CN106554251A - A kind of method that C-4-fraction prepares sec-butyl alcohol and ethanol after utilization ether - Google Patents
A kind of method that C-4-fraction prepares sec-butyl alcohol and ethanol after utilization ether Download PDFInfo
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- CN106554251A CN106554251A CN201510624969.0A CN201510624969A CN106554251A CN 106554251 A CN106554251 A CN 106554251A CN 201510624969 A CN201510624969 A CN 201510624969A CN 106554251 A CN106554251 A CN 106554251A
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- acetic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a kind of method that C-4-fraction prepares sec-butyl alcohol and ethanol after utilization ether, comprises the following steps：Step i, after ether, C-4-fraction and acetic acid are reacted in the presence of the first catalyst, obtain the sec-Butyl Acetate crude product containing acetic acid；Step ii, hydrogen and the sec-Butyl Acetate crude product containing acetic acid are reacted in the presence of the second catalyst, isolate liquefied mixture in the mixture obtained from reaction；Step iii, by carrying out rectifying to the liquefied mixture, respectively obtains ethanol and sec-butyl alcohol product.The method process is simple that the present invention is provided, control are flexible, high-efficiency environment friendly, low production cost, are an effective ways of C-4-fraction comprehensive utilization after ether.
Description
Technical field
The present invention relates to petrochemical industry.Further, it is related to a kind of using C-4-fraction preparation Zhong Ding after ether
A kind of method of alcohol and ethanol.
Background technology
With the C-4-fraction of the change of fossil resources general layout, ethylene plant and oil plant it is more and more valuable, but I
The utilization current to C-4-fraction of state is simultaneously insufficient, using it is most be isobutene and fourth two in C-4-fraction
Alkene.Butadiene is not contained in refinery casing head, etherification reaction, the C-4-fraction of ethylene plant can be directly carried out
In butadiene containing about 45%, need to carry out etherification reaction after Butadiene Extraction again.Methyl- tert fourth is produced at present
The technology of base ether (MTBE) is very ripe, and there is ether-based device in each petroleum chemical enterprise, is evaporated by mixing carbon four
Dividing and methyl tertiary butyl ether(MTBE) being prepared with methyl alcohol reaction, isobutene reacts completely, and after remaining ether, C-4-fraction is alkane
With the mixture of monoolefine (1- butylene, Trans-2-butene and cis-2-butene), wherein monoolefine is valuable chemical industry
Raw material, but be not fully used.
Sec-Butyl Acetate, i.e. sec-butyl acetate, acetic acid dibutyl ester, are one of four kinds of isomers of butyl acetate,
It is for colourless, the inflammable, liquid with fruit taste, in most of the cases all similar to the performance of other isomers,
Dissolvable various kinds of resin and organic matter.Its boiling point is lower than conventional n-butyl acetate and isobutyl acetate, evaporation speed
Degree is very fast.Sec-Butyl Acetate has many uses general, it is adaptable to medicine, coating, high-grade paint, ink, resin and
Acetic acid dehydration and solvent, while MTBE can also be substituted, as the additive of gasoline, be a kind of purposes very
Extensive fine chemicals.In recent years, with butylene and acetic acid as raw material, with strong acidic ion resin as catalysis
The production technology of agent has the advantages that environmental pollution is little, low production cost, causes R＆D institution and manufacturing enterprise
Extensive concern.
The catalyst of the production sec-Butyl Acetate disclosed in prior art includes strong acidic ion resin, miscellaneous many
Acid, solid super-strong acid and molecular sieve catalyst.Commercial plant built at present is strong acidic ion resin
Catalyst, but raw material C 4 olefin used needs purification, and lock out operation complexity is loaded down with trivial details, and energy consumption is higher.
Sec-butyl alcohol is the raw material for producing MEK, also serves as solvent.The preparation method of sec-butyl alcohol has indirect hydration
Method and direct hydration method, current commercial plant all adopt direct hydration method.The technique needs the carbon tetraene of high concentration
Hydrocarbon is raw material, and a large amount of C 4 olefins are recycled, and energy consumption is higher.
