CN105566059A - Method for preparing ethanol and co-producing mixed solvent through acetic acid hydrogenation - Google Patents
Method for preparing ethanol and co-producing mixed solvent through acetic acid hydrogenation Download PDFInfo
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Abstract
The invention provides a low-energy consumption method for preparing ethanol and co-producing a mixed solvent through acetic acid hydrogenation. The method comprises 1, gas phase hydrogenation, 2, gas-liquid separation, 3, esterification reaction and 4, product refining: feeding a liquid product B into a neutralization reactor, adding an alkaline substance into the reactor, carrying out a neutralization reaction process, feeding the neutralization product into a first rectifying tower, feeding a part of the first rectifying tower top fraction back to a gas phase hydrogenation reactor, feeding the first rectifying tower bottom fraction into a second rectifying tower, feeding a part of the second rectifying tower top fraction back to the gas phase hydrogenation reactor, collecting a part of the second rectifying tower top fraction as a mixed solvent, wherein the mixed solvent comprises ethanol, ethyl acetate and water according to an ethanol-ethyl acetate mass ratio of 1: 0.05-1.1, has water content of 1-15wt% and an acidity value of 0-30mg/L and the second rectifying tower bottom fraction contains water, acetate and butanol, feeding the second rectifying tower bottom fraction into a third rectifying tower, and carrying out separation to obtain a third rectifying tower bottom fraction containing water, acetate and butanol and a third rectifying tower top fraction containing ethanol and water, wherein the third rectifying tower top fraction has ethanol content of 85-95wt% and an acidity value of 0-25mg/L. The method can reduce energy consumption and improve ethanol product quality.
Description
Technical field
The present invention relates to a kind of method of producing ethanol, more particularly, relate to a kind of by the method for acetic acid Hydrogenation for highly selective alcohol product.
Background technology
Ethanol be find the earliest, a kind of fatty alcohol that purposes is the widest, be also the main component of wine.The industrial process of current ethanol mainly contains fermentation method and ethylene hydration method.Ethylene hydration method develops along with the rise of petrochemical complex, comprises indirect hydration method and direct hydration method.In recent years by the raising of production cost of ethylene, in China, ethylene process is in end-of-life state substantially.The main raw material of fermentation method is farm crop (comprising corn, sugarcane, Chinese sorghum, cassava, paddy etc.), obtains ethanol by utilizing the amylofermentation in farm crop.
The raw material that the main alcohol production enterprise of China uses is corn, wheat and cassava (mainly relying on import).In fact grain cost sharp rises in recent years, and therefore ethanol also exists the problem of striving grain with people.The non-grain ethanol raw material such as cassava, sweet sorghum price is also expected to rise always, and is that the two generations ethanol technology distance application of representative also has more difficulty to need to solve with cellulosic ethanol.
Acetic acid is a kind of important industrial chemicals, and the production technique of acetic acid has grain fermentation method, methanol carbonylation, oxidation of ethylene method, oxidation of ethanol method, acetaldehyde oxidation and ethane oxidation method etc.
Over nearly 10 years, acetic acid consumption still mainly concentrates on traditional field, and consumption structure considerable change does not occur, and does not form new demand growth point to support newly-increased production capacity.Estimate that China's acetic acid demand in 2012 is less than about 4,800,000 tons, problem of excess production capacity is given prominence to, and even occurs that namely new device stops production after driving.Therefore the downstream use exploitation of acetic acid is extremely urgent.
Use acetic acid to comprise two kinds as the approach of raw material production alcohol product, one is that acetic acid generates acetic ester through esterification, and then acetic ester hydrogenation generates ethanol, then carries out refined raw producing and ethanol product; Two is that acetic acid direct hydrogenation generates ethanol, then produces alcohol product through treating process.First method is compared second method and has been had more esterification process, and a large amount of ethanol needs circulation as esterification feed, corresponding add the size of hydrogenator and the interchanger of front and back thereof size and energy consumption, at least partly treating process also put and be twice, its advantage is that the corrosion strength of hydrogenation process may be lower, but also there is acetic acid more or less in its process, still there is corrodibility.But the key of second method develops the catalyzer of acetic acid direct hydrogenation, this difficult problem is also that many investigators select the first acetic acid through the reason of the method for esterification repeated hydrogenation.
