CN102942446B - A kind of method reclaiming the acetic ester preparation of ethanol by hydrogenating of hydrogen recirculation - Google Patents
A kind of method reclaiming the acetic ester preparation of ethanol by hydrogenating of hydrogen recirculation Download PDFInfo
- Publication number
- CN102942446B CN102942446B CN201210510900.1A CN201210510900A CN102942446B CN 102942446 B CN102942446 B CN 102942446B CN 201210510900 A CN201210510900 A CN 201210510900A CN 102942446 B CN102942446 B CN 102942446B
- Authority
- CN
- China
- Prior art keywords
- gas
- temperature
- hydrogen
- product
- acetic ester
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The present invention relates to a kind of method by acetic ester hydrogenation continuous production ethanol, the method adopts pressure-variable adsorption (PSA) device to reclaim hydrogen boost cycle again in product gas phase, and utilize the gas mixture of reaction heat hot acetic acid ester, circulating hydrogen and fresh hydrogen, unstripped gas after preheating enters reactor after middle pressure steam heating, realizes high acetate transformation efficiency and high ethanol selectivity under catalyst action.Reaction principal product ethanol, a small amount of by product and the liquefaction of unreacted acetic ester are separated and are obtained head product by the gas product be obtained by reacting after gas-liquid separation.The method utilizes the recirculation of PSA recovery hydrogen significantly can reduce the use of raw hydrogen, and make full use of reaction heat preheating reaction raw materials and reduce heating and cooling energy consumption, flow process simply controls easy.
Description
Technical field
The present invention relates to a kind of production method of ethanol.Especially, the present invention relates to a kind of method adopting pressure-variable adsorption to reclaim the acetic ester gas phase hydrogenation synthesizing alcohol of hydrogen recirculation.Belong to chemical technology field.
Background technology
Ethanol (CH
3cH
2oH) be a kind of important industrial chemicals, be widely used in the manufacturing of paint, coating, ink, medicine and food etc. at chemical industry and other industrial circle; Ethanol is again a kind of important clean energy simultaneously, and its oxygen level is high, the latent heat of vaporization is higher, the capability of antidetonance is good, as vehicle fuel, possesses the good characteristics such as burning is more complete, CO quantity discharged is lower, has worldwide obtained and promoted and accreditation.
The feature of National energy distribution is " oil-poor many coals ", and it is the development of Material synthesis ethanol route that the national conditions that petroleum resources are relatively deficient limit with oil.Relative to being in high-order oil price, coal price relative moderate.In recent years, domestic Coal Chemical Industry scale expands rapidly, causes the price of Coal Chemical Industry product acetic acid constantly to decline.Therefore developing with coal is raw material, can be given full play to the advantage of rich coal resources in China by the Technology of acetic ester preparation of ethanol through hydrogenation.
What reported take acetic ester as technique at present more employing Cu series catalysts of catalytic material preparation of ethanol by hydrogenating, and in reaction, acetic ester transformation efficiency can reach more than 95%, and ethanol selectivity can reach more than 97%.And in order to effectively suppress side reaction to occur, it is greatly excessive that hydrogen in reaction needs, and the mol ratio of hydrogen and acetic ester is generally 20 ~ 100:1.In the production technique of routine, because a large amount of nonreactive hydrogen (containing a small amount of inert component and by product) circulates in reactive system circulation loop, affecting hydrogenation reaction effect for ensureing that inert component and hydrogenation byproduct accumulate in circulation gas, needing circulation gas part to speed to put.Put the fresh hydrogen additional amount caused owing to speeding and significantly higher than the fresh hydrogen tolerance needed for hydrogenation reaction, a large amount of wastes of hydrogen can be caused.Simultaneously, reaction product needs at least to be cooled to normal temperature just to be made to coagulate components condense and is separated, and then the hydrogen of the circulating hydrogen of low temperature after being separated, fresh hydrogen and circulation also reheated enter reactor, do like this and certainly will consume amount of heat, cause tremendous economic to lose.
