CN1844076A - Method for mass producing butyl acetate by reactive distillation method and using sulfuric acid as catalyst - Google Patents
Method for mass producing butyl acetate by reactive distillation method and using sulfuric acid as catalyst Download PDFInfo
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- CN1844076A CN1844076A CNA2006100392802A CN200610039280A CN1844076A CN 1844076 A CN1844076 A CN 1844076A CN A2006100392802 A CNA2006100392802 A CN A2006100392802A CN 200610039280 A CN200610039280 A CN 200610039280A CN 1844076 A CN1844076 A CN 1844076A
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 69
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 title claims description 89
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 title claims description 49
- 239000003054 catalyst Substances 0.000 title claims description 23
- 238000000066 reactive distillation Methods 0.000 title claims description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 claims abstract description 29
- 239000007791 liquid phase Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000012071 phase Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 25
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims abstract description 16
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims abstract description 16
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000032050 esterification Effects 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 229940043232 butyl acetate Drugs 0.000 claims description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 35
- 150000002148 esters Chemical class 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000009835 boiling Methods 0.000 claims description 20
- 241000282326 Felis catus Species 0.000 claims description 19
- 238000011084 recovery Methods 0.000 claims description 16
- 238000011031 large-scale manufacturing process Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 11
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000013517 stratification Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010924 continuous production Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 12
- 238000004508 fractional distillation Methods 0.000 abstract 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 229910021653 sulphate ion Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000011973 solid acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DNXWZVLDYKWEGG-UHFFFAOYSA-N C(C)(=O)OCCCC.S(O)(O)(=O)=O Chemical compound C(C)(=O)OCCCC.S(O)(O)(=O)=O DNXWZVLDYKWEGG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 isobutyl ester Chemical class 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The refers to a mass production method of isobutyl acetate which uses hydric sulphate as accelerant by reaction fractional distillation, using ethyl acetate and butyl alcohol as raw material, concentrated sulfuric acid as accelerant, continue producing isobutyl acetate by reaction fractional distillation, the whole production system contains three towers, reaction fractionating tower, azeotropy tower and eater fractionating tower, the reaction fractionating tower, azeotropy tower are setted side by side. The ethyl acetate, butyl alcohol and concentrated sulfuric acid are drived into feeder column plate of reaction fractionating tower after esterification prereaction, the gas phase of prereactor going into feeding phase of reaction fractionating tower, the gas phase on top of reaction fractionating tower going into column plate of cellar of azeotropy towder, the liquid phase of towder bottom going into mesomere of eater fractionating tower, the butyl product is continue discharged from side tower. This invention combines the technique which using sulfuric as accelerant by mean improvement of reaction fractional distillation technique, not only ustilizing the advanced technology of reaction fractional distillation, but also making the liquid accelerant's characters of convenience to operate, easy to enlarge production scale getted adequate use.
Description
Technical field:
The present invention relates to a kind of method of producing butylacetate, especially relate to a kind of with sulfuric acid as catalyzer and reaction rectification method combine continuously, the mass-producing ground method of producing butylacetate.
Background technology:
Butylacetate is a kind of esters solvent of environment-friendly type, degrades easily at occurring in nature, and aromatic hydrocarbon solvents such as alternative toluene, dimethylbenzene are widely used in coating, paint, printing ink, tackiness agent and medicine and other fields.
The early stage production method of butylacetate generally with sulfuric acid as catalyzer, advanced row intermittent type esterification after reaction finishes, neutralizes with soda ash etc., distills refining then.Adopt such intermittent reaction technology, the one, production efficiency can't be improved, and production capacity is difficult to improve, and energy consumption is big, the production cost height; The 2nd, the quality of product is also bad, is difficult to reach the requirement of GB/T 3729-91 " industrial acetic butyl ester " premium grads.
Last century the nineties, development and application along with reaction rectification technique, domesticly also begin to have unit research to produce butylacetate with this technology, but generally all need to be used as catalyzer, do not see that making the technology that catalyzer combines with reaction rectification method with liquid has been applied to suitability for industrialized production with solid acids such as heteropolyacids.
With the solid acid as catalyst many defectives are arranged: the one, this catalyzer is very expensive, uses after for some time, and its catalytic activity also can reduce, and replacing is got up pretty troublesome, and use cost is very high; The 2nd, the easy efflorescence of solid catalyst, not only loss is big, and causes accumulated impurity in esterifying kettle or the reaction fractionating tower easily, influences the steam output of material, and finally has influence on the quality of product; The 3rd, solid catalyst is difficult to accomplish homogeneous catalysis unlike liquid catalyst, and the solid heat-transfer effect is difficult to accomplish evenly cause local superheating easily, and problems such as reactant coking influence the quality and the production efficiency of product; The 4th, adopt solid acid as catalyzer, be difficult to throughput is improved, the annual production of single complete equipment all less than 10,000 tons, is difficult to form the production capacity of mass-producing basically.So far do not see yet and adopt the solid acid as catalyst, successfully use the report of mass producing butyl acetate by reactive distillation method.
