CN105585428B - A kind of alcohol product with Low acid - Google Patents
A kind of alcohol product with Low acid Download PDFInfo
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Abstract
The invention provides a kind of alcohol product of Low acid, ethanol content is 99.9~92wt% in described alcohol product, and using the acid number of Acetometer as 0~5mg/L, UV transmittance is 50~95 at 220nm.
Description
Technical field
The present invention relates to a kind of alcohol product, more specifically to a kind of high-quality alcohol product with Low acid.
Background technology
Ethanol is to find a kind of fatty alcohol earliest, that purposes is most wide, and the main component of wine.The industry of ethanol is raw at present
Production method mainly has fermentation method and ethylene hydration method.Ethylene hydration method is accompanied by the rise of petrochemical industry and developed, including
Indirect hydration method and direct hydration method.Improved in recent years by production cost of ethylene, in China, ethylene process is substantially at stopping 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 ethanol.
The raw material that the main alcohol production enterprise in China uses is corn, wheat and cassava (relying primarily on import).Thing
The problem of grain cost sharp rises in recent years in reality, therefore ethanol with people there is also grain is striven.The non-grain ethanol such as cassava, sugar grass is former
Material price is also expected to rise always, and using the cellulosic ethanol difficult needs also more as the two generation ethanol technology distances application of representative
Solve.
Acetic acid is a kind of important industrial chemicals, and the production technology of acetic acid has grain fermentation method, methanol carbonylation, ethene
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 significant change does not occur for consumption structure, without shape
Cheng Xin demand growth point 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 stopped production after there is new equipment driving.Therefore the downstream use exploitation of acetic acid is extremely urgent.
The approach of alcohol product is produced using acetic acid as raw material includes two kinds, first, acetic acid generates acetate through esterification,
Then acetate is hydrogenated to ethanol, then carries out refined raw producing and ethanol product；Second, acetic acid direct hydrogenation generates ethanol, then through essence
Process processed produces alcohol product.First method has had more esterification process compared to second method, and a large amount of ethanol need to follow
Ring accordingly adds size and its size and energy consumption of front and rear heat exchanger, at least portion of hydrogenation reactor as esterification feed
Point subtractive process, which is also put, to be twice, and its advantage is that the corrosion strength of hydrogenation process may be lower, but during it also or it is more or
Acetic acid less be present, still suffer from corrosivity.But the key of second method is to develop the catalyst of acetic acid direct hydrogenation,
The reason for 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 the existing many of research data, such as Sinopec, Celanese companies of the U.S.
A large amount of patent applications are have submitted Deng with regard to acetic acid hydrogenation.It is open such as PCT application enters the CN102414153A of National Phase in China
Acetic acid is hydrogenated into crude ethanol product first, unreacted acetic acid is then isolated 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 ethanol in the 3rd tower.Additionally or alternatively, second is evaporated
Go out thing and deliver to the 4th tower, be separated into the 4th distillate and the 4th residue containing acetaldehyde, then the 4th distillate is returned and reacted
To improve ethanol yield, the 4th residue is used as solvent or in ester production system.In these patents, acetic acid typically passes through
The mode of rectifying removes first, can thus reduce material requirement in later separation, so as to realize the reduction of cost of investment, but
It is that so there is also some problems：Accounting for the most of second alcohol and water of product quality needs by vaporization, therefore rectifying depickling
Energy consumption it is high, and extracting tower size is larger and material requires higher, cost of investment is high；And in the rectifying point of reality
From in, it is understood that there may be tower top has denier acetic acid, and it is all to acidity to be used as alcohol fuel and industrial alcohol product
There is strict demand, therefore cause product unqualified when operation is fluctuated.
Acid number is the important indicator of alcohol product, and acid number is lower, and its application surface is more extensive, the effect obtained in actual applications
Fruit is more preferable, therefore alcohol product is in addition to the indexs such as purity, and its acid number is also abnormal important.