The content of the invention
To overcome defect present in above-mentioned prior art, the invention provides a kind of using C-4-fraction system after ether
The method of standby secondary butyl ester and ethanol, without the butane and alkene that specially separate after ether in C-4-fraction, makes ether
Carbon four is reacted under catalyst action with acetic acid afterwards, obtains the sec-Butyl Acetate crude product containing acetic acid, Wu Xufen
The mixture of sec-butyl alcohol, second alcohol and water be can be obtained by from purification direct hydrogenation, be obtained by conventional rectification
Highly purified ethanol and sec-butyl alcohol product.
The method that C-4-fraction prepares sec-butyl alcohol and ethanol after a kind of utilization ether of present invention offer, including：
Step i, after ether, C-4-fraction and acetic acid are reacted in the presence of the first catalyst, are obtained containing acetic acid
Sec-Butyl Acetate crude product；
Step ii, hydrogen and the sec-Butyl Acetate crude product containing acetic acid are anti-in the presence of the second catalyst
Should, liquefied mixture is isolated in the mixture obtained from reaction；
Step iii, carries out rectifying to the liquefied mixture, respectively obtains ethanol and sec-butyl alcohol product.
According to present invention offer, after the ether, C-4-fraction is referred to and is evaporated using the carbon four from ethylene plant and oil plant
The C-4-fraction after isobutene synthesizing methyl tertbutyl ether in point.After the ether C-4-fraction be mainly alkane and
The mixture of monoolefine, its main component include iso-butane, normal butane, 1- butylene, Trans-2-butene, cis- 2-
Butylene.
According to said method, in step i, with after ether C-4-fraction and acetic acid as raw material, in the first catalyst
In the presence of, the alkene and acetic acid after ether in C-4-fraction is reacted, and obtains the sec-Butyl Acetate containing acetic acid
Crude product.In the process, the alkane after ether in C-4-fraction is not involved in reaction, discharges from reaction system.
The present invention one preferred embodiment in, the carbon in step i, after ether in C-4-fraction
Alkatetraenes is 0.70-0.95 with the mol ratio of acetic acid, and after ether, the weight space velocity of C-4-fraction is 1-3h-1。
The present invention another preferred embodiment in, in step i, reaction temperature is 70-95
DEG C, preferred 85-90 DEG C, pressure is 1.0-3.5MPa, preferred 1.5-2MPa.
The present invention another preferred embodiment in, in step i, first catalyst can
Think H type macropore strong acid cation exchanger resins or molecular sieve catalyst, preferably H types macropore strong acid sun
Ion exchange resin, more preferably NKC-9 or DA-340 cation exchange resin catalysts.
It is according to said method, in step ii, secondary with the acetic acid containing acetic acid obtained in hydrogen and step i
Butyl ester crude product is raw material, is reacted in the presence of the second catalyst and acetic acid, generates liquefied mixture.
The yield that sec-butyl alcohol is generated by this process is far above and prepares sec-butyl alcohol by the aquation of alkene.Product
Comprising sec-butyl alcohol, ethanol, water and unreacted hydrogen, the hydrogen as gas phase is first separated, must
The liquefied mixture containing sec-butyl alcohol, second alcohol and water is arrived.In the process, sec-Butyl Acetate and acetic acid turn
Rate reaches 100%, sec-butyl alcohol and the selectivity of ethanol is more than 99.5%.
The present invention one preferred embodiment in, in step ii, hydrogen is thick with sec-Butyl Acetate
The mol ratio of the sec-Butyl Acetate in product is 15-30, and the weight space velocity of sec-Butyl Acetate is 2-3h-1。
The present invention another preferred embodiment in, in step ii, reaction temperature is 260-360
DEG C, preferably 280-300 DEG C, pressure is 2.5-4.5MPa, preferably 2.5-3.0MPa.
The present invention another preferred embodiment in, in step ii, second catalyst can
Think CuO-NiO/Al2O3、NiO/Al2O3Or CuO-ZnO/Al2O3, preferably CuO-NiO/Al2O3。
Above-mentioned catalyst can be prepared by coprecipitation, and concrete operations are referred to《Catalyst Design and preparation technology》
Translator is write (：Xu Yue；Publishing house：Chemical Industry Press；Publication date：2003-05-01；Page 254).