Summary of the invention
The object of the present invention is to provide a kind of method of new acetic ester preparation of ethanol by hydrogenating, the method optimizes reaction process, and economize in raw materials hydrogen largely, saves water coolant and heating steam simultaneously, thus economizes in raw materials and energy, reduce costs.
On the one hand, the invention provides a kind of method by acetic ester shortening continuous production ethanol, said method comprising the steps of:
I) high-temperature hydrogen 5 that temperature is 170-240 DEG C will be obtained after fresh hydrogen 2 preheating;
Ii) be acetic ester 3 after the preheating of 190-250 DEG C by obtaining temperature after acetic ester 1 preheating;
Iii) by step I) high-temperature hydrogen 5 and the step I i that obtain) acetic ester 3 after the preheating that obtains mix after by pressure be 3-5MPa, temperature is that the middle pressure steam of 300-500 DEG C gasifies and is heated to 230-290 DEG C;
Iv) the material that described step I ii) obtains being isolated to temperature is the unstripped gas 8 of 230-290 DEG C and the acetic ester 7 that is not gasified totally, carries out hydrogenation reaction, obtain the high-temperature product gas 9 that temperature is 250-310 DEG C to described unstripped gas 8; By described high-temperature product gas 9 respectively with acetic ester 1 and fresh hydrogen 2 heat exchange, obtain the gas product 11 that temperature is the cooling of 60-90 DEG C; The gas product 11 of described cooling is cooled again and obtains the product gas-liquid 12 that temperature is the gas-liquid two-phase of 30-40 DEG C; Gas-liquid separation is carried out to the product gas-liquid 12 of described gas-liquid two-phase and obtains head product 13 and circulation gas 14; Described circulation gas 14 is removed organic composition wherein through pressure-variable adsorption, obtain the parsing thing 17 of pressure-variable adsorption and the gas product 15 of pressure-variable adsorption, the gas product 15 of described pressure-variable adsorption obtains circulating hydrogen 16 and is used as fresh hydrogen 2 and retrieval system reaction after boosting; With
V) the parsing thing 17 of pressure-variable adsorption is separated together with head product 13, obtains alcohol product 18 and drop a hint 19.
Preferably, described method also comprises the steps vi): by described step I v) in the acetic ester 7 be not gasified totally that obtains turn back to described step I ii) in mix with the acetic ester 3 after described preheating, high-temperature hydrogen 5 after by pressure be 3-5MPa, temperature is that the middle pressure steam of 300-500 DEG C gasifies and is heated to 230-290 DEG C.
Preferably, described step I v) in the purity of circulating hydrogen 16 that obtains be more than 95 % by mole, more preferably more than 96 % by mole.
Preferably, the temperature of described high-temperature hydrogen 5 is 170-235 DEG C, is more preferably 200-230 DEG C.
Preferably, described acetic ester 1 be selected from ritalin and vinyl acetic monomer one or more, and be more preferably vinyl acetic monomer.
Preferably, the temperature of the acetic ester 3 after described preheating is 220-240 DEG C.
Preferably, the temperature of described unstripped gas 8 is 250-270 DEG C.
On the other hand, present invention also offers a kind of for the equipment by acetic ester shortening continuous production ethanol, described equipment comprises:
Gas-liquid separator 23,26,31, for being separated with liquid phase gas phase;
Hydrogen preheater 20,21,25, for carrying out the exchange of heat;
The hydrogenator 24 be connected with described gas-liquid separator 23, for changing into high-temperature product gas 9 by unstripped gas 8;
The pressure-swing absorption apparatus 27 be connected with described gas-liquid separator 26, for removing the organic composition in circulation gas;
Be connected to the recycle compressor 28 between described pressure-swing absorption apparatus 27 and described hydrogen preheater 21, for the circulation gas boosting removing organic composition is obtained circulating hydrogen 16;
The gasifier 22 be connected with described hydrogen preheater 20,21 and described gas-liquid separator 23 respectively, for gasifying to the acetic ester 3 after preheating, high-temperature hydrogen 5 and the acetic ester 7 that is not gasified totally.
