CN103657155A - Ethyl acetate separating equipment, and device and method for preparing ethyl acetate - Google Patents
Ethyl acetate separating equipment, and device and method for preparing ethyl acetate Download PDFInfo
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- CN103657155A CN103657155A CN201310473485.1A CN201310473485A CN103657155A CN 103657155 A CN103657155 A CN 103657155A CN 201310473485 A CN201310473485 A CN 201310473485A CN 103657155 A CN103657155 A CN 103657155A
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- ethyl acetate
- water
- oil phase
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 636
- 238000000034 method Methods 0.000 title abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 206
- 239000000463 material Substances 0.000 claims abstract description 91
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 150000002148 esters Chemical class 0.000 claims description 188
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 158
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 156
- 239000002351 wastewater Substances 0.000 claims description 133
- 238000000926 separation method Methods 0.000 claims description 117
- 238000005886 esterification reaction Methods 0.000 claims description 112
- 230000032050 esterification Effects 0.000 claims description 94
- 238000007599 discharging Methods 0.000 claims description 66
- 230000008676 import Effects 0.000 claims description 62
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 54
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 32
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 30
- 239000012141 concentrate Substances 0.000 claims description 24
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 17
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 16
- 229940090181 propyl acetate Drugs 0.000 claims description 16
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 15
- 238000007710 freezing Methods 0.000 claims description 12
- 230000008014 freezing Effects 0.000 claims description 12
- 238000007670 refining Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 230000001133 acceleration Effects 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000004062 sedimentation Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000013461 design Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Natural products CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 238000001311 chemical methods and process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000895 extractive distillation Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004148 unit process Methods 0.000 description 2
- 102000007698 Alcohol dehydrogenase Human genes 0.000 description 1
- 108010021809 Alcohol dehydrogenase Proteins 0.000 description 1
- 229920002160 Celluloid Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
The invention discloses ethyl acetate separating equipment, and a device and a method for preparing ethyl acetate. The separating equipment comprises a tank body and a water collecting bag, wherein one side of the tank body is provided with a material inlet; a baffle for reducing the speed of materials at the inlet just faces the material inlet; the side edge of the tank body is provided with an inner heat exchange pipe in a penetrating mode; the bottom of the tank body is also provided with an oil phase outlet; the water collecting bag is arranged on the bottom of the tank body, and is positioned between the material inlet and the oil phase outlet; the water collecting bag is externally coated with an external heat exchange pipe; the bottom of the water collecting bag is provided with a water phase outlet; the size of the tank body meets the requirements synchronously in the formula shown in the specification. The device for preparing ethyl acetate comprises the separating equipment which is used by the preparation method. The separating equipment and the device are simple and easy to operate, can be used for separating completely without introduction of other substances, and can be used for separating high-quality ethyl acetate, and the content of ethyl acetate of a prepared ethyl acetate product reaches 99.9% above.
Description
Technical field
The present invention relates to the separation equipment of ethyl acetate, the device of preparing ethyl acetate and preparation method.
Background technology
Ethyl acetate is important fine chemical material, has excellent dissolubility, evaporation rate and drip-dry feature, is widely used in the fields such as coating, medicine, adhesive, artificial leather, celluloid in industry.Along with World Economics sustained, stable growth, environmental requirement increasingly stringent, benzene kind solvent price, toxicity are high again, adopt high-grade solvent to produce the products such as coating, ink, adhesive and have become trend of the times, thereby impel the rapid growth of ethyl acetate demand.
The raw materials for production situation of countries in the world ethyl acetate is different, there is multiple production of ethyl technology, the main production technology of ethyl acetate has four kinds: acetic acid and ethyl esterification method, alcohol dehydrogenase method, ethene Acetic and acetaldehyde condensation method, and the production method of China most of ethyl acetate factory is to adopt esterification process, this is the cause because the methanol carbonyl synthetic method of China is produced acetic acid technical development speed in recent years.Some large-scale methanol carbonyl synthesized acetic acid enterprise auxiliary constructions have production of ethyl device, and built device has the 200kt/a of Wujing Chemical Co., Ltd., Shanghai Ethyl Acetate Plant, the Jiangsu 200kt/a of Suo Pu group Ethyl Acetate Plant, gold Yimeng, the Shandong 180kt/a of group company Ethyl Acetate Plant, the Yangtze River 100kt/a of acetyl Chemical Co., Ltd. Ethyl Acetate Plant and the Anhui 300kt/a of Hua Yi Chemical Co., Ltd. Ethyl Acetate Plant etc.
The technical process that esterification process is prepared ethyl acetate is to make a certain proportion of acetic acid and ethanol enter esterifier, adds sulfuric acid as catalyst simultaneously, under steam-heated condition, in esterifier, mixes and carries out esterification.Reacted solution produces ester, water, alcohol, azeotropic acid system, enters esterification treating column separated, and tower top material obtains thick ester after cooling, yet tends to aborning run into the separation problem of thick ester (main component is ethyl acetate, second alcohol and water).
According to pertinent literature, the separation method of ethyl acetate, second alcohol and water has rectifying separation, azeotropic distillation (adding entrainer), extractive distillation with salt, extracting rectifying etc. conventionally, by By consulting literatures data, show that these methods respectively have superiority and inferior position, rear three kinds of separation methods are not seen the report of large production equipment at present.Above-mentioned separation method all exists following defect: distillation and separation method product quality has fluctuation, moisture and amount of alcohol is more in the thick ester obtaining due to reactive distillation, therefore thick ester is before entering follow-up rectifying, moisture in thick ester and amount of alcohol need be carried out to initial gross separation, and general separation equipment is bad in ester phase and water layered effect, moisture and the amount of alcohol that causes ethyl acetate product increases, thereby affects product quality and output.Azeotropic distillation method is in order to improve the relative volatility of ethanol to ethyl acetate, reaches identical column plate that purity requires few, and entrainer has ether, pentamethylene, methyl formate etc., and owing to introducing entrainer, flow process is complicated with respect to rectifying.Extractive distillation with salt method is method separating ethyl acetate, the second alcohol and water that adopts first rectifying after extraction, but increases the problems such as a set of extraction equipment and salt solution evaporation concentration equipment, salting liquid etching apparatus simultaneously, cannot heavy industrialization.Extraction rectifying method is by adding extractant to destroy the azeotropic point of ethyl acetate, second alcohol and water ternary azeotrope, extractant has C2-4 alcohols, acetic acid, water etc., need to first extract two steps of rectifying again and carry out, owing to introducing extractant, flow process is complicated with respect to rectifying.
In prior art, the separation equipment of ethyl acetate and separation method operation are comparatively complicated, and have defect separately, so far, the relevant report that not yet has the separation equipment of ethyl acetate simple to operation, has restricted the preparation technology's of ethyl acetate development greatly, and this phenomenon is urgently to be resolved hurrily.
Summary of the invention
It is of low quality that technical problem to be solved by this invention is to overcome the isolated ethyl acetate of separation equipment of existing ethyl acetate, the content of the water content of ester in mutually and the oil phase in water is all higher, or need to introduce other materials makes separation process complicated, or cause the defects such as equipment corrosion, a kind of separation equipment of new ethyl acetate, the device of preparing ethyl acetate and preparation method are provided.This separation equipment and device are simple to operation, thoroughly separated, do not introduce other materials, can isolate high-quality ethyl acetate, and the content of the ethyl acetate making reaches more than 99.9%.
In the separation process of ethyl acetate, because the density difference of ethyl acetate and water is very little, layered effect is undesirable, causes in water content in ethyl acetate and water organic content higher, to separation process, has brought very large difficulty.In order to improve purity and the quality of ethyl acetate, improve ethyl acetate in thick ester and the layered effect of water, inventor conducts in-depth research the separation equipment of ethyl acetate, has finally obtained technical scheme of the present invention.
One of object of the present invention is, a kind of separation equipment of ethyl acetate is provided.Described separation equipment comprises: an a tank body and bag that catchments, one side of described tank body is provided with a material inlet, over against described material inlet place, one baffle plate for reducing inlet feed speed is set, the space for Flow of Goods and Materials is left in the bottom of described baffle plate and described tank body, the side of described tank body is equipped with an interior heat exchanger tube, and the space for Flow of Goods and Materials is left in the bottom of described interior heat exchanger tube and described tank body; The bottom of described tank body is also provided with an oil phase outlet; The described bag that catchments is arranged at the bottom of described tank body, between described material inlet and described oil phase outlet, the described outside of wrapping of catchmenting is coated with outer heat exchanger tube; The bottom of the described bag that catchments is provided with a water outlet; The size of described tank body meets following requirement simultaneously:
Wherein:
D is the diameter of described tank body, m;
L is the length of described tank body, m;
L
1for the described bag that catchments from length of straight flange, m; And L
1=(0.2-0.25) L;
Q
(thick ester)for the volume flow of thick ester, m
3/ s;
U is the sinking speed of water, m/s; According to the different fluidised forms of water, the computing formula of the sinking speed u of water is as shown in table 1:
The computing formula of the sinking speed of table 1 water
Wherein, Reynolds number R
ecomputing formula be:
In the computing formula of the sinking speed u of water, each alphabetical implication and numerical value are as follows:
D is water diameter, and its value is 100-200 μ m;
ρ
sfor the density of water, its value is 967kg/m
3;
ρ is the density of oil phase, and its value is 887kg/m
3;
G is acceleration of gravity;
μ is the viscosity of oil phase, and its value is 0.411cp.
In the present invention, described separation equipment is preferably a horizontal separator.
In the present invention, described baffle plate is preferably perpendicular to the bottom of described tank body.Described baffle plate and described tank body preferably weld by angle steel.Described baffle plate is preferably circular baffle plate.
In the present invention, preferably, described side is to be provided with the side of material inlet or the side of a side relative with described material inlet; Better is the side that is provided with material inlet.
In the present invention, preferably, on described interior heat exchanger tube, be provided with some fins.According to this area general knowledge, described fin is the sheet metal that a kind of thermal conductivity is strong, in order to increase the material disturbance of described heat exchanger tube, improves heat exchange efficiency.
In the present invention, preferably, the exposed junction of described interior heat exchanger tube is provided with one first chilled water import and one first chilled water outlet.Preferably, the position of the first described chilled water import is positioned at the below of the first described chilled water outlet.
In the present invention, preferably, the external one first freezing unit of described interior heat exchanger tube, the chilled water in the first described freezing unit, by described interior heat exchanger tube, reduces the temperature in described tank body.
In the present invention, preferably, described outer heat exchanger tube is provided with one second chilled water import and the second chilled water outlet.Preferably, the position of the second described chilled water import is positioned at the below of the second described chilled water outlet.
In the present invention, preferably, the external one second freezing unit of described outer heat exchanger tube, the chilled water in the second described freezing unit, by described outer heat exchanger tube, reduces the temperature in the described bag that catchments.
In the present invention, preferably, the outer symmetrical of described tank body is provided with one group for supporting the bearing of described tank body.
