CN105566060B - The method of acetic acid preparation of ethanol through hydrogenation - Google Patents
The method of acetic acid preparation of ethanol through hydrogenation Download PDFInfo
- Publication number
- CN105566060B CN105566060B CN201410541401.8A CN201410541401A CN105566060B CN 105566060 B CN105566060 B CN 105566060B CN 201410541401 A CN201410541401 A CN 201410541401A CN 105566060 B CN105566060 B CN 105566060B
- Authority
- CN
- China
- Prior art keywords
- acetic acid
- ethanol
- hydrogenation
- product
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention provides a kind of methods of low energy consumption acetic acid preparation of ethanol through hydrogenation, comprising the following steps: (1) gas phase hydrogenation；(2) gas-liquid separation；(3) esterification；(4) product purification: liquid-phase product B is sent to first rectifying column, first overhead fraction contains acetaldehyde, ethyl acetate, acetone, first tower bottom distillate is the coarse ethanol product containing ethyl alcohol, ethyl acetate and water, and the first overhead fraction part returns in gas phase hydrogenation reaction device；First tower bottom distillate is sent to neutralization reactor, alkaline matter is added and carries out neutralization reaction；First tower bottom distillate after neutralization is sent to second rectifying column, it is separated into the second overhead fraction containing second alcohol and water and the second tower bottom distillate containing water, butanol and acetate, ethanol content is 85~95wt%, 0~25mg/L of acidity value in second overhead fraction.This method can reduce energy consumption, improve the quality of alcohol product.
Description
Technical field
The present invention relates to a kind of methods for producing ethyl alcohol, add hydrogen to prepare Gao Xuan by acetic acid more specifically to a kind of
The method of selecting property alcohol product.
Background technique
Ethyl alcohol be discovery earliest, a kind of main component of the most wide fatty alcohol and wine of purposes.The industry of ethyl alcohol is raw at present
Production method mainly has fermentation method and ethylene hydration method.Ethylene hydration method is the rise along with petrochemical industry and develops, including
Indirect hydration method and direct hydration method.In recent years by the raising of production cost of ethylene, in China, ethylene process is substantially at halt production shape
State.The primary raw material of fermentation method is crops (including corn, sugarcane, sorghum, cassava, paddy etc.), by using in crops
Amylofermentation obtain ethyl alcohol.
The raw material that main ethyl alcohol manufacturing enterprise of China uses is corn, wheat and cassava (relying primarily on import).It is true
On in recent years grain cost sharp rise, therefore there is also strive grain with people with ethyl alcohol.The non-grain ethanol raw material such as cassava, sugar grass
Price is also expected to rise always, and is applied using cellulosic ethanol as two generation ethyl alcohol technology distances of representative and needed to solve there are also more difficulty
Certainly.
Acetic acid is a kind of important industrial chemicals, and the production technology of acetic acid has grain fermentation method, methanol carbonylation, ethylene
Oxidizing process, oxidation of ethanol method, acetaldehyde oxidation and ethane oxidation method etc..
Acetic acid consumption in the past 10 years is still concentrated mainly on traditional field, and there is no significant changes for consumption structure, without shape
The demand growth point of Cheng Xin supports newly-increased production capacity.It is expected that China's acetic acid demand in 2012 is less than 4,800,000 tons or so, production capacity mistake
Surplus outstanding problem, or even stop production after there is new equipment driving.Therefore the downstream use exploitation of acetic acid is extremely urgent.
Use acetic acid as the approach of raw material production alcohol product including two kinds, first is that acetic acid generates acetate through esterification,
Then acetate is hydrogenated to ethyl alcohol, then carries out refined raw producing and ethanol product；Second is that acetic acid direct hydrogenation generates ethyl alcohol, then through essence
Process processed produces alcohol product.First method has had more esterification process compared to second method, and a large amount of ethyl alcohol needs follow
Ring has increase accordingly the size and energy consumption, at least portion of the size of hydrogenator and its heat exchanger of front and back as esterification feed
Point subtractive process, which is also put, to be twice, its advantage is that the corrosion strength of hydrogenation process may be lower, but during it also or mostly or
There are acetic acid less, and there are still corrosivity.But the key of second method is to develop the catalyst of acetic acid direct hydrogenation,
The reason of this problem is also the method that many researchers select the first acetic acid through being esterified repeated hydrogenation.