For acetic acid direct hydrogenation, investigator and research data have many, as Sinopec, Celanese company of the U.S. etc. have submitted a large amount of patent application with regard to acetic acid hydrogenation.Such as PCT application enters the CN102414153A of National Phase in China, disclose and first acetic acid is hydrogenated into crude ethanol product, then in first tower, unreacted acetic acid is isolated, the overhead product of first tower is isolated in second tower the second overhead product containing vinyl acetic monomer, obtain the second resistates containing second alcohol and water, the second resistates is separated into overhead product containing ethanol and moisture resistates in the 3rd tower.In addition, selectively the second overhead product is delivered to the 4th tower, be separated into the 4th overhead product containing acetaldehyde and the 4th resistates, then by the 4th overhead product Returning reacting system to improve ethanol yield, the 4th resistates is used as solvent or is used in ester production.In these patents, first acetic acid generally removed by the mode of rectifying, so just can reduce material requirement in later separation, thus realize the reduction of cost of investment, but so also there are some problems: the second alcohol and water accounting for the quality product overwhelming majority needs by vaporization, therefore the energy consumption of rectifying depickling is high, and the size of extracting tower is comparatively large and material requires higher, and cost of investment is high; And in the rectifying separation of reality, the situation that tower top exists denier acetic acid may be there is, and be all have strict demand to acidity as alcohol fuel and industrial alcohol product, therefore in the situations such as operation fluctuation, cause product defective.
It is the method for ethanol that the present invention proposes a kind of acetic acid direct hydrogenation with less energy-consumption and low material consumption level, and the present inventor, through research careful in a large number, finds to this method reduce material consumption level and cost of investment.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method that less energy-consumption acetic acid hydrogenation produces ethanol, and the method can reduce energy consumption, improves the quality of alcohol product.
A kind of acetic acid hydrogenation of the present invention produces the method for ethanol, comprises the following steps:
(1) gas phase hydrogenation: form steam feed stream by after acetic acid raw material and hydrogen preheating, is incorporated into described steam feed stream in the reactor that hydrogenation catalyst is housed and carries out hydrogenation reaction;
(2) gas-liquid separation: hydrogenation reaction thing condensation step 1 obtained, in gas-liquid separator after gas-liquid separation, obtains gaseous products A and liquid-phase product A, gaseous products A and loops back gas phase hydrogenation reaction device at least partly and use;
(3) esterification: after the liquid-phase product A in step 2 is carried out esterification in the esterifier that esterifying catalyst is housed, loops back gas phase hydrogenation reaction device at least partly after obtaining gaseous products B and liquid-phase product B, gaseous products B cooling and uses;
(4) product purification: liquid-phase product B is delivered to neutralization reactor, add alkaline matter and carry out neutralization reaction, product introduction first rectifying tower after neutralization, first overhead fraction contains acetaldehyde, vinyl acetic monomer, acetone, first tower bottom distillate is for containing ethanol, the coarse ethanol product of water, first overhead fraction part returns in gas phase hydrogenation reaction device, first tower bottom distillate is delivered to Second distillation column, second overhead fraction contains ethanol, water, the second described overhead fraction part returns in hydrogenator, part is as the extraction of mixed type solvent product, described mixed type solvent comprises ethanol, vinyl acetic monomer and water, wherein the mass ratio of ethanol and vinyl acetic monomer is 1:0.05 ~ 1.1, water-content is 1 ~ 15wt%, acidity value 0 ~ 30mg/L, second tower bottom distillate contains water, acetate and butanols, second tower bottom distillate is delivered to the 3rd rectifying tower, be separated into the 3rd tower bottom distillate of moisture, acetate and butanols and the 3rd overhead fraction containing second alcohol and water, ethanol content 85 ~ 95wt%, acidity value 0 ~ 25mg/L in the 3rd described overhead fraction.
Concrete technical scheme is as follows:
The reaction pressure of gas phase hydrogenation reaction is 0.5 ~ 5MPa, and acetic acid is hydrogenated into the crude ethanol product containing water, vinyl acetic monomer, acetaldehyde, acetone, butanols and acetic acid by the mol ratio 10 ~ 40 of hydrogen and acetic acid.