So make esters product realization low energy High-efficient Production such as butylacetate; must adopt this modern technique of reaction rectification method; and to make this technology really obtain the industrial application of mass-producing, for esterification, must adopt the such liquid of the vitriol oil as catalyzer.Reaction rectification method is by the isolating mode of limit coronite, the process that heats up again after not only can making production process avoid the reactant experience repeatedly to lower the temperature, thereby significantly reduce the consumption of steam equal energy source, and a content that goes on foot target product in the crude product that generates is significantly improved, reduced the complicacy that a back one-step refining is purified, and can significantly reduce energy consumption, reduce production costs.But this technology is generally only seen the report of employing solid acid as catalyzer, and adopts solid acid as catalyzer, then has above-mentioned said a series of defectives.Can not adopt the reason of liquid acid in these reports, be that mainly liquid catalyst can be mingled in the final product, causes more serious corrosion to heating containers such as reaction fractionating tower and reboilers as catalyzer.Liquid catalyst and reaction rectification technique are combined, must adopt and heat-stable concentrated acid corrosive material to make reaction fractionating tower and reboiler, to make liquid acid catalyst realize continuous the separation as much as possible by easy, rational technology simultaneously, again product be made with extra care at last with crude product.
Chinese patent ZL 94108405.1 has disclosed the method and apparatus of producing n-butyl acetate with continuous catalyzing rectifying, what but its reactive distillation equipment adopted is a tower device, and the n-butyl acetate content of its generation has only (95-97) %, only be equivalent to the requirement of salable product in the GB/T 3729-91 standard, do not reach contemporary butylacetate user's service requirements far away.
Chinese patent ZL 97121674.6 discloses the production technique of continuous processing butylacetate, as catalyzer, does not adopt reaction rectification method with heteropolyacid.
The method of Chinese patent ZL 00107970.0 disclosed continuous production butylacetate though adopt sulfuric acid as catalyzer, does not adopt reaction rectification method yet.
Summary of the invention:
The object of the invention is to overcome above-mentioned deficiency; be can only merely utilize before the industrial community of butylacetate sulfuric acid as the catalyzer of esterification to enhance production capacities easily; though perhaps adopted some principles of reaction rectification method; but do not adopt sulfuric acid as catalyzer; thereby production capacity is difficult to problems such as expansion; providing a kind of is the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid; by the reaction rectification technique on the classical meaning is reasonably improved; make this technology can with combine well with the technology of sulfuric acid as catalyzer; a kind of modern technique of both having utilized reaction rectification method is provided, makes the liquid catalyst handled easily again; the characteristics that are easy to expand the scale of production are not fully exerted.
The object of the present invention is achieved like this: a kind of is the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid; it is characterized in that: it is to be raw material with acetate and butanols; the vitriol oil is a catalyzer; adopt reaction rectification method continuous production butylacetate; whole production system includes three towers; be respectively reaction fractionating tower, azeotrope column and ester rectifying tower, reaction fractionating tower and azeotrope column are arranged in juxtaposition, and its concrete processing method is as follows:
A) raw acetic acid pumps into the acetate preheater and carries out preheating, and butanols then pumps into the butanols preheater and carries out preheating, after both mix by the proportioning of setting, continuously from 1
#The bottom of pre-reactor enters, and the catalyzer vitriol oil is then through the sulfuric acid storage tank, with the flow set from 1
#The top of pre-reactor flows into, and these materials carry out the esterification pre-reaction in pre-reactor, and reacted liquid phase is from 1
#The top overflow of pre-reactor enters 2
#The top of pre-reactor, liquid phase is by 2
#Flow out the bottom of pre-reactor, squeezes into feed tray between reaction fractionating tower rectifying section and the stripping section through the reaction fractionating tower fresh feed pump, and the gas phase of two pre-reactors then directly enters the feed zone of reaction fractionating tower by pipeline,
B) at the stripping section of reaction fractionating tower, water in the liquid phase and butanols, butylacetate form the lower ternary azeotrope of boiling point, take away by gas phase, at the bottom of the reaction fractionating tower liquid phase consist of butylacetate and a small amount of sulfuric acid, for containing acid ester just,
C) will contain the first ester of acid is communicated with in the reboiler, butylacetate is steamed, realize just ester and vitriolic initial gross separation, because a small amount of sulfuric acid also can be carried secretly out by gas phase along with the ebullient liquid phase, such component is passed through a gas-liquid separator again, liquid composition is back in the reboiler, and just the ester gas phase then forwards the road, back to
In the liquid phase of reactive distillation tower bottom was formed, sulfuric acid sank to the bottom, adopted acid proof pump, and the acid that bottom sulfur acid amount is higher/ester mixture pump is to the top of reaction fractionating tower rectifying section,
D) gaseous component of reactive distillation cat head contains butylacetate, butanols, water and acetate, they directly enter the bottom column plate of azeotrope column by pipeline, and component such as high boiling acetate at the bottom of the azeotrope column, pump into the top of reaction fractionating tower rectifying section by acid proof pump, continue on for carrying out esterification, the gas phase of azeotrope column cat head contains butylacetate, fourth alcohol and water, they feed the azeotrope column condenser, condensed liquid phase flows into oil/water stratification device, after the layering, oil phase is as the backflow of azeotrope column, and water reclaims or discharging
E) to go purified ester gas phase just to the road, back by what gas-liquid separator was told, enter the stage casing of ester rectifying tower, further separate, low-boiling-point substance steams from cat head continuously, after 16 condensations of low-boiling-point substance condenser, partial reflux is to the top of ester rectifying tower, and rest part pumps into acid/pure mixing tank, mixes with raw material acid and alcohol; The butylacetate finished product is then from the continuous discharging of tower side; Then blowback acid of the still liquid/pure mixing tank of this tower mixes retrieval system with raw material.
