CN102617344B - Preparation method of carboxylic acid vinyl ester - Google Patents
Preparation method of carboxylic acid vinyl ester Download PDFInfo
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- CN102617344B CN102617344B CN201210063308.1A CN201210063308A CN102617344B CN 102617344 B CN102617344 B CN 102617344B CN 201210063308 A CN201210063308 A CN 201210063308A CN 102617344 B CN102617344 B CN 102617344B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract description 45
- 229920001567 vinyl ester resin Polymers 0.000 title abstract description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 50
- 239000007791 liquid phase Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001661 cadmium Chemical class 0.000 claims abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 16
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 16
- 230000004907 flux Effects 0.000 claims description 9
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 239000005639 Lauric acid Substances 0.000 claims description 4
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 claims description 4
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 48
- 238000000034 method Methods 0.000 abstract description 23
- 230000004087 circulation Effects 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 13
- 230000009466 transformation Effects 0.000 abstract description 9
- 230000005587 bubbling Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000010992 reflux Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009834 vaporization Methods 0.000 abstract 1
- 230000008016 vaporization Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 9
- 239000000376 reactant Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000066 reactive distillation Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- 238000004590 computer program Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000005514 two-phase flow Effects 0.000 description 2
- 238000006886 vinylation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- -1 carboxylate salt Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000012804 iterative process Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 description 1
- PVLBCXWFQZZIGP-UHFFFAOYSA-L zinc;nonanoate Chemical compound [Zn+2].CCCCCCCCC([O-])=O.CCCCCCCCC([O-])=O PVLBCXWFQZZIGP-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of carboxylic acid vinyl ester. The method comprises the following steps of: undergoing a gas-liquid reaction on acetylene and carboxylic acid in a circulatory flow bubbling reactor under the action of a liquid phase catalyst, wherein the catalyst is a zinc salt or cadmium salt of the carboxylic acid; a honeycomb duct is arranged in the reactor; and a rectifying device is arranged on the top of the reactor; introducing acetylene from the bottom of the reactor; introducing a vaporization product into the rectifying device from the top of the reactor for separating; and conveying a liquid phase catalyst solution and a reflux liquid drained from the rectifying tower to the bottom of the reactor through the honeycomb duct to form high-speed circulation in the reactor. A loop reactor is adopted, and reaction rectification is used together, so that the reaction efficiency is increased greatly through the loop reactor, the transformation ratio of a product is increased through a reaction rectification technology, and the reaction energy consumption is lowered.
Description
Technical field
The present invention relates to the method that carboxylic acid and acetylene are catalytically conveted to vinyl ester.
Background technology
Known carboxylic acid and acetylene reaction generate method that vinyl ester is conventional referring to Ullman ' s Encyclopedia of Industrial Chemistry, A27,430-434.The reaction of acetylene and carboxylic acid is as follows:
R-COOH+C
2H
2→R-COO-CH＝CH
2
The catalyzer that this reaction is used is the zinc salt of carboxylic acid in reactant normally, its can be dissolved in (DE1238010, DE1210810) in excessive carboxylic acid or boiling point higher than the inert solvent of temperature of reaction as in paraffin oil.Because reaction is carried out under normal pressure, so need to there be very high acetylene circulation.According to the vapor partial pressure of reactant and product, the vinyl ester of generation, unreacted carboxylic acid are discharged reactor with together with excessive circulation acetylene, through gas-liquid separation, by method purified products such as rectifying.
The method that is best suited at present suitability for industrialized production vinyl acetate is solid-phase catalyst method and liquid-phase catalyst method, and the catalyzer of use is the zinc salt of carboxylic acid in reactant.
The catalyzer of solid phase method is to the solid catalyst forming on the inert supports such as gac, aluminum oxide, silicon oxide by catalyzer appendix.Carboxylic acid is heated more than boiling point, with gas phase mode and together charging of acetylene, under the effect of catalyzer, the vinyl carboxylates generating together leaves reactor with vapor form and excessive acetylene, after cooling, through separation, purifying, obtain target product, excessive acetylene recycles.Solid-phase catalyst method is applicable to low-boiling carboxylic acid, as the carboxylic acid that carbon number is less than 5, has been widely used in the production of vinyl-acetic ester.
It is larger that patent CN1232445 has described carbon number, the ethene esterification process of the solid-phase catalyst of the carboxylic acid that boiling point is higher, and for the carboxylic acid about 10 carbon, with gas-phase feed, vapor temperature will approach 300 ℃, cause industrialization operational difficulty.And under high temperature lipid acid have decompose, condensation forms the tendency of by product.
Liquid-phase catalysis agent method is take corresponding salts of carboxylic acids as catalyzer, is dissolved in raw material carboxylic acid as stationary phase, and raw material carboxylic acid is from reactor bottom liquid phase feeding, and acetylene is from reactor bottom normal pressure gas-phase feed.Acetylene and carboxylic acid are gas and liquid phase inhomogeneous reactions, and the temperature of this reaction is lower, are generally 210 ℃ ± 50.The generating vinyl carboxylate esterification that is greater than 200 ℃ for boiling point, the general employing liquid phase method that is applicable to.
For the production of vinyl acetate, in order to obtain maximum carboxylic acid transformation efficiency when empty, conventionally improve the concentration of catalyzer as far as possible, generally all require catalyzer.Due to, the concentration that is of being somebody's turn to do (weight ratio) more than 70%.For example, described in US3646077, use 80% catalyst content, when the carboxylic acid of trade(brand)name Versatic acid911 is empty, transformation efficiency can reach considerable 830g/L.h.But, for for example tertiary n-nonanoic acid of some carboxylic acid (Diisobutylene is that raw material is through the synthetic height branched carboxylic acids obtaining of KOCH), 2 ethyl hexanoic acid, the straight-chain carboxylic acids such as sad, capric acid and lauric acid, catalyzer solubleness is therein very low, even under temperature of reaction, (as 200-220 ℃) still can separate out a large amount of carboxylate salt crystallizations, causes effective reaction space to reduce and makes catalyzer lose katalysis.In addition, also separating out of catalyzer can blocking pipe, causes operational difficulty.Have bibliographical information, for the vinylation reaction of tertiary n-nonanoic acid, when empty, transformation efficiency can only reach 300g/L.h, and 2 ethyl hexanoic acid can only reach 260g/L.h.
In addition, industrial, prepare in vinyl ester solution-air two phase reaction used, in order to obtain high conversion and speed of reaction, two-phase will contact as far as possible.So comprise that this class gas liquid reaction of vinyl ester is all generally to carry out in bubble tower or high-speed stirring reactor.For this purpose, CN1183093 discloses a kind of tubular reactor, for vinyl ester reaction, gas-liquid mixed flow in tubular reactor, improve liquid phase mass transfer coefficient, cause liquid phase close contact, thereby obtained, reduce temperature of reaction, improve space-time efficiency, greatly reduce the effect of acetylene internal circulating load.But, in order to reach gas-liquid, fully mix, need to pass through liquid-phase catalyst high-speed circulating, very large turbulivity is provided, in this invention, provide reaction needed that the estimation equation of dynamic range is provided.The data that provide according to this invention, the throughput of 4kg/h need to provide 1.1m
3the catalyst flow of/h, more trouble, needs in time the vinyl ester in the catalyzer that is rich in vinyl ester of circulation in a large number to be separated, and could effectively the catalyzer of poor vinyl ester be turned back in reaction zone, therefore, the very large difficulty of existence is amplified in industrialization.
Summary of the invention
The object of this invention is to provide a kind of preparation method of the vinyl ester with high speed of response and carboxylic acid transformation efficiency.
The object of the invention is to be achieved through the following technical solutions:
A kind of preparation method of vinyl carboxylates, by acetylene and carboxylic acid under the effect of liquid-phase catalyst, react in reactor, described catalyzer is zinc salt or the cadmium salt of described carboxylic acid, in described reactor, thrust-augmenting nozzle is installed, top at described reactor is provided with rectifier unit, described acetylene imports from the bottom of described reactor, the vaporized product producing enters described rectifier unit from reactor head and separates, and the phegma of described carboxylic acid and liquid-phase catalyst and rectifying tower is delivered directly to the bottom of described reactor through described thrust-augmenting nozzle.
Described catalyzer is dissolved in described carboxylic acid, and the content of catalyzer in carboxylic acid solution is 35～50% (weight), and preferred catalyst content is 40～45% (weight).The flux of described acetylene is 8～15 times (mol/mol) of described carboxylic acid feed amount.
Described reactor is bubble tower, the length-to-diameter ratio 5～15: 1 of described bubble tower.Preferably, the length-to-diameter ratio of described bubble tower is 8～10: 1.
According to one embodiment of present invention, the length of described bubble tower is 400cm, diameter 45cm.According to one embodiment of present invention, the diameter of described thrust-augmenting nozzle is 20cm, and described rectifying tower is filled the dumped packing of diameter 5mm, high 5mm, and the theoretical plate number of rectifying tower is 20, tower diameter is 50mm.
Described carboxylic acid is branched carboxylic acids or the straight-chain carboxylic acid of containing 7～18 carbon.Preferably, described carboxylic acid is new n-nonanoic acid, neodecanoic acid, new undeeanoic acid, new tridecylic acid, different n-nonanoic acid, isocaprylic acid or lauric acid.
In preparation method of the present invention, catalyzer is zinc salt or the cadmium salt of carboxylic acid, is dissolved in superfluous carboxylic acid, or is dissolved in the solvent of boiling point higher than temperature of reaction.Temperature of reaction generally exceedes 200 ℃, and a large amount of acetylene circulations at utmost mix reaction solution.Vapor partial pressure makes vinyl acetate and unreacted carboxylic acid discharge with vapor form, passes through fractionation by distillation after condensation.
In order to improve the mass transfer coefficient of bubbling style reactor, esterification of the present invention is carried out in bubble tower, acetylene imports from reactor bottom, thrust-augmenting nozzle is installed in reactor, by acetylene bubbling, form the density difference in reaction zone and thrust-augmenting nozzle, thereby in formation reaction zone, reaction solution (being rich in acetylene) upwards, the downward circulation of water conservancy diversion liquid in pipe (poor acetylene).Fresh carboxylic acid is added to reactor bottom by thrust-augmenting nozzle, and such benefit is: in reaction process, reaction zone is rich in carboxylic acid all the time, and reactor head is rich in the vinyl ester of generation all the time, is convenient to vinyl ester and flashes to gas phase with higher concentration.
The present invention adopts the loop reactor technology developing from bubble tower basis, combines the mode of using reactive distillation.Loop reactor technology has improved reaction efficiency greatly, and reaction rectification technique has improved the transformation efficiency of product, has reduced energy consumption of reaction.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the equipment that uses of preparation method of the present invention.
Wherein:
A: acetylene charging+acetylene circulation; R: reactor; B: carboxylic acid feed;
F: reactive distillation column; C: extraction product; D: product reflux; E: circulation acetylene
Embodiment
For gas-liquid blistering reaction, in the situation that reaction zone volume is certain, the length-to-diameter ratio of reaction tower is necessary parameter, and the present invention is applicable to length-to-diameter ratio 5～15: 1 bubbling style reaction tower.If length-to-diameter ratio is too small, for example, below 5: 1, gas retention time is short, and internal circulating load is excessive; Length-to-diameter ratio is excessive, and acetylene static pressure is excessive, causes Hazard Factor.Optimal length-to-diameter ratio is 8～10: 1.
In invention in the past, it is excessive that inventor is devoted to reduce acetylene, in the present invention, acetylene be Local Phase to excessive, in whole system, acetylene total amount does not improve.
While increasing to a certain extent acetylene flux, carboxylic acid conversion rate can obviously be accelerated, this be due to, increase acetylene flux, relatively increase the concentration of one of reactant, nature can improve the transformation efficiency of another reactant; For loop reactor, improve gas speed, liquid velocity in draft tube can improve thereupon, thereby increases the turbulence state of reaction solution, by increasing mass transfer, can improve speed of response.
Although the raising of acetylene flux is favourable to ethene esterification in theory, but, in actual production, can not improve acetylene flux unlimitedly, this be because: 1, along with the increase of acetylene flux, acetylene gas stripping increases, increasing carboxylic acid has little time reaction and is just distilled out of, and causes carboxylic acid content in product greatly to increase, reduced raw material reaction efficiency, increased product separation burden; 2, after reactant circulation increases, in circulating system, resistance increases substantially, and finally makes internal circulating load reach capacity, even if now increase acetylene flux, reaction solution circular flow can not continue to increase yet.
Below the computation process of determining acetylene internal circulating load and reaction solution internal circulating load is described.
Described loop reactor reaction solution is the motion that relies on the density difference of gas-liquid two-phase in the interior liquid phase statical head of thrust-augmenting nozzle and reaction zone to produce impellent formation heat siphon type, acetylene flux is larger, described density difference is just larger, circulation power is just larger, resistance mainly comes from draft-tube diameter, has following circulation power and resistance balancing type in reactor:
[L
CD(ρ
L-ρ
tp)]g≥ΔP
T (1)
Wherein: L
cD-------height for reactor
ρ
l-------water conservancy diversion liquid in pipe mean density
ρ
tpthe mean density of two-phase in-------reactor
G-------universal gravity constant
Δ P
t------liquid phase circulation total pressure drop
Equation (1) left side is the static pressure that above-mentioned density difference produces, and the right is liquid circulation total pressure drop.
More loaded down with trivial details owing to calculating, preferably adopt computer to calculate, computer program can be consulted document Peterson J N et al, Computer Programs for Chemical Engineers, 1978. preferably
Hand computation method can be consulted the 4th edition 639-page of < < chemical technique design manual > >.
Here the computation process that underdraws, in (1) formula
ρ
tp＝ρ
gR
g+ρ
LR
L (2)
R
L＝1-R
g (3)
Wherein:
R
g: gaseous phase volume mark in reactor
ρ
tp: the mean density of two-phase in reactor
R
l: liquid phase volume mark in reactor
Press Martinelli method:
R
g＝1-(1/(X
tt-2+21/X
tt+1))
0.5 (4)
X
tt＝((1-x)/x)
0.9(ρ
g/ρ
L)
0.5(μ
L/μ
g)
0.1 (5)
When formula (4) the right and left equates, the internal circulating load of reactor is described just in time, the actual production situation of this reboiler is good; When the left side is greater than the right, illustrate that internal circulating load is inadequate, should increase internal circulating load.During calculating, should make both sides equate, this is an iterative process as far as possible.
In formula (5), x represents gas point rate, and acetylene air flow determines that gas divides rate.
Wherein: R
gvapour phase volume fraction in-------reactor
R
lliquid phase volume mark in-------reactor
X-------gas divides rate
ρ
ggas density in-------reactor
μ
l-------liquid phase viscosity
μ
g-------gaseous viscosity
Equation (1) the right is liquid phase circulation total pressure drop Δ P
t:
ΔP
T＝ΔP
1+ΔP
1+ΔP
3
Wherein:
Δ P
1------thrust-augmenting nozzle liquid phase flow friction pressure drop
Δ P
2the frictional pressure drop of------reactor two-phase flow
Δ P
3------reactor two-phase flow is accelerated loss
Δ P
1, Δ P
2, Δ P
3by caliber, pipe range and medium physical property, determined, can calculate according to hydromeehanics formula, be omitted here.
According to one embodiment of present invention, at the long 400mm of bubbling reactor, diameter 40mm, in the situation that thrust-augmenting nozzle length is 350mm, when thrust-augmenting nozzle minimum pipe is 20mm, can meet acetylene internal circulating load 400ml/h, and now, reactant circular flow is 72kg/h.
The second,, by reactive distillation, improve feed stock conversion.
The stripping effect causing because high speed acetylene circulates, take steam discharge port to connect the mode (accompanying drawing) of separation column, make because the carboxylic acid that gas stripping does not have enough time to react is directly back to reactor bottom by reactive distillation tower bottom, testing data of the present invention shows, the stock liquid carboxylic acid temperature refluxing is 190-195 ℃, concentration is more than 90%, top ethylene base ester concentration reaches 98%, can be effectively that product is Fen Li with raw material, especially, by side line extraction technology, further isolate low-molecular-weight by product, product content can reach more than 99%, need not be further purified.
Those skilled in the art can, according to the method for calculation of rectifying tower, determine the specification of rectifying tower.
The present invention is low for some catalysts solubility, can not improve by improving catalyst content side chain and the non-branched carboxylic acids of throughput, there is prior meaning, for example, for tertiary n-nonanoic acid, 2 ethyl hexanoic acid, comprise the straight-chain carboxylic acids such as sad, capric acid and lauric acid, by method of the present invention, catalyst content can be reduced to its solubleness level, when empty, transformation efficiency reaches industrial more significance level.
Below by specific embodiment, method of the present invention is elaborated.
Example 1 (the present invention)
One embodiment of the present of invention shown in Figure 1.In production unit of the present invention, carry out continuous vinylation reaction, reactor R length is 400cm, and diameter is 45cm, draft-tube diameter is 20cm, rectifying tower F fills the dumped packing of 5mm × 5mm (diameter × height), 20 blocks of theoretical trays, rectifying tower tower diameter 50mm.From the B pipe of reactor R, add new n-nonanoic acid solution (from the carboxylic acid obtaining by oxo process the iso-butylene dimerization) 640ml that contains 40% new zinc pelargonate, reaction solution is heated to 220 ℃, with 0.4m
3the speed of/h passes into acetylene gas from A, and excessive circulation acetylene overflows and returns to A from tower top E.By regulating the flow of backflow D and extraction C, control the content of adopting exit vinyl acetate.Test-results sees the following form.
Example 2 (simultaneous test)
Equipment is with example 1, and just acetylene air flow is 0.15m
3/ h.
Example 3 (contrast experiment)
Equipment and condition are with example 1, just without rectifying tower F.
Example 4 (contrast experiment)
Equipment and condition are with example 1, and just draft-tube diameter changes 10mm into.
Example 5 (the present invention)
Equipment and condition, with example 1, just add the neodecanoic acid solution 640ml that contains 60% zinc neodecanoate in reactor R.
Example 6 (contrast experiment)
Equipment and condition, with example 5, are not just installed rectifying tower.
Example 7 (the present invention)
Other equipment and condition are with example 1, and just rectifying tower F changes the extraction of band side line into, at the bottom of tower, to 20 blocks of theoretical trays of product extraction mouth, adopt and export to 15 theoretical versions of tower top.Overhead collection light constituent by product.
The experimental result of above-mentioned each example is as follows:
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Reactor diameter, mm | 45 | 45 | 45 | 45 | 45 | 45 | 45 |
| Reactor length, mm | 400 | 400 | 400 | 400 | 400 | 400 | 400 |
| Draft-tube diameter, mm | 20 | 20 | 20 | 10 | 20 | 20 | 20 |
| Catalytic amount, l | 0.640 | 0.640 | 0.640 | 0.640 | 0.640 | 0.640 | 0.640 |
| Temperature of reaction, ℃ | 220 | 220 | 220 | 220 | 220 | 220 | 220 |
| Acetylene flow, m 3/h | 0.4 | 0.15 | 0.4 | 0.4 | 0.7 | 0.7 | 0.7 |
| Vinyl acetate, g/h (product) | 310 | 70 | 290 | 240 | 604 | 570 | 600 |
| RZA.t/m 3·h | 0.48 | 0.11 | 0.45 | 0.38 | 0.94 | 0.89 | 0.94 |
| Acetylene/vinyl acetate, mol/mol | 10.60 | 17.60 | 11.33 | 13.69 | 9.52 | 10.09 | 9.58 |
| Vinyl acetate content, % | 96 | 88 | 70 | 81 | 98 | 89 | 99 |
Note: RZA is unit reaction volume output hourly, unit: ton/cubic meter hour
By above-mentioned test-results, can find out, the method that increases acetylene internal circulating load in the present invention and increase thrust-augmenting nozzle caliber can significantly improve speed of response and reduce catalyst content, and the method that rectifying tower is installed on reactor of the present invention can solve the high shortcoming of product Raw carboxylic acid content causing due to the increase of acetylene internal circulating load.Example 1 shows, uses method of the present invention, even reduce catalyst content in order to reduce catalyzer crystallinity, speed of response is also greatly improved, and the content of vinyl acetate in reaction product is high.Although transformation efficiency is not significantly improved when empty in example 5, product purity significantly improves.In example 7, on rectifying tower F, increased side line extraction, removed light constituent by product, further improved the content of product vinyl acetate, do not needed can obtain qualified the finished product through rectifying again.
Claims (10)
1. the preparation method of a vinyl carboxylates, by acetylene and carboxylic acid under the effect of liquid-phase catalyst, in reactor, react, described catalyzer is zinc salt or the cadmium salt of described carboxylic acid, it is characterized in that: in described reactor, thrust-augmenting nozzle is installed, top at described reactor is provided with rectifier unit, described acetylene imports from the bottom of described reactor, the vaporized product producing enters described rectifier unit from reactor head and separates, the phegma of described carboxylic acid and liquid-phase catalyst and rectifying tower is delivered directly to the bottom of described reactor through described thrust-augmenting nozzle.
2. preparation method according to claim 1, is characterized in that: described catalyzer is dissolved in described carboxylic acid, and the content of catalyzer in carboxylic acid solution is 35～50% (weight).
3. preparation method according to claim 1, is characterized in that: the flux of described acetylene is 8～15 times (mol/mol) of described carboxylic acid feed amount.
4. according to the preparation method described in any one in claim 1～3, it is characterized in that: described reactor is bubble tower the length-to-diameter ratio 5～15: 1 of described bubble tower.
5. preparation method according to claim 4, is characterized in that: the length-to-diameter ratio of described bubble tower is 8～10: 1.
6. preparation method according to claim 4, is characterized in that: the length of described bubble tower is 400cm, diameter 45cm.
7. preparation method according to claim 4, is characterized in that: the diameter of described thrust-augmenting nozzle is 20cm.
8. preparation method according to claim 4, is characterized in that: the theoretical plate number of described rectifying tower is 20, tower diameter is 50mm, fills the dumped packing of diameter 5mm, high 5mm in rectifying tower.
9. preparation method according to claim 4, is characterized in that: described carboxylic acid is branched carboxylic acids or the straight-chain carboxylic acid of containing 7～18 carbon.
10. preparation method according to claim 7, is characterized in that: described carboxylic acid is new n-nonanoic acid, neodecanoic acid, new undeeanoic acid, new tridecylic acid, different n-nonanoic acid, isocaprylic acid or lauric acid.
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Citations (5)
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|---|---|---|---|---|
| US3031496A (en) * | 1959-05-13 | 1962-04-24 | Chemical Construction Corp | Vinyl acetate process |
| DE1134665B (en) * | 1959-03-25 | 1962-08-16 | Hoechst Ag | Process for the production of vinyl esters |
| GB1125055A (en) * | 1967-04-27 | 1968-08-28 | Shell Int Research | Improvements in or relating to the preparation of vinyl esters |
| CN1290684A (en) * | 1999-06-02 | 2001-04-11 | 奥克森诺奥勒芬化学股份有限公司 | Method for catalytically heterogeneous reaction, particularly carboxylic V inylenation |
| CN1958543A (en) * | 2006-11-29 | 2007-05-09 | 北京工商大学 | Method for preparing fat to control oxidation product by using gas lift type common loop reactor |
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2012
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1134665B (en) * | 1959-03-25 | 1962-08-16 | Hoechst Ag | Process for the production of vinyl esters |
| US3031496A (en) * | 1959-05-13 | 1962-04-24 | Chemical Construction Corp | Vinyl acetate process |
| GB1125055A (en) * | 1967-04-27 | 1968-08-28 | Shell Int Research | Improvements in or relating to the preparation of vinyl esters |
| CN1290684A (en) * | 1999-06-02 | 2001-04-11 | 奥克森诺奥勒芬化学股份有限公司 | Method for catalytically heterogeneous reaction, particularly carboxylic V inylenation |
| CN1958543A (en) * | 2006-11-29 | 2007-05-09 | 北京工商大学 | Method for preparing fat to control oxidation product by using gas lift type common loop reactor |
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