In the present invention, about being described as follows of the deterministic process of the size of tank body:
In the present invention, thick ester enters from the material inlet of described tank body, hits and touches with described baffle plate, reduces after thick ester speed, and thick ester flows along described tank base.In mobile process, thick ester carries out heat exchange, temperature reduction, water and separation of oil with the chilled water in described interior heat exchange coil.Separated for water and oil phase, need to study fully to the vertical sedimentation time of the time of staying of thick ester and water.
On the one hand, in order to guarantee the separated of water in described thick ester and oil phase, the vertical sedimentation time of water must be less than the time of staying of thick ester.On the other hand, enter in the thick ester of tank body, water and oil phase are all minimum drops, cannot pass through gravitational settling, make it and separation of oil.Only have water to accumulate to certain degree, can get off by gravitational settling; When water particle diameter is 100-200 μ m, while being preferably 150 μ m, can realize the separated of water and oil phase; And in order to make water and oil phase (being ester phase) reach above-mentioned separation condition, the time of staying of thick ester must, in the scope of 15min-40min, be preferably 20min.
Particularly, the deterministic process of the size of described tank body is as follows:
(1) the vertical sedimentation time T of described water
(water)computing formula be:
Wherein:
D is the diameter of described tank body, m;
U is the sinking speed of water, m/s; According to the different fluidised forms of water, the computing formula of the sinking speed u of water is as shown in table 1:
Wherein, Reynolds number R
ecomputing formula be:
In the computing formula of the sinking speed u of water, each alphabetical implication and numerical value are as follows:
D is water diameter, and its value, for 100-200 μ m, is preferably 150 μ m;
ρ
sfor the density of water, its value is 967kg/m
3;
ρ is the density of oil phase, and its value is 887kg/m
3;
G is acceleration of gravity; Its value is 9.8m/s
2.
μ is the viscosity of oil phase, and its value is 0.411cp.
(2) time of staying T of described thick ester
(thick ester)computing formula be:
Wherein:
L is the length of described tank body, m;
L
1for the described bag that catchments from length of straight flange, m; And L
1value be preferably (0.1-0.3) L, that better is (0.2-0.25) L.
Conventional according to this area, the described bag that catchments from length of straight flange, refer to the weld seam of described catchment bag and described tank body, and the material inlet of described tank body over against end socket between horizontal range.L-L
1be from one end of the bottom of the described tank body near described material inlet to the horizontal range of the center line of the described bag that catchments.
Q
(thick ester)for the volume flow of thick ester, m
3/ s;
D is the diameter of tank body, m.
(3) the vertical sedimentation time T of water
(water)be less than the time of staying T of thick ester
(thick ester), that is:
By can be calculated:
Through above-mentioned theory, derive, can obtain the diameter D of described tank body and the relation between length L, then according to selecting in chemical process design manual (the 4th edition volume two) pattern about horizontal ellipse head container of the 637th page of the 35th chapter and the table 35-8 of basic parameter.
Preferably, the flow when described thick ester is 83.5m
3100,000 tons of left and right of/h(ethyl acetate annual production) time, the diameter D of described tank body is 3m, and length L is 8m.
Preferably, the flow when described thick ester is 40m
350,000 tons of left and right of/h(ethyl acetate annual production) time, the diameter D of described tank body is 2.2m, and length L is 5.8m.
Preferably, the flow when described thick ester is 20m
32.5 ten thousand tons of left and right of/h(ethyl acetate annual production) time, the diameter D of described tank body is 1.8m, and length L is 5.6m.
Preferably, the flow when described thick ester is 10m
3during/h (10,000 tons of left and right of ethyl acetate annual production), the diameter D of described tank body is 1.4m, and length L is 4.8m.
Preferably, the flow when described thick ester is 5m
3during/h (0.5 ten thousand tons of left and right of ethyl acetate annual production), the diameter D of described tank body is 1m, and length L is 3.4m.
In the present invention, the vertical sedimentation time T of described water
(water)more short better.
In the present invention, described effect of catchmenting bag is: water is entered catchment bag, with the chilled water heat exchange in described outer heat exchanger tube, water is further lowered the temperature, and is conducive to the separated of water and oil phase.
In the present invention, the described bag that catchments is of a size of the size of this area routine.Preferably, the size of the described bag that catchments is calculated according to following formula:
V=Q
(water)* T
(thick ester)
Wherein, Q
(water)for the volume flow of water, m
3/ h; Conventional according to this area, Q
(water)by ASPEN PLUS process stream, account and calculate.
Wherein:
D is the diameter of described tank body, m;
L is the length of described tank body, m;
L
1for the described bag that catchments from length of straight flange, m; And L
1value be preferably (0.1-0.3) L, that better is (0.2-0.25) L;
Q
(thick ester)for the volume flow of thick ester, m
3/ s.
Preferably, the size of the described bag that catchments can be selected from chemical process design manual (the 4th edition volume two) pattern about horizontal ellipse head container of the 637th page of the 35th chapter and the table 35-8 of basic parameter.
In the present invention, when the flow of described thick ester is 83.5m
3during/h, the volume of the bag that preferably catchments is 1m
3, the catchment internal diameter of bag and the length of straight tube are 0.8m and 1.6m.
In the present invention, the area of described interior heat exchanger tube is the area of this area routine; The area of described interior heat exchanger tube calculates according to following formula: be preferably:
Q=m·Cp·(T
1-T
2)=K·S·Δt
m；
Wherein:
Q is the thermic load of heat exchanger tube, KW;
S is the area of heat exchanger tube, m
2;
M is the mass flow of thick ester, kg/h;
Cp is the specific heat capacity of thick ester, and its value is 2.212KJ/kg ℃;
T
1for the inlet temperature of described material, ℃; Being generally 40-60 ℃, is preferably 45 ℃;
T
2for the outlet temperature of described material, ℃; Being generally 5-35 ℃, is preferably 20 ℃;
△t
m=（T
1-t
1）+（T
2-t
2）
T
1for the temperature in the first described chilled water import, ℃; Being generally 5-10 ℃, is preferably 5 ℃ and 7 ℃;
T
2for the temperature in the first described chilled water outlet, ℃; Being generally 10-20 ℃, is preferably 10 ℃ and 12 ℃;
And t
1< t
2;
K is overall heat-transfer coefficient: those skilled in the art, when selecting overall heat-transfer coefficient K, are generally to select according to the hot coefficient in total reception room of the 603rd page of unit processes in chemical synthesis of < < petrochemical industry design manual > > the 3rd volume the 5th chapter heat exchanger table 5-24 submergence coil heat exchanger.Generally speaking, its value is 370-540W/m
2℃.
Two of object of the present invention is, a kind of device of preparing ethyl acetate is provided, and described device comprises: the separation equipment of the separation equipment of an esterifying kettle, an esterification column, an esterification column tower top buffer, one first ethyl acetate, a concentration tower, a concentration tower tower top buffer, one second ethyl acetate, a treating column, a waste water tower and a low ester tower; The separation equipment that the separation equipment of the first described ethyl acetate and the separation equipment of the second ethyl acetate are ethyl acetate as above;
The outlet of described esterifying kettle connects the first import of described esterification column, the first tower top outlet of described esterification column connects the first entrance of described esterification column tower top buffer, the outlet of described esterification column tower top buffer connects the material inlet of the separation equipment of the first described ethyl acetate, the second import of the first import of the concentration tower described in the oil phase outlet of the separation equipment of the first described ethyl acetate connects respectively and described esterification column, the first tower top outlet of described concentration tower connects the first import of described concentration tower tower top buffer, the outlet of described concentration tower tower top buffer connects the material inlet of the separation equipment of the second described ethyl acetate, the import of the second import of the concentration tower described in the oil phase outlet of the separation equipment of the second described ethyl acetate connects respectively and described low ester tower, the second tower bottom outlet of described concentration tower connects the import of described treating column, described treating column tower top is provided with first tower top outlet flowing out for ethyl acetate, the water outlet of the separation equipment of the first described ethyl acetate is connected the waste water import of described waste water tower, the second entrance of the second entrance of the esterification column tower top buffer described in the second tower bottom outlet of described waste water tower connects respectively and described concentration tower tower top buffer with the water outlet of the separation equipment of the second described ethyl acetate.
Preferably, the second tower bottom outlet of described esterification column connects the second import of described esterifying kettle.
Preferably, at the bottom of described treating column tower, be also provided with a second tower bottom outlet flowing out for high-boiling components.
Preferably, the tower top of described low ester tower is provided with first tower top outlet flowing out for low ester.
Preferably, be provided with one second tower bottom outlet at the bottom of the tower of described low ester tower, the second described tower bottom outlet connects the triple feed inlet of described esterifying kettle.
Preferably, the first tower top outlet of described waste water tower connects the 4th import of described esterifying kettle.
Preferably, described device also comprises a cooler.Preferably, the second tower bottom outlet of described waste water tower connects respectively the second import of described esterification column tower top buffer and the second import of described concentration tower tower top buffer by a cooler.
Preferably, the described device of preparing ethyl acetate also comprises a condenser.Preferably, the first tower top outlet of described esterification column connects after described condenser, then is connected with the first import of described esterification column tower top buffer.
Three of object of the present invention is, a kind of preparation method of ethyl acetate is provided, and described preparation method comprises the following steps:
(1) esterification: acetic acid, ethanol and catalyst for esterification reaction are mixed in described esterifying kettle, react under 101 ℃ of-110 ℃ of temperature conditions, obtain head product; Described acetic acid and ethanol mass ratio are (1.05-1.3): 1, and the mass flow of described catalyst for esterification reaction is the 1%-5% that passes into the gross mass of acetic acid in esterifying kettle and ethanol for 1 hour;
(2) rectifying: the head product rectifying in described esterification column obtaining in step (1), then be condensed to 45 ℃-60 ℃, obtain thick ester; The condition of described esterification column is controlled: top temperature is 69-72 ℃, and middle temperature is 72-78 ℃, and tower reactor temperature is 101-110 ℃, and tower actual plate number is 48-52 piece.