The present invention proposes a kind of method that acetic acid direct hydrogenation horizontal with low energy consumption and low material consumption is ethanol, described
Method can avoid the problem of energy consumption is higher in the prior art, and the present inventor reduces thing by a large amount of careful researchs
The gentle cost of investment of water consumption, the alcohol product that particularly present invention obtains has ultralow acid number, so as to have high quality
And application prospect.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of high-quality alcohol product of Low acid.
A kind of alcohol product of Low acid of the present invention, in described alcohol product ethanol content be 99.9~
92wt%, using the acid number of Acetometer as 0~5mg/L, UV transmittance is 50~95% at 220nm.
Concrete technical scheme is：
The alcohol product of the Low acid of the present invention is obtained by following preparation method, and the preparation method includes following step
Suddenly：
(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 thing that step 1 is obtained condenses, and in gas-liquid separator after gas-liquid separation, obtains
To gaseous products A and liquid-phase product A, gaseous products A is at least partly recycled back to the use of gas phase hydrogenation reaction device；
(3) esterification：Liquid-phase product A in step 2 is subjected to ester in the esterifier equipped with esterification catalyst
After changing reaction, gaseous products B and liquid-phase product B are obtained, gas phase hydrogenation reaction device is at least partly recycled back to after gaseous products B coolings
Use；
(4) secondary gas-liquid separation：Secondary gas-liquid separation is carried out after the liquid-phase product B that step 3 obtains is cooled down, obtains liquid phase
Products C and gas phase products C, gaseous products C portion return to hydrogenation reactor and used；
(5) product purification：Liquid-phase product C is delivered into neutralization reactor, alkaline matter is added and carries out neutralization reaction, after neutralization
Product enter first rectifying column, ethyl acetate, the acetone that the first overhead fraction contains acetaldehyde, content is 0~0.1wt%, the
One tower bottom distillate is the coarse ethanol product containing ethanol, water, and the first overhead fraction part is returned in gas phase hydrogenation reaction device, by the
One tower bottom distillate is sent to Second distillation column, and the second overhead fraction contains ethanol, water, and the second tower bottom distillate contains water, ethanol, butanol
And acetate, 85~95wt% of ethanol content, 0~25mg/L of acidity value in the second described overhead fraction.
The reaction pressure of gas phase hydrogenation reaction is 0.5~5MPa, hydrogen and acetic acid mol ratio 10~40, and acetic acid is hydrogenated with
Into the crude ethanol product containing water, ethyl acetate, acetaldehyde, acetone, butanol and acetic acid.
Acetic acid content in the liquid-phase product A that gas-liquid separation obtains is less than 0~2wt%, 0~8wt% of ethyl acetate content.
The content of ethyl acetate is 0~0.1wt% in the first tower bottom distillate after product purification, ethanol in the second overhead fraction
Content is 85~95wt%, 0~25mg/L of acidity value.
Acetic acid gas phase hydrogenation catalyst is on a catalyst or by catalyst carrier point selected from load in described 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,
In IVB, VB, VIB, VIIB, Group VIIIB, lanthanide series metal and IIIA, IVA, VA, 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 in metallic catalyst.More specifically, described hydrogenation catalyst is selected from following：
Hydrogenation catalyst is selected from the cobalt that load disperses on a catalyst or by catalyst carrier and is catalyzed in the step (1)
Agent, wherein cobalt tenor account for 15wt%~45wt% of overall catalyst weight, the described catalyst also noble metal containing trace,
The ratio of one or more of the wherein described trace noble metal in palladium, platinum and rhenium, its weight and cobalt weight metal is 1:
100~1:300.
Hydrogenation catalyst is selected from the cobalt that load disperses on a catalyst or by catalyst carrier and is catalyzed in the step (1)
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%；
Hydrogenation catalyst is selected from the cobalt that load disperses on a catalyst or by catalyst carrier and is catalyzed in the step (1)
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；
Hydrogenation catalyst is selected from the cobalt that load disperses on a catalyst or by catalyst carrier and is catalyzed in the step (1)
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.
