n platform side reaction device, the liquid phase feeding pipeline that 9-returns to n platform side reaction device from rectifying tower, 10-n platform side reaction device, the isobutylene feed pipeline of 11-n platform 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 2 side reaction devices of rectifying tower to the, the 2nd side reaction device of 14-, the isobutylene feed pipeline of the 2nd side reaction device of 15-, 16-returns the liquid phase pipeline of rectifying tower from the 1st side reaction device, esterification reaction product and unreacted reactant return the distillation column reactor rectification zone by this pipeline, the liquid phase feeding pipeline that 17-returns from 1 side reaction device of tower bottom of rectifying tower to the, the tower reactor material enters the 1st side reaction device by this pipeline, the 1st side reaction device of 18-, the organic carboxyl acid feeding line of the 1st side reaction device of 19-, the isobutylene feed pipeline of the 1st side reaction device of 20-, 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 specifying the present invention, be illustrated below by embodiment.
The technical process of following examples is all carried out according to the described technical process shown in Figure 1 of description of drawings.
Embodiment 1:
At internal diameter 1.0m, stage number is in the rectifying tower of 30 blocks of column plates, with the long-pending 5m of 2 stage bodies
3Tank reactor link to each other, wherein the tower reactor material enters First side reaction device, side reaction device outlet material enters the 5th block of column plate (stage number is counted from bottom to top); Enter the 2nd reactor from the 6th rectifiying plate material out, side reaction device outlet material enters the 11st block of column plate, and the material between rectifying tower and the side reaction device passes through pump delivery.
Every in-built 150kg ion-exchange resin catalyst of 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, iso-butylene to the feed flow rates of the 1st, 2 side reaction device be respectively 3.5,1.5kmol/h.35 ℃ of esterification reaction temperatures, each side reaction device pressure is 0.15MPa, the rectifying tower working pressure is 0.1MPa.The rectifying tower operating reflux ratio is 1.5, and the rectifying quantity of reflux is 10kmol/h, and the overhead extraction amount is 5kmol/h, is 3kmol/h from rectifying tower to the flow rate that is attached thereto the side reaction device charging that connects.After reaction and rectification device is stable, 97.5 ℃ of rectifying tower cat head temperature, 118 ℃ of tower reactor temperature, 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%.The acetic acid transformation efficiency 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, with the long-pending 3m of 4 stage bodies
3Tank reactor link to each other, wherein the tower reactor material enters First side reaction device, side reaction device outlet material enters the 1st block of column plate (stage number is counted from bottom to top); Enter the 2nd side reaction device from the 2nd 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 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 rectifiying plate material out, side reaction device outlet material enters the 7th block of column plate; Material between rectifying tower and the side reaction device passes through pump delivery.
Every in-built 80kgY molecular sieve catalyst of side reaction device (Y molecular sieve that the Lanzhou Petrochemical catalyst plant is produced).Vinylformic acid is 5kmol/h to the feed flow rates of the 1st side reaction device, iso-butylene to the feed flow rates of the 1st, 2,3,4 side reaction device be respectively 2.0,1.5,1.0,0.5kmol/h.20 ℃ of esterification reaction temperatures, side reaction device pressure 0.2MPa, the rectifying tower working pressure is 0.01MPa.The rectifying tower operating reflux ratio is 1.5, and the rectifying quantity of reflux is 7.5kmol/h, and the overhead extraction amount is 5kmol/h, is 3kmol/h from rectifying tower to the flow rate that is attached thereto the side reaction device charging that connects.After reaction and rectification device is stable, 62 ℃ of rectifying tower cat head temperature, 98 ℃ of tower reactor temperature, the massfraction of overhead extraction component is: iso-butylene 0.20%, tert-butyl acrylate 98.80%, diisobutylene 0.45%, vinylformic acid 0.55%.The 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, with the long-pending 3m of 3 stage bodies
3Tank reactor link to each other, wherein the tower reactor material enters First side reaction device, side reaction device outlet material enters the 2nd block of column plate (stage number is counted from bottom to top); Enter the 2nd side reaction device from the 3rd 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 rectifiying plate material out, side reaction device outlet material enters the 8th block of column plate, and the material between rectifying tower and the side reaction device passes through pump delivery.
Every the in-built 100kg HZSM-5 of side reaction device 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 to the feed flow rates of the 1st, 2,3 side reaction device be respectively 3.75,2.25,1.5kmol/h.80 ℃ of esterification reaction temperatures, side reaction device pressure 1.0MPa, the rectifying tower working pressure is 0.005MPa.The rectifying tower operating reflux ratio is 1.5, and the rectifying quantity of reflux is 7.5kmol/h, and the overhead extraction amount is 5kmol/h, is 5kmol/h from rectifying tower to the flow rate that is attached thereto the side reaction device charging that connects.After reaction and rectification device is stable, 67.6 ℃ of rectifying tower cat head temperature, 106.2 ℃ of tower reactor temperature, 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%.The 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, with the long-pending 3m of 10 stage bodies
3Tank reactor link to each other, wherein the tower reactor material enters First side reaction device, side reaction device outlet material enters the 1st block of column plate (stage number is counted from bottom to top); Enter the 2nd side reaction device from the 2nd 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 rectifiying plate material out, side reaction device outlet material enters the 5th block of column plate, enter k platform side reaction device from k+1 piece rectifiying plate material out according to this, side reaction device outlet material enters k piece column plate, enter the 10th side reaction device from the 11st rectifiying plate material out, side reaction device outlet material enters the 10th block of column plate, and the material between rectifying tower and the side reaction device passes through pump delivery.
Every in-built 40kg ion-exchange resin catalyst of 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 side reaction device.40 ℃ of esterification reaction temperatures, side reaction device pressure 0.3MPa, the rectifying tower working pressure is 0.01MPa.The rectifying tower operating reflux ratio is 2, and the rectifying quantity of reflux is 10kmol/h, and the overhead extraction amount is 5kmol/h, is 2kmol/h from rectifying tower to the flow rate that is attached thereto the side reaction device charging that connects.After reaction and rectification device is stable, 61 ℃ of rectifying tower cat head temperature, 94 ℃ of tower reactor temperature, the massfraction of overhead extraction component is: iso-butylene 0.15%, the propionic acid tert-butyl ester 99.34%, diisobutylene 0.16%, propionic acid 0.35%.The propionic acid transformation efficiency is 99.38%, the selectivity 99.81% of the propionic acid tert-butyl ester.
Claims (9)
1. an organic carboxyl acid and the iso-butylene esterification reaction rectification coupling method of producing tert-butyl ester compounds, it is characterized in that the method adopts the reaction and rectification device that mainly is comprised of rectifying tower and the coupling of side reaction device, 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, thereby consists of the reactive distillation district; Iso-butylene passes into each the side reaction device that is connected with rectifying tower continuously, tower reactor material and organic carboxyl acid enter First side reaction device, after iso-butylene generation esterification, return the distillation column reactor rectification zone, in each side reaction device catalyzer is housed, the tower reactor material enters successively each side reaction device and carries out esterification, returns the distillation column reactor rectification zone after the reaction; Esterification reaction product carries out rectifying in the rectifying tower rectification zone, and gained tert-butyl ester compounds is discharged by cat head; Described rectifying tower working pressure is at 0.002～0.1MPa; Temperature in each side reaction device is at 20～80 ℃, and esterification reaction pressure is controlled at 0.1～1.0Mpa.
2. method according to claim 1, the mole proportioning that it is characterized in that described iso-butylene total amount and described organic carboxyl acid is 1.0～1.5: 1, preferred 0.95～1.1: 1.
3. method according to claim 1 is characterized in that described organic carboxyl acid is the saturated or unsaturated fatty acids that contains 1～4 carbon atom, the perhaps lipid acid of halogen substituent; Preferable 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 all links to each other with rectifying tower, 1～10 of side reaction device number of units, preferred 3～4.
5. method according to claim 4 is characterized in that when side reaction device number of units was many, it was 1～99% that the iso-butylene that passes into each side reaction device accounts for the ratio that always passes into total amount, preferred 20 ~ 80%.
6. method according to claim 1 is characterized in that rectifying tower rectification zone stage number at the 5-50 piece, preferred 10-30 piece.
7. method according to claim 1 is characterized in that distillation column reactor rectification zone stage number at the 2-20 piece, preferred 3-10 piece.
8. method according to claim 1 is characterized in that the stage number at interval between the sides adjacent reactor is at 1～5.
9. method according to claim 1 is characterized in that the interval stage number of turnover material on rectifying tower that is connected with the side reaction device is 1～5.
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| CN105801408A (en) * | 2016-05-13 | 2016-07-27 | 中建安装工程有限公司 | Reaction distillation device and method for producing high-purity n-butyl acrylate |
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| CN106397189A (en) * | 2016-08-30 | 2017-02-15 | 江西盛伟科技股份有限公司 | Synthesis method of tert-butyl chloroacetate |
| CN114507131A (en) * | 2022-01-24 | 2022-05-17 | 华谊合丰特种化学淄博有限公司 | Synthesis method of tert-butyl (meth) acrylate |
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| CN105801408A (en) * | 2016-05-13 | 2016-07-27 | 中建安装工程有限公司 | Reaction distillation device and method for producing high-purity n-butyl acrylate |
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