CN104649902A - Production method of sec-butyl acetate - Google Patents
Production method of sec-butyl acetate Download PDFInfo
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- CN104649902A CN104649902A CN201310581832.2A CN201310581832A CN104649902A CN 104649902 A CN104649902 A CN 104649902A CN 201310581832 A CN201310581832 A CN 201310581832A CN 104649902 A CN104649902 A CN 104649902A
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- tower
- water
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- rectification column
- azeotropy rectification
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- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 159
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 115
- 150000001336 alkenes Chemical class 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000005191 phase separation Methods 0.000 claims abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012071 phase Substances 0.000 claims description 66
- 238000000605 extraction Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 24
- 239000008346 aqueous phase Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 abstract description 19
- 238000010533 azeotropic distillation Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000005201 scrubbing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 78
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 10
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 230000001502 supplementing effect Effects 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 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 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing sec-butyl acetate, which comprises the following steps: after the C4 fraction reacts with acetic acid, products containing unreacted C4, sec-butyl acetate, acetic acid and C8 olefin enter a first separation tower, unreacted C4 is removed from the tower top, unreacted C4 enters the lower part of a water scrubber, desalted water is injected into the upper part of the water scrubber, the unreacted C4 after water scrubbing is discharged from the tower top of the water scrubber, washing water at the tower bottom enters a first azeotropic rectifying tower as an azeotropic agent together with a product extracted from the tower bottom of the first separation tower, acetic acid is extracted from the tower bottom of the first azeotropic rectifying tower, after the tower top product is subjected to phase separation in a phase separation tank, an upper sec-butyl acetate phase product enters a second azeotropic rectifying tower, a lower water phase product enters a second separation tower, a high-purity sec-butyl acetate product is obtained from the tower bottom of the second azeotropic rectifying tower, after the tower top product is subjected to phase separation in a phase separation tank, an upper layer product is extracted from the tower bottom, a lower water phase product enters the second separation tower, and water is returned, and the product at the tower top is used as an entrainer and returns to the second azeotropic distillation tower.
Description
Technical field
The present invention relates to a kind of production method of sec-butyl acetate, belong to organic chemical industry field.
Background technology
Sec-butyl acetate has that solubility property is strong, evaporation rate is moderate, extraction yield is high, toxicity is little, the residual advantage such as few, has become one of domestic environmentally friendly solvent with strongest influence power; In addition it also has the features such as octane value is high, nontoxic, non-corrosiveness, oxygen level are low, and be can as the new chemical product of gasoline addO-on therapy, market development has a extensive future.
The method of domestic and international traditional mode of production sec-butyl acetate take sulfuric acid as catalyst acetic acid and butanols reaction, and utilize the n-butene in C4 and the direct catalytic Synthesis of sec-Butyl Acetate of acetic acid, significantly can reduce production cost, be the mainstream technology of producing sec-butyl acetate at present.
Patent US1994330115A discloses a kind of method utilizing acetic acid and 1-butylene and 2-butylene Reactive Synthesis sec-butyl acetate, adopt acidic cation-exchange resin as catalyzer, mentioning for its separation method utilizes distillation just sec-butyl acetate can be separated from reaction mixture, but does not announce concrete separation method.
Patent CN200710192465.1 discloses a kind of method preparing sec-butyl acetate with product separating technique, it is characterized in that being that raw material adopts catalytic rectification process catalytic Synthesis of sec-Butyl Acetate with hybrid C 4, unreacted hybrid C 4 or butylene steam from catalytic distillation column overhead, reacted product mixtures sends into azeotropy rectification column, add entrainer, azeotropy rectification column overhead product natural layering, entrainer or entrainer and part sec-butyl acetate pass back into azeotropic distillation column overhead, the sec-butyl acetate carrying a small amount of entrainer enters treating tower, sec-butyl acetate is obtained after rectifying in treating tower, azeotropy rectification column materials at bottom of tower capable of circulation time reactive system.