According to said method, the reaction of step i and ii can be carried out in the reactor, and the reactor is pipe
Formula reactor, tank reactor or tower reactor.
According to said method, in step i, after ether, C-4-fraction and acetic acid are logical from reactor head respectively
Enter reactor；In step ii, hydrogen and sec-Butyl Acetate crude product are passed through from the top of reactor respectively
Reactor.
According to said method, in step iii, water and ethanol form azeotropic mixture, by ethanol and Zhong Ding
The mixture of alcohol carries out rectifying separation, can respectively obtain sec-butyl alcohol product and the alcohol product containing water.
According to said method, by the separable water of rectifying and ethanol are carried out to the alcohol product containing water, so as to
To absolute ethyl alcohol product.
One of the present invention preferred embodiment in, it is described react the mixture that obtains also include it is unreacted
Hydrogen.
The present invention another preferred embodiment in, said method also include step iv, will be above-mentioned not anti-
Hydrogen return to step ii answered is recycled as reaction raw materials.
The present invention another preferred embodiment in, the acetic acid be purity more than 99.5% glacial acetic acid.
According to the preparation method that the present invention is provided, without numerous and diverse process for separating and purifying, can just obtain highly purified
Sec-butyl alcohol and alcohol product, the method process is simple that the present invention is provided, control are flexible, and high-efficiency environment friendly is produced into
This is low, is an effective way of C-4-fraction comprehensive utilization after ether.
Description of the drawings
Process charts of the Fig. 1 for the one embodiment according to the method for providing of the invention.
Description of symbols：A- first reactors, B- second reactors, the first knockout towers of C-, the second knockout towers of D-,
E- first rectifying columns, F- Second distillation columns；C-4-fraction after 1- ethers, 2- acetic acid, 3- are obtained in first reactor
Mixture, 4- butanes and the unreacted alkene of very small amount, 5- contain the sec-Butyl Acetate crude product of acetic acid,
6- hydrogen, the 6 '-hydrogen that recycles, the mixture that 7- is obtained in second reactor, 8- are obtained in second reactor
The sec-butyl alcohol that arrives, the mixture of second alcohol and water, 9- sec-butyl alcohols, the mixture of 10- second alcohol and waters, 11- water, 12-
Ethanol.
Specific embodiment
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is described in detail, but be the invention is not restricted to following
Explanation.If no special instructions, the percentage in the present invention is mass percent.
Embodiment 1
Reaction raw materials：Acetic acid is glacial acetic acid of the purity more than 99.5%, and hydrogen is hydrogen that purity is 99.99%.
After ether, C-4-fraction includes iso-butane 44.19%, normal butane 13.23%, 1- butylene 14.05%, t-2- butylene
16.55%th, isobutene 0.23% and c-2- butylene 11.75%.First catalyst adopts H type macropore strong acid benzene second
Alkene series cationic ion-exchange resin, the trade mark is NKC-9, and the first catalyst of 50g is loaded in first reactor A.
Second catalyst is using the CuO-NiO/Al prepared by coprecipitation2O3, the second catalyst of 50g is loaded into the
In two reactor Bs.
Wherein, CuO-NiO/Al is prepared by following methods2O3Catalyst：By the nitre of 0.1mol/L, 100ml
Sour copper solution is mixed with the zinc nitrate zinc liquid of 0.1mol/L, 100ml, adds the nitric acid of 0.6mol/L, 100ml
Aluminum solutions, add the sodium carbonate liquor of 0.8mol/L, 400ml after stirring, by precipitating, washing, be dried,
Roasting, the method for shaping are prepared from.
Step i：After ether C 4 fraction 1 and acetic acid 2 respectively with measuring pump from the top of first reactor A after pan feeding
Reacted in the presence of first catalyst, obtained mixture 3.Reaction condition is：Reaction bed temperature is
90 DEG C, pressure is 1.5MPa, and in C-4-fraction, C 4 olefin and acetic acid mol ratio are 0.8, the weight of C-4-fraction
Amount air speed is 3h-1。
Mixture 3 flows into the first knockout tower C from first reactor bottom and carries out gas-liquid separation, butane and pole
A small amount of unreacted alkene 4 is discharged from the top of the first knockout tower C, the sec-Butyl Acetate crude product 5 containing acetic acid
Flow out from the first knockout tower C bottoms.