For acetic acid direct hydrogenation, researcher and research data there are many, such as Sinopec, Celanese company of the U.S.
Hydrogen is added to have submitted a large amount of patent applications Deng with regard to acetic acid.Such as PCT application enters the CN102414153A of National Phase in China, it is open
Acetic acid is hydrogenated into crude ethanol product first, then isolates unreacted acetic acid in first tower, by first tower
Distillate isolates the second distillate containing ethyl acetate in second tower, obtains the second residue of the alcohol and water containing second, the
Two residues are separated into distillate and aqueous residue containing ethyl alcohol in third tower.Additionally or alternatively, second is evaporated
Object is sent to the 4th tower out, is separated into the 4th distillate and the 4th residue containing acetaldehyde, then the 4th distillate is returned and is reacted
To improve ethanol yield, the 4th residue is used as solvent or is used in ester production system.In these patents, acetic acid generally passes through
The mode of rectifying removes first, can thus reduce material requirement in later separation, thus realize the reduction of cost of investment, but
It is that there is also some problems in this way: accounts for the most of second alcohol and water of product quality and need through vaporization, therefore rectifying depickling
Energy consumption it is high, and extracting tower size is larger and material is more demanding, cost of investment is high；And in the rectifying of reality point
From in, it is understood that there may be tower top the case where there are denier acetic acid, and be all to acidity as alcohol fuel and industrial alcohol product
There is strict demand, therefore causes product unqualified when operating fluctuation.
The present invention proposes that a kind of acetic acid direct hydrogenation with low energy consumption and low material consumption level is the method for ethyl alcohol, the present invention
People is by a large amount of careful researchs, and this method reduce material consumption level and costs of investment for discovery.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of low energy consumption acetic acid preparation of ethanol through hydrogenation, this method energy
Energy consumption is enough reduced, the quality of alcohol product is improved.
A kind of method of acetic acid preparation of ethanol through hydrogenation of the present invention, comprising the following steps:
(1) gas phase hydrogenation: steam feed stream will be formed after acetic acid raw material and hydrogen preheating, the steam feed stream is introduced
Hydrogenation reaction is carried out into the reactor equipped with hydrogenation catalyst；
(2) gas-liquid separation: the hydrogenation reaction object that step 1 is obtained condenses, and in gas-liquid separator after gas-liquid separation, obtains
Gas phase hydrogenation reaction device is at least partly recycled back to gaseous products A and liquid-phase product A, gaseous products A to use；
(3) the liquid-phase product A in step 2 esterification: is subjected to ester in the esterifier equipped with esterification catalyst
After changing reaction, gaseous products B and liquid-phase product B are obtained, is at least partly recycled back to gas phase hydrogenation reaction device after gaseous products B is cooling
It uses；
(4) product purification: liquid-phase product B is sent to first rectifying column, the first overhead fraction contain acetaldehyde, ethyl acetate,
Acetone, the first tower bottom distillate are the coarse ethanol product containing ethyl alcohol, ethyl acetate and water, and the first overhead fraction part returns to gas phase
In hydrogenator；First tower bottom distillate is sent to neutralization reactor, alkaline matter is added and carries out neutralization reaction；After neutralizing
First tower bottom distillate send and be separated into the second overhead fraction containing second alcohol and water to second rectifying column and containing water, fourth
Second tower bottom distillate of pure and mild acetate, ethanol content is 85~95wt% in second overhead fraction, acidity value 0~
25mg/L。
Specific technical solution is as follows:
The reaction pressure of gas phase hydrogenation reaction is 0.5~5MPa, the molar ratio 10~40 of hydrogen and acetic acid, by acetic acid plus hydrogen
At the crude ethanol product containing water, ethyl acetate, acetaldehyde, acetone, butanol and acetic acid.
The acetic acid content in liquid-phase product A that gas-liquid separation obtains is less than 0~2wt%, 0~8wt% of ethyl acetate content.