Hydrogenation catalyst is selected from the cobalt that load disperses on a catalyst or by catalyst carrier and is catalyzed in the step (1)
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 containing 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 the content of wherein 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 its content accounts for overall catalyst weight
0.5wt%~15wt%, described carrier be selected from silica, diatomite, calcium silicates, zirconium oxide, at least one of titanium oxide,
Its content accounts for 20wt%~80wt% of overall catalyst weight.
Step (1) hydrogenation catalyst contains carrier, cobalt element, silver element, and the content of wherein 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 described carrier is selected from
Silica, diatomite, calcium silicates, zirconium oxide, at least one of titanium oxide, its content account for the 20wt% of overall catalyst weight~
80wt%.
Hydrogenation catalyst contains carrier, cobalt element, alkali earth metal, IB races element, wherein cobalt member in the step (1)
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 described carrier is oxide, and it contains
Amount accounts for 10wt%~80wt% of overall catalyst weight.
In the step (1) hydrogenation catalyst be selected from silicon dioxide carried platinum-tin catalyst, activated carbon supported palladium-
It is a kind of in rhenium catalyst.
In the step (1) hydrogenation catalyst be Sinopec Beijing Chemical Research Institute application patent in one kind or
Combination, specific patent are: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, it can be modified suitable for the catalyst of acetic acid preparation of ethanol by hydrogenating before use through any-mode.For example, utilize expansion
Hole agent or hydro-thermal process mode adjust the pore structure of carrier to improve the selectivity of catalyst and stability；And for example, by
Prepare carrier process and add certain metallic compound to adjust the acid-base property of carrier to improve catalyst activity；And for example, by carrying
Certain metal is added in body as lanthanum etc. to improve the stability of catalyst, this can effectively improve catalyst life；Further, can be by right
Catalyst carries out surface silicon alkylation or aluminium alkylation processing adjusts its surface special nature and urged to reduce some compounds
The loss of the deposition or active component on agent surface is to extend catalyst life.
For those skilled in the art, can be gained enlightenment according to discussed in detail above so as to the catalysis to the present 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 that 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 is carried out at ambient 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 hydrogenation can also be carried out under elevated pressure, for example, the process conditions of acetic acid hydrogenation are：Vinegar
The liquid phase feeding volume space velocity of acid is 0.05~1.5h-1, the mol ratio of hydrogen and acetic acid is 5~30:1, 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 the ratio between percent by volume, the volume of feed volume and catalyst in the unit interval.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 recovery heat and cooling, then carries out gas-liquid separation, gas
Body recycles through compressor, then suitably fills into some fresh hydrogen, and liquid enters follow-up separation phase.
Although present invention uses the catalyst of very high activity, reacting coarse product also has a certain amount of unreacted acetic acid
In the presence of this is probably during industrial implementation, and solid phase of the invention needs to exist with certain particle diameter (1~8mm), due to anti-
Device is answered many non-ideal mobility status to be present, short circuit, channel, dead angle as everyone knows etc., Another reason is exactly catalyst
There can be activity decrease in last stage reaction.
After the present invention is by described high activated catalyst, the control of the acetic acid content that is exported after hydrogenation reaction 2wt% with
It is interior, 1.5wt% is optimized for, situation about more optimizing is 1wt%.
Acetic acid content play the role of for the product quality of ethanol it is important, such as acid number in industrial alcohol chinese national standard
No more than 10mg/L, acid number is no more than 56mg/L in alcohol fuel Chinese national standard, therefore it is necessary to remove acetic acid in crude product
's.Prior art is mainly removed acetic acid by way of rectifying, and accounting for the most of second alcohol and water of product quality needs to pass through
Vaporization, therefore the energy consumption of rectifying depickling is high, and the size of extracting tower is larger higher with material requirement, and cost of investment is high；
And in the rectifying separation of reality, it is understood that there may be tower top has denier acetic acid, and is used as alcohol fuel and industry
Alcohol product is all to have strict demand to acidity, therefore causes product unqualified when operation is fluctuated.Acidity value is
The main measurement index of alcohol product, particularly when being applied in alcohol fuel, the acetic acid of denier will cause engine
Doubled with the corrosion rate of oil circuit, and also a certain degree of can influence the stability of oil product, therefore cause oil quality to decline.