Step ii：The sec-Butyl Acetate crude product 5 containing acetic acid flowed out from the first knockout tower C bottoms passes through meter
Pump is measured by inflow second reactor B at the top of second reactor, meanwhile, hydrogen 6 is also flowed by the top of second reactor
Enter second reactor B, the sec-Butyl Acetate crude product 5 containing acetic acid and hydrogen in the presence of the second catalyst
6 are reacted, and obtain mixture 7.Reaction condition is：Reaction bed temperature is 300 DEG C, and pressure is 2.5MPa,
Hydrogen is 20 with sec-Butyl Acetate mol ratio, and the weight space velocity of sec-Butyl Acetate is 2h-1。
Mixture 7 is flowed out from second reactor bottom, and into the second knockout tower D, gas-liquid separation obtains unreacted
Hydrogen 6 ' and ethanol, sec-butyl alcohol and water liquefied mixture 8.
Step iii：After liquefied mixture 8 is flowed out from the bottom of the second knockout tower D, first rectifying column E is flowed into,
Sec-butyl alcohol is separated with ethanol, water by rectifying, respectively obtain sec-butyl alcohol 9 and the ethanol containing water 10, wherein
Sec-butyl alcohol 9 is flowed out from the bottom of first rectifying column E, and the ethanol 10 containing water is from the bottom of first rectifying column E
Flow out, into Second distillation column F, Jing after Second distillation column F rectifying, ethanol 12 is from the top of Second distillation column F
Portion flows out, and water 11 is then flowed out from the bottom of Second distillation column F.
Step iv, 6 ' return to step ii of unreacted hydrogen are recycled.
Reaction condition and reaction result such as Tables 1 and 2.
Embodiment 2
Reaction raw materials：Acetic acid is glacial acetic acid of the purity more than 99.5%, and hydrogen is hydrogen that purity is 99.99%.
After ether C-4-fraction include iso-butane 0.25%, normal butane 20.45%, 1- butylene 5.31%, t-2- butylene 43.72%,
Isobutene 0.10%, c-2- butylene 30.17%.First catalyst is using H type macropore strong acids phenylethylene sun
Ion exchange resin, the trade mark are NKC-9, and the first catalyst of 60g is loaded in first reactor A.Second urges
Agent adopts CuO-NiO/Al2O3, preparation method is same as Example 1, and the second catalyst of 50g is loaded the
In two reactor Bs.
Step i：Operation is same as Example 1, and difference is：Reaction bed temperature is 85 DEG C, instead
Pressure is answered to be 2.0MPa.
Step ii：Operation is same as Example 1, and difference is：Reaction bed temperature is 280 DEG C,
Reaction pressure is 3.0MPa, and hydrogen is 25 with sec-Butyl Acetate mol ratio.
The operation of step iii and step iv is same as Example 1.
Reaction condition and reaction result are as shown in table 1, table 2 and table 3.
The result of the test of 1 step i of table
| Project | Embodiment 1 | Embodiment 2 |
| Catalyst bed depth (DEG C) | 90 | 85 |
| Reaction pressure (MPa) | 1.5 | 2.0 |
| C 4 olefin/acetic acid (mol ratio) | 0.8 | 0.8 |
| C 4 fraction weight space velocity (h after ether-1) | 2 | 2 |
| Sec-Butyl Acetate is selective (%) | 99.5 | 99.3 |
| C 4 olefin conversion ratio (%) | 85 | 80 |
The result of the test of 2 step ii of table
| Project | Embodiment 1 | Embodiment 2 |
| Reactor top temperature (DEG C) | 300 | 280 |
| Reactor top pressure (MPa) | 2.5 | 3.0 |
| Hydrogen/sec-Butyl Acetate (mol ratio) | 20 | 25 |
| Sec-Butyl Acetate weight space velocity (h-1) | 2 | 2 |
| Sec-Butyl Acetate and acetic acid conversion ratio (%) | 100 | 100 |
| Sec-butyl alcohol is selective (%) | 99.5 | 99.8 |
| Ethanol selectivity (%) | 99.5 | 99.8 |
According to data in table, the method provided by the present invention, it is capable of carbon four after the utilization ether of high conversion
Cut, need not numerous and diverse process for separating and purifying, just can high selectivity obtain sec-butyl alcohol and ethanol, be carbon after ether
One effective way of four cuts comprehensive utilization.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and the present invention is carried out in without departing substantially from scope and spirit of the present invention
Revision.Although the present invention described in which is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, conversely, the present invention to can be extended to other all with identical function
Methods and applications.