Ethyl acetate content is 0~0.1wt% in first tower bottom distillate during product purification；
Acetic acid gas phase hydrogenation catalyst is selected from load on a catalyst or by catalyst carrier point in the step (1)
The catalyst of scattered at least one metal active constituent.The metal active constituent be selected from IB, IIB of the periodic table of elements, IIIB,
IVB, VB, VIB, VIIB, Group VIIIB, lanthanide series metal and IIIA, IVA, VA, in Group VIA metal one or two with
On combination.It is furthermore preferred that acetic acid gas phase hydrogenation catalyst is load cobalt series catalyst, molybdenum series catalyst or expensive in (1)
One or more of metallic catalyst.More specifically, the hydrogenation catalyst is selected from following:
The cobalt that hydrogenation catalyst is selected from that load disperses on a catalyst or by catalyst carrier in the step (1) is catalyzed
Agent, wherein cobalt tenor accounts for 15wt%~45wt% of overall catalyst weight, the catalyst also containing the noble metal of trace,
Wherein the trace noble metal is selected from one of palladium, platinum and rhenium or a variety of, and the ratio of weight and cobalt weight metal is 1:
100~1:300.
The cobalt that hydrogenation catalyst is selected from that load disperses on a catalyst or by catalyst carrier in the step (1) is catalyzed
Agent, hydrogenation catalyst is selected from the Co catalysts that load disperses on a catalyst or by catalyst carrier in the step (1), described
Catalyst also contain boron, wherein cobalt tenor accounts for 10wt%~50wt% of overall catalyst weight, and boron accounts for overall catalyst weight
1.0wt%~10wt%；
The cobalt that hydrogenation catalyst is selected from that load disperses on a catalyst or by catalyst carrier in the step (1) is catalyzed
Agent, hydrogenation catalyst is selected from the Co catalysts that load disperses on a catalyst or by catalyst carrier in the step (1), described
Catalyst also contain bismuth, wherein cobalt tenor accounts for 10wt%~50wt% of overall catalyst weight, and wherein cobalt tenor accounts for
10wt%~50wt% of overall catalyst weight, bismuth metal account for 0.1wt%~50wt% of overall catalyst weight；
The cobalt that hydrogenation catalyst is selected from that load disperses on a catalyst or by catalyst carrier in the step (1) is catalyzed
Agent, hydrogenation catalyst is selected from the Co catalysts that load disperses on a catalyst or by catalyst carrier in the step (1), described
Catalyst also contain tin, wherein cobalt tenor accounts for 10wt%~50wt% of overall catalyst weight, and wherein cobalt tenor accounts for
10wt%~50wt% of overall catalyst weight, tin metal account for 10wt%~40wt% of overall catalyst weight.
The cobalt that hydrogenation catalyst is selected from that load disperses on a catalyst or by catalyst carrier in the step (1) is catalyzed
Agent, hydrogenation catalyst is selected from the Co catalysts that load disperses on a catalyst or by catalyst carrier in the step (1), described
Catalyst also contain silver, wherein cobalt tenor accounts for 10wt%~50wt% of overall catalyst weight, and it is total that silver metal accounts for catalyst
0.1wt%~10wt% of weight.
Hydrogenation catalyst contains carrier, cobalt element, group vib element in the step (1), and wherein the content of cobalt element, which accounts for, urges
15wt%~50wt% of agent gross weight, group vib element are selected from least one of molybdenum, tungsten, chromium, and content accounts for overall catalyst weight
0.5wt%~15wt%, the carrier be selected from silica, diatomite, calcium silicates, zirconium oxide, titanium oxide at least one,
Its content accounts for 20wt%~80wt% of overall catalyst weight.
Step (1) hydrogenation catalyst contains carrier, cobalt element, silver element, and wherein the content of cobalt element accounts for catalyst
15wt%~50wt% of gross weight, the content of silver element account for 0.1wt%~10wt% of overall catalyst weight, and the carrier is selected from
At least one of silica, diatomite, calcium silicates, zirconium oxide, titanium oxide, content account for the 20wt% of overall catalyst weight~
80wt%.
Hydrogenation catalyst contains carrier, cobalt element, alkali earth metal, IB race element in the step (1), wherein cobalt member
The content of element accounts for 15wt%~50wt% of overall catalyst weight, the content of alkali earth metal account for the 1wt% of overall catalyst weight~
The content of 30wt%, IB race element accounts for 0.1wt%~15.0wt% of overall catalyst weight, and the carrier is oxide, contains
Amount accounts for 10wt%~80wt% of overall catalyst weight.