Preferably, described equipment also comprises temperature-sensing valve 30, is controlled the middle pressure steam amount of described gasifier 22 by described temperature-sensing valve 30, and then controls the temperature entering the unstripped gas 8 of described hydrogenator 24.
Preferably, described gasifier 22 is also for making liquid phase fully contact and reduce gas phase drag.
The present invention can be realized by following embodiment:
A) in interchanger (also claiming hydrogen preheater) 21, obtain high-temperature hydrogen 5 after heat exchange after being mixed by the circulating hydrogen 16 that fresh hydrogen 2 and technique finally obtain, its temperature is 170-240 DEG C;
B) acetic ester 3 after acetic ester 1 being obtained preheating after heat exchange in interchanger (also claiming acetic ester preheater) 20, temperature is 190-250 DEG C;
C) after being mixed by the acetic ester 3 after high-temperature hydrogen 5, preheating, by pressure, to be 3-5MPa temperature be that the middle pressure steam of 300-500 DEG C gasifies and is heated to 230-290 DEG C;
D) by described step c) material that obtains is isolated to the acetic ester 7 that temperature is 230-290 DEG C of unstripped gas 8 and is not gasified totally; Be that 230-290 DEG C of unstripped gas 8 enters hydrogenator 24 and carry out hydrogenation reaction by the temperature after being separated, obtain the high-temperature product gas 9 that temperature is 250-310 DEG C; By high-temperature product gas 9 respectively with acetic ester 1, fresh hydrogen 2 after interchanger 20 and 21 heat exchange, obtain the gas product 11 that temperature is the cooling of 60-90 DEG C; The gas product 11 of cooling is recycled water in interchanger (also claiming Heat Exchanger in Circulating Water System) 25, is cooled to the product gas-liquid 12 that 30-40 DEG C obtains gas-liquid two-phase; Again the product gas-liquid 12 of gas-liquid two-phase is carried out in gas-liquid separator 26 gas-liquid separation and obtain head product 13 and circulation gas 14; Circulation gas 14 is removed the organic composition in circulation gas 14 through pressure-variable adsorption (PSA) device 27, after recycle compressor 28 boosts, obtain circulating hydrogen 16 and be used as fresh hydrogen 2 and retrieval system reaction; Now, namely described circulating hydrogen 16 mixes hydrogen 4 with the mixture of fresh hydrogen 2;
E) pressure-variable adsorption (PSA) is resolved thing 17 to enter together with head product 13 in the gas-liquid separator 31 of low voltage product, be isolated to alcohol product 18 and drop a hint 19.
An optional embodiment, above-mentioned embodiment also comprises step f): the described acetic ester 7 be not gasified totally is turned back to after mixing with the acetic ester 3 after described preheating, high-temperature hydrogen 5 in described step c) that to be 3-5MPa temperature be that the middle pressure steam of 300-500 DEG C gasifies and is heated to 230-290 DEG C by pressure, circulation like this, finally separates the acetic ester of seldom not yet vaporizing with gas-liquid separator 23;
In the above-described embodiment, described acetic ester is selected from one or more in ritalin and vinyl acetic monomer; Preferably, described acetic ester is vinyl acetic monomer.
In the above-described embodiment, in described step a), the temperature of high-temperature hydrogen 5 is 170-235 DEG C, is preferably 200-230 DEG C; In described step c), control the unstripped gas temperature into hydrogenator by the middle pressure steam amount controlling vaporizer, the gasifier adopted to ensure that liquid phase fully contacts the gas-liquid mass transfer (contact) equipment that also gas phase drag is little; In described step b), the temperature of the acetic ester 3 after preheating is 190-250 DEG C, and preferably, temperature is 220-240 DEG C; In described step d), the temperature of unstripped gas 8 is 230-290 DEG C, is preferably 250-270 DEG C; In described step d), circulation gas 14 adopts PSA to remove organism and obtains the higher circulating hydrogen of hydrogen purity 16 and be used as fresh hydrogen 2 and retrieval system reaction.