Claims (10)
1. a kind of method that C-4-fraction prepares sec-butyl alcohol and ethanol after utilization ether, comprises the following steps：
Step i, after ether, C-4-fraction and acetic acid are reacted in the presence of the first catalyst, are obtained containing acetic acid
Sec-Butyl Acetate crude product；
Step ii, hydrogen and the sec-Butyl Acetate crude product containing acetic acid are anti-in the presence of the second catalyst
Should, liquefied mixture is isolated in the mixture obtained from reaction；
Step iii, by carrying out rectifying to the liquefied mixture, respectively obtains ethanol and sec-butyl alcohol product.
2. method according to claim 1, it is characterised in that in step i, carbon four evaporates after ether
C 4 olefin in point is 0.70-0.95 with the mol ratio of acetic acid, and after ether, the weight space velocity of C-4-fraction is 1-3h-1。
3. method according to claim 1 and 2, it is characterised in that in step i, reaction temperature
Spend for 70-95 DEG C, preferred 85-90 DEG C, pressure is 1.0-3.5MPa, preferred 1.5-2MPa.
4. the method according to any one of claim 1-3, it is characterised in that in step i,
First catalyst is H type macropore strong acid cation exchanger resins.
5. the method according to any one of claim 1-4, it is characterised in that in step ii,
The mol ratio of the sec-Butyl Acetate in hydrogen and sec-Butyl Acetate crude product is 15-30, the weight of sec-Butyl Acetate
Air speed is 2-3h-1。
6. the method according to any one of claim 1-5, it is characterised in that in step ii,
Reaction temperature is 260-360 DEG C, and preferably 280-300 DEG C, pressure is 2.5-4.5MPa, preferably
2.5-3.0MPa。
7. the method according to any one of claim 1-6, it is characterised in that second catalyst is
CuO-NiO/Al2O3、NiO/Al2O3Or CuO-ZnO/Al2O3。
8. the method according to any one of claim 1-7, it is characterised in that step i and ii's
Reaction is carried out in the reactor, and the reactor is tubular reactor, tank reactor or tower reactor.
9. method according to claim 1, it is characterised in that the mixture that the reaction is obtained also includes
Unreacted hydrogen.
10. method according to claim 9, it is characterised in that methods described also includes step iv, will
Unreacted hydrogen return to step ii is recycled as reaction raw materials.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017507A (en) * | 2017-12-04 | 2018-05-11 | 福州大学 | A kind of method of fixed bed-reactive distillation Joint Production high-purity sec-butyl alcohol |
| CN114436850A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Method for co-producing monoethylamine and sec-butylamine by supergravity method |
| CN114436827A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Method for coproducing ethylamine and sec-butylamine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172492A (en) * | 2011-12-23 | 2013-06-26 | 北京石油化工学院 | Preparation method of sec-butyl alcohol |
| CN103508884A (en) * | 2012-06-15 | 2014-01-15 | 中国石油化工股份有限公司 | Method for preparing sec-butyl acetate through utilizing etherification C4 fraction |
-
2015
- 2015-09-25 CN CN201510624969.0A patent/CN106554251A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172492A (en) * | 2011-12-23 | 2013-06-26 | 北京石油化工学院 | Preparation method of sec-butyl alcohol |
| CN103508884A (en) * | 2012-06-15 | 2014-01-15 | 中国石油化工股份有限公司 | Method for preparing sec-butyl acetate through utilizing etherification C4 fraction |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017507A (en) * | 2017-12-04 | 2018-05-11 | 福州大学 | A kind of method of fixed bed-reactive distillation Joint Production high-purity sec-butyl alcohol |
| CN114436850A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Method for co-producing monoethylamine and sec-butylamine by supergravity method |
| CN114436827A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Method for coproducing ethylamine and sec-butylamine |
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Application publication date: 20170405 |