Hydrogenation catalyst is selected from silicon dioxide carried platinum-tin catalyst, activated carbon supported palladium-in the step (1)
It is a kind of in rhenium catalyst.
In the step (1) hydrogenation catalyst be the application of Sinopec Beijing Chemical Research Institute one of patent or
Combination, specific patent are as follows: CN 201210429219.4, CN201210429218.X, CN201210429995.4,
CN201210429959.8、CN201210429785.5、CN201210430033.0、CN201210429960.0、
CN201210429958.3、CN201210428055.3、CN201210429720.0、CN201210428802.3。
In addition, the catalyst for being suitable for acetic acid preparation of ethanol by hydrogenating can be modified through any way before use.For example, using expanding
Hole agent or hydro-thermal process mode adjust the pore structure of carrier to improve the selectivity and stability of catalyst；For another example, by
It prepares carrier process and certain metallic compound is added to adjust the acid-base property of carrier to improve catalyst activity；For another example, by carrying
The stability that certain metal improves catalyst as lanthanum etc. is added in body, this can effectively improve catalyst life；In addition, can by pair
Catalyst carries out surface silicon alkylation or aluminium alkylation processing adjusts its surface special nature and urging to reduce certain compounds
The loss of the deposition or active component on agent surface is to extend catalyst life.
For those skilled in the art, can gain enlightenment according to being discussed in detail above to catalysis of the invention
Agent carrier and preparation method do various changes.For example, any of hydrogenation catalyst, catalyst carrier or modified can be used
Catalyst carrier.
In the inventive solutions, the gas phase hydrogenation reaction device can be fixed bed form or other Dichlorodiphenyl Acetates add
The useful form of hydrogen technique.The process conditions of gas phase hydrogenation reaction, can be according to acetic acid conversion ratio and ethanol yield without particular/special requirement
It is adjusted.For example, hydrogenation reaction carries out under normal pressure, and reaction temperature is 200 DEG C~350 DEG C, the liquid phase feeding of acetic acid
Volume space velocity is 0.05~0.5h-1.Acetic acid adds hydrogen that can also carry out under elevated pressure, for example, acetic acid adds the process conditions of hydrogen are as follows: vinegar
The liquid phase feeding volume space velocity of acid is 0.05~1.5h-1, the molar ratio of hydrogen and acetic acid is 5~30:1, and reaction temperature is 80 DEG C
~150 DEG C, reaction pressure is 3.0 to 9.0MPa.The liquid phase feeding volume space velocity refers to that the flow of acetic acid is fed according to acetic acid
When percent by volume, the ratio between the volume of feed volume and catalyst in the unit time.The liquid phase feeding volume space velocity of acetic acid
The treating capacity of reactor is affected, and influences the composition and its content of reaction product.
After gas phase hydrogenation reaction device, liquid-phase product A is by heat exchange recycling heat and cooling, then carries out gas-liquid separation, gas
Body is used through compressor cycle, then suitably fills into some fresh hydrogen, and liquid enters subsequent separation phase.
Although there are also a certain amount of unreacted acetic acid for reacting coarse product present invention uses the catalyst of very high activity
In the presence of this may be during industrial implementation, and solid phase needs of the invention exist with certain partial size (1~8mm), due to anti-
Answer device there are many non-ideal mobility status, short circuit, channel, dead angle as everyone knows etc., Another reason is exactly catalyst
There can be activity decline in last stage reaction.
The present invention pass through the high activated catalyst after, hydrogenator outlet acetic acid content control 2wt% with
It is interior, it is optimized for 1.5wt%, more optimized situation is 1wt%.