Compared with prior art, method by acetic ester hydrogenation continuous production ethanol of the present invention adopts pressure-variable adsorption (PSA) device to reclaim hydrogen boost cycle again in product gas phase, and utilize the gas mixture of reaction heat hot acetic acid ester, circulating hydrogen and fresh hydrogen, unstripped gas after preheating enters reactor after middle pressure steam heating, realizes high acetate transformation efficiency and high ethanol selectivity under catalyst action.Reaction principal product ethanol, a small amount of by product and the liquefaction of unreacted acetic ester are separated and are obtained head product by the gas product be obtained by reacting after gas-liquid separation.The method utilizes the recirculation of PSA recovery hydrogen significantly can reduce the use of raw hydrogen, and make full use of reaction heat preheating reaction raw materials and reduce heating and cooling energy consumption, flow process simply controls easy.In brief, method of the present invention optimizes hydrogen recycle flow process and to economize in raw materials largely hydrogen; Optimize heat exchanger network and save water coolant and heating steam, thus saved raw material and energy, reduce cost.
Accompanying drawing explanation
Below, describe embodiments of the invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 shows the process flow diagram according to method of the present invention; Wherein,
1-acetic ester; 2-fresh hydrogen; Acetic ester after 3-preheating; 4-mixing hydrogen; 5-high-temperature hydrogen; Acetic ester after 6-gasification; The acetic ester that 7-is not gasified totally; 8-unstripped gas; 9-high-temperature product gas; Gas product after 10-cooling; The gas product of 11-cooling; The product gas-liquid of 12-gas-liquid two-phase; 13-head product; 14-circulation gas; The gas product of 15-pressure-variable adsorption; 16-circulating hydrogen; 17-PSA resolves thing; 18-alcohol product; 19-drops a hint; 20-interchanger (acetic ester preheater); 21-interchanger (hydrogen preheater); 22-gasifier; 23,26,31-gas-liquid separator; 24-hydrogenator; 25-interchanger (Heat Exchanger in Circulating Water System); 27-pressure-swing absorption apparatus; 28-recycle compressor; 29-temperature sensor and 30-temperature-sensing valve, unlabelled line is pipeline.
Embodiment
Referring to specific embodiment, the present invention is described.It will be appreciated by those skilled in the art that these embodiments only for illustration of object of the present invention, its scope do not limited the present invention in any way.
embodiment
Below in conjunction with Fig. 1, embodiment is described.In the middle part of hydrogenator 24, load the hydrogenation Cu series catalysts of 3.5L, equigranular porcelain ring with catalyzer is equipped with at reactor two ends, take vinyl acetic monomer as raw material, and the reaction pressure of hydrogenation reaction is 2.5MPa(gauge pressure).
Acetic ester 1 pumps into acetic ester preheater 20 by highly pressurised liquid fresh feed pump, wherein the inlet amount of acetic ester 1 is 2.65kg/h, in acetic ester preheater 20, heat exchange preheating is there is with the high-temperature product gas 9 from hydrogenator 24, and 240 DEG C are heated in acetic ester preheater 20, obtain the acetic ester after preheating 3, the acetic ester 3 after preheating enters the bottom of gasifier 22.In reaction, the mixing hydrogen 4 obtained after fresh hydrogen 2 being mixed with circulating hydrogen 16 is fed in hydrogen preheater 21, obtains the high-temperature hydrogen 5 that temperature is 220 DEG C after heat exchange, and wherein, the flow of mixing hydrogen 4 is 48m
3/ h.Initial reaction stage, by circulation gas 14 directly emptying, makes circulating hydrogen 16 start charging after system stability, and by regulating the amount of fresh hydrogen 2 in reaction process, the mol ratio keeping hydrogen and acetic ester is about 70:1.