Compare with the production method of existing butylacetate, the present invention has following characteristics:
1, the tower plant modification in the general application of reaction rectification method has been become reaction fractionating tower and azeotrope column two-tower type device arranged side by side, can make the separating effect of reactive distillation better, be unlikely making tower do very highly simultaneously again.
2, the tower body inwall lining teflon of reaction fractionating tower, filler is taked the graphite medium, prevents that well reaction mass from comprising the corrosion of sulfuric acid catalyst to system.
3, by strict control proportion of raw materials, when making the reaction mass of liquid phase arrive at the bottom of the reactive distillation Tata, acetate and butanols just complete reaction fall, and generate butylacetate, or butanols is excessive slightly little by little;
4, the temperature at the bottom of the reactive distillation Tata is controlled in the higher scope, make water and some lower boiling azeotropes etc. can not remain at the bottom of the tower, the content of butyl ester then reaches about 98% at the bottom of the tower, makes the vitriol oil simultaneously under anhydrous condition, and the corrosion of equipment at the bottom of the tower is alleviated greatly.
5, adopt graphite to soak the tetrafluoroethylene material, solved the etching problem of this reboiler well as the supporting reboiler of reaction fractionating tower.
6, our gas-liquid mixture that reboiler is steamed, separate through a gas-liquid separator earlier, the rectifying tower that the first ester of gas phase is delivered to the road, back goes to make with extra care, liquid phase then is back in the reboiler, sulfuric acid in the liquid phase that prevents to take out of with gas phase because of boiling is brought to the road, back and goes, the system in road, corrosion back.
7, for the bigger acid/ester mixture of reactive distillation tower bottom sulfuric acid content, then, make catalyzer obtain recycling with the top of the less acid proof pump pump of flow to the reaction fractionating tower rectifying section, realize cleaner production.
Taked above-mentioned a series of ameliorative measure, just realized having made full use of both advantages with the combination of sulfuric acid as catalyzer and this technology of reaction rectification method, citing in the industry of large-scale production acetic ester has showed good effect.
Aforesaid liquid acid catalyst and reaction rectification method process combined have been adopted, the energy consumption that butylacetate is produced descends 30%, thereby production cost is obviously descended, and the thick ester content that obtains is near the level of butylacetate acceptable end product (main content is near 98%), lower boiling composition seldom, so the ester rectifying tower need not be too high, just can make the raw material that continuously produces reach the requirement of premium grads.
Adopt such processing method; not only realized the combination of liquid catalyst and reaction rectification technique; make mass-producing ground continuous production butylacetate become possibility; and by reaction rectification method is improved; prevented of the corrosion of tart liquid catalyst effectively, made the cost of facility investment obtain effective control reaction and refining system.
Description of drawings:
Fig. 1 is technological process of production figure of the present invention.
Among the figure: 1-acetate preheater, 2-butanols preheater, 3-sulfuric acid storage tank, 4-1
#Pre-reactor, 5-2
#Pre-reactor, 6-reaction fractionating tower, 7-reaction fractionating tower reboiler, the 8-gas-liquid separator, 9-azeotrope column, 10-azeotrope column condenser, 11-oil/water stratification device, the 12-recovery tower, 13-recovery tower reboiler, 14-ester rectifying tower, 15-butyl ester rectifying tower reboiler, 16-low-boiling-point substance condenser, 17-butyl ester product condenser, 18-gaseous effluent cooler.
Embodiment:
Referring to Fig. 1, whole production system mainly is made up of four towers, is respectively reaction fractionating tower 6, azeotrope column 9, recovery tower 12 and ester rectifying tower 14.Reaction fractionating tower and azeotrope column can be merged into a tower, are about to the top that azeotrope column places reaction fractionating tower, the reaction fractionating tower on the classical meaning that Here it is.But like this, this tower will be done very highly, need build corresponding off-set facility and protect this tower and keep its normal operation, and or not very economical.For this reason, the present invention is divided into two towers with the reaction fractionating tower on the classical meaning---reaction fractionating tower and azeotrope column in the practical application.The specific embodiment of the present invention is as follows:
Raw acetic acid pumps into acetate preheater 1 and carries out preheating, and butanols then pumps into butanols preheater 2 and carries out preheating, after both mix by the proportioning of setting, continuously from 1
#The bottom of pre-reactor 4 enters, and the catalyzer vitriol oil is then through sulfuric acid storage tank 3, with the flow set from 1
#The top of pre-reactor flows into, and these materials carry out the esterification pre-reaction in pre-reactor.Reacted liquid phase is from 1
#The top overflow of pre-reactor enters 2
#The top of pre-reactor 5 is 2
#Esterification is near equilibrium state in the pre-reactor, and liquid phase is by 2
#Flow out the bottom of pre-reactor, squeezes into feed tray between reaction fractionating tower rectifying section and the stripping section through the reaction fractionating tower fresh feed pump.The gas phase of two pre-reactors then directly enters the feed zone of reaction fractionating tower by pipeline.
At the stripping section of reaction fractionating tower, water in the liquid phase and butanols, butylacetate form the lower ternary azeotrope of boiling point, are taken away by gas phase, thereby have reduced the moisture in the liquid phase, and esterification can be carried out fully.When reactant is fallen the bottom of reaction fractionating tower, do not had moisture basically, liquid phase consists of butylacetate and a small amount of sulfuric acid at the bottom of the reaction fractionating tower.After testing, the butylacetate content of reactive distillation tower bottom is near 98%, only owing to wherein contain composition such as sulfuric acid, so directly extraction.Because the bottoms material of reaction fractionating tower has not had moisture basically, sulfuric acid to tower at the bottom of the corrosion of equipment alleviate greatly.
So first ester of acid that contains is communicated with in the employing thermostable acid corrosive reboiler 7, utilizes the characteristics of sulfuric acid boiling point very high (330 ℃), in the reboiler heating, butylacetate is steamed, realize just ester and vitriolic initial gross separation.Because a small amount of sulfuric acid also can be carried secretly out by gas phase along with the ebullient liquid phase, we pass through a gas-liquid separator 8 again with such component, liquid composition is back in the reboiler, forwards corrosion compositions such as then no longer containing sulfuric acid in the gas phase of going in the road, back basically to.
Because vitriolic density is big more a lot of than butylacetate, so in the liquid phase of reactive distillation tower bottom is formed, sulfuric acid trends towards sinking to the bottom, adopt the acid proof pump that flow is less, the acid that bottom sulfur acid amount is higher/ester mixture pump is to the top of reaction fractionating tower rectifying section, make catalyzer obtain recycling, realize cleaner production.
The gaseous component of reactive distillation cat head contains butylacetate, butanols, water and acetate, they directly enter the bottom column plate of azeotrope column by pipeline, and component such as high boiling acetate at the bottom of the azeotrope column pumps into the top of reaction fractionating tower rectifying section by acid proof pump, continues on for carrying out esterification.The gas phase of azeotrope column cat head contains butylacetate, fourth alcohol and water, and they feed azeotrope column condenser 10, and condensed liquid phase flows into oil/water stratification device 11.After the layering, oil phase is as the backflow of azeotrope column, and water enters recovery tower, reclaims wherein a spot of butanols and butylacetate.
What the recovery tower cat head steamed is the azeotrope of butanols, butyl ester and water, turns back to the azeotrope column condenser, after condensation, carries out layering in oil/water separator.Be water basically then at the bottom of the tower of recovery tower, pump into and be discharged into waste water processing station after the waste water condenser condenses and go to handle.
Recovery tower also can consider need not because through aqueous phase that oil/the water stratification device branches away, butanols and butylacetate seldom, (processing condition are controlled well, the content of said components≤0.5%.) go to reclaim wherein organic words with a tower again, the cost of energy consumption offsets with the value that reclaims raw material saving.
To go purified ester gas phase just to the road, back by what separator was told, enter the stage casing of ester rectifying tower, further separate.Low-boiling-point substance steams from cat head continuously, and after 16 condensations of low-boiling-point substance condenser, partial reflux is to the top of ester rectifying tower, and rest part pumps into acid/pure mixing tank, mixes with raw material acid and alcohol; The butyl ester finished product is then from the continuous discharging in the appropriate location of tower side; Then blowback acid of the still liquid/pure mixing tank of this tower mixes retrieval system with raw material.
Utilize the concrete processing condition of this method production n-butyl acetate as follows:
The temperature controlling range of acetate and butanols preheater is (100-110) ℃, and pressure range is (125-175) kPa, and preferred range is (105-110) ℃, and pressure range is (145-165) kPa.
Feed preheater is selected such temperature range, mainly is to consider the effect that should make raw material reach preheating, for next step pre-reaction provides energy, temperature is controlled at below the boiling point of corresponding raw material again.Under the normal pressure, the boiling point of acetate is 118.1 ℃, and the boiling point of propyl carbinol is 117.5 ℃.The selection of pressure range mainly is to consider that the material that will make preceding road can flow to the road, back and go, and makes each tower be in the state of atmospheric distillation, avoids the with high investment and high operation cost that adopts negative pressure equipment to cause.
The weight proportion of acetate and propyl carbinol is 1.6: 1～1: 1.3, or volume proportion is 1.23: 1～1: 1.69, and the weight ratio of preferred acetate and propyl carbinol is 1: 1.20～1: 1.28, and volume ratio is 1: 1.56～1: 1.66.
Adopting such proportioning raw materials, mainly is the ratio for the theory consumption of calculating by molecular weight near raw material, and when making raw material limit coronite be separated at the bottom of the reaction fractionating tower, raw material has just in time reacted.But in the different steps (such as initial period and end of a period stage) of producing, proportion of raw materials can be different, so totally need the scope of a broad.And the density of acetate is 1.05g/cm under the normal temperature
3, the density of propyl carbinol is 0.81g/cm
3, the ratio of both density is 1.3: 1.
1
#With 2
#The temperature controlling range of pre-reactor is (100～115) ℃, and pressure range is (120～170) kPa, and preferred range is (108～112) ℃, and pressure range is (140～160) kPa.
1
#With 2
#The temperature control of pre-reactor should be considered the energy requirement that esterification is required, improves the speed of reaction, and the temperature of controlling reactor is no more than the boiling point of raw material and principal product again.Under the normal pressure, the boiling point of n-butyl acetate is 126.1 ℃.
The tower top temperature span of control of reaction fractionating tower is (88～110) ℃, and pressure range is (120～135) kPa, and preferred range is (95～102) ℃, and pressure range is (125～132) kPa; The column bottom temperature span of control is (100～150) ℃, and pressure range is (135～170) kPa, and preferred range is (125～136) ℃, and pressure range is (145～155) kPa.
Azeotrope column tower top temperature scope is (85～100) ℃, and pressure range is (98～105) kPa, and preferred range is (88～93) ℃, and pressure range is (99～102) kPa; The column bottom temperature scope is (88～110) ℃, and pressure range is (120～135) kPa, and preferred range is (96～100) ℃, and pressure range is (125～132) kPa.
If with two reaction fractionating towers and azeotrope column and to together, then the temperature controlling range of cat head is (85～100) ℃, and pressure range is (98～105) kPa, and preferred range is (88～93) ℃, and pressure range is (99～102) kPa; Temperature controlling range at the bottom of the tower is (100～150) ℃, and pressure range is (135～170) kPa, and preferred range is (125～136) ℃, and pressure range is (145～155) kPa.
What the present invention adopted is the technology of atmospheric distillation, so the pressure of azeotropic cat head should be normal pressure, temperature is then near the azeotropic temperature of ternary azeotrope.
If the employing recovery tower, then the temperature controlling range of cat head is (90～105) ℃, and pressure range is (98～105) kPa, and preferred range is (97～100) ℃, and pressure range is (99～102) kPa; Temperature controlling range at the bottom of the tower is (95～110) ℃, and pressure range is (110～130) kPa, and preferred range is (100～105) ℃, and pressure range is (115～125) kPa.
The tower top temperature span of control of butyl ester rectifying tower is (100～125) ℃, and pressure range is (98～105) kPa, and preferred range is (120～125) ℃, and pressure range is (99～102) kPa; The temperature controlling range of tower side extraction n-butyl acetate is (125-130) ℃, and pressure range is (102-115) kPa, and preferred range is (126-128) ℃, and pressure range is (105-110) kPa; Temperature controlling range at the bottom of the tower is (130～150) ℃, and pressure range is (110～130) kPa, and preferred range is (130～145) ℃, and pressure range is (115～125) kPa.
Suitably reduce the material feeding amount, can decrease but the output of product is also corresponding so that the quality of the final product that generates further improves.
Adopt above-mentioned technical process also can produce isobutyl acetate, only because the density of propyl carbinol and isopropylcarbinol is different, the volume proportion of raw material can be different.In addition, because the boiling point of isobutyl ester is lower than the boiling point of positive butyl ester, so the temperature controlling range club difference in the processing condition.
Utilize the concrete processing condition of this method production isobutyl acetate as follows:
When producing isobutyl acetate with isopropylcarbinol, because the boiling point of isopropylcarbinol is 108 ℃, the temperature controlling range of butanols preheater is low when using propyl carbinol, be (90-100) ℃, pressure range is (125-175) kPa, preferred range is (95-100) ℃, and pressure range is (145-165) kPa.
Correspondingly, the temperature controlling range of acetate preheater also will reduce a bit, is (90-100) ℃ that pressure range is (125-175) kPa, and preferred range is (95-100) ℃, and pressure range is (145-165) kPa.
The weight proportion of acetate and isopropylcarbinol is 1.6: 1～1: 1.3, or volume proportion is 1.45: 1～1: 1.43, and the weight ratio of preferred acetate and isopropylcarbinol is 1: 1.20～1: 1.28, and volume ratio is 1: 1.32～1: 1.41.
Adopt of the reaction of the reason of such proportioning raw materials, and the density of isopropylcarbinol is 0.95g/cm under the normal temperature with acetate and propyl carbinol
3, the density ratio of acetate and isopropylcarbinol is 1.1: 1.
1
#With 2
#The temperature controlling range of pre-reactor is (95～105) ℃, and pressure range is (120～170) kPa, and preferred range is (100～105) ℃, and pressure range is (140～160) kPa.Selecting such pre-reaction temperature, mainly is that the boiling point of also having considered isobutyl acetate is 118 ℃ because the boiling point of raw material isopropylcarbinol is lower.
The reaction conditions of each tower is except that temperature slightly the difference, and pressure-controlling condition and reason are with the control condition and the reason of n-butyl acetate.
The tower top temperature span of control of reaction fractionating tower is (85～102) ℃, and preferred range is (90～98) ℃; The column bottom temperature span of control is (100～135) ℃, and preferred range is (117～128) ℃.
Azeotrope column tower top temperature scope is (85～95) ℃, and preferred range is (87～92) ℃; The column bottom temperature scope is (85～100) ℃, and preferred range is (90～97) ℃.
If with two reaction fractionating towers and azeotrope column and to together, then the temperature controlling range of cat head is (85～95) ℃, and preferred range is (87～92) ℃; Temperature controlling range at the bottom of the tower is (100～135) ℃, and preferred range is (117～128) ℃.
If the employing recovery tower, then the temperature controlling range of cat head is (80～100) ℃, and preferred range is (85～98) ℃; Temperature controlling range at the bottom of the tower is (95～110) ℃, and preferred range is (98～105) ℃.
The tower top temperature span of control of butyl ester rectifying tower is (90～115) ℃, and preferred range is (110～115) ℃; The temperature of tower side extraction isobutyl acetate is (115-125) ℃, and preferred range is (117-120) ℃; Temperature controlling range at the bottom of the tower is (120～140) ℃, and preferred range is (125～140) ℃.
Adopt such technical process, according to the physical properties of raw material and product, appropriate change proportion of raw materials and reaction control condition also can the production ethyl acetate and acetate product such as isopropyl acetate.
Embodiment one
It is about 99.5% acceptable end product that acetate adopts main content, and flow is 4.3T/h, and propyl carbinol adopts content greater than 99.5% premium grads, and flow is 5.4T/h, and the vitriol oil adopts content greater than 98% premium grads, and flow is 0.05T/h.
The temperature of acetate and butanols preheater is 108 ℃, and pressure is 155kPa, and 1
#With 2
#The temperature of pre-reactor is 110 ℃, pressure 150kPa; The tower top temperature of reaction fractionating tower is 100 ℃, and pressure 130kPa, column bottom temperature are 130 ℃, pressure 150kPa; The azeotrope column tower top temperature is 91 ℃, and pressure 100kPa, column bottom temperature are 98 ℃, pressure 130kPa; The recovery tower tower top temperature is 98 ℃, and pressure 100kPa, column bottom temperature are 103 ℃, pressure 120kPa; Butyl ester rectifying tower tower top temperature is 122 ℃, and pressure is 100kPa, and the drop temperature of tower side n-butyl acetate finished product is 126.5 ℃, and pressure 105kPa, column bottom temperature are 135 ℃, pressure 120kPa.To the detection of taking a sample of the first ester at the bottom of the reactive distillation Tata, the content of n-butyl acetate reaches 97.9%, and extraction n-butyl acetate 8.3T/h, the content of n-butyl acetate are 99.58%, and other indexs all reach the requirement of premium grads.
Embodiment two
The flow of raw acetic acid is 4.0T/h, the flow of propyl carbinol is 5.0T/h, other processing condition are all constant, at the beginning of at the bottom of reaction fractionating tower 5 towers in the ester content of n-butyl acetate be 98.3%, extraction n-butyl acetate 7.7T/h, the content of n-butyl acetate is 99.91%, and other indexs all reach the requirement of premium grads.
Embodiment three
It is about 99.5% acceptable end product that acetate adopts main content, and flow is 4.3T/h, and isopropylcarbinol adopts content greater than 99.3% premium grads, and flow is 5.4T/h, and the vitriol oil adopts content greater than 98% premium grads, and flow is 0.05T/h.
The temperature of acetate and butanols preheater is 98 ℃, and pressure is 155kPa, and 1
#With 2
#The temperature of pre-reactor is 102 ℃, pressure 150kPa; The tower top temperature of reaction fractionating tower is 95 ℃, and pressure 130kPa, column bottom temperature are 120 ℃, pressure 150kPa; The azeotrope column tower top temperature is 90 ℃, and pressure 100kPa, column bottom temperature are 95 ℃, pressure 130kPa; The recovery tower tower top temperature is 92 ℃, and pressure 100kPa, column bottom temperature are 103 ℃, pressure 120kPa; The temperature of butyl ester rectifying tower cat head is 112 ℃, pressure 100kPa, and the extraction temperature of tower side isobutyl acetate is 118.5 ℃, pressure 105kPa, column bottom temperature are 130 ℃, pressure 120kPa.To the first ester sampling analysis at the bottom of his Tata of reactive distillation, the content of isobutyl acetate is 97.8%, and extraction isobutyl acetate 8.2T/h, the content of isobutyl acetate are 99.52%, and other indexs all satisfy user's service requirements.
Claims (10)
1, a kind of is the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid; it is characterized in that: it is to be raw material with acetate and butanols; the vitriol oil is a catalyzer; adopt reaction rectification method continuous production butylacetate; whole production system includes three towers; be respectively reaction fractionating tower, azeotrope column and ester rectifying tower, reaction fractionating tower and azeotrope column are arranged in juxtaposition, and its concrete processing method is as follows:
A) raw acetic acid pumps into the acetate preheater and carries out preheating, and butanols then pumps into the butanols preheater and carries out preheating, after both mix by the proportioning of setting, continuously from 1
#The bottom of pre-reactor enters, and the catalyzer vitriol oil is then through the sulfuric acid storage tank, with the flow set from 1
#The top of pre-reactor flows into, and these materials carry out the esterification pre-reaction in pre-reactor, and reacted liquid phase is from 1
#The top overflow of pre-reactor enters 2
#The top of pre-reactor, liquid phase is by 2
#Flow out the bottom of pre-reactor, squeezes into feed tray between reaction fractionating tower rectifying section and the stripping section through the reaction fractionating tower fresh feed pump, and the gas phase of two pre-reactors then directly enters the feed zone of reaction fractionating tower by pipeline,
B) at the stripping section of reaction fractionating tower, water in the liquid phase and butanols, butylacetate form the lower ternary azeotrope of boiling point, take away by gas phase, at the bottom of the reaction fractionating tower liquid phase consist of butylacetate and a small amount of sulfuric acid, for containing acid ester just,
C) will contain the first ester of acid is communicated with in the reboiler, butylacetate is steamed, realize just ester and vitriolic initial gross separation, because a small amount of sulfuric acid also can be carried secretly out by gas phase along with the ebullient liquid phase, such component is passed through a gas-liquid separator again, liquid composition is back in the reboiler, and just the ester gas phase then forwards the road, back to
In the liquid phase of reactive distillation tower bottom was formed, sulfuric acid sank to the bottom, adopted acid proof pump, and the acid that bottom sulfur acid amount is higher/ester mixture pump is to the top of reaction fractionating tower rectifying section,
D) gaseous component of reactive distillation cat head contains butylacetate, butanols, water and acetate, they directly enter the bottom column plate of azeotrope column by pipeline, and component such as high boiling acetate at the bottom of the azeotrope column, pump into the top of reaction fractionating tower rectifying section by acid proof pump, continue on for carrying out esterification, the gas phase of azeotrope column cat head contains butylacetate, fourth alcohol and water, they feed the azeotrope column condenser, condensed liquid phase flows into oil/water stratification device, after the layering, oil phase is as the backflow of azeotrope column, and water reclaims or discharging
E) to go purified ester gas phase just to the road, back by what gas-liquid separator was told, enter the stage casing of ester rectifying tower, further separate, low-boiling-point substance steams from cat head continuously, after 16 condensations of low-boiling-point substance condenser, partial reflux is to the top of ester rectifying tower, and rest part pumps into acid/pure mixing tank, mixes with raw material acid and alcohol; The butyl ester finished product is then from the continuous discharging of tower side; Then blowback acid of the still liquid/pure mixing tank of this tower mixes retrieval system with raw material.
2, according to claim 1 a kind of be the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid, it is as follows to it is characterized in that utilizing this method to produce the concrete processing condition of n-butyl acetate:
The temperature controlling range of acetate and butanols preheater is 100-110 ℃, and pressure range is 125-175kPa,
The weight proportion of acetate and propyl carbinol is 1.6: 1～1: 1.3, or volume proportion is 1.23: 1～1: 1.69,
1
#With 2
#The temperature controlling range of pre-reactor is 100～115 ℃, and pressure range is 120～170kPa,
The tower top temperature span of control of reaction fractionating tower is 88～110 ℃, and pressure range is 120～135kPa, and the column bottom temperature span of control is 100～150 ℃, and pressure range is 135～170kPa,
Azeotrope column tower top temperature scope is 85～100 ℃, and pressure range is 98～105kPa, and the column bottom temperature scope is 88～110 ℃, and pressure range is 120～135kPa,
The tower top temperature span of control of butyl ester rectifying tower is 100～125 ℃, pressure range is 98～105kPa, the temperature controlling range of tower side extraction n-butyl acetate is 125-130 ℃, pressure range is 102-115kPa, temperature controlling range at the bottom of the tower is 130～150 ℃, and pressure range is 110～130kPa.
3, according to claim 2 a kind of be the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid, it is as follows to it is characterized in that utilizing this method to produce the concrete processing condition of n-butyl acetate:
The temperature controlling range of acetate and butanols preheater is 105-110 ℃, and pressure range is 145-165kPa,
The weight proportion of acetate and propyl carbinol is 1: 1.20～1: 1.28, and volume ratio is 1: 1.56～1: 1.66.