Acetic acid content has important role for the product quality of ethyl alcohol, such as acid value in industrial alcohol chinese national standard
No more than 10mg/L, acid value is no more than 56mg/L in alcohol fuel Chinese national standard, therefore it is necessary for removing acetic acid in crude product
's.The prior art is mainly removed acetic acid by way of rectifying, is accounted for the most of second alcohol and water needs of product quality and is passed through
Vaporization, therefore the energy consumption of rectifying depickling is high, and the size of extracting tower is larger more demanding with material, cost of investment is high；
And in the rectifying of reality separation, it is understood that there may be tower top the case where there are denier acetic acid, and as alcohol fuel and industry
Alcohol product is all to have strict demand to acidity, therefore cause product unqualified when operating fluctuation.Acidity value is
The main measurement index of alcohol product, especially when being applied in alcohol fuel, the acetic acid of denier will make engine
Doubled with the corrosion rate of oil circuit, and can also a degree of stability for influencing oil product, therefore oil quality is caused to decline.
The inventors discovered that the control of neutralization reactor is extremely important for the separation of subsequent product, it is of the invention successful
One of important control parameter, for control neutralization reactor PH 8.0~11.0, more optimized value is 8.5~10.
For the alkaline matter of neutralization, ammonium carbonate, ammonium hydrogen carbonate, ammonium hydroxide, caustic soda, sodium carbonate, bicarbonate can be selected from
One of sodium, potassium hydroxide, calcium hydroxide, preferred alkali are the aqueous solution of caustic soda.
Neutralization reactor position selection effect of the invention is important, the present invention claims position be inventor warp
It crosses and derives test meticulously, by material test, the inventors discovered that the material corrosion rate after neutralizing is greatly reduced,
0.01mm/a can be lower than in common carbon steel material medium-rate, product color is limpid, and if will not be in the acetic acid in material
With discovery needs material using higher level, and even so, tower reactor product still has certain color, therefore neutralizes anti-
Equipment investment can be reduced before answering device to be disposed close to the rectifying column of reactor as best one can, and tower reactor liquid color degree is dropped
It is low.
Meanwhile the present invention, by carefully investigating discovery, the addition of the alkali acetate that alkali is formed with acetic acid in other words is to micro-
The separation of amount component is of great significance, therefore the selection of neutralization reactor position also resides in the quality meaning of product
This: the inventors discovered that, acetate in the liquid phase in the presence of will affect the separation of acetaldehyde, although inventor is not desired to be limited by theory
System, but this may be to occur since the presence of salt changes the relative volatility of acetaldehyde so as to cause as the acetaldehyde of light component
In the tower reactor liquid phase that it is theoretically not in, the present inventor has found in experimental test, and the presence of acetate can make
The acetaldehyde of tower reactor is more than 100wtppm, it is well known that the content of aldehyde has a major impact the quality of alcohol, and aldehyde few as far as possible has
Conducive to the use of ethyl alcohol in all fields, including alcohol fuel, industrial alcohol, daily aspect etc..
It is well known that the present inventor is had found by the test on small-sized rectification process device, in (such as ASPEN software mould
It is quasi-) it can be achieved in theoretical calculation in the case of acetic acid is kept completely separate, test result shows that the acid content in alcohol product is higher,
Many times in test, acidity value overwhelming majority situation more than product Chinese national standard requirement, acidity value substantially all 10~
100mg/L or so.
Micro acetic acid control of export not only passes through the selection of high activated catalyst, the combination for reactor and reactor
Also it requires, preferred mode is one or two or more calandria type fixed bed reactor, self-heating reactor and tower anti-
Device is answered, the preferred combination with self-heating reactor and shell and tube reactor, and have inlet temperature poor.
After acetic acid neutralization with alkali, the loss of acetic acid material will lead to, it is clear that this is that inventor is unwilling to see, because
This present invention increases an esterifier after hydrogenator, ethyl acetate is converted by acetic acid, due to ethyl acetate
It is that can be recycled back to reactor to be hydrogenated to ethyl alcohol in the method for the invention.The present inventor by being found after careful investigation,
Gas-liquid separation and the matching of esterifier can greatly reduce.After gas-liquid separation, the crude product part of condensation or complete
Portion is by an esterifier, and the temperature control of esterifier is 80~130 DEG C, and the design optimization of esterifier is insulated
Bed reactor.The intermediate esterifier is filled with esterification catalyst, and the esterification catalyst is selected from ion exchange resin, divides
One of sub- sieve, aluminium oxide, super acids.Preferred esterification catalyst is strong acidic ion resin and super acids, such as U.S.