The inventors discovered that separation of the control of neutralization reactor for subsequent product is extremely important, it is of the invention successful
One of important control parameter, neutralization reactor PH is 8.0~11.0 for control, and the value more optimized is 8.5~10.
For the alkaline matter of neutralization, ammonium carbonate, ammonium hydrogen carbonate, ammoniacal liquor, caustic soda, sodium carbonate, bicarbonate can be selected from
One kind in sodium, potassium hydroxide, calcium hydroxide, preferred alkali are the aqueous solution of caustic soda.
The position selection of neutralization reactor is important to the effect of the present invention, and the position of application claims is inventor's warp
Cross and derive experiment meticulously, by material test, the inventors discovered that the material corrosion speed after neutralization is greatly reduced,
It can be less than 0.01mm/a in common carbon steel material medium-rate, product color is limpid, and if not by the acetic acid in material
With find to need to use the material of higher level, even so, tower reactor product still has certain color, therefore neutralizes anti-
Answer device to reduce equipment investment before being placed on rectifying column, and tower reactor liquid color degree is reduced.
It is well known that the present inventor is had found by the experiment on small-sized rectification process device, in (such as ASPEN softwares mould
Intend) in the case of acetic acid can be achieved in theoretical calculation be kept completely separate, result of the test shows that the acid content in alcohol product is higher,
In many times testing, 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 is not only by the selection of high activated catalyst, the combination for reactor and reactor
Also require, preferable mode is one or more than two calandria type fixed bed reactors, self-heating reactor and tower anti-
Device is answered, the preferred combination with self-heating reactor and shell and tube reactor, and it is poor with inlet temperature.
After being neutralized due to acetic acid and alkali, the loss of acetic acid material can be caused, it is clear that this is that inventor is unwilling to see, because
This present invention adds an esterifier after hydrogenation reactor, acetic acid is converted into ethyl acetate, due to ethyl acetate
It is that can be recycled back to reactor to be hydrogenated to ethanol 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 adiabatic
Bed reactor.Described middle esterifier is filled with esterification catalyst, and described esterification catalyst is selected from ion exchange resin, divided
One kind in sub- sieve, aluminum oxide, super acids.Preferred esterification catalyst is strong acidic ion resin and super acids, such as U.S.
A-15 of Rhom and Hass's production etc..The mode of optimization is, after gas phase hydrogenation reaction device, obtains coarse ethanol product and first cools down
It is by esterifier among the liquid phase feeding after separation, gas phase is further to 60~130 DEG C, then by one-level gas-liquid separation
Product purification is sent into after cooling and gas-liquid separation.Can be most by way of described two 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 the ratio of each component carry out the use of appropriate selection gas-liquid separator and esterifier, can also be provided according to the present invention
Various technical inspirations technical scheme is modified.
Compared with the conventional method, the inventive method can be effectively reduced the acetic acid content in product, and this, which is not only helped, carries
The quality of high final alcohol product, and can also effectively reduce the energy consumption of subsequent separation process.
Brief description of the drawings
Fig. 1 is the process chart of the present invention, wherein
R101：Gas phase hydrogenation reaction device
E101：Condenser
V101：Gas-liquid separator
E102：Condenser
R102：Esterifier
R201：Neutralization reactor
T201：First rectifying column
T202：Second distillation column
V202：Gas-liquid separator
Embodiment
Following examples are citing descriptions more detailed to the present invention, but the invention is not limited in these embodiments.
In the present embodiment, specific flow chart is as shown in annex map 1.