Acetic acid content in the liquid-phase product A that gas-liquid separation obtains is less than 0 ~ 2wt%, vinyl acetic monomer content 0 ~ 8wt%.
The content <0.1wt% of vinyl acetic monomer in first tower bottom distillate after product purification, in the second overhead fraction, ethanol content is higher than 91wt%.
Acetic acid gas phase hydrogenation catalyzer is be selected from load on a catalyst or the catalyzer of at least one metal active constituent of catalyzed agent carrier dispersion in described step (1).Described metal active constituent to be selected from IB, the IIB of the periodic table of elements, IIIB, IVB, VB, VIB, VIIB, Group VIIIB, lanthanide series metal and IIIA, IVA, VA, VIA race metal one or more combination.Preferred, in described (1), acetic acid gas phase hydrogenation catalyzer is one or more in Supported Co series catalysts, molybdenum series catalyst or noble metal catalyst.More specifically, described hydrogenation catalyst is selected from following:
Hydrogenation catalyst is selected from load on a catalyst or the cobalt catalyst of catalyzed agent carrier dispersion in described step (1), wherein cobalt metal content accounts for the 15wt% ~ 45wt% of overall catalyst weight, the precious metal of described catalyzer also containing trace, wherein said trace noble metal be selected from palladium, platinum and rhenium one or more, the ratio of its weight and cobalt weight metal is 1:100 ~ 1:300.
Hydrogenation catalyst is selected from load on a catalyst or the cobalt catalyst of catalyzed agent carrier dispersion in described step (1), hydrogenation catalyst is selected from load on a catalyst or the cobalt catalyst of catalyzed agent carrier dispersion in described step (1), described catalyzer is also containing boron, wherein cobalt metal content accounts for the 10wt% ~ 50wt% of overall catalyst weight, and boron accounts for the 1.0wt% ~ 10wt% of overall catalyst weight;
Hydrogenation catalyst is selected from load on a catalyst or the cobalt catalyst of catalyzed agent carrier dispersion in described step (1), hydrogenation catalyst is selected from load on a catalyst or the cobalt catalyst of catalyzed agent carrier dispersion in described step (1), described catalyzer is also containing bismuth, wherein cobalt metal content accounts for the 10wt% ~ 50wt% of overall catalyst weight, wherein cobalt metal content accounts for the 10wt% ~ 50wt% of overall catalyst weight, and bismuth metal accounts for the 0.1wt% ~ 50wt% of overall catalyst weight;
Hydrogenation catalyst is selected from load on a catalyst or the cobalt catalyst of catalyzed agent carrier dispersion in described step (1), hydrogenation catalyst is selected from load on a catalyst or the cobalt catalyst of catalyzed agent carrier dispersion in described step (1), described catalyzer is also containing tin, wherein cobalt metal content accounts for the 10wt% ~ 50wt% of overall catalyst weight, wherein cobalt metal content accounts for the 10wt% ~ 50wt% of overall catalyst weight, and tin metal accounts for the 10wt% ~ 40wt% of overall catalyst weight.
Hydrogenation catalyst is selected from load on a catalyst or the cobalt catalyst of catalyzed agent carrier dispersion in described step (1), hydrogenation catalyst is selected from load on a catalyst or the cobalt catalyst of catalyzed agent carrier dispersion in described step (1), described catalyzer is also containing silver, wherein cobalt metal content accounts for the 10wt% ~ 50wt% of overall catalyst weight, and silver metal accounts for the 0.1wt% ~ 10wt% of overall catalyst weight.
In described step (1), hydrogenation catalyst contains carrier, cobalt element, group vib element, wherein the content of cobalt element accounts for the 15wt% ~ 50wt% of overall catalyst weight, group vib element is selected from least one in molybdenum, tungsten, chromium, its content accounts for the 0.5wt% ~ 15wt% of overall catalyst weight, described carrier is selected from least one of silicon oxide, diatomite, Calucium Silicate powder, zirconium white, titanium oxide, and its content accounts for the 20wt% ~ 80wt% of overall catalyst weight.
Described step (1) hydrogenation catalyst contains carrier, cobalt element, silver element, wherein the content of cobalt element accounts for the 15wt% ~ 50wt% of overall catalyst weight, the content of silver element accounts for the 0.1wt% ~ 10wt% of overall catalyst weight, described carrier is selected from least one of silicon oxide, diatomite, Calucium Silicate powder, zirconium white, titanium oxide, and its content accounts for the 20wt% ~ 80wt% of overall catalyst weight.
In described step (1), hydrogenation catalyst contains carrier, cobalt element, alkali earth metal, IB race element, wherein the content of cobalt element accounts for the 15wt% ~ 50wt% of overall catalyst weight, the content of alkali earth metal accounts for the 1wt% ~ 30wt% of overall catalyst weight, the content of IB race element accounts for the 0.1wt% ~ 15.0wt% of overall catalyst weight, described carrier is oxide compound, and its content accounts for the 10wt% ~ 80wt% of overall catalyst weight.
In described step (1), hydrogenation catalyst is selected from silicon dioxide carried platinum-tin catalyst, activated carbon supported palladium-rhenium catalyst a kind of.
Hydrogenation catalyst is one in the patent of Sinopec Beijing Chemical Research Institute application or combination in described step (1), and concrete patent is: CN201210429219.4, CN201210429218.X, CN201210429995.4, CN201210429959.8, CN201210429785.5, CN201210430033.0, CN201210429960.0, CN201210429958.3, CN201210428055.3, CN201210429720.0, CN201210428802.3.
In addition, the catalyzer being applicable to acetic acid preparation of ethanol by hydrogenating before use can through any-mode modification.Such as, utilize expanding agent or hydrothermal treatment consists mode to regulate the pore structure of carrier to improve selectivity of catalyst and stability; And for example, by adding certain metallic compound and regulate the acid-basicity of carrier to improve catalyst activity preparing carrier process; And for example, by adding certain metal in the carrier as the stability to improve catalyzer such as lanthanum, this effectively can improve catalyst life; Further, regulate its surperficial special property to reduce some compound in the deposition of catalyst surface or the loss of active ingredient with the extending catalyst life-span by carrying out surface silicon alkylation or aluminium alkylation process to catalyzer.
For those skilled in the art, can gain enlightenment according to above detailed description in detail thus various change is made to support of the catalyst of the present invention and preparation method.Such as, any known hydrogenation catalyst, support of the catalyst or modified support of the catalyst can be adopted.
In the inventive solutions, described gas phase hydrogenation reaction device can be the useful form of fixed bed form or other Dichlorodiphenyl Acetate hydrogenation techniques.The processing condition of gas phase hydrogenation reaction, without particular requirement, can regulate according to acetic acid transformation efficiency and ethanol yield.For example, hydrogenation reaction is carried out at ambient pressure, and temperature of reaction is 200 DEG C ~ 350 DEG C, and the liquid phase feeding volume space velocity of acetic acid is 0.05 ~ 0.5h
-1.Acetic acid hydrogenation also can carry out under elevated pressure, and such as, the processing condition of acetic acid hydrogenation are: the liquid phase feeding volume space velocity of acetic acid is 0.05 ~ 1.5h
-1, the mol ratio of hydrogen and acetic acid is 5 ~ 30:1, and temperature of reaction is 80 DEG C ~ 150 DEG C, and reaction pressure is 3.0 to 9.0MPa.Described liquid phase feeding volume space velocity refers to that the flow of acetic acid is according to percent by volume during acetic acid charging, the ratio of the feed volume in the unit time and the volume of catalyzer.The liquid phase feeding volume space velocity of acetic acid affects the treatment capacity of reactor, and affects composition and the content thereof of reaction product.
After gas phase hydrogenation reaction device, liquid-phase product A reclaims heat and cooling through heat exchange, then carries out gas-liquid separation, and gas recycles through compressor, more suitably fills into some fresh hydrogen, and liquid enters follow-up separation phase.