The preparation method that patent CN200910005679.2 discloses a kind of sec-butyl acetate comprises: C4 alkene with under addition reaction condition, contacts with acetic acid, reacts by (1) in the presence of a catalyst several times; (2) step (1) gained reaction product is carried out rectifying separation, from overhead extraction C4 light constituent, extraction bottom product at the bottom of tower; (3) bottom product step (2) obtained and water carry out azeotropic distillation, and sec-butyl acetate and C8 alkene are with the form of azeotrope from overhead extraction, and acetic acid is from extraction at the bottom of tower; (4) azeotrope that step (3) obtains is carried out oily water separation after condensation, obtain water-phase product and the oil-phase product containing C8 alkene and sec-butyl acetate; (5) oil-phase product step (4) obtained and water carry out azeotropic distillation, and C8 alkene is with the form of azeotrope from overhead extraction, and sec-butyl acetate is from extraction at the bottom of tower.
Prior art does not all mention the treatment process of unreacted C4, and this part C4 mono-aspect can be carried acetic acid secretly and show acid, still needs process therefore can produce a large amount of acid waste water, can increase the loss of acetic acid in whole technological process on the other hand in follow-up application process.Prior art is the recycle of not mentioned azeotropic water and the relevant content of discharge of wastewater also.
Summary of the invention
The present invention seeks to overcome in prior art and unreacted C4 component not to be processed and azeotropic water does not have the deficiency of recycle, propose new sec-butyl acetate separation method.
The method comprises: after C 4 fraction and acetic acid react in fixed-bed reactor, containing unreacted C4, sec-butyl acetate, the product of acetic acid and C8 alkene enters the first knockout tower, first knockout tower tower top deviates from unreacted C4, unreacted C4 enters water wash column bottom, de-salted water injects water wash column top, water wash column tower top discharges the unreacted C4 after washing, water wash column bottom product washing water enter the first azeotropy rectification column as entrainer together with the first knockout tower bottom product, first azeotropy rectification column overhead product phase-splitting in the first phase separation tank, upper strata sec-butyl acetate phase product after phase-splitting enters the second azeotropy rectification column together with the de-salted water as entrainer, lower floor's aqueous phase product introduction second knockout tower, second azeotropy rectification column overhead product phase-splitting in the second phase separation tank, upper strata product extraction after phase-splitting, lower floor's aqueous phase product introduction second knockout tower, the water reclaimed at the bottom of second knockout tower tower can return water wash column as de-salted water, second knockout tower overhead product can return the second azeotropy rectification column as entrainer.
The fixed-bed reactor of C4 of the present invention and acetic acid building-up reactions can be fixed-bed reactor, also can be that the series connection of multiple fixed-bed reactor uses, macropore strong acid cation exchange resin catalyst is loaded in reactor, if model is the catalyzer of A-35, K-300, D-06.Temperature of reaction is 50 ~ 120 DEG C, and reaction pressure is 1.0 ~ 3.0MPa, and the olefin molar ratio in acetic acid and C 4 fraction is 1 ~ 3.
First knockout tower of the present invention can be flashing tower, also can be rectifying tower, preferred rectifying tower, number of theoretical plate 3 ~ 20, reflux ratio 0.5 ~ 5, working pressure 0.2 ~ 0.6MPa, tower top temperature 30 ~ 70 DEG C, bottom temperature 80 ~ 200 DEG C.
Water wash column of the present invention, the various fillers that the filler loaded can be known to the skilled person, as QH-1, QH-2 or QH-3 filler of Tsing-Hua University, balance progression 3 ~ 20, working pressure 0.6 ~ 3MPa, temperature 10 ~ 60 DEG C.
First azeotropy rectification column of the present invention, number of theoretical plate 10 ~ 200, reflux ratio 1 ~ 100, working pressure 0.1 ~ 0.6MPa, tower top temperature 60 ~ 200 DEG C, bottom temperature 100 ~ 300 DEG C; Second azeotropy rectification column, number of theoretical plate 10 ~ 200, reflux ratio 1 ~ 500, working pressure 0.1 ~ 0.5MPa, tower top temperature 60 ~ 100 DEG C, bottom temperature 100 ~ 150 DEG C.
First azeotropy rectification column of the present invention and the second azeotropy rectification column, also can the products of extraction simultaneously at the bottom of side line and tower by extraction product at the bottom of side line or tower.
Second knockout tower of the present invention, number of theoretical plate 10 ~ 100, reflux ratio 1 ~ 200, working pressure 0.1 ~ 0.3MPa, tower top temperature 80 ~ 120 DEG C, bottom temperature 100 ~ 150 DEG C.
First knockout tower of the present invention, the second knockout tower, the first azeotropy rectification column and the second azeotropy rectification column can be packing towers, also can be tray columns, also can be filler and board-like compound tower.
According to method provided by the invention, the very low sec-butyl acetate product of acetic acid, C8 alkene and sec-butyl alcohol content can be isolated from the product of C4 and acetic acidreaction, and whole sepn process environmental protection, no acidic discharge of wastewater.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention.
1-C4 cut in figure, 2-acetic acid, 3-fixed-bed reactor, 4-reaction product, 5-first knockout tower, 6-first knockout tower overhead streams stock, 7-first knockout tower tower bottom flow stock, 8, 28-de-salted water, 9-water wash column, the remaining C4 of 10-, 11-water wash column tower bottom flow stock, 12-first azeotropy rectification column, 13-first phase splitter, 14-first phase splitter upper stream stock, 15-first phase splitter underflow stock, 16-first azeotropy rectification column tower bottom flow stock, 17-second azeotropy rectification column, 18-second phase splitter, 19-second phase splitter upper stream stock, 20-second phase splitter underflow stock, 21-second azeotropy rectification column tower bottom flow stock, 22-second knockout tower, 23-return tank, 24-second knockout tower overhead streams stock, 25-second knockout tower tower bottom flow stock, 26-first azeotropy rectification column pump-around stream stock, 27-second azeotropy rectification column pump-around stream stock.
Embodiment
Contrast Fig. 1 to be below described in detail to method of the present invention.
Fixed-bed reactor 3 are entered after C 4 fraction 1 and acetic acid 2 mix, reaction product 4 enters the first knockout tower 5, first knockout tower overhead streams stock 6 enters the bottom of water wash column 9, de-salted water 8 enters the top of water wash column 9, water wash column overhead streams stock 10 is for washing away the remaining C4 of acetic acid, and water wash column tower bottom flow stock 11 is the de-salted water containing a small amount of acetic acid.
First knockout tower tower bottom flow stock 7 and enter the first azeotropy rectification column containing the de-salted water 11 of a small amount of acetic acid, acetic acid is at the bottom of the first azeotropy rectification column tower 16 and/or side line 26 extraction, sec-butyl acetate, C8 alkene and sec-butyl alcohol form azeotrope respectively and enter the first phase splitter 13 from the first azeotropy rectification column overhead extraction and carry out oily water separation with water, the some aqueous phase product obtained and part oil-phase product return in the first azeotropy rectification column as backflow by azeotropic proportion of composing, remaining oil-phase product 14 enters the second azeotropy rectification column 17, remaining water-phase product 15 enters the second knockout tower 22.
The tower top oil-phase product 14 of de-salted water 28 and the first azeotropy rectification column enters the second azeotropy rectification column, sec-butyl acetate is at the bottom of the second azeotropy rectification column tower 21 and/or side line 27 extraction, C8 alkene and sec-butyl alcohol form azeotrope respectively and enter the second phase splitter 18 from the second azeotropy rectification column overhead extraction and carry out oily water separation with water, the some aqueous phase product obtained and part oil-phase product return conduct backflow in the second azeotropy rectification column by azeotropic proportion of composing, obtain oil-phase product 19 and water-phase product 20.
Second azeotropy rectification column water-phase product 20 and the first azeotropy rectification column water-phase product 15 enter the second knockout tower 22 and are separated, second knockout tower overhead streams stock 24 is mainly containing sec-butyl acetate and water, return the second azeotropy rectification column, second knockout tower tower bottom flow stock 25 is high-purity water, returns water wash column supplementing as de-salted water.
By way of example the present invention is described in further detail below.
Embodiment 1:
According to the flow process shown in Fig. 1, C 4 fraction 1 forms (mass percent) and is: Trimethylmethane 41.6%, normal butane 13.3%, n-butene 17.3%, iso-butylene 0.2%, maleic 13.5%, anti-butylene 15.1%, total butylene 45.1%.
Be enter fixed-bed reactor 3 after the C 4 fraction 1 of 1000kg/h and the acetic acid 2 of 1205kg/h mix by flow, butylene total conversion rate is 79.8%, reaction product 4 enters the first knockout tower 5, first knockout tower overhead streams stock 6 is the bottom entering water wash column 9 containing the C 4 fraction of acetic acid 0.1%, flow is the top that the de-salted water 8 of 200kg/h enters water wash column 9, water wash column overhead streams stock 10 is for washing away the remaining C4 of acetic acid, and water wash column tower bottom flow stock 11 is the de-salted water containing a small amount of acetic acid.
First knockout tower tower bottom flow stock 7 and enter the first azeotropy rectification column containing the de-salted water 11 of a small amount of acetic acid, acetic acid is from 16 extraction at the bottom of the first azeotropy rectification column tower, sec-butyl acetate, C8 alkene and sec-butyl alcohol form azeotrope respectively and enter phase splitter 13 from the first azeotropy rectification column overhead extraction and carry out oily water separation with water, the some aqueous phase product obtained and part oil-phase product return in the first azeotropy rectification column as backflow by azeotropic proportion of composing, remaining oil-phase product 14 enters the second azeotropy rectification column 17, and remaining water-phase product 15 enters the second knockout tower 22.
Flow is that the de-salted water 28 of 18kg/h and the tower top oil-phase product 14 of the first azeotropy rectification column enter the second azeotropy rectification column, sec-butyl acetate is from 21 extraction at the bottom of the second azeotropy rectification column tower, C8 alkene and sec-butyl alcohol form azeotrope respectively and enter phase splitter 18 from the second azeotropy rectification column overhead extraction and carry out oily water separation with water, the some aqueous phase product obtained and part oil-phase product return conduct backflow in the second azeotropy rectification column by azeotropic proportion of composing, obtain oil-phase product 19 and water-phase product 20.
Second azeotropy rectification column water-phase product 20 and the first azeotropy rectification column water-phase product 15 enter the second knockout tower 22 and are separated, second knockout tower overhead streams stock 24 is mainly containing sec-butyl acetate and water, return the second azeotropy rectification column, second knockout tower tower bottom flow stock 25 is high-purity water, returns water wash column supplementing as de-salted water.The flow of the operational condition of concrete tower and stream stock and composition are in table 1 and table 2.
Table 1
| First knockout tower | First azeotropy rectification column | Second azeotropy rectification column | Second knockout tower | |
| Number of theoretical plate | 10 | 30 | 40 | 20 |
| Feed entrance point | 6 | 20 | 26 | 12 |
| Reflux ratio | 0.6 | 3 | 8 | 50 |
| Tower top temperature/DEG C | 49.4 | 78.4 | 66.1 | 77.0 |
| Bottom temperature/DEG C | 169.5 | 117.2 | 108.8 | 99.6 |
| Working pressure/MPa | 0.5 | Normal pressure | Normal pressure | Normal pressure |
| Side line position | — | — | — | — |
Table 2
| Stream stock | 4 | 6 | 7 | 10 | 11 | 14 | 15 | 16 | 19 | 20 | 21 | 24 | 25 |
| Flow (kg/h) | 2207.0 | 603.9 | 1603.1 | 603.1 | 200.8 | 777.2 | 195.8 | 830.9 | 74.0 | 27.7 | 693.5 | 10.0 | 213.5 |
| Quality forms | |||||||||||||
| C4 | 0.273 | 0.999 | 1.000 | ||||||||||
| Acetic acid | 0.371 | 0.001 | 0.510 | 0.000 | 0.004 | 0.000 | 0.000 | 0.990 | 0.000 | 0.000 | 0.000 | 0.000 | 0.000 |
| Sec-butyl acetate | 0.339 | 0.000 | 0.466 | 0.000 | 0.000 | 0.933 | 0.038 | 0.009 | 0.485 | 0.013 | 0.993 | 0.776 | 0.000 |
| Water | 0.000 | 0.000 | 0.000 | 0.000 | 0.996 | 0.013 | 0.960 | 0.001 | 0.008 | 0.968 | 0.001 | 0.139 | 1.000 |
| C8 | 0.016 | 0.000 | 0.023 | 0.000 | 0.000 | 0.046 | 0.000 | 0.000 | 0.429 | 0.000 | 0.006 | 0.000 | 0.000 |
| Sec-butyl alcohol | 0.001 | 0.000 | 0.001 | 0.000 | 0.000 | 0.008 | 0.002 | 0.000 | 0.078 | 0.019 | 0.000 | 0.085 | 0.000 |
Embodiment 2:
According to the flow process shown in Fig. 1, C 4 fraction 1 forms (mass percent) and is: Trimethylmethane 41.6%, normal butane 13.3%, n-butene 18.3%, iso-butylene 0.2%, maleic 12.5%, anti-butylene 15.1%, total butylene 45.1%.
Be enter fixed-bed reactor 3 after the C 4 fraction 1 of 1000kg/h and the acetic acid 2 of 1306kg/h mix by flow, butylene total conversion rate is 82.8%, reaction product 4 enters the first knockout tower 5, first knockout tower overhead streams stock 6 is the bottom entering water wash column 9 containing the C 4 fraction of acetic acid 0.1%, flow is the top that the de-salted water 8 of 200kg/h enters water wash column 9, water wash column overhead streams stock 10 is for washing away the remaining C4 of acetic acid, and water wash column tower bottom flow stock 11 is the de-salted water containing a small amount of acetic acid.
First knockout tower tower bottom flow stock 7 and enter the first azeotropy rectification column containing the de-salted water 11 of a small amount of acetic acid, acetic acid is from 16 extraction at the bottom of the first azeotropy rectification column tower, sec-butyl acetate, C8 alkene and sec-butyl alcohol form azeotrope respectively and enter phase splitter 13 from the first azeotropy rectification column overhead extraction and carry out oily water separation with water, the some aqueous phase product obtained and part oil-phase product return in the first azeotropy rectification column as backflow by azeotropic proportion of composing, remaining oil-phase product 14 enters the second azeotropy rectification column 17, and remaining water-phase product 15 enters the second knockout tower 22.
Flow is that the de-salted water 28 of 18kg/h and the tower top oil-phase product 14 of the first azeotropy rectification column enter the second azeotropy rectification column, sec-butyl acetate is from 21 extraction at the bottom of the second azeotropy rectification column tower, C8 alkene and sec-butyl alcohol form azeotrope respectively and enter phase splitter 18 from the second azeotropy rectification column overhead extraction and carry out oily water separation with water, the some aqueous phase product obtained and part oil-phase product return conduct backflow in the second azeotropy rectification column by azeotropic proportion of composing, obtain oil-phase product 19 and water-phase product 20.
Second azeotropy rectification column water-phase product 20 and the first azeotropy rectification column water-phase product 15 enter the second knockout tower 22 and are separated, second knockout tower overhead streams stock 24 is mainly containing sec-butyl acetate and water, return the second azeotropy rectification column, second knockout tower tower bottom flow stock 25 is high-purity water, returns water wash column supplementing as de-salted water.The flow of the operational condition of concrete tower and stream stock and composition are in table 3 and table 4.
Table 3
| First knockout tower | First azeotropy rectification column | Second azeotropy rectification column | Second knockout tower | |
| Number of theoretical plate | 10 | 28 | 38 | 22 |
| Feed entrance point | 6 | 19 | 26 | 12 |
| Reflux ratio | 0.6 | 4 | 6 | 40 |
| Tower top temperature/DEG C | 49.4 | 78.4 | 66.1 | 77.0 |
| Bottom temperature/DEG C | 169.5 | 117.1 | 108.7 | 99.7 |
| Working pressure/MPa | 0.5 | Normal pressure | Normal pressure | Normal pressure |
| Side line position | — | — | — | — |
Table 4
| Stream stock | 4 | 6 | 7 | 10 | 11 | 14 | 15 | 16 | 19 | 20 | 21 | 24 | 25 |
| Flow (kg/h) | 2308.0 | 591.4 | 1716.6 | 590.5 | 200.9 | 802.7 | 196.1 | 918.8 | 75.4 | 27.7 | 717.6 | 10.0 | 213.8 |
| Quality forms | |||||||||||||
| C4 | 0.256 | 0.998 | 1.000 | ||||||||||
| Acetic acid | 0.392 | 0.002 | 0.528 | 0.000 | 0.005 | 0.000 | 0.000 | 0.991 | 0.000 | 0.000 | 0.000 | 0.000 | 0.000 |
| Sec-butyl acetate | 0.335 | 0.000 | 0.450 | 0.000 | 0.000 | 0.935 | 0.039 | 0.008 | 0.493 | 0.014 | 0.993 | 0.803 | 0.000 |
| Water | 0.000 | 0.000 | 0.000 | 0.000 | 0.995 | 0.012 | 0.959 | 0.001 | 0.007 | 0.967 | 0.001 | 0.110 | 1.000 |
| C8 | 0.016 | 0.000 | 0.021 | 0.000 | 0.000 | 0.045 | 0.000 | 0.000 | 0.421 | 0.000 | 0.006 | 0.000 | 0.000 |
[0046]
| Sec-butyl alcohol | 0.001 | 0.000 | 0.001 | 0.000 | 0.000 | 0.008 | 0.002 | 0.000 | 0.079 | 0.019 | 0.000 | 0.087 | 0.000 |
Embodiment 3:
According to the flow process shown in Fig. 1, C 4 fraction 1 forms (mass percent) and is: Trimethylmethane 41.6%, normal butane 13.3%, n-butene 17.3%, iso-butylene 0.2%, maleic 13.5%, anti-butylene 15.1%, total butylene 45.1%.
Be enter fixed-bed reactor 3 after the C 4 fraction 1 of 1000kg/h and the acetic acid 2 of 1306kg/h mix by flow, butylene total conversion rate is 85.6%, reaction product 4 enters the first knockout tower 5, first knockout tower overhead streams stock 6 is the bottom entering water wash column 9 containing the C 4 fraction of acetic acid 0.1%, flow is the top that the de-salted water 8 of 210kg/h enters water wash column 9, water wash column overhead streams stock 10 is for washing away the remaining C4 of acetic acid, and water wash column tower bottom flow stock 11 is the de-salted water containing a small amount of acetic acid.
First knockout tower tower bottom flow stock 7 and enter the first azeotropy rectification column containing the de-salted water 11 of a small amount of acetic acid, acetic acid is 16 extraction simultaneously at the bottom of the first azeotropy rectification column side line 26 and tower, sec-butyl acetate, C8 alkene and sec-butyl alcohol form azeotrope respectively and enter phase splitter 13 from the first azeotropy rectification column overhead extraction and carry out oily water separation with water, the some aqueous phase product obtained and part oil-phase product return in the first azeotropy rectification column as backflow by azeotropic proportion of composing, remaining oil-phase product 14 enters the second azeotropy rectification column 17, and remaining water-phase product 15 enters the second knockout tower 22.
Flow is that the de-salted water 28 of 18kg/h and the tower top oil-phase product 14 of the first azeotropy rectification column enter the second azeotropy rectification column, sec-butyl acetate is 21 extraction simultaneously at the bottom of the second azeotropy rectification column side line 27 and tower, C8 alkene and sec-butyl alcohol form azeotrope respectively and enter phase splitter 18 from the second azeotropy rectification column overhead extraction and carry out oily water separation with water, the some aqueous phase product obtained and part oil-phase product return conduct backflow in the second azeotropy rectification column by azeotropic proportion of composing, obtain oil-phase product 19 and water-phase product 20.
Second azeotropy rectification column water-phase product 20 and the first azeotropy rectification column water-phase product 15 enter the second knockout tower 22 and are separated, second knockout tower overhead streams stock 24 is mainly containing sec-butyl acetate and water, return the second azeotropy rectification column, second knockout tower tower bottom flow stock 25 is high-purity water, returns water wash column supplementing as de-salted water.The flow of the operational condition of concrete tower and stream stock and composition are in table 5 and table 6.
Table 5
| First knockout tower | First azeotropy rectification column | Second azeotropy rectification column | Second knockout tower | |
| Number of theoretical plate | 10 | 30 | 40 | 30 |
| Feed entrance point | 6 | 20 | 26 | 20 |
| Reflux ratio | 1 | 2 | 8 | 20 |
[0055]
| Tower top temperature/DEG C | 49.4 | 78.4 | 66.8 | 77.2 |
| Bottom temperature/DEG C | 169.5 | 117.1 | 108.6 | 99.7 |
| Working pressure/MPa | 0.5 | Normal pressure | Normal pressure | Normal pressure |
| Side line position/stage number | — | 25 | 36 | — |
Table 6
Embodiment 4:
According to the flow process shown in Fig. 1, C 4 fraction 1 forms (mass percent) and is: Trimethylmethane 41.2%, normal butane 13.7%, n-butene 16.3%, iso-butylene 0.2%, maleic 14.5%, anti-butylene 15.1%, total butylene 45.1%.