First by acetic acid raw material, material and the pre- thermosetting steam feed stream of hydrogen are returned, 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, wherein (1) cobalt, cobalt tenor account for the 18wt% of overall catalyst weight；(2) molybdenum and tin, catalysis is accounted for respectively
The 3wt% and 34wt% of agent gross weight；(3) boron and bismuth, account for the 2wt% and 5wt% of overall catalyst weight respectively, and surplus is titanium dioxide
Silicon.Acetic acid is hydrogenated into crude ethanol product.The process conditions 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, reaction temperature is 220 DEG C, reaction pressure 4.5MPa.In crude product after hydrogenation
It is 62.6wt% to remove on-condensible gas (hydrogen, CO, CO2, CH4, C2H6) outer ethanol content, ethyl acetate 6wt%, acetic acid
1.0wt%, water 30wt%, surplus are acetaldehyde, ether and butanol.Then the mixed material from hydrogenation reactor R101 is existed
80~84 DEG C are cooled in E101.The gas-liquid separation in V101 by condensed material, the liquid phase after separation enter esterification R102
(79~84 DEG C of inlet temperature), the isolated gas phase containing hydrogen continues to cool down into E102, wherein liquid phase and gas phase quality
Than being about 6.1~6.3:1 or so.Esterification catalyst in esterifier R102 generates macropore for Beijing chemical research research institute
Strongly acidic styrene's cation ion exchange resin, particle diameter~1mm.Gas phase portion after E102 coolings returns to hydrogenation reactor,
Liquid phase enters neutralization reactor R103, and acetic acid content is 91wtppm wherein in liquid phase.
In R102 exits, the acetic acid content of liquid phase is 0.25wt%, and the liquid phase is cooled into 20 DEG C through subcooler E103
After carry out secondary gas-liquid separation, gas phase portion returns to hydrogenation reactor, and liquid phase enters in neutralization reactor, and neutralization reactor is pipe
Formula reactor, mean residence time 18min, the alkali used export liquid phase P H for 30wt% causticity sodium water solution after neutralization
It is worth for 8.8~9.0 or so.
Liquid-phase product after neutralization is delivered into first rectifying column T201, the rectifying column is plate column, and composition of tower shell material is common
Carbon steel material, the first overhead fraction are 15 with tower bottom distillate mass ratio:100, wherein overhead fraction ethanol mass fraction is
42.5wt%, ethyl acetate content is 41wtppm in tower reactor cut.70wt% in first overhead fraction is returned into hydrogenation reaction
Device, from the second tower tower reactor liquid as extraction water with entering the first tower reactor cut mass ratio for 8:100.First rectifying column kettle product
Color is limpid.
First tower reactor cut is sent into Second distillation column T202, the rectifying column is packed tower, and composition of tower shell material is common carbon
Steel, the second tower bottom distillate and the second overhead fraction being separated into by Second distillation column, wherein tower reactor cut delivers to wastewater treatment, the
Water content is 9.0wt% in two overhead fractions, and acidity value is 2.0mg/L after titration, and remaining indices meets industrial alcohol
Chinese Industrial Standards (CIS) requirement.The UV transmittance of the product is 91% at 220nm.
After second overhead fraction is delivered into the dehydration of molecular sieve tower, water content 0.15wt%, remaining indices meet
The requirement of alcohol fuel Chinese Industrial Standards (CIS), the acid number of particularly product are significantly less than national normal value.