Although present invention uses very highly active catalyzer, reacting coarse product also has a certain amount of unreacted acetic acid to exist, this may be in industrial implementation process, solid phase needs of the present invention exist with certain particle diameter (1 ~ 8mm), because reactor exists many imperfect mobility status, short circuit as everyone knows, channel, dead angle etc., Another reason is exactly that catalyzer can exist activity decrease at last stage reaction.
The present invention is by after described high activated catalyst, and the acetic acid content of hydrogenator outlet controls, within 2wt%, to be optimized for 1.5wt%, and situation about more optimizing is 1wt%.
Acetic acid content has important effect for the product quality of ethanol, and as acid number in industrial alcohol CNS can not more than 10mg/L, in alcohol fuel Chinese national standard, acid number is no more than 56mg/L, and it is necessary for therefore removing acetic acid in thick product.Acetic acid removes mainly through the mode of rectifying by prior art, and the second alcohol and water accounting for the quality product overwhelming majority needs by vaporization, and therefore the energy consumption of rectifying depickling is high, and the size of extracting tower is comparatively large and material requires higher, and cost of investment is high; And in the rectifying separation of reality, the situation that tower top exists denier acetic acid may be there is, and all have strict demand to acidity as alcohol fuel and industrial alcohol product, therefore in the situations such as operation fluctuation, cause product defective.Acidity value is the main measurement index of alcohol product, particularly when being applied in alcohol fuel, the acetic acid of denier will make the erosion rate of engine and oil circuit double, and to a certain degree can affect the stability of oil product, therefore causes oil quality to decline.
The present inventor finds that the control of neutralization reactor is extremely important for the separation of subsequent product, is one of successful important control parameter of the present invention, and control neutralization reactor PH 8.0 ~ 11.0, the value more optimized is 8.5 ~ 10.
For the alkaline matter of neutralization, can be selected from the one in volatile salt, bicarbonate of ammonia, ammoniacal liquor, caustic soda, sodium carbonate, sodium bicarbonate, potassium hydroxide, calcium hydroxide, preferred alkali is the aqueous solution of caustic soda.
The position of neutralization reactor is selected effect of the present invention to be important, the position of application claims is that contriver is through test of meticulously deriving, through material test, the present inventor finds that the material corrosion speed after neutralization significantly reduces, can lower than 0.01mm/a at common carbon steel material medium-rate, product color is limpid, if and not by material acetic acid neutralization, find the material needing to use higher level, even so, still there is certain color in tower reactor product, therefore facility investment can be reduced before neutralization reactor is placed on rectifying tower, and tower bottoms body colour degree is reduced.
As everyone knows, the present inventor is found by the test on small-sized rectification process device, (as ASPEN software simulation) Theoretical Calculation can realize acetic acid when being separated completely, test-results shows that the acid content in alcohol product is higher, in many times test, acidity value overwhelming majority situation is above the requirement of product Chinese national standard, and acidity value is substantially all at about 10 ~ 100mg/L.
The acetic acid control of export of trace is not by means of only the selection of high activated catalyst, combination for reactor and reactor also has requirement, preferred mode is more than one or two calandria type fixed bed reactor, autothermal reactor and tower reactor, the preferred combination with autothermal reactor and shell and tube reactor, and there is temperature in difference.
Due in acetic acid and alkali and after, the loss of acetic acid material can be caused, obviously this is that contriver is unwilling to see, therefore the present invention adds an esterifier after hydrogenator, acetic acid is converted into vinyl acetic monomer, because vinyl acetic monomer is can loop back reactor to be hydrogenated to ethanol in the method for the invention.The present inventor is by finding after careful investigation, and the coupling of gas-liquid separation and esterifier can greatly reduce.After gas-liquid separation, the crude product of condensation is some or all of passes through an esterifier, and the temperature of esterifier controls to be 80 ~ 130 DEG C, the design optimization adiabatic reactor reactor of esterifier.Described middle esterifier is filled with esterifying catalyst, and described esterifying catalyst is selected from the one in ion exchange resin, molecular sieve, aluminum oxide, super acids.Preferred esterifying catalyst is strong acidic ion resin and super acids, as the A-15 etc. that Rhom and Hass of the U.S. produces.The mode optimized is, after gas phase hydrogenation reaction device, obtain coarse ethanol product and be first cooled to 60 ~ 130 DEG C, then through one-level gas-liquid separation, esterifier in the middle of the liquid phase after being separated is sent into, gas phase is cooled further with gas-liquid separation after send into product purification.Farthest material consumption can be reduced in conjunction with the mode of ester reactor by described secondary gas-liquid separator.
The present invention also invents extraction part mixed solvent in the process being included in rectifying, described mixed solvent comprises ethanol, vinyl acetic monomer and water, wherein the mass ratio of ethanol and vinyl acetic monomer is 1:0.05 ~ 1.1, be preferably 1:0.1 ~ 0.9, water-content is 1 ~ 15wt%, be more preferably 1 ~ 7wt%, acidity value is 0 ~ 30mg/L, 0 ~ 5mg/L in optimization situation.This part solvent can as the generation raw material of vinyl acetic monomer (another kind of Conventional solvents), directly can also use in all cases as low-toxic solvent, because solvability is close with boiling point, therefore it replaces the purposes of acetates etc., and this solvent phase is ultralow acidity for the feature of traditional vinyl acetic monomer.Through overtesting and in conjunction with the checking of analog calculation, the extraction of this partial solvent in the Gross Output economic benefit situation not affecting device, can greatly reduce energy consumption and the material consumption level of device.
In embodiments of the present invention, those skilled in the art can carry out the use of appropriate selection gas-liquid separator and esterifier according to the ratio of each component in the gas phase hydrogenation reaction crude product of factory's reality, and the various technology enlightenments that also can provide according to the present invention are modified to technical scheme of the present invention.
Compared with the conventional method, the inventive method can reduce the acetic acid content in product effectively, and this not only contributes to the quality improving final alcohol product, and effectively can also reduce the energy consumption of subsequent separation process.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention, wherein
R101: gas phase hydrogenation reaction device
E101: condenser
V101: gas-liquid separator
E102: condenser
R102: esterifier
R103: neutralization reactor
E103: water cooler
V201: gas-liquid separator
V202: gas-liquid separator
R201: neutralization reactor
T201: the first rectifying tower
T202: Second distillation column
T203: the three rectifying tower
Embodiment
Following examples describe the present invention's citing specifically, but the present invention is not limited to these embodiments.In the present embodiment, concrete schema is as shown in annex map 1.
First by acetic acid raw material, return material and hydrogen pre-thermosetting steam feed stream, being incorporated into by described steam feed stream is equipped with in the reactor R101 of gas phase hydrogenation catalyzer, the catalyzer of acetic acid gas phase hydrogenation is the acetic acid hydrogenation catalyzer that Beijing Chemical Research Institute produces, (1) cobalt, wherein cobalt metal content accounts for the 18wt% of overall catalyst weight; (2) molybdenum and tin, accounts for 3wt% and 34wt% of overall catalyst weight respectively; (3) boron and bismuth, accounts for 2wt% and 5wt% of overall catalyst weight respectively, and surplus is silicon-dioxide.Acetic acid is hydrogenated into crude ethanol product.The processing condition of acetic acid gas phase hydrogenation are: the liquid phase volume air speed of acetic acid is 0.80h
-1, the mol ratio of hydrogen and acetic acid is 20:1, and temperature of reaction is 220 DEG C, and reaction pressure is 4.5MPa.Removing noncondensable gas (hydrogen, CO, CO2, CH4, C2H6) outer ethanol content in thick product after hydrogenation is 62.6wt%, vinyl acetic monomer 6wt%, acetic acid 1.0wt%, water 30wt%, and surplus is acetaldehyde, ether and butanols.Subsequently the mixture from hydrogenator R101 is cooled to 80 ~ 84 DEG C in E101.By the gas-liquid separation in V101 of condensed material, liquid phase after separation enters esterification R102 (temperature in 79 ~ 84 DEG C), be separated the gas phase obtained containing hydrogen and enter E102 continuation cooling, wherein liquid phase and gas phase mass ratio are about about 6.1 ~ 6.3:1.Esterifying catalyst in esterifier R102 is that Beijing chemical research research institute generates macropore strong acid polystyrene cationic ion resin, particle diameter ~ 1mm.Return hydrogenator at the cooled gas phase portion of E102, liquid phase enters neutralization reactor R103, and wherein in liquid phase, acetic acid content is 91wtppm.