1
#With 2
#The temperature controlling range of pre-reactor is 108～112 ℃, and pressure range is 140～160kPa,
The tower top temperature span of control of reaction fractionating tower is 95～102 ℃, and pressure range is 125～132kPa; The column bottom temperature span of control is 125～136 ℃, and pressure range is 145～155kPa,
Azeotrope column tower top temperature scope is 88～93 ℃, and pressure range is 99～102kPa; The column bottom temperature scope is 96～100 ℃, and pressure range is 125～132kPa,
The tower top temperature span of control of butyl ester rectifying tower is 120～125 ℃, and pressure range is 99～102kPa; The temperature controlling range of tower side extraction n-butyl acetate is 126-128 ℃, and pressure range is 105-110kPa; Temperature controlling range at the bottom of the tower is 130～145 ℃, and pressure range is 115～125kPa.
4, according to claim 1 a kind of be the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid, it is as follows to it is characterized in that utilizing this method to produce the concrete processing condition of isobutyl acetate:
The temperature controlling range of butanols preheater is 90-100 ℃, and pressure range is 125-175kPa,
The temperature controlling range of acetate preheater is 90-100 ℃, and pressure range is 125-175kPa,
The weight proportion of acetate and isopropylcarbinol is 1.6: 1～1: 1.3, or volume proportion is 1.45: 1～1: 1.43,
1
#With 2
#The temperature controlling range of pre-reactor is 95～105 ℃, and pressure range is 120～170kPa,
The tower top temperature span of control of reaction fractionating tower is 85～102 ℃, and pressure range is 120～135kPa; The column bottom temperature span of control is 100～135 ℃, and pressure range is 135～170kPa,
Azeotrope column tower top temperature scope is 85～95 ℃, and pressure range is 98～105kPa; The column bottom temperature scope is 85～100 ℃, and pressure range is 120～135kPa,
The tower top temperature span of control of butyl ester rectifying tower is 90～115 ℃, and pressure range is 98～105kPa; The temperature of tower side extraction isobutyl acetate is 115-125 ℃, and pressure range is 102～115kPa; Temperature controlling range at the bottom of the tower is 120～140 ℃, and pressure range is 110～130kPa.
5, according to claim 4 a kind of be the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid, it is as follows to it is characterized in that utilizing this method to produce the concrete processing condition of isobutyl acetate:
The temperature controlling range of butanols preheater is 95-100 ℃, and pressure range is 145-165kPa,
The temperature controlling range of acetate preheater is 95-100 ℃, and pressure range is 145-165kPa,
The weight proportion of acetate and isopropylcarbinol is 1: 1.20～1: 1.28, and volume ratio is 1: 1.32～1: 1.41,
1
#With 2
#The temperature controlling range of pre-reactor is 100～105 ℃, and pressure range is 140～160kPa,
The tower top temperature span of control of reaction fractionating tower is 90～98 ℃, and pressure range is 125～132kPa; The column bottom temperature span of control is 117～128 ℃, and pressure range is 145～155kPa,
Azeotrope column tower top temperature scope is 87～92 ℃, and pressure range is 99～102kPa; The column bottom temperature scope is 90～97 ℃, and pressure range is 125～132kPa,
The tower top temperature span of control of butyl ester rectifying tower is 110～115 ℃, and pressure range is 99～102
KPa; The temperature of tower side extraction isobutyl acetate is 117-120 ℃, and pressure range is 105～110kPa; Temperature controlling range at the bottom of the tower is 125～140 ℃, and pressure range is 115～125kPa.
6; according to claim 1～5 one of them described a kind of be the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid; it is characterized in that flowing into oil/water stratification device by the liquid phase after the azeotrope column condenser condenses; after the layering; water enters recovery tower; reclaim wherein a spot of butanols and butylacetate; what the recovery tower cat head steamed is butanols; the azeotrope of butyl ester and water; turn back to the azeotrope column condenser; after condensation; in oil/water separator, carry out layering; water at the bottom of the tower of recovery tower pumps into and is discharged into waste water processing station after the waste water condenser condenses and goes to handle.
7, according to claim 6 a kind of be the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid; it is characterized in that the temperature controlling range of utilizing this method to produce the recovery tower cat head of n-butyl acetate is 90～105 ℃; pressure range is 98～105kPa; temperature controlling range at the bottom of the tower is 95～110 ℃, and pressure range is 110～130kPa.
8, according to claim 6 a kind of be the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid, it is characterized in that the temperature controlling range of utilizing this method to produce the recovery tower cat head of isobutyl acetate is 80～100 ℃, pressure range is 98～105kPa; Temperature controlling range at the bottom of the tower is 95～110 ℃, and pressure range is 110～130kPa.
9, according to claim 1～5 one of them described a kind of be the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid, it is characterized in that the tower body inwall lining teflon of described reaction fractionating tower, filler is taked the graphite medium.
10, according to claim 1～5 one of them described a kind of be the method for catalyst reaction rectification method large-scale production butylacetate with sulfuric acid, it is characterized in that adopting graphite to soak the tetrafluoroethylene material as the supporting reboiler of reaction fractionating tower.
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| CN102690197A (en) * | 2012-05-29 | 2012-09-26 | 江门谦信化工发展有限公司 | Method for preparing acetic acid mixed butyl ester by continuous reaction and rectification |
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| BE1014031A3 (en) * | 1997-07-04 | 2003-03-04 | Basf Ag | THE PREPARATION OF ESTERS. |
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