Claims (13)
1. a kind of preparation method of the alcohol product of Low acid, including：
(1) gas phase hydrogenation：Steam feed stream will be formed after acetic acid raw material and hydrogen preheating, the steam feed stream is incorporated into dress
Have and hydrogenation reaction is carried out in the reactor of hydrogenation catalyst；
(2) gas-liquid separation：The hydrogenation reaction thing 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：Liquid-phase product A in step 2 is carried out being esterified instead in the esterifier equipped with esterification catalyst
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 coolings makes
With；
(4) secondary gas-liquid separation：Secondary gas-liquid separation is carried out after the liquid-phase product B that step 3 obtains is cooled down, obtains liquid-phase product
C and gas phase products C, gaseous products C portion return to hydrogenation reactor and used；
(5) product purification：Liquid-phase product C is delivered into neutralization reactor, alkaline matter is added and carries out neutralization reaction, the production after neutralization
Product enter first rectifying column, ethyl acetate, the acetone that the first overhead fraction contains acetaldehyde, content is 0~0.1wt%, the first tower
Bottom cut is the coarse ethanol product containing ethanol, water, and the first overhead fraction part is returned in gas phase hydrogenation reaction device, by the first tower
Bottom cut is sent to Second distillation column, and the second overhead fraction contains ethanol, water, and the second tower bottom distillate contains water, ethanol, butanol and vinegar
Hydrochlorate, 85~95wt% of ethanol content, 0~25mg/L of acidity value in the second described overhead fraction.
2. preparation method according to claim 1, it is characterised in that the pH of described neutralization reactor is 8.0~11.0.
3. preparation method according to claim 1, it is characterised in that the pH of described neutralization reactor is 8.5~10.
4. preparation method according to claim 1, it is characterised in that the alkaline matter in step (5) is selected from ammonium carbonate, carbon
One kind in sour hydrogen ammonium, ammoniacal liquor, caustic soda, sodium carbonate, sodium acid carbonate, potassium hydroxide, calcium hydroxide.
5. preparation method according to claim 4, it is characterised in that the alkaline matter in step (5) is selected from the water of caustic soda
Solution.
6. preparation method according to claim 1, it is characterised in that in the liquid-phase product A that step (2) gas-liquid separation obtains
Acetic acid content be less than 0~2wt%, 0~8wt% of ethyl acetate content.
7. preparation method according to claim 1, it is characterised in that hydrogenation reactor is one or two with upper tube array
Formula fixed bed reactors, self-heating reactor and tower reactor.
8. preparation method according to claim 1, it is characterised in that the temperature of described esterification is 80~130 DEG C.
9. preparation method according to claim 1, it is characterised in that described esterification catalyst is selected from ion exchange resin, molecule
One kind in sieve, aluminum oxide, super acids.
10. preparation method according to claim 9, it is characterised in that described esterification catalyst is selected from strong acidic ion tree
Fat and super acids.
11. preparation method according to claim 1, it is characterised in that the reaction pressure of step (1) is 0.5~5MPa, hydrogen
The mol ratio 10~40 of gas and acetic acid, the liquid phase feeding volume space velocity of acetic acid is 0.05~1.5h-1。
12. preparation method according to claim 1, it is characterised in that liquid-phase product A is obtained after gas phase hydrogenation reaction, first
60~130 DEG C are cooled to, then by one-level gas-liquid separation, the liquid phase after separation is sent into middle esterifier, gained liquid phase
Product purification is sent into after further gas-liquid separation.
13. preparation method according to claim 1, it is characterised in that alcohol product is using the acid number of Acetometer as 0~2mg/
L。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB397938A (en) * | 1931-03-05 | 1933-09-07 | Du Pont | Improvements in or relating to the hydrogenation of carboxylic acids |
| CN103140460A (en) * | 2011-04-26 | 2013-06-05 | 国际人造丝公司 | Process to reduce ethanol recycled to hydrogenation reactor |
| CN105566064A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Method for preparation of ethanol by acetic acid hydrogenation |
-
2014
- 2014-10-22 CN CN201410569413.1A patent/CN105585428B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB397938A (en) * | 1931-03-05 | 1933-09-07 | Du Pont | Improvements in or relating to the hydrogenation of carboxylic acids |
| CN103140460A (en) * | 2011-04-26 | 2013-06-05 | 国际人造丝公司 | Process to reduce ethanol recycled to hydrogenation reactor |
| CN105566064A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Method for preparation of ethanol by acetic acid hydrogenation |
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