Be 0.25wt% at the acetic acid content of R102 exit liquid phase, this liquid phase is cooled to 20 DEG C of laggard row gas-liquid separations through supercooler E103, gas phase portion returns hydrogenator, liquid phase enters in neutralization reactor, neutralization reactor is tubular reactor, mean residence time is 18min, and the alkali of employing is the caustic soda aqueous solution of 30wt%, and after neutralization, outlet liquid phase P H value is about 8.8 ~ 9.0.
Liquid-phase product after neutralization is delivered to the first rectifying tower T201, this rectifying tower is tray column, and composition of tower shell material is plain carbon stool material, and the first overhead fraction and tower bottom distillate mass ratio are 2.5:100, wherein overhead fraction ethanol massfraction is 31.5wt%, and in tower reactor cut, acetaldehyde is 2wtppm.70wt% in first overhead fraction is returned hydrogenator.
First tower reactor cut is sent into Second distillation column, this rectifying tower is packing tower, composition of tower shell material is plain carbon stool, second overhead fraction and tower bottom distillate mass ratio are 5:100, extraction water is 1:100 with entering the first tower reactor cut mass ratio, in overhead fraction, ethanol massfraction is 85wt%, water-content 8wt%, and acid number is 2mg/L.Second overhead fraction all as solvent extraction, water-content 1.8wt% in this solvent, ethanol content 78wt%, vinyl acetic monomer content 20.2wt%.Vinyl acetic monomer content 8wtppm in second tower reactor cut, color is limpid.
Second tower reactor cut is sent in the 3rd rectifying tower, this rectifying tower is packing tower, composition of tower shell material is plain carbon stool, the 3rd tower bottom distillate and the 3rd overhead fraction is separated into by the 3rd rectifying tower, wherein tower reactor cut delivers to wastewater treatment, in 3rd overhead fraction, water-content is 8.8wt%, and after titration, acidity value is 1.5mg/L, and indices all meets the requirement of industrial alcohol Chinese Industrial Standards (CIS).
After second overhead fraction being delivered to the dehydration of molecular sieve tower, water-content is 0.15wt%, and all the other indices all meet the requirement of alcohol fuel Chinese Industrial Standards (CIS).
Claims (12)
1. acetic acid hydrogenation produces a method for ethanol, comprises the following steps:
(1) gas phase hydrogenation: form steam feed stream by after acetic acid raw material and hydrogen preheating, is incorporated into described steam feed stream in the reactor that hydrogenation catalyst is housed and carries out hydrogenation reaction;
(2) gas-liquid separation: hydrogenation reaction thing condensation step 1 obtained, in gas-liquid separator after gas-liquid separation, obtains gaseous products A and liquid-phase product A, gaseous products A and loops back gas phase hydrogenation reaction device at least partly and use;
(3) esterification: after the liquid-phase product A in step 2 is carried out esterification in the esterifier that esterifying catalyst is housed, loops back gas phase hydrogenation reaction device at least partly after obtaining gaseous products B and liquid-phase product B, gaseous products B cooling and uses;
(4) product purification: liquid-phase product B is delivered to neutralization reactor, add alkaline matter and carry out neutralization reaction, product introduction first rectifying tower after neutralization, first overhead fraction contains acetaldehyde, vinyl acetic monomer, acetone, first tower bottom distillate is the coarse ethanol product containing ethanol, water, first overhead fraction part returns in gas phase hydrogenation reaction device, and the first tower bottom distillate is delivered to Second distillation column; Second overhead fraction contains ethanol, water, the second described overhead fraction part returns in hydrogenator, part is as the extraction of mixed type solvent product, described mixed type solvent comprises ethanol, vinyl acetic monomer and water, wherein the mass ratio of ethanol and vinyl acetic monomer is 1:0.05 ~ 1.1, water-content is 1 ~ 15wt%, acidity value 0 ~ 30mg/L; Second tower bottom distillate contains water, acetate and butanols; Second tower bottom distillate is delivered to the 3rd rectifying tower, be separated into the 3rd tower bottom distillate of moisture, acetate and butanols and the 3rd overhead fraction containing second alcohol and water, ethanol content 85 ~ 95wt%, acidity value 0 ~ 25mg/L in the 3rd described overhead fraction.
2. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that the PH of described neutralization reactor is 8.0 ~ 11.0.
3. a kind of acetic acid hydrogenation according to claim 2 produces the method for ethanol, it is characterized in that the PH of described neutralization reactor is 8.5 ~ 10.
4. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, and the alkaline matter that it is characterized in that in step (4) is selected from the one in volatile salt, bicarbonate of ammonia, ammoniacal liquor, caustic soda, sodium carbonate, sodium bicarbonate, potassium hydroxide, calcium hydroxide.
5. a kind of acetic acid hydrogenation according to claim 4 produces the method for ethanol, it is characterized in that the alkaline matter in step (4) is selected from the aqueous solution of caustic soda.
6. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that the acetic acid content in the liquid-phase product A that step (2) gas-liquid separation obtains is less than 0 ~ 2wt%, vinyl acetic monomer content 0 ~ 8wt%.
7. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that hydrogenator is more than one or two calandria type fixed bed reactor, autothermal reactor and tower reactor.
8. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that the temperature of described esterification is 80 ~ 130 DEG C.
9. a kind of acetic acid hydrogenation according to claim 1 produces the method for ethanol, it is characterized in that described esterifying catalyst is selected from the one in ion exchange resin, molecular sieve, aluminum oxide, super acids.
10. a kind of acetic acid hydrogenation according to claim 8 produces the method for ethanol, it is characterized in that described described esterifying catalyst is selected from strong acidic ion resin and super acids.
11. a kind of acetic acid hydrogenation according to claim 1 produce the method for ethanol, and it is characterized in that the reaction pressure of step (1) is 0.5 ~ 5MPa, the mol ratio 10 ~ 40 of hydrogen and acetic acid, the liquid phase feeding volume space velocity of acetic acid is 0.05 ~ 1.5h
-1.
12. a kind of acetic acid hydrogenation according to claim 1 produce the method for ethanol, it is characterized in that after gas phase hydrogenation reaction, obtain liquid-phase product A, first be cooled to 60 ~ 130 DEG C, again through one-level gas-liquid separation, by be separated after liquid phase send in the middle of esterifier, gas phase is cooled further with gas-liquid separation after send into product purification.
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| CN103025690A (en) * | 2010-07-09 | 2013-04-03 | 国际人造丝公司 | Esterification of vapor crude product in the production of alcohols |
| CN103113187A (en) * | 2013-02-19 | 2013-05-22 | 新地能源工程技术有限公司 | Method for producing ethanol and coproducing ethyl acetate with acetic acid |
| CN103785412A (en) * | 2012-10-31 | 2014-05-14 | 中国石油化工股份有限公司 | Carboxylic acid hydrogenation catalyst, preparation method and application thereof |
| CN103785413A (en) * | 2012-10-31 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrogenation catalyst, and preparation method and application thereof |
| US20140275641A1 (en) * | 2013-03-15 | 2014-09-18 | Celanese International Corporation | Ethanol and ethyl acetate production using an acetic acid and acetic anhydride mixed feed |
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2014
- 2014-10-14 CN CN201410541382.9A patent/CN105566059A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103025690A (en) * | 2010-07-09 | 2013-04-03 | 国际人造丝公司 | Esterification of vapor crude product in the production of alcohols |
| CN103785412A (en) * | 2012-10-31 | 2014-05-14 | 中国石油化工股份有限公司 | Carboxylic acid hydrogenation catalyst, preparation method and application thereof |
| CN103785413A (en) * | 2012-10-31 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrogenation catalyst, and preparation method and application thereof |
| CN103113187A (en) * | 2013-02-19 | 2013-05-22 | 新地能源工程技术有限公司 | Method for producing ethanol and coproducing ethyl acetate with acetic acid |
| US20140275641A1 (en) * | 2013-03-15 | 2014-09-18 | Celanese International Corporation | Ethanol and ethyl acetate production using an acetic acid and acetic anhydride mixed feed |
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