(3) separation: after the thick ester in step (2) is mixed in described esterification column tower top buffer with extractant, obtain mixed liquor A, described mixed liquor A enters the separation equipment of the first described ethyl acetate, described mixed liquor A is cooled to 10 ℃-30 ℃, water-oil separating, obtains oil phase A and waste water A; Described extractant is discharging material at the bottom of the tower of described waste water tower; The addition of described extractant is the quality 1/40-1/10 of described thick ester; In the separation equipment of described ethyl acetate, the time of staying of described thick ester is 15min-40min;
(4) concentrate: the oil phase A obtaining in step (3) branches to described concentration tower and described esterification column, branches to oil phase A concentrate in described concentration tower of described concentration tower, and described concentration tower tower top discharging, obtains oil phase B; The condition of described concentration tower is controlled: top temperature is 68-72 ℃, and middle temperature is 72-74 ℃, and tower reactor temperature is 75-80 ℃, and tower actual plate number is 48-52 piece;
(5) it is separated again: after described oil phase B mixes in described concentration tower tower top buffer with extractant, obtain mixed liquid B, described mixed liquid B enters the separation equipment of the second ethyl acetate, and described mixed liquid B is cooled to 10 ℃-30 ℃, water-oil separating, obtains oil phase C and waste water C; Described extractant is discharging material at the bottom of the tower of waste water tower; The addition of described extractant is the 1/40-1/10 of the quality of described oil phase B; In the separation equipment of described ethyl acetate, the described oil phase B time of staying is 15min-40min;
(6) concentrate again: the oil phase C obtaining in step (5) branches to described concentration tower and described low ester tower, branches to the described oil phase C concentrate in described concentration tower in described concentration tower, and discharging at the bottom of described concentration tower tower, obtains oil phase D; The condition of described concentration tower is controlled: top temperature is 68-72 ℃, and middle temperature is 72-74 ℃, and tower reactor temperature is 75-80 ℃, and tower actual plate number is 48-52 piece;
(7) refining: described oil phase D is refining in described treating column, and described treating column tower top discharging, obtains ethyl acetate; The condition of described treating column is controlled: top temperature for 78-80 ℃, middle temperature be 79-81 ℃, tower reactor temperature is 83-85 ℃, tower actual plate number is 48-52 piece;
Waste water C described in waste water A described in step (3) and step (5) flow to described waste water tower, separated in described waste water tower, discharging material at the bottom of the tower of waste water tower, the condition of described waste water tower is controlled: top temperature is 70-72 ℃, middle temperature is 74-78 ℃, tower reactor temperature is 98-103 ℃, and tower actual plate number is 48-60 piece; At the bottom of the tower of described waste water tower, discharging material branches in described esterification column tower top buffer and described concentration tower tower top buffer, as extractant.
Below, concrete technology step and the condition for the preparation method of above-mentioned ethyl acetate is specifically described:
In step (1), described catalyst for esterification reaction is the catalyst of this area routine, is preferably sulfuric acid.Described sulfuric acid is preferably 98% the concentrated sulfuric acid; Described percentage is mass percent.The grade of the described concentrated sulfuric acid is certified products and above grade in GBT534-2002 industrial sulphuric acid standard.
In step (1), the mass flow of described catalyst be preferably within 1 hour, pass into acetic acid in esterifying kettle and ethanol gross mass 3%.
According to this area general knowledge, in step (1), 101 ℃ of-110 ℃ of temperature conditions in described esterifying kettle are provided by hot coil Steam Heating in esterifying kettle.
In step (1), described head product preferably comprises: the ethyl acetate of 23.1%-29.13%, the acetic acid of 62.6%-68.6%, the water of 7%-8% and the ethanol of 0.5%-0.9%; In step (1), what described head product was better comprises: 26.1% ethyl acetate, 65.6% acetic acid, 7.6% water and 0.7% ethanol; Described percentage is the mass percent that accounts for head product.
In step (2), the method for described rectifying is the method for this area routine; The method of described rectifying is preferably: described head product contacts and passes through the filler in described esterification column tower, carries out quality, exchange heat.The filler of described esterification column tower top is the filler of this area routine, is preferably metal corrugated plate filler, and that better is metal corrugated plate filler CY700.The temperature of the filler of described esterification column is preferably 70-106 ℃; Wherein, those skilled in the art all know: the CY of metal corrugated plate filler CY700 is filler model, and 700 is specific area, and peak height is 4.3, hydraulic diameter 5,45 °, angle of inclination, voidage 85～90%, theoretical cam curve 8～10, Pressure Drop 3.5～5mmH
2o/m.
In step (2), the temperature of the head product after described rectifying is preferably 69-72 ℃, and better is 70.2 ℃.
In step (2), the method for described condensation and condition are method and the condition of this area routine.Described condensation is preferably carried out in condenser.Described condensed temperature is preferably 45 ℃.
In step (2), described thick ester preferably comprises: the ethanol of the ethyl acetate of 88%-93%, the water of 5%-8% and 1%-2%, described percentage is the mass percent that accounts for thick ester.
In step (3), described cooling is preferably for being cooled to 20 ℃.
In step (3), described oil phase A preferably comprises: the ethyl acetate of 93.3%-97.3%, the acetic acid of 0.0014%-0.0018%, the water of 3%-4%, the Ethyl formate of the ethanol of 1.2%-1.6%, 0.01%-0.02%, the ethyl propionate of the methyl acetate of 0.01%-0.02%, 0.002%-0.0025% and the propyl acetate of 0.004%-0.008%; Described better the comprising of oil phase A: 95.3% ethyl acetate, 0.0016% acetic acid, 3.24% water, 1.42% ethanol, 0.0126% Ethyl formate, 0.0177% methyl acetate, 0.0021% ethyl propionate and 0.006% propyl acetate; Described percentage is the mass percent that accounts for oil phase A.
In step (3), described extractant (be the tower of waste water tower at the bottom of discharging material) comprising: 99.99% water and 0.01% acetic acid, described percentage is the mass percent that accounts for extractant.
In step (4), described oil phase B preferably comprises: the ethyl acetate of 87.7%-91.7%, the water of 5%-7%, the ethanol of 4%-4.5%, the methyl acetate of the Ethyl formate of 0.03%-0.004% and 0.03%-0.004%; In step (4), described better the comprising of oil phase B: 89.7% ethyl acetate, 5.96% water, 4.26% ethanol, 0.035% Ethyl formate and 0.045% methyl acetate; Described percentage is the mass percent that accounts for described oil phase B.
In step (5), preferably, the inlet temperature in described concentration tower tower top buffer of described oil phase B is 45 ℃-60 ℃.
In step (5), described cooling is preferably for being cooled to 20 ℃.
In step (5), described oil phase C preferably comprises: the Ethyl formate of the water of 88.7%-92.72% ethyl acetate, 4.5%-5%, the ethanol of 4%-5%, 0.04%-0.041% and 0.065%-0.07% methyl acetate; In step (5), described better the comprising of oil phase C: 90.7% ethyl acetate, 4.98% water, 4.21% ethanol, 0.0405% Ethyl formate and 0.0695% methyl acetate; Described percentage is the mass percent that accounts for oil phase C.
In step (5), described extractant (be the tower of waste water tower at the bottom of discharging material) comprising: 99.99% water and 0.01% acetic acid, described percentage is the mass percent that accounts for extractant.
In step (6), described oil phase D preferably comprises: the ethyl acetate of 99.6%-99.9%, the acetic acid of 0.002%-0.0026%, the water of 0.006%-0.0065%, the methyl acetate of the ethanol of 0.08%-0.083%, 0.002%-0.0023%, the propyl acetate of the ethyl propionate of 0.04%-0.045% and 0.05%-0.055%; In step (6), described better the comprising of oil phase D: 99.81% ethyl acetate, 0.0024% acetic acid, 0.0063% water, 0.0818% ethanol, 0.0021% methyl acetate, 0.0434% ethyl propionate and 0.054% propyl acetate; Described percentage is the mass percent that accounts for oil phase D.
In step (6), branch to described oil phase C rectifying in described low ester tower of described low ester tower, described low ester column overhead discharging, obtains low Ester, and discharging at the bottom of described low ester tower tower, obtains backflow product.
Preferably, the condition in described low ester tower is controlled and is: top temperature is 68-72 ℃, and middle temperature is 70-74 ℃, and tower reactor temperature is 72-76 ℃, and plate number is 48-52 piece.
Described low Ester preferably comprises: the ethyl acetate of 67.3%-71.3%, the water of 11%-13%, the ethanol of 10%-12%, the methyl acetate of the Ethyl formate of 3%-4% and 4%-5%; Described better the comprising of low Ester: 68.3% ethyl acetate, 12.5% water, 11.5% ethanol, 3.2% Ethyl formate and 4.5% methyl acetate; Described percentage is the mass percent that accounts for described low Ester.
Preferably, described low Ester flows out by the first tower top outlet of described low ester tower.
Described backflow product preferably comprises: the ethanol of the ethyl acetate of 94.1%-98.1%, the water of 4%-5% and 4%-5%; Described better the comprising of backflow product: 96.1% ethyl acetate, 4.3% water and 4.1% ethanol; Described percentage is the mass percent that accounts for backflow product.
Preferably, described backflow product flows into described esterifying kettle by the second tower bottom outlet of described low ester tower.
In step (7), preferably, in described treating column, discharging at the bottom of described treating column tower, obtains higher boiling Ester, and described higher boiling Ester comprises propyl acetate and ethyl propionate; Described higher boiling Ester flows out by the second tower bottom outlet of described treating column.
In the present invention, preferably, at the bottom of the tower of described waste water tower, discharging material material comprises: 99.99% water and 0.01% acetic acid, described percentage is the mass percent that accounts for discharging material at the bottom of the tower of waste water tower.
In the present invention, preferably, at the bottom of the tower of described waste water tower, discharging material, after described cooler is cooling, then is back in described esterification column tower top buffer and described concentration tower tower top buffer.
In the present invention, preferably, after the waste water A described in step (3) is separated in described waste water tower with the waste water C described in step (5), described waste water column overhead discharging, obtains waste water tower separator.
In the present invention, described waste water tower separator preferably comprises: the ethanol of the ethyl acetate of 54%-56%, the water of 14.5%-15.5% and 29.5%-31%; Described better the comprising of waste water tower separator: 54.7% ethyl acetate, 15.1% water and 30.2% ethanol; Described percentage is the mass percent that accounts for waste water tower separator.
Preferably, described waste water tower separator flow in described esterifying kettle through the tower top outlet of described waste water tower.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can be combined, and obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is: the separation equipment of ethyl acetate of the present invention is simple to operation, thoroughly separated, do not introduce other materials, can isolate high-quality ethyl acetate, reduce ethanol content and water content in product, the purity 99.9% of the ethyl acetate making.The equipment of preparing ethyl acetate of the present invention is simple to operation, can prepare the ethyl acetate that purity is very high, and the purity of the ethyl acetate preparing reaches 99.9%.
Accompanying drawing explanation
Fig. 1 is the separation equipment of the ethyl acetate of embodiment 1.
Fig. 2 is the separation equipment of the ethyl acetate of embodiment 2.
Fig. 3 is the separation equipment of the ethyl acetate of embodiment 3.
Fig. 4 is the device of preparing ethyl acetate of embodiment 6.
Fig. 5 is the device of preparing ethyl acetate of embodiment 7.
The specific embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to conventional method and condition, or selects according to catalogue.
The separation equipment of a kind of ethyl acetate as shown in Figure 1.