The A-15 etc. of Rhom and Hass's production.The mode of optimization is, after gas phase hydrogenation reaction device, obtains coarse ethanol product and first cools down
To 60~130 DEG C, using level-one gas-liquid separation, the liquid phase after separation is sent into intermediate esterifier, gas phase is further
Product purification is sent into after cooling and gas-liquid separation.It can be most by way of the second level gas-liquid separator combination ester reactor
The reduction material consumption of big degree.
In the present invention is implemented, those skilled in the art can be according to the actual gas phase hydrogenation reaction crude product of factory
In each component ratio come it is appropriate selection gas-liquid separator and esterifier use, can also provide according to the present invention
Various technical inspirations modify to technical solution of the present invention.
Compared with the conventional method, the method for the present invention can be effectively reduced the acetic acid content in product, this, which is not only helped, mentions
The quality of high final alcohol product, and the energy consumption of subsequent separation process can also be effectively reduced.
Detailed description of the invention
Fig. 1 is process flow chart of the invention, wherein
R101: gas phase hydrogenation reaction device
E101: condenser
V101: gas-liquid separator
E102: condenser
R102: esterifier
T201: first rectifying column
T202: Second distillation column
R201: neutralization reactor
Specific embodiment
Following embodiment is to describe to more detailed citing of the invention, but the invention is not limited to these embodiments.
In the present embodiment, specific flow chart is as shown in annex map 1.
First by acetic acid raw material, return material and the pre- thermosetting steam feed stream of hydrogen, the steam feed stream is introduced
Into the reactor R101 equipped with gas phase hydrogenation catalyst, the catalyst of acetic acid gas phase hydrogenation is Beijing Chemical Research Institute's production
Acetic acid hydrogenation catalyst, catalyst contain: (1) cobalt, wherein cobalt tenor accounts for the 18wt% of overall catalyst weight；(2) molybdenum and tin,
The 3wt% and 34wt% of overall catalyst weight are accounted for respectively；(3) boron and bismuth account for the 2wt% and 5wt% of overall catalyst weight, surplus respectively
For silica.The catalyst passes through ball milling-coprecipitation preparation.Acetic acid is hydrogenated into crude ethanol product.
The process conditions of acetic acid gas phase hydrogenation are as follows: the liquid phase volume air speed of acetic acid is 0.80h-1, mole of hydrogen and acetic acid
Than for 20:1, reaction temperature is 220 DEG C, reaction pressure 4.5MPa.In crude product after adding hydrogen remove on-condensible gas (hydrogen,
CO, CO2, CH4, C2H6) outer ethanol content is 62.6wt%, ethyl acetate 6wt%, acetic acid 1.0wt%, water 30wt%, surplus
For acetaldehyde, ether and butanol.The mixed material from hydrogenator R101 is then cooled to 80~84 DEG C in E101.It will
The gas-liquid separation in V101 of condensed material, the liquid phase after separation enter esterification R102 (79~84 DEG C of inlet temperature), separation
It obtains the gas phase containing hydrogen and enters E102 continuing to cool down, wherein liquid phase and gas phase mass ratio are about 6.1~6.3:1 or so.Ester
Change reactor R102 in esterification catalyst be Beijing chemical research research institute generate macropore strong acid polystyrene cation from
Subtree rouge, partial size~1mm.Hydrogenator is returned in E102 gas phase portion after cooling, liquid phase enters first rectifying column, wherein
Acetic acid content is 91wtppm in liquid phase.
In the exit R102, the acetic acid content of liquid phase is 0.25wt%, which is cooled to 20 DEG C through subcooler E103
After carry out gas-liquid separation, gas phase portion returns to hydrogenator, and liquid phase enters first rectifying column T201.First rectifying column T201 is
Plate column, composition of tower shell material are ordinary carbon steel material, and extraction water is 7.8:100, the first tower with the first tower reactor fraction mass ratio is entered
Tops and tower bottom distillate mass ratio are that ethyl acetate content is 28wtppm in 8:100 tower reactor fraction.It will be in the first overhead fraction
60wt% return hydrogenator.
The tower bottom distillate of T201 tower is sent into neutralization reactor R201, the tank reactor of use, mean residence time
For 25min, it is 8.8~9.0 or so that the alkali used, which exports liquid phase P H value for the causticity sodium water solution of 30wt%, after neutralization,.