By acetic ester 3 and after high-temperature hydrogen 5, preheating, optionally, the acetic ester 7(be not gasified totally is represented by dashed line) be blended in gasifier 22 that to be 3-5MPa temperature be that the middle pressure steam of 300-500 DEG C gasifies and is heated to 250 DEG C by pressure.After heat exchange, the acetic ester of the overwhelming majority is vaporized and enters subsequent processing with hydrogen by the discharge of gas-liquid separator 23 top, the acetic ester 7 be not gasified totally of minute quantity is returned to the bottom of gasifier 22 by gas-liquid separator 23 simultaneously, carries out cyclically gasification operation.Present method controls the aperture of temperature-sensing valve 30 by temperature sensor 29 temperature sensor thus controls middle pressure steam amount to control the temperature of the imported materials gas 8 of hydrogenator 24 simultaneously, described temperature is controlled as 250 DEG C, and the molar fraction of other components the such as wherein molar fraction of hydrogen is 96.6%, the molar fraction of acetic ester is 1.4%, nitrogen is 2.0%.Unstripped gas 8 enters hydrogenator 24 and Cu series catalysts contact reacts, obtains high-temperature product gas 9.The transformation efficiency of acetic ester is to 98.5% by analysis, and hydrogenator 24 exports each component in high-temperature product gas 9 counts with molar fraction: hydrogen 95.1%, acetic ester 0.3%, ethanol 2.6%, other components 2.0% such as water, nitrogen.Because reaction is thermopositive reaction, exports high-temperature product gas 9 temperature at hydrogenator 24 and be increased to 270 DEG C.High-temperature product gas 9 and acetic ester 1 are down to 242 DEG C after heat exchange in hydrogen preheater 20, are cooled to 82 DEG C of gas products 11 obtaining cooling after the gas product 10 after cooling enters hydrogen preheater 21 and mixes hydrogen 4 heat exchange.The gas product 11 of cooling is recycled water and is cooled to 40 DEG C in Heat Exchanger in Circulating Water System 25, obtains the product gas-liquid 12 of gas-liquid two-phase.
The product gas-liquid 12 of gas-liquid two-phase enters gas product liquid/gas separator 26 and carries out gas-liquid separation, obtains circulation gas 14 and head product 13.Gas product liquid/gas separator 26 top gas (circulation gas 14) temperature out is 40 DEG C, and wherein each component of gas is counted with molar fraction: hydrogen 96.9%, acetic ester 0.1%, ethanol 0.8%, other components 2.1% such as water, nitrogen; The temperature of bottom liquid phases head product 13 is 40 DEG C, and wherein each component composition of liquid phase head product 13 is counted with molar fraction: hydrogen 0.2%, acetic ester 0.6%, ethanol 94.7%, other components 4.4% such as water, nitrogen.Carry out separation with gas-liquid separator 31 pairs of head products 13 of low voltage product and obtain product 18, its temperature is 40 DEG C, and in product 18, each component composition is counted with molar fraction: hydrogen 0.06%, acetic ester 0.6%, alcohol 95 .2%, other components 4.2% such as water, nitrogen.
Above-mentioned circulation gas 14 is obtained after the organic substance that pressure-variable adsorption (PSA) device 27 removes wherein comparatively pure hydrogen (that is, the gas product 15 of pressure-variable adsorption), its each component is counted with molar fraction: hydrogen 99.8%, other components 0.2% such as nitrogen.After recycle compressor 28 boosts, obtain circulating hydrogen 16 again and be back to system response.
Be 98.5% according to the average conversion of analytical results acetic ester, the average selectivity of ethanol is 98.8%.
In the prior art, because a large amount of nonreactive hydrogen (containing a small amount of inert component and by product) circulates in reactive system circulation loop, hydrogenation reaction effect is affected for ensureing that inert component and hydrogenation byproduct accumulate in circulation gas, need circulation gas part to speed to put, and the volume ratio of putting with circulating of speeding is generally 0.08-0.1.But, calculate based on the inlet amount of the present embodiment