Described separation equipment comprises: tank body 1 and the bag 14 that catchments, one side of described tank body 1 is provided with material inlet 11, over against described material inlet 11 places, be provided for reducing the baffle plate 12 of inlet feed speed, described baffle plate 12 leaves the space for Flow of Goods and Materials with the bottom of described tank body 1, the side of described tank body 1 is equipped with interior heat exchanger tube 13, and described interior heat exchanger tube 13 leaves the space for Flow of Goods and Materials with the bottom of described tank body 1; The bottom of described tank body 1 is also provided with oil phase outlet 15; The described bag 14 that catchments is arranged at the bottom of described tank body 1, between described material inlet 11 and described oil phase outlet 15, described catchmenting wrapped 14 outside and is coated with outer heat exchanger tube 141; The bottom of the described bag 14 that catchments is provided with water outlet 142; The size of described tank body 1 meets following requirement simultaneously:
with
Wherein:
D is the diameter of described tank body 1, m;
L is the length of described tank body 1, m;
L
1for the described bag 14 that catchments from length of straight flange, m; And L
1=(0.2-0.25) L;
Q
(thick ester)for the volume flow of thick ester, m
3/ s;
U is the sinking speed of water, m/s; According to the different fluidised forms of water, the computing formula of the sinking speed u of water is as shown in table 1:
The computing formula of the sinking speed of table 1 water
Wherein, Reynolds number R
ecomputing formula be:
In the computing formula of the sinking speed u of water, each alphabetical implication and numerical value are as follows:
D is water diameter, and its value is 100-200 μ m;
ρ
sfor the density of water, its value is 967kg/m
3;
ρ is the density of oil phase, and its value is 887kg/m
3;
G is acceleration of gravity;
μ is the viscosity of oil phase, and its value is 0.411cp.
The computational methods of the size of tank body are as follows:
(1) the vertical sedimentation time T of described water
(water)computing formula be:
Wherein:
D is the diameter of described tank body, m;
U is the sinking speed of water, m/s; According to the different fluidised forms of water, the computing formula of the sinking speed u of water is as shown in table 1:
Wherein, Reynolds number R
ecomputing formula be:
In the computing formula of the sinking speed u of water, each alphabetical implication and numerical value are as follows:
D is water diameter, and its value is 150 μ m;
ρ
sfor the density of water, its value is 967kg/m
3;
ρ is the density of oil phase, and its value is 887kg/m
3;
G is acceleration of gravity; Its value is 9.8m/s
2;
μ is the viscosity of oil phase, and its value is 0.411cp;
(2) time of staying T of described thick ester
(thick ester)computing formula be:
Wherein:
L is the length of described tank body, m;
L
1for the described bag that catchments from length of straight flange, m; And L
1for 1/8L;
L-L
1be the bottom of described tank body, from the one end of the material inlet near described to the horizontal range of the described bag that catchments;
Q
(thick ester)for the volume flow of thick ester, m
3/ s; In the present embodiment, Q
(thick ester)for 83.5m
3/ h(wherein the flow of water and ester phase is respectively 3.1m
3/ h and 80.4m
3/ h);
D is the diameter of tank body, m;
(3) the vertical sedimentation time T of water
(water)be less than the time of staying T of thick ester
(thick ester), that is:
By can be calculated:
Suppose that water body is positioned at laminar region, being calculated as of the sinking speed u of water:
Reynolds number now
=887*0.0024*0.00015 ÷ 0.411 ÷ 1000=0.774 (10
-4<R
eit is <1), therefore former that to establish laminar region correct; The sinking speed u of water is 0.0024m/s;
According to the vertical sedimentation time T of water
(water)be less than the time of staying T of thick ester
(thick ester), the result of calculation obtaining is:
The diameter D of tank body and the relation between length L meet: DL>=14.7m
2;
（4）
Result of calculation is:
The diameter D of tank body and the relation between length L meet: 60.7m
3≤ LD
2≤ 162m
3;
(5) selection of size
According to the applicable equipment about selecting in the pattern of horizontal ellipse head container and the form of basic parameter of the 637th page of the 35th chapter of chemical process design manual (the 4th edition volume two).
In the present embodiment, the diameter D of the described tank body that selection obtains is 3m, and length L is 8m.
(6) check of tank body size:
When tank diameter D is 3m, when length L is 8m,
Now, meet the vertical sedimentation time T of water
(water)be less than the time of staying T of thick ester
(thick ester); And the time of staying T of thick ester
(thick ester)within the scope of 15min-40min;
Therefore, the diameter D of the described tank body that selection obtains is 3m, and length L is 8m, meets the demands.
Embodiment 2
The separation equipment of a kind of ethyl acetate as shown in Figure 2.Described separation equipment is preferably horizontal separator.
Described separation equipment comprises: tank body 1 and the bag 14 that catchments;
One side of described tank body 1 is provided with material inlet 11, over against described material inlet 11 places, be provided for reducing the baffle plate 12 of inlet feed speed, described baffle plate 12 is perpendicular to the bottom of described tank body 1, described baffle plate 12 preferably welds by angle steel with described tank body 1, described baffle plate 12 is circular baffle plate, and described baffle plate 12 leaves the space for Flow of Goods and Materials with the bottom of described tank body 1;
The side of described tank body 1 is equipped with interior heat exchanger tube 13, on described interior heat exchanger tube 13, is provided with some fins, and described interior heat exchanger tube 13 leaves the space for Flow of Goods and Materials with the bottom of described tank body 1;
The exposed junction of described interior heat exchanger tube 13 is provided with the first chilled water import 132 and the first chilled water outlet 131, and the position of the first described chilled water import 132 is positioned at the below of the first described chilled water outlet 131; External the first freezing unit of described interior heat exchanger tube 13, the chilled water in the first described freezing unit, by described interior heat exchanger tube 13, reduces the temperature in described tank body 1;
The bottom of described tank body 1 is also provided with oil phase outlet 15;
The described bag 14 that catchments be arranged at described tank body 1 bottom, at described material inlet 11 and described oil phase, export between 15, the outside of the described bag 14 that catchments is coated with outer heat exchanger tube 141, described outer heat exchanger tube 141 is provided with the second chilled water import 1412 and the second chilled water outlet 1411, preferably, the position of the second described chilled water import 1412 is positioned at the below of the second described chilled water outlet 1411; External the second freezing unit of described outer heat exchanger tube 141, the chilled water in the second described freezing unit, by described outer heat exchanger tube 141, reduces the temperature in the described bag that catchments;
The bottom of the described bag 14 that catchments is provided with water outlet 142;
The outer symmetrical of described tank body 1 is provided with one group for supporting the bearing 16 of described tank body 1.
The calculating of tank body size is with embodiment 1, and the flow of thick ester is 83.5m
3/ h, the tank body calculating is of a size of: diameter D is 3m, and length L is 8m.
The separation equipment of a kind of ethyl acetate as shown in Figure 3.
Described separation equipment comprises: tank body 1 and the bag 14 that catchments, one side of described tank body 1 is provided with material inlet 11, over against described material inlet 11 places, be provided for reducing the baffle plate 12 of inlet feed speed, described baffle plate 12 leaves the space for Flow of Goods and Materials with the bottom of described tank body 1, the side of described tank body 1 is equipped with interior heat exchanger tube 13, and described interior heat exchanger tube 13 leaves the space for Flow of Goods and Materials with the bottom of described tank body 1; The bottom of described tank body 1 is also provided with oil phase outlet 15; The described bag 14 that catchments is arranged at the bottom of described tank body 1, between described material inlet 11 and described oil phase outlet 15, described catchmenting wrapped 14 outside and is coated with outer heat exchanger tube 141; The bottom of the described bag 14 that catchments is provided with water outlet 142; The size of described tank body 1 meets following requirement simultaneously:
The calculating of tank body size is with embodiment 1, and the flow of thick ester is 40m
3/ h, the diameter D of the tank body calculating is 2.2m, length L is 5.8m.
Embodiment 4
As the calculating of the size of the bag that catchments in embodiment 1 or 2.
The computing formula of size of bag of catchmenting is:
V=Q
(water)* T
(thick ester)
Wherein, Q
(water)for the volume flow of water, Q in this embodiment
(water)value be 3.1m
3/ h;
Wherein:
L is the length of described tank body, is 8m;
L
1for the described bag that catchments from length of straight flange, L
1for 1/8L;
D is the diameter of tank body, is 3m;
T
(thick ester)value be 17.7min as described in Example 3:
From chemical process design manual (the 4th edition volume two) pattern about horizontal ellipse head container of the 637th page of the 35th chapter and the table 35-8 of basic parameter, select again the size of the bag that catchments.In the present embodiment, selecting the volume wrapping that catchments obtaining is 1m
3, the catchment internal diameter of bag and the length of straight tube are 0.8m and 1.6m.
Embodiment 5
As the calculating of the size of the interior heat exchanger tube in embodiment 1 or 2.
The computing formula of the size of interior heat exchanger tube is:
Q=m·Cp·(T
1-T
2)=K·S·Δt
m；
Wherein:
Q is the thermic load of heat exchanger tube, KW;
S is the area of heat exchanger tube, m
2;
M is the mass flow of thick ester, kg/h; When the volume flow of thick ester is 83.5m
3during/h, as calculated the mass flow of thick ester is 76347kg/h;
C
pfor the specific heat capacity of thick ester, its value is 2.212KJ/kg ℃;
T
1for the inlet temperature of described material, it is 45 ℃;
T
2for the outlet temperature of described material, 20 ℃;
T
1for the temperature in the first described chilled water import, ℃, be 7 ℃;
T
2for the temperature in the first described chilled water outlet, ℃, be 12 ℃;
K is overall heat-transfer coefficient: the hot coefficient in total reception room according to the 603rd page of unit processes in chemical synthesis of < < petrochemical industry design manual > > the 3rd volume the 5th chapter heat exchanger table 5-24 submergence coil heat exchanger is selected.Generally speaking, in the present embodiment, its value is 370W/m
2℃.
Result of calculation: the area of heat exchanger tube is 137.8m
2.
Embodiment 6
As shown in Figure 4: a kind of device of preparing ethyl acetate.
Described device comprises: esterifying kettle 3, esterification column 4, esterification column tower top buffer 6, the separation equipment 1 of concentration tower tower top buffer 7, the first ethyl acetate, the separation equipment 2 of the second ethyl acetate, concentration tower 8, waste water tower 9, treating column 10 and low ester tower 11; The separation equipment 1 of the first described ethyl acetate and the separation equipment 2 of the second ethyl acetate are respectively arbitrary in the separation equipment of the ethyl acetate in embodiment 1,2 or 3;
The outlet of described esterifying kettle 3 connects the first import of described esterification column 4, the first tower top outlet of described esterification column 4 connects the first entrance of described esterification column tower top buffer 6, the outlet of described esterification column tower top buffer 6 connects the material inlet of the separation equipment 1 of the first described ethyl acetate, the second import of the first import of the concentration tower 8 described in the oil phase outlet of the separation equipment 1 of the first described ethyl acetate connects respectively and described esterification column 4, the first tower top outlet of described concentration tower 8 connects the first import of described concentration tower tower top buffer 7, the outlet of described concentration tower tower top buffer 7 connects the material inlet of the separation equipment 2 of the second described ethyl acetate, the import of the second import of the concentration tower 8 described in the oil phase outlet of the separation equipment 2 of the second described ethyl acetate connects respectively and described low ester tower 11, the second tower bottom outlet of described concentration tower 8 connects the import of described treating column 10, described treating column 10 tower tops are provided with first tower top outlet flowing out for ethyl acetate, the water outlet of the separation equipment 1 of the first described ethyl acetate is connected the waste water import of described waste water tower 9, the second entrance of the second entrance of the esterification column tower top buffer 6 described in the second tower bottom outlet of described waste water tower 9 connects respectively and described concentration tower tower top buffer 7 with the water outlet of the separation equipment 2 of the second described ethyl acetate.
As shown in Figure 5: a kind of device of preparing ethyl acetate.
Described device comprises: esterifying kettle 3, esterification column 4, esterification column tower top buffer 6, the separation equipment 1 of concentration tower tower top buffer 7, the first ethyl acetate, the separation equipment 2 of the second ethyl acetate, concentration tower 8, waste water tower 9, treating column 10, low ester tower 11, cooler 12 and condenser 5; The separation equipment 1 of the first described ethyl acetate and the separation equipment 2 of the second ethyl acetate are respectively arbitrary in the separation equipment of the ethyl acetate in embodiment 1,2 or 3;
The outlet of described esterifying kettle 3 connects the first import of described esterification column 4;
The first tower top outlet of described esterification column 4 connects after described condenser 5, is connected the second import of the esterifying kettle 3 described in the second tower bottom outlet of described esterification column 4 connects with the first import of described esterification column tower top buffer 6;
The outlet of described esterification column tower top buffer 6 connects the material inlet of the separation equipment 1 of the first described ethyl acetate, the second import of the first import of the concentration tower 8 described in the oil phase outlet of the separation equipment 1 of the first described ethyl acetate connects respectively and described esterification column 4;
The first tower top outlet of described concentration tower 8 connects the first import of described concentration tower tower top buffer 7;
The outlet of described concentration tower tower top buffer 7 connects the material inlet of the separation equipment 2 of the second described ethyl acetate, the import of the second import of the concentration tower 8 described in the oil phase outlet of the separation equipment 2 of the second described ethyl acetate connects respectively and described low ester tower 11, the second tower bottom outlet of described concentration tower 8 connects the import of described treating column 10, and described treating column 10 tower tops are provided with first tower top outlet flowing out for ethyl acetate;
At the bottom of described treating column 10 tower tops, be also provided with the second tower bottom outlet flowing out for high-boiling components;
The water outlet of the separation equipment 1 of the first described ethyl acetate is connected the waste water import of described waste water tower 9 with the water outlet of the separation equipment 2 of the second described ethyl acetate, the second import of the second import of the esterification column tower top buffer 6 described in the second tower bottom outlet of described waste water tower 9 connects respectively by cooler 12 and described concentration tower tower top buffer 7, the first tower top outlet of described waste water tower 9 connects the 4th import of described esterifying kettle 3;
The tower top of described low ester tower 11 is provided with the first tower top outlet flowing out for low ester; At the bottom of the tower of described low ester tower 11, be provided with the second tower bottom outlet, the second described tower bottom outlet connects the triple feed inlet of described esterifying kettle 3.
Embodiment 8
A preparation method for ethyl acetate, adopts the device of preparing as described in Example 6 ethyl acetate, as shown in Figure 4.
Described preparation method comprises the following steps:
(1) esterification: acetic acid, ethanol and catalyst for esterification reaction are mixed in described esterifying kettle 3, react under 101 ℃ of temperature conditions, obtain head product; Described acetic acid and ethanol mass ratio are 1.05:1, the mass flow of described catalyst for esterification reaction be within 1 hour, pass into acetic acid in esterifying kettle 3 and ethanol gross mass 5%; Described catalyst for esterification reaction is 98% the concentrated sulfuric acid;
(2) rectifying: the head product rectifying in described esterification column 4 obtaining in step (1), then be condensed to 45 ℃, obtain thick ester; The condition of described esterification column is controlled: top temperature is 69 ℃, and middle temperature is 78 ℃, and tower reactor temperature is 110 ℃, and tower actual plate number is 48;
(3) separation: by the thick ester in step (2) and extractant at described esterification column tower top buffer after 6 interior mixing, obtain mixed liquor A, described mixed liquor A enters the separation equipment 1 of the first described ethyl acetate, described mixed liquor A is cooled to 10 ℃, water-oil separating, obtains oil phase A and waste water A; Described extractant is discharging material at the bottom of the tower of described waste water tower 9; The addition of described extractant is the quality 1/40 of described thick ester; In the separation equipment of described ethyl acetate, the time of staying of described thick ester is 20min;
(4) concentrate: the oil phase A obtaining in step (3) branches to described concentration tower 8 and described esterification column, branches to oil phase A concentrate in described concentration tower 8 of described concentration tower 8, and described concentration tower tower top discharging, obtains oil phase B; The condition of described concentration tower 8 is controlled: top temperature is 68 ℃, and middle temperature is 72-74 ℃, and tower reactor temperature is 75 ℃, and tower actual plate number is 48;
(5) separated again: described oil phase B with extractant after described 7 interior mixing of column overhead concentration tower tower top buffer, obtain mixed liquid B, described mixed liquid B enters the separation equipment 2 of the second ethyl acetate, and described mixed liquid B is cooled to 20 ℃, water-oil separating, obtains oil phase C and waste water C; Described extractant is discharging material at the bottom of the tower of waste water tower 9; The addition of described extractant be described oil phase B quality 1/10; In the separation equipment of described ethyl acetate, the described oil phase B time of staying is 20min;
(6) concentrate again: the oil phase C obtaining in step (5) branches to described concentration tower 8 and described low ester tower 11, branches to the described oil phase C concentrate in described concentration tower 8 in described concentration tower 8, and discharging at the bottom of described concentration tower tower, obtains oil phase D; The condition of described concentration tower 8 is controlled: top temperature is 72 ℃, and middle temperature is 74 ℃, and tower reactor temperature is 80 ℃, and tower actual plate number is 52;
(7) refining: described oil phase D is refining in described treating column 10, and described treating column tower top discharging, obtains ethyl acetate; The condition of described treating column 10 is controlled: top temperature is that 78 ℃, middle temperature are 79 ℃, and tower reactor temperature is 83 ℃, and tower actual plate number is 48;
Waste water C described in waste water A described in step (3) and step (5) flow to described waste water tower 9, separated in described waste water tower 9, discharging material at the bottom of the tower of waste water tower, the condition of described waste water tower is controlled: top temperature is 70 ℃, middle temperature is 74 ℃, tower reactor temperature is 98 ℃, and tower actual plate number is 48; At the bottom of the tower of described waste water tower, discharging material branches in described esterification column tower top buffer 6 and described concentration tower tower top buffer 7, as extractant.
A preparation method for ethyl acetate, adopts the device of preparing as described in Example 6 ethyl acetate, as shown in Figure 4.
Described preparation method comprises the following steps:
(1) esterification: acetic acid, ethanol and catalyst for esterification reaction are mixed in described esterifying kettle 3, provide under 110 ℃ of temperature conditions in the interior hot coil Steam Heating of esterifying kettle 3, reaction, obtains head product; Described acetic acid and ethanol mass ratio are 1.3:1, the mass flow of described catalyst for esterification reaction be within 1 hour, pass into acetic acid in esterifying kettle 3 and ethanol gross mass 3%; Described catalyst for esterification reaction is 98% the concentrated sulfuric acid;
In step (1), described head product comprises: 26.1% ethyl acetate, 65.6% acetic acid, 7.6% water and 0.7% ethanol; Described percentage is the mass percent that accounts for head product;
(2) rectifying: the head product rectifying in described esterification column 4 obtaining in step (1), then be condensed to 45 ℃, obtain thick ester; The condition of described esterification column is controlled: top temperature is 72 ℃, and middle temperature is 78 ℃, and tower reactor temperature is 101 ℃, and tower actual plate number is 52;
In step (2), the filler of esterification column 4 tower tops is metal corrugated plate filler CY700; The temperature of the filler of described esterification column 4 is preferably 70-106 ℃; Described head product contacts and passes through the filler in described esterification column tower, carries out quality, exchange heat, is rectifying;
In step (2), the temperature of the head product after described rectifying is 70.2 ℃;
In step (2), described thick ester comprises: the ethanol of the ethyl acetate of 88%-93%, the water of 5%-8% and 1%-2%, and described percentage is the mass percent that accounts for thick ester;
(3) separation: by the thick ester in step (2) and extractant at described esterification column tower top buffer after 6 interior mixing, obtain mixed liquor A, described mixed liquor A enters the separation equipment 1 of the first described ethyl acetate, described mixed liquor A is cooled to 20 ℃, water-oil separating, obtains oil phase A and waste water A; Described extractant is discharging material at the bottom of the tower of described waste water tower 9; The addition of described extractant is the quality 1/10 of described thick ester; In the separation equipment of described ethyl acetate, the time of staying of described thick ester is 40min;
In step (3), described oil phase A comprises: 95.3% ethyl acetate, 0.0016% acetic acid, 3.24% water, 1.42% ethanol, 0.0126% Ethyl formate, 0.0177% methyl acetate, 0.0021% ethyl propionate and 0.006% propyl acetate; Described percentage is the mass percent that accounts for oil phase A;
In step (3), described extractant comprises 99.99% water and 0.01% acetic acid, and described percentage is the mass percent that accounts for extractant;
(4) concentrate: the oil phase A obtaining in step (3) branches to described concentration tower 8 and described esterification column, branches to oil phase A concentrate in described concentration tower 8 of described concentration tower 8, and described concentration tower tower top discharging, obtains oil phase B; The condition of described concentration tower 8 is controlled: top temperature is 72 ℃, and middle temperature is 74 ℃, and tower reactor temperature is 80 ℃, and tower actual plate number is 52;
In step (4), described oil phase B comprises: 89.7% ethyl acetate, 5.96% water, 4.26% ethanol, 0.035% Ethyl formate and 0.045% methyl acetate; Described percentage is the mass percent that accounts for described oil phase B;
(5) separated again: described oil phase B and extractant are at described concentration tower tower top buffer after 7 interior mixing, obtain mixed liquid B, described mixed liquid B enters the separation equipment 2 of the second ethyl acetate, and described mixed liquid B is cooled to 20 ℃, water-oil separating, obtains oil phase C and waste water C; Described extractant is discharging material at the bottom of the tower of waste water tower 9; The addition of described extractant be described oil phase B quality 1/40; In the separation equipment of described ethyl acetate, the described oil phase B time of staying is 15min-40min;
In step (5), the inlet temperature in described concentration tower tower top buffer 7 of described oil phase B is 45 ℃;
In step (5), described extractant comprises 99.99% water and 0.01% acetic acid, and described percentage is the mass percent that accounts for extractant;
In step (5), described oil phase C comprises: 90.7% ethyl acetate, 4.98% water, 4.21% ethanol, 0.0405% Ethyl formate and 0.0695% methyl acetate; Described percentage is the mass percent that accounts for oil phase C;
(6) concentrate again: the oil phase C obtaining in step (5) branches to described concentration tower 8 and described low ester tower 11, branches to the described oil phase C concentrate in described concentration tower 8 in described concentration tower 8, and discharging at the bottom of described concentration tower tower, obtains oil phase D;
The condition of described concentration tower 8 is controlled: top temperature is 68 ℃, and middle temperature is 74 ℃, and tower reactor temperature is 80 ℃, and tower actual plate number is 48-52 piece;
Described oil phase D comprises: 99.81% ethyl acetate, 0.0024% acetic acid, 0.0063% water, 0.0818% ethanol, 0.0021% methyl acetate, 0.0434% ethyl propionate and 0.054% propyl acetate; Described percentage is the mass percent that accounts for oil phase D;
Branch to described oil phase C rectifying in described low ester tower 11 of described low ester tower 11, described low ester tower 11 tower top dischargings, obtain low Ester, and discharging at the bottom of described low ester tower 11 towers, obtains backflow product;
Condition in described low ester tower 11 is controlled: top temperature is 68 ℃, and middle temperature is 74 ℃, and tower reactor temperature is 76 ℃, and plate number is 52;
Described low Ester comprises: 68.3% ethyl acetate, 12.5% water, 11.5% ethanol, 3.2% Ethyl formate and 4.5% methyl acetate; Described percentage is the mass percent that accounts for described low Ester; Described low Ester flows out by the first tower top outlet of described low ester tower 11;
Described backflow product comprises: 96.1% ethyl acetate, 4.3% water and 4.1% ethanol; Described percentage is the mass percent that accounts for backflow product; Described backflow product flows into described esterifying kettle 3 by the second tower bottom outlet of described low ester tower 11;
(7) refining: described oil phase D is refining in described treating column 10, and described treating column 10 tower top dischargings, obtain ethyl acetate; The condition of described treating column 10 is controlled: top temperature is that 80 ℃, middle temperature are 81 ℃, and tower reactor temperature is 85 ℃, and tower actual plate number is 52;
In described treating column 10, discharging at the bottom of described treating column 10 towers, obtains higher boiling Ester, and described higher boiling Ester comprises propyl acetate and ethyl propionate; Described higher boiling Ester flows out by the second tower bottom outlet of described treating column 10;
Waste water C described in waste water A described in step (3) and step (5) flow to described waste water tower 9, separated in described waste water tower 9, discharging material at the bottom of the tower of waste water tower, the condition of described waste water tower 9 is controlled: top temperature is 70 ℃, middle temperature is 78 ℃, tower reactor temperature is 103 ℃, and tower actual plate number is 48;
At the bottom of the tower of described waste water tower, discharging material branches in described esterification column tower top buffer 6 and described concentration tower tower top buffer 7, as extractant.
After waste water A described in step (3) is separated in described waste water tower 9 with the waste water C described in step (5), described waste water tower 9 tower top dischargings, obtain waste water tower separator; Described waste water tower separator comprises: 54.7% ethyl acetate, 15.1% water and 30.2% ethanol; Described percentage is the mass percent that accounts for waste water tower separator; Described waste water tower separator flow in described esterifying kettle 3 through the tower top outlet of described waste water tower 9.
A preparation method for ethyl acetate, adopts the device of preparing as described in Example 7 ethyl acetate, as shown in Figure 5.
Described preparation method comprises the following steps:
(1) esterification: acetic acid, ethanol and catalyst for esterification reaction are mixed in described esterifying kettle 3, react under 110 ℃ of temperature conditions, obtain head product; Described acetic acid and ethanol mass ratio be (1.05:1, the mass flow of described catalyst for esterification reaction is the 1%-5% that passes into the gross mass of acetic acid in esterifying kettle 3 and ethanol for 1 hour; Described catalyst for esterification reaction is 98% the concentrated sulfuric acid;
(2) rectifying: the head product rectifying in described esterification column 4 obtaining in step (1), then be condensed to 45 ℃, obtain thick ester; The condition of described esterification column is controlled: top temperature is 72 ℃, and middle temperature is 78 ℃, and tower reactor temperature is 110 ℃, and tower actual plate number is 52;
(3) separation: by the thick ester in step (2) and extractant at described esterification column tower top buffer after 6 interior mixing, obtain mixed liquor A, described mixed liquor A enters the separation equipment 1 of the first described ethyl acetate, described mixed liquor A is cooled to 30 ℃, water-oil separating, obtains oil phase A and waste water A; Described extractant is discharging material at the bottom of the tower of described waste water tower 9; The addition of described extractant is the quality 1/10 of described thick ester; In the separation equipment of described ethyl acetate, the time of staying of described thick ester is 40min;
(4) concentrate: the oil phase A obtaining in step (3) branches to described concentration tower 8 and described esterification column, branches to oil phase A concentrate in described concentration tower 8 of described concentration tower 8, and described concentration tower tower top discharging, obtains oil phase B; The condition of described concentration tower 8 is controlled: top temperature is 68 ℃, and middle temperature is 74 ℃, and tower reactor temperature is 80 ℃, and tower actual plate number is 48;
(5) separated again: described oil phase B and extractant are at described concentration tower tower top buffer after 7 interior mixing, obtain mixed liquid B, described mixed liquid B enters the separation equipment 2 of the second ethyl acetate, and described mixed liquid B is cooled to 10 ℃, water-oil separating, obtains oil phase C and waste water C; Described extractant is discharging material at the bottom of the tower of waste water tower 9; The addition of described extractant be described oil phase B quality 1/10; In the separation equipment of described ethyl acetate, the described oil phase B time of staying is 15min;
(6) concentrate again: the oil phase C obtaining in step (5) branches to described concentration tower 8 and described low ester tower 11, branches to the described oil phase C concentrate in described concentration tower 8 in described concentration tower 8, and discharging at the bottom of described concentration tower tower, obtains oil phase D; The condition of described concentration tower 8 is controlled: top temperature is 68 ℃, and middle temperature is 72 ℃, and tower reactor temperature is 80 ℃, and tower actual plate number is 48;
(7) refining: described oil phase D is refining in described treating column 10, and described treating column 10 tower top dischargings, obtain ethyl acetate; The condition of described treating column 10 is controlled: top temperature is that 78 ℃, middle temperature are 81 ℃, and tower reactor temperature is 85 ℃, and tower actual plate number is 48-52 piece;
Waste water C described in waste water A described in step (3) and step (5) flow to described waste water tower 9, separated in described waste water tower 9, obtains discharging material at the bottom of the tower of waste water tower; The condition of described waste water tower is controlled: top temperature is 72 ℃, and middle temperature is 78 ℃, and tower reactor temperature is 103 ℃, and tower actual plate number is 60; At the bottom of the tower of waste water tower, discharging material is after described cooler 12 is cooling, and at the bottom of the tower of described waste water tower, discharging material branches in described esterification column tower top buffer 6 and described concentration tower tower top buffer 7, as extractant.
A preparation method for ethyl acetate, adopts the device of preparing as described in Example 7 ethyl acetate, as shown in Figure 5.
Described preparation method comprises the following steps:
(1) esterification: acetic acid, ethanol and catalyst for esterification reaction are mixed in described esterifying kettle 3, provide under 101 ℃ of-110 ℃ of temperature conditions in the interior hot coil Steam Heating of esterifying kettle 3, reaction, obtains head product; Described acetic acid and ethanol mass ratio are 1.3:1, the mass flow of described catalyst for esterification reaction be within 1 hour, pass into acetic acid in esterifying kettle 3 and ethanol gross mass 1%; Described catalyst for esterification reaction is 98% the concentrated sulfuric acid;
In step (1), described head product comprises: 26.1% ethyl acetate, 65.6% acetic acid, 7.6% water and 0.7% ethanol; Described percentage is the mass percent that accounts for head product;
(2) rectifying: the head product rectifying in described esterification column 4 obtaining in step (1), then be condensed to 60 ℃, obtain thick ester; Described being condensate in condenser 5 carried out; The condition of described esterification column 4 is controlled: top temperature is 69 ℃, and middle temperature is 78 ℃, and tower reactor temperature is 110 ℃, and tower actual plate number is 52;
In step (2), the filler of esterification column 4 tower tops is metal corrugated plate filler CY700; The temperature of the filler of described esterification column 4 is preferably 70-106 ℃; Described head product contacts and passes through the filler in described esterification column tower, carries out quality, exchange heat, is rectifying;
In step (2), the temperature of the head product after described rectifying is preferably 72 ℃.
In step (2), described thick ester comprises: the ethanol of the ethyl acetate of 88%-93%, the water of 5%-8% and 1%-2%, and described percentage is the mass percent that accounts for thick ester;
(3) separation: by the thick ester in step (2) and extractant at described esterification column tower top buffer after 6 interior mixing, obtain mixed liquor A, described mixed liquor A enters the separation equipment 1 of the first described ethyl acetate, described mixed liquor A is cooled to 30 ℃, water-oil separating, obtains oil phase A and waste water A; Described extractant is discharging material at the bottom of the tower of described waste water tower 9; The addition of described extractant is the quality 1/40 of described thick ester; In the separation equipment of described ethyl acetate, the time of staying of described thick ester is 40min;
In step (3), described oil phase A comprises: 95.3% ethyl acetate, 0.0016% acetic acid, 3.24% water, 1.42% ethanol, 0.0126% Ethyl formate, 0.0177% methyl acetate, 0.0021% ethyl propionate and 0.006% propyl acetate; Described percentage is the mass percent that accounts for oil phase A;
In step (3), described extractant comprises 99.99% water and 0.01% acetic acid, and described percentage is the mass percent that accounts for extractant;
(4) concentrate: the oil phase A obtaining in step (3) branches to described concentration tower 8 and described esterification column, branches to oil phase A concentrate in described concentration tower 8 of described concentration tower 8, and described concentration tower tower top discharging, obtains oil phase B; The condition of described concentration tower 8 is controlled: top temperature is 68 ℃, and middle temperature is 72-74 ℃, and tower reactor temperature is 75 ℃, and tower actual plate number is 48;
In step (4), described oil phase B comprises: 89.7% ethyl acetate, 5.96% water, 4.26% ethanol, 0.035% Ethyl formate and 0.045% methyl acetate; Described percentage is the mass percent that accounts for described oil phase B;
(5) separated again: described oil phase B and extractant are at described concentration tower tower top buffer after 7 interior mixing, obtain mixed liquid B, described mixed liquid B enters the separation equipment 2 of the second ethyl acetate, and described mixed liquid B is cooled to 30 ℃, water-oil separating, obtains oil phase C and waste water C; Described extractant is discharging material at the bottom of the tower of waste water tower 9; The addition of described extractant be described oil phase B quality 1/40; In the separation equipment of described ethyl acetate, the described oil phase B time of staying is 40min;
In step (5), the inlet temperature in described concentration tower tower top buffer 7 of described oil phase B is 60 ℃;
In step (5), described extractant comprises 99.99% water and 0.01% acetic acid, and described percentage is the mass percent that accounts for extractant;
In step (5), described oil phase C comprises: 90.7% ethyl acetate, 4.98% water, 4.21% ethanol, 0.0405% Ethyl formate and 0.0695% methyl acetate; Described percentage is the mass percent that accounts for oil phase C;
(6) concentrate again: the oil phase C obtaining in step (5) branches to described concentration tower 8 and described low ester tower 11, branches to the described oil phase C concentrate in described concentration tower 8 in described concentration tower 8, and discharging at the bottom of described concentration tower tower, obtains oil phase D; The condition of described concentration tower 8 is controlled: top temperature is 68 ℃, and middle temperature is 72 ℃, and tower reactor temperature is 80 ℃, and tower actual plate number is 52;
Described oil phase D comprises: 99.81% ethyl acetate, 0.0024% acetic acid, 0.0063% water, 0.0818% ethanol, 0.0021% methyl acetate, 0.0434% ethyl propionate and 0.054% propyl acetate; Described percentage is the mass percent that accounts for oil phase D;
Branch to described oil phase C rectifying in described low ester tower 11 of described low ester tower 11, described low ester tower 11 tower top dischargings, obtain low Ester, and discharging at the bottom of described low ester tower 11 towers, obtains backflow product;
Condition in described low ester tower 11 is controlled: top temperature is 68 ℃, and middle temperature is 74 ℃, and tower reactor temperature is 76 ℃, and plate number is 52;
Described low Ester comprises: 68.3% ethyl acetate, 12.5% water, 11.5% ethanol, 3.2% Ethyl formate and 4.5% methyl acetate; Described percentage is the mass percent that accounts for described low Ester; Described low Ester flows out by the first tower top outlet of described low ester tower 11;
Described backflow product comprises: 96.1% ethyl acetate, 4.3% water and 4.1% ethanol; Described percentage is the mass percent that accounts for backflow product; Described backflow product flows into described esterifying kettle 3 by the second tower bottom outlet of described low ester tower 11;
(7) refining: described oil phase D is refining in described treating column 10, and described treating column 10 tower top dischargings, obtain ethyl acetate; The condition of described treating column 10 is controlled: top temperature is that 78 ℃, middle temperature are 81 ℃, and tower reactor temperature is 85 ℃, and tower actual plate number is 52;
In described treating column 10, discharging at the bottom of described treating column 10 towers, obtains higher boiling Ester, and described higher boiling Ester comprises propyl acetate and ethyl propionate; Described higher boiling Ester flows out by the second tower bottom outlet of described treating column 10;
Waste water C described in waste water A described in step (3) and step (5) flow to described waste water tower 9, separated in described waste water tower 9, discharging material at the bottom of the tower of waste water tower, the condition of described waste water tower 9 is controlled: top temperature is 70 ℃, middle temperature is 74 ℃, tower reactor temperature is 103 ℃, and tower actual plate number is 48-60 piece; At the bottom of the tower of waste water tower, discharging material is after described cooler 12 is cooling, and at the bottom of the tower of described waste water tower, discharging material branches in described esterification column tower top buffer 6 and described concentration tower tower top buffer 7, as extractant;
After waste water A described in step (3) is separated in described waste water tower 9 with the waste water C described in step (5), described waste water tower 9 tower top dischargings, obtain waste water tower separator; Described waste water tower separator comprises: 54.7% ethyl acetate, 15.1% water and 30.2% ethanol; Described percentage is the mass percent that accounts for waste water tower separator; Described waste water tower separator flow in described esterifying kettle 3 through the tower top outlet of described waste water tower 9.
Claims (10)
1. a separation equipment for ethyl acetate, is characterized in that: described separation equipment comprises: an a tank body and bag that catchments; One side of described tank body is provided with a material inlet, over against described material inlet place, one baffle plate for reducing inlet feed speed is set, the space for Flow of Goods and Materials is left in the bottom of described baffle plate and described tank body, the side of described tank body is equipped with an interior heat exchanger tube, and the space for Flow of Goods and Materials is left in the bottom of described interior heat exchanger tube and described tank body; The bottom of described tank body is also provided with an oil phase outlet; The described bag that catchments is arranged at the bottom of described tank body, between described material inlet and described oil phase outlet, the described outside of wrapping of catchmenting is coated with outer heat exchanger tube; The bottom of the described bag that catchments is provided with a water outlet; The size of described tank body meets following requirement simultaneously:
Wherein:
D is the diameter of described tank body, m;
L is the length of described tank body, m;
L
1for the described bag that catchments from length of straight flange, m; And L
1=(0.2-0.25) L;
Q
(thick ester)for the volume flow of thick ester, m
3/ s;
U is the sinking speed of water, m/s; According to the different fluidised forms of water, the computing formula of the sinking speed u of water is as shown in table 1:
The computing formula of the sinking speed of table 1 water
Wherein, Reynolds number R
ecomputing formula be:
In the computing formula of the sinking speed u of water, each alphabetical implication and numerical value are as follows:
D is water diameter, and its value is 100-200 μ m;
ρ
sfor the density of water, its value is 967kg/m
3;
ρ is the density of oil phase, and its value is 887kg/m
3;
G is acceleration of gravity;
μ is the viscosity of oil phase, and its value is 0.411cp.
2. separation equipment as claimed in claim 1, is characterized in that: described separation equipment is a horizontal separator;
Described baffle plate is perpendicular to the bottom of described tank body; Described baffle plate and described tank body weld by angle steel; Described baffle plate is preferably circular baffle plate;
Described side is to be provided with the side of material inlet or the side of a side relative with described material inlet;
On described interior heat exchanger tube, be provided with some fins;
The exposed junction of described interior heat exchanger tube is provided with one first chilled water import and one first chilled water outlet; Preferably, the position of the first described chilled water import is positioned at the below of the first described chilled water outlet;
The external one first freezing unit of described interior heat exchanger tube, the chilled water in the first described freezing unit, by described interior heat exchanger tube, reduces the temperature in described tank body;
Described outer heat exchanger tube is provided with one second chilled water import and the second chilled water outlet; Preferably, the position of the second described chilled water import is positioned at the below of the second described chilled water outlet;
The external one second freezing unit of described outer heat exchanger tube, the chilled water in the second described freezing unit, by described outer heat exchanger tube, reduces the temperature in the described bag that catchments;
The outer symmetrical of described tank body is provided with one group for supporting the bearing of described tank body;
Preferably, the flow when described thick ester is 83.5m
3during/h, the diameter D of described tank body is 3m, and length L is 8m; Preferably, the flow when described thick ester is 40m
3during/h, the diameter D of described tank body is 2.2m, and length L is 5.8m; Preferably, the flow when described thick ester is 20m
3during/h, the diameter D of described tank body is 1.8m, and length L is 5.6m; Preferably, the flow when described thick ester is 10m
3during/h, the diameter D of described tank body is 1.4m, and length L is 4.8m; Preferably, the flow when described thick ester is 5m
3during/h, the diameter D of described tank body is 1m, and length L is 3.4m.
3. separation equipment as claimed in claim 1, is characterized in that: the size of the described bag that catchments is calculated according to following formula:
V=Q
(water)* T
(thick ester)
Wherein, Q
(water)for the volume flow of water, m
3/ h;
Wherein:
D is the diameter of described tank body, m;
L is the length of described tank body, m;
L
1for the described bag that catchments from length of straight flange, m; And L
1value be preferably (0.1-0.3) L, that better is (0.2-0.25) L;
Q
(thick ester)for the volume flow of thick ester, m3/s;
Preferably, the flow when described thick ester is 83.5m
3during/h, the volume of the bag that catchments is 1m
3, the catchment internal diameter of bag and the length of straight tube are 0.8m and 1.6m.
4. separation equipment as claimed in claim 1, is characterized in that: the area of described interior heat exchanger tube calculates according to following formula:
Q＝m·Cp·(T
1-T
2)＝K·S·Δt
m
Wherein:
Q is the thermic load of heat exchanger tube, KW;
S is the area of heat exchanger tube, m
2;
M is the mass flow of thick ester, kg/h;
Cp is the specific heat capacity of thick ester, and its value is 2.212KJ/kg ℃;
T
1for the inlet temperature of described material, ℃; T
1for 40-60 ℃, be preferably 45 ℃;
T
2for the outlet temperature of described material, ℃; T
2for 5-35 ℃, be preferably 20 ℃;
△t
m=（T
1-t
1）+（T
2-t
2）
T
1for the temperature in the first described chilled water import, ℃; t
1for 5-10 ℃, it is preferably 5 ℃ and 7 ℃;
T
2for the temperature in the first described chilled water outlet, ℃; t
2for 10-20 ℃, it is preferably 10 ℃ and 12 ℃;
And t
1< t
2;
K is overall heat-transfer coefficient: its value is 370-540W/m
2℃.
5. a device of preparing ethyl acetate, is characterized in that: described device comprises: the separation equipment of the separation equipment of an esterifying kettle, an esterification column, an esterification column tower top buffer, one first ethyl acetate, a concentration tower, a concentration tower tower top buffer, one second ethyl acetate, a treating column, a waste water tower and a low ester tower; The separation equipment of the first described ethyl acetate and the separation equipment of the second ethyl acetate are the separation equipment of the ethyl acetate as described in any one in claim 1-4;
The outlet of described esterifying kettle connects the first import of described esterification column, the first tower top outlet of described esterification column connects the first entrance of described esterification column tower top buffer, the outlet of described esterification column tower top buffer connects the material inlet of the separation equipment of the first described ethyl acetate, the second import of the first import of the concentration tower described in the oil phase outlet of the separation equipment of the first described ethyl acetate connects respectively and described esterification column, the first tower top outlet of described concentration tower connects the first import of described concentration tower tower top buffer, the outlet of described concentration tower tower top buffer connects the material inlet of the separation equipment of the second described ethyl acetate, the import of the second import of the concentration tower described in the oil phase outlet of the separation equipment of the second described ethyl acetate connects respectively and described low ester tower, the second tower bottom outlet of described concentration tower connects the import of described treating column, described treating column tower top is provided with first tower top outlet flowing out for ethyl acetate, the water outlet of the separation equipment of the first described ethyl acetate is connected the waste water import of described waste water tower, the second entrance of the second entrance of the esterification column tower top buffer described in the second tower bottom outlet of described waste water tower connects respectively and described concentration tower tower top buffer with the water outlet of the separation equipment of the second described ethyl acetate.
6. device as claimed in claim 5, is characterized in that: the second tower bottom outlet of described esterification column connects the second import of described esterifying kettle;
At the bottom of described treating column tower, be also provided with a second tower bottom outlet flowing out for high-boiling components;
The tower top of described low ester tower is provided with first tower top outlet flowing out for low ester;
At the bottom of the tower of described low ester tower, be provided with one second tower bottom outlet; The second described tower bottom outlet connects the triple feed inlet of described esterifying kettle;
The first tower top outlet of described waste water tower connects the 4th import of described esterifying kettle;
Described device also comprises a cooler; The second import of the second import of the esterification column tower top buffer described in the second tower bottom outlet of described waste water tower connects respectively by a cooler and described concentration tower tower top buffer;
The described device of preparing ethyl acetate also comprises a condenser; The first tower top outlet of described esterification column connects after described condenser, then is connected with the first import of described esterification column tower top buffer.
7. a preparation method for ethyl acetate, is characterized in that: it uses equipment as claimed in claim 5; Described preparation method comprises the following steps:
(1) esterification: acetic acid, ethanol and catalyst for esterification reaction are mixed in described esterifying kettle, react under 101 ℃ of-110 ℃ of temperature conditions, obtain head product; Described acetic acid and ethanol mass ratio are (1.05-1.3): 1, and the mass flow of described catalyst for esterification reaction is the 1%-5% that passes into the gross mass of acetic acid in esterifying kettle and ethanol for 1 hour;
(2) rectifying: the head product rectifying in described esterification column obtaining in step (1), then be condensed to 45 ℃-60 ℃, obtain thick ester; The condition of described esterification column is controlled: top temperature is 69-72 ℃, and middle temperature is 72-78 ℃, and tower reactor temperature is 101-110 ℃, and tower actual plate number is 48-52 piece;
(3) separation: after the thick ester in step (2) is mixed in described esterification column tower top buffer with extractant, obtain mixed liquor A, described mixed liquor A enters the separation equipment of the first described ethyl acetate, described mixed liquor A is cooled to 10 ℃-30 ℃, water-oil separating, obtains oil phase A and waste water A; Described extractant is discharging material at the bottom of the tower of described waste water tower; The addition of described extractant is the quality 1/40-1/10 of described thick ester; In the separation equipment of described ethyl acetate, the time of staying of described thick ester is 15min-40min;
(4) concentrate: the oil phase A obtaining in step (3) branches to described concentration tower and described esterification column, branches to oil phase A concentrate in described concentration tower of described concentration tower, and described concentration tower tower top discharging, obtains oil phase B; The condition of described concentration tower is controlled: top temperature is 68-72 ℃, and middle temperature is 72-74 ℃, and tower reactor temperature is 75-80 ℃, and tower actual plate number is 48-52 piece;
(5) it is separated again: after described oil phase B mixes in described concentration tower tower top buffer with extractant, obtain mixed liquid B, described mixed liquid B enters the separation equipment of the second ethyl acetate, and described mixed liquid B is cooled to 10 ℃-30 ℃, water-oil separating, obtains oil phase C and waste water C; Described extractant is discharging material at the bottom of the tower of waste water tower; The addition of described extractant is the 1/40-1/10 of the quality of described oil phase B; In the separation equipment of described ethyl acetate, the described oil phase B time of staying is 15min-40min;
(6) concentrate again: the oil phase C obtaining in step (5) branches to described concentration tower and described low ester tower, branches to the described oil phase C concentrate in described concentration tower in described concentration tower, and discharging at the bottom of described concentration tower tower, obtains oil phase D; The condition of described concentration tower is controlled: top temperature is 68-72 ℃, and middle temperature is 72-74 ℃, and tower reactor temperature is 75-80 ℃, and tower actual plate number is 48-52 piece;
(7) refining: described oil phase D is refining in described treating column, and described treating column tower top discharging, obtains ethyl acetate; The condition of described treating column is controlled: top temperature for 78-80 ℃, middle temperature be 79-81 ℃, tower reactor temperature is 83-85 ℃, tower actual plate number is 48-52 piece;
Waste water C described in waste water A described in step (3) and step (5) flow to described waste water tower, separated in described waste water tower, discharging material at the bottom of the tower of waste water tower, the condition of described waste water tower is controlled: top temperature is 70-72 ℃, middle temperature is 74-78 ℃, tower reactor temperature is 98-103 ℃, and tower actual plate number is 48-60 piece; At the bottom of the tower of described waste water tower, discharging material branches in described esterification column tower top buffer and described concentration tower tower top buffer, as extractant.
8. preparation method as claimed in claim 7, is characterized in that: it uses equipment as claimed in claim 6;
In step (1), described catalyst for esterification reaction is sulfuric acid; Described sulfuric acid is preferably 98% the concentrated sulfuric acid; Described percentage is mass percent; The mass flow of described catalyst be preferably within 1 hour, pass into acetic acid in esterifying kettle and ethanol gross mass 3%;
In step (1), described head product comprises: the ethyl acetate of 23.1%-29.13%, the acetic acid of 62.6%-68.6%, the water of 7%-8% and the ethanol of 0.5%-0.9%; In step (1), described head product preferably comprises: 26.1% ethyl acetate, 65.6% acetic acid, 7.6% water and 0.7% ethanol; Described percentage is the mass percent that accounts for head product;
In step (2), the temperature of the filler of described esterification column is 70-106 ℃;
In step (2), the temperature of the head product after described rectifying is 69-72 ℃, is preferably 70.2 ℃;
In step (2), described condensed temperature is preferably 45 ℃;
In step (2), described thick ester comprises: the ethanol of the ethyl acetate of 88%-93%, the water of 5%-8% and 1%-2%, and described percentage is the mass percent that accounts for thick ester;
In step (3), described cooling is preferably for being cooled to 20 ℃;
In step (3), described oil phase A comprises: the ethyl acetate of 93.3%-97.3%, the acetic acid of 0.0014%-0.0018%, the water of 3%-4%, the Ethyl formate of the ethanol of 1.2%-1.6%, 0.01%-0.02%, the ethyl propionate of the methyl acetate of 0.01%-0.02%, 0.002%-0.0025% and the propyl acetate of 0.004%-0.008%; Described oil phase A preferably comprises: 95.3% ethyl acetate, 0.0016% acetic acid, 3.24% water, 1.42% ethanol, 0.0126% Ethyl formate, 0.0177% methyl acetate, 0.0021% ethyl propionate and 0.006% propyl acetate; Described percentage is the mass percent that accounts for oil phase A;
In step (3), described extractant comprises: 99.99% water and 0.01% acetic acid, and described percentage is the mass percent that accounts for extractant;
In step (4), described oil phase B comprises: the ethyl acetate of 87.7%-91.7%, the water of 5%-7%, the ethanol of 4%-4.5%, the methyl acetate of the Ethyl formate of 0.03%-0.004% and 0.03%-0.004%; In step (4), described oil phase B preferably comprises: 89.7% ethyl acetate, 5.96% water, 4.26% ethanol, 0.035% Ethyl formate and 0.045% methyl acetate; Described percentage is the mass percent that accounts for described oil phase B;
In step (5), the inlet temperature in described concentration tower tower top buffer of described oil phase B is 45 ℃-60 ℃;
In step (5), described cooling is preferably for being cooled to 20 ℃;
In step (5), described oil phase C comprises: the Ethyl formate of the water of 88.7%-92.72% ethyl acetate, 4.5%-5%, the ethanol of 4%-5%, 0.04%-0.041% and 0.065%-0.07% methyl acetate; In step (5), described oil phase C preferably comprises: 90.7% ethyl acetate, 4.98% water, 4.21% ethanol, 0.0405% Ethyl formate and 0.0695% methyl acetate; Described percentage is the mass percent that accounts for oil phase C;
In step (5), described extractant comprises: 99.99% water and 0.01% acetic acid, and described percentage is the mass percent that accounts for extractant;
In step (6), described oil phase D comprises: the ethyl acetate of 99.6%-99.9%, the acetic acid of 0.002%-0.0026%, the water of 0.006%-0.0065%, the methyl acetate of the ethanol of 0.08%-0.083%, 0.002%-0.0023%, the propyl acetate of the ethyl propionate of 0.04%-0.045% and 0.05%-0.055%; In step (6), described oil phase D preferably comprises: 99.81% ethyl acetate, 0.0024% acetic acid, 0.0063% water, 0.0818% ethanol, 0.0021% methyl acetate, 0.0434% ethyl propionate and 0.054% propyl acetate; Described percentage is the mass percent that accounts for oil phase D.
9. preparation method as claimed in claim 7 or 8, is characterized in that: it uses equipment as claimed in claim 6; Described preparation method comprises the following steps:
In step (6), branch to described oil phase C rectifying in described low ester tower of described low ester tower, described low ester column overhead discharging, obtains low Ester, and discharging at the bottom of described low ester tower tower, obtains backflow product;
Described low Ester preferably comprises: the ethyl acetate of 67.3%-71.3%, the water of 11%-13%, the ethanol of 10%-12%, the methyl acetate of the Ethyl formate of 3%-4% and 4%-5%; Described better the comprising of low Ester: 68.3% ethyl acetate, 12.5% water, 11.5% ethanol, 3.2% Ethyl formate and 4.5% methyl acetate; Described percentage is the mass percent that accounts for described low Ester;
Preferably, the condition in described low ester tower is controlled and is: top temperature is 68-72 ℃, and middle temperature is 70-74 ℃, and tower reactor temperature is 72-76 ℃, and tower actual plate number is 48-52 piece;
Preferably, described low Ester flows out by the first tower top outlet of described low ester tower;
Described backflow product preferably comprises: the ethanol of the ethyl acetate of 94.1%-98.1%, the water of 4%-5% and 4%-5%; Described better the comprising of backflow product: 96.1% ethyl acetate, 4.3% water and 4.1% ethanol; Described percentage is the mass percent that accounts for backflow product;
Preferably, described backflow product flows into described esterifying kettle by the second tower bottom outlet of described low ester tower.
10. preparation method as claimed in claim 7 or 8, is characterized in that: it uses equipment as claimed in claim 6; Described preparation method comprises the following steps:
In step (7), in described treating column, discharging at the bottom of described treating column tower, obtains higher boiling Ester, and described higher boiling Ester comprises propyl acetate and ethyl propionate; Described higher boiling Ester flows out by the second tower bottom outlet of described treating column;
At the bottom of the tower of described waste water tower, discharging material is after described cooler is cooling, then is back in described esterification column tower top buffer and described concentration tower tower top buffer, as extractant;
After waste water A described in step (3) is separated in described waste water tower with the waste water C described in step (5), described waste water column overhead discharging, obtains waste water tower separator;
Described waste water tower separator preferably comprises: the ethanol of the ethyl acetate of 54%-56%, the water of 14.5%-15.5% and 29.5%-31%; Described better the comprising of waste water tower separator: 54.7% ethyl acetate, 15.1% water and 30.2% ethanol; Described percentage is the mass percent that accounts for waste water tower separator;
Preferably, described waste water tower separator flow in described esterifying kettle through the tower top outlet of described waste water tower.
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| CN105067603A (en) * | 2015-07-22 | 2015-11-18 | 上海人民塑料印刷厂 | Method for detecting water or alcohols in ethyl ester and method for separating water |
| CN105837444A (en) * | 2016-05-26 | 2016-08-10 | 安庆盛峰化工股份有限公司 | Ester recovery mechanism for diisobutyl phthalate production |
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