The first tower reactor fraction after neutralization is sent into Second distillation column T202, which is packed tower, and composition of tower shell material is
Ordinary carbon steel is separated into the second tower bottom distillate and the second overhead fraction by Second distillation column, and wherein tower reactor fraction is sent to waste water
It handles, water content is 8.8wt% in the second overhead fraction, and acidity value is 1.5mg/L after titration, and indices meet industrial second
The requirement of alcohol Chinese Industrial Standards (CIS).
Second overhead fraction is sent to the dehydration of molecular sieve tower, water content 0.15wt%, remaining indices meet
The requirement of alcohol fuel Chinese Industrial Standards (CIS).
Claims (11)
1. a kind of method of acetic acid preparation of ethanol through hydrogenation, comprising the following steps:
(1) gas phase hydrogenation: steam feed stream will be formed after acetic acid raw material and hydrogen preheating, the steam feed stream is introduced into dress
Have and carries out hydrogenation reaction in the reactor of hydrogenation catalyst；
(2) gas-liquid separation: the hydrogenation reaction object that step 1 is obtained condenses, and in gas-liquid separator after gas-liquid separation, obtains gas
Phase product A and liquid-phase product A, gaseous products A are at least partly recycled back to the use of gas phase hydrogenation reaction device；
(3) esterification: the liquid-phase product A in step 2 is carried out to be esterified in the esterifier equipped with esterification catalyst anti-
Ying Hou obtains gaseous products B and liquid-phase product B, and being at least partly recycled back to gas phase hydrogenation reaction device after gaseous products B is cooling makes
With；
(4) product purification: liquid-phase product B is sent to first rectifying column, and the first overhead fraction contains acetaldehyde, ethyl acetate, acetone,
First tower bottom distillate is the coarse ethanol product containing ethyl alcohol, ethyl acetate and water, and the first overhead fraction part returns to gas phase hydrogenation
In reactor；First tower bottom distillate is sent to neutralization reactor, alkaline matter is added and carries out neutralization reaction；By after neutralization
One tower bottom distillate send be separated into second rectifying column the second overhead fraction containing second alcohol and water and containing water, butanol and
Second tower bottom distillate of acetate, ethanol content is 85~95wt%, 0~25mg/ of acidity value in second overhead fraction
L；
Liquid-phase product A is obtained after gas phase hydrogenation reaction, is first cooled to 60~130 DEG C, using level-one gas-liquid separation, will be separated
Liquid phase afterwards is sent into intermediate esterifier, will be sent into product purification after gas phase further cooling and gas-liquid separation.
2. a kind of method of acetic acid preparation of ethanol through hydrogenation according to claim 1, it is characterised in that in the step (4)
Ethyl acetate content is 0~0.1wt% in first tower bottom distillate, and the PH of neutralization reactor is 8.0~11.
3. a kind of method of acetic acid preparation of ethanol through hydrogenation according to claim 1, it is characterised in that the neutralization reaction
The PH of device is 8.5~10.
4. a kind of method of acetic acid preparation of ethanol through hydrogenation according to claim 1, it is characterised in that the alkalinity in step (4)
Substance in ammonium carbonate, ammonium hydrogen carbonate, ammonium hydroxide, caustic soda, sodium carbonate, sodium bicarbonate, potassium hydroxide, calcium hydroxide one
Kind.
5. a kind of method of acetic acid preparation of ethanol through hydrogenation according to claim 4, it is characterised in that the alkalinity in step (4)
Substance is selected from the aqueous solution of caustic soda.
6. a kind of method of acetic acid preparation of ethanol through hydrogenation according to claim 1, it is characterised in that step (2) gas-liquid separation
The obtained acetic acid content in liquid-phase product A is less than 0~2wt%, 0~8wt% of ethyl acetate content.
7. a kind of method of acetic acid preparation of ethanol through hydrogenation according to claim 1, it is characterised in that hydrogenator one
Platform or two or more calandria type fixed bed reactor, self-heating reactor and tower reactor.
8. a kind of method of acetic acid preparation of ethanol through hydrogenation according to claim 1, it is characterised in that the esterification
Temperature be 80~130 DEG C.