Be enter fixed-bed reactor 3 after the C 4 fraction 1 of 1000kg/h and the acetic acid 2 of 1200kg/h mix by flow, butylene total conversion rate is 81.2%, reaction product 4 enters the first knockout tower 5, first knockout tower overhead streams stock 6 is the bottom entering water wash column 9 containing the C 4 fraction of acetic acid 0.1%, flow is the top that the de-salted water 8 of 200kg/h enters water wash column 9, water wash column overhead streams stock 10 is for washing away the remaining C4 of acetic acid, and water wash column tower bottom flow stock 11 is the de-salted water containing a small amount of acetic acid.
First knockout tower tower bottom flow stock 7 and enter the first azeotropy rectification column containing the de-salted water 11 of a small amount of acetic acid, acetic acid is 16 extraction simultaneously at the bottom of the first azeotropy rectification column side line 26 and tower, sec-butyl acetate, C8 alkene and sec-butyl alcohol form azeotrope respectively and enter phase splitter 13 from the first azeotropy rectification column overhead extraction and carry out oily water separation with water, the some aqueous phase product obtained and part oil-phase product return in the first azeotropy rectification column as backflow by azeotropic proportion of composing, remaining oil-phase product 14 enters the second azeotropy rectification column 17, and remaining water-phase product 15 enters the second knockout tower 22.
Flow is that the de-salted water 28 of 18kg/h and the tower top oil-phase product 14 of the first azeotropy rectification column enter the second azeotropy rectification column, sec-butyl acetate is 21 extraction simultaneously at the bottom of the second azeotropy rectification column side line 27 and tower, C8 alkene and sec-butyl alcohol form azeotrope respectively and enter phase splitter 18 from the second azeotropy rectification column overhead extraction and carry out oily water separation with water, the some aqueous phase product obtained and part oil-phase product return conduct backflow in the second azeotropy rectification column by azeotropic proportion of composing, obtain oil-phase product 19 and water-phase product 20.
Second azeotropy rectification column water-phase product 20 and the first azeotropy rectification column water-phase product 15 enter the second knockout tower 22 and are separated, second knockout tower overhead streams stock 24 is mainly containing sec-butyl acetate and water, return the second azeotropy rectification column, second knockout tower tower bottom flow stock 25 is high-purity water, returns water wash column supplementing as de-salted water.The flow of the operational condition of concrete tower and stream stock and composition are in table 7 and table 8.
Table 7
| First knockout tower | First azeotropy rectification column | Second azeotropy rectification column | Second knockout tower | |
| Number of theoretical plate | 14 | 32 | 38 | 28 |
| Feed entrance point | 7 | 20 | 26 | 19 |
| Reflux ratio | 0.8 | 3 | 18 | 15 |
| Tower top temperature/DEG C | 49.4 | 78.5 | 66.7 | 77.1 |
| Bottom temperature/DEG C | 169.5 | 117.2 | 108.6 | 99.6 |
| Working pressure/MPa | 0.5 | Normal pressure | Normal pressure | Normal pressure |
| Side line position/stage number | — | 25 | 36 | — |
Table 8
Claims (8)
1. the production method of a sec-butyl acetate, it is characterized in that: after C 4 fraction and acetic acid react in fixed-bed reactor, containing unreacted C4, sec-butyl acetate, the product of acetic acid and C8 alkene enters the first knockout tower, first knockout tower tower top deviates from unreacted C4, unreacted C4 enters water wash column bottom, de-salted water injects water wash column top, water wash column tower top discharges the unreacted C4 after washing, water wash column bottom product washing water enter the first azeotropy rectification column as entrainer together with the first knockout tower bottom product, extraction acetic acid at the bottom of first azeotropy rectification column side line and/or tower, first azeotropy rectification column overhead product phase-splitting in the first phase separation tank, upper strata sec-butyl acetate phase product after phase-splitting enters the second azeotropy rectification column together with the de-salted water as entrainer, lower floor's aqueous phase product introduction second knockout tower, the secondary butyl ester product of extraction high purity acetic acid at the bottom of second azeotropy rectification column side line and/or tower, second azeotropy rectification column overhead product phase-splitting in the second phase separation tank, upper strata product extraction after phase-splitting, lower floor's aqueous phase product introduction second knockout tower, the hydromining reclaimed at the bottom of second knockout tower tower goes out or returns water wash column as de-salted water, second knockout tower overhead product extraction or return the second azeotropy rectification column as entrainer.
2. the method for claim 1, is characterized in that the fixed-bed reactor of described C 4 fraction and acetic acid building-up reactions are fixed-bed reactor or the series connection of multiple fixed-bed reactor.
3. the method for claim 1, it is characterized in that the temperature of reaction of described C 4 fraction and acetic acid building-up reactions is 50 ~ 120 DEG C, reaction pressure is 1.0 ~ 3.0MPa, and the olefin molar ratio in acetic acid and C 4 fraction is 1 ~ 3.
4. the method for claim 1, is characterized in that the first described knockout tower, number of theoretical plate 3 ~ 20, reflux ratio 0.5 ~ 5, working pressure 0.2 ~ 0.6MPa, tower top temperature 30 ~ 70 DEG C, bottom temperature 80 ~ 200 DEG C.
5. the method for claim 1, is characterized in that described water wash column, balance progression 3 ~ 20, working pressure 0.6 ~ 3MPa, temperature 10 ~ 60 DEG C.
6. the method for claim 1, is characterized in that the first described azeotropy rectification column, number of theoretical plate 10 ~ 200, reflux ratio 1 ~ 100, working pressure 0.1 ~ 0.6MPa, tower top temperature 60 ~ 200 DEG C, bottom temperature 100 ~ 300 DEG C.
7. the method for claim 1, is characterized in that the second described azeotropy rectification column, number of theoretical plate 10 ~ 200, reflux ratio 1 ~ 500, working pressure 0.1 ~ 0.5MPa, tower top temperature 60 ~ 100 DEG C, bottom temperature 100 ~ 150 DEG C.
8. the method for claim 1, is characterized in that the second described knockout tower, number of theoretical plate 10 ~ 100, reflux ratio 1 ~ 200, working pressure 0.1 ~ 0.3MPa, tower top temperature 80 ~ 120 DEG C, bottom temperature 100 ~ 150 DEG C.
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| CN114644556A (en) * | 2020-12-21 | 2022-06-21 | 山东石大胜华化工集团股份有限公司 | A kind of device and process method for preparing propionate |
| CN114917602A (en) * | 2022-05-20 | 2022-08-19 | 胜华新能源科技(东营)有限公司 | A kind of device and process method for preparing propionate |
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| CN101168506A (en) * | 2007-11-30 | 2008-04-30 | 胡先念 | Preparation method for sec-butyl acetate with product separating technique |
| CN101481307A (en) * | 2009-01-13 | 2009-07-15 | 湖南瑞源石化股份有限公司 | Method for separating acetic acid and sec-butyl acetate from reaction products |
| CN101486640A (en) * | 2009-01-13 | 2009-07-22 | 湖南瑞源石化股份有限公司 | Preparation of sec-butyl acetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101168506A (en) * | 2007-11-30 | 2008-04-30 | 胡先念 | Preparation method for sec-butyl acetate with product separating technique |
| CN101481307A (en) * | 2009-01-13 | 2009-07-15 | 湖南瑞源石化股份有限公司 | Method for separating acetic acid and sec-butyl acetate from reaction products |
| CN101486640A (en) * | 2009-01-13 | 2009-07-22 | 湖南瑞源石化股份有限公司 | Preparation of sec-butyl acetate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114644556A (en) * | 2020-12-21 | 2022-06-21 | 山东石大胜华化工集团股份有限公司 | A kind of device and process method for preparing propionate |
| CN114917602A (en) * | 2022-05-20 | 2022-08-19 | 胜华新能源科技(东营)有限公司 | A kind of device and process method for preparing propionate |
| CN114917602B (en) * | 2022-05-20 | 2023-08-25 | 胜华新能源科技(东营)有限公司 | Device and technological method for preparing propionate |
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