9. a kind of method of acetic acid preparation of ethanol through hydrogenation according to claim 1, it is characterised in that the catalyzing esterification
Agent is selected from one of ion exchange resin, molecular sieve, aluminium oxide, super acids.
10. a kind of method of acetic acid preparation of ethanol through hydrogenation according to claim 1, it is characterised in that the catalyzing esterification
Agent is selected from strong acidic ion resin and super acids.
11. a kind of method of acetic acid preparation of ethanol through hydrogenation according to claim 1, it is characterised in that the reaction of step (1)
Pressure is 0.5~5MPa, and the molar ratio 10~40 of hydrogen and acetic acid, acetic acid is hydrogenated to containing water, ethyl acetate, acetaldehyde, third
The crude ethanol product of ketone, butanol and acetic acid, the liquid phase feeding volume space velocity of acetic acid are 0.05~1.5h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410541401.8A CN105566060B (en) | 2014-10-14 | 2014-10-14 | The method of acetic acid preparation of ethanol through hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410541401.8A CN105566060B (en) | 2014-10-14 | 2014-10-14 | The method of acetic acid preparation of ethanol through hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105566060A CN105566060A (en) | 2016-05-11 |
| CN105566060B true CN105566060B (en) | 2019-02-19 |
Family
ID=55876776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410541401.8A Active CN105566060B (en) | 2014-10-14 | 2014-10-14 | The method of acetic acid preparation of ethanol through hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105566060B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286022A (en) * | 2017-06-16 | 2017-10-24 | 山东康宝生化科技有限公司 | The method and device of dimethylamine is extracted in a kind of high kjeldahl nitrogen waste water from Sucralose |
Citations (2)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8975450B2 (en) * | 2013-03-15 | 2015-03-10 | Celanese International Corporation | Ethanol and ethyl acetate production using an acetic acid and acetic anhydride mixed feed |
-
2014
- 2014-10-14 CN CN201410541401.8A patent/CN105566060B/en active Active
Patent Citations (2)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105566060A (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101544539B (en) | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate | |
| CN105622337B (en) | Novel reactive distillation coupling process and device for separating liquid-phase product of ethylene glycol prepared from coal | |
| CN109422624A (en) | A kind of preparation method of 1,3 butylene glycol | |
| CN103787830A (en) | Method for producing ethanol by acetic acid hydrogenation | |
| CN105566063A (en) | Ethanol preparation method | |
| CN107141213A (en) | A kind of method of acetic acid synthesis from methanol carbonylation | |
| CN104557454B (en) | A kind of method of acetic acid Hydrogenation for high-quality ethanol | |
| CN101544537A (en) | Method for producing low carbon chemical ethanol from C6 sugar alcohol | |
| CN105418372B (en) | A kind of method of acetic acid hydrogenation production ethanol | |
| CN105566064B (en) | A kind of method of acetic acid preparation of ethanol through hydrogenation | |
| CN105566060B (en) | The method of acetic acid preparation of ethanol through hydrogenation | |
| CN105566057B (en) | A kind of method of acetic acid hydrogenation production ethanol | |
| CN105481649B (en) | A kind of method that acetic acid hydrogenation prepares ethanol | |
| CN105198704A (en) | Method for low-energy consumption acetic acid hydrogenation production of ethanol | |
| CN105566058B (en) | The method of acetic acid hydrogenation production ethanol | |
| CN105585428B (en) | A kind of alcohol product with Low acid | |
| CN104211569A (en) | Method for production of ethanol by direct hydrogenation of acetic acid | |
| CN109096063A (en) | The method for purifying polyoxymethylene dimethyl ethers | |
| CN106831413B (en) | The method for producing ethyl acetate | |
| CN106187692A (en) | A kind of containing ethanol with the mixed solvent of ethyl acetate | |
| CN110668920A (en) | Method for preparing ethanol and co-producing cyclohexanol by using reactive distillation method | |
| CN104557453B (en) | A kind of method of acetic acid preparation of ethanol through hydrogenation | |
| CN114432724B (en) | Process system and method for isopropanol dehydration reaction and process system and method for preparing propylene from acetone | |
| CN104428275A (en) | Thermochemically produced ethanol compositions | |
| CN105566059A (en) | Method for preparing ethanol and co-producing mixed solvent through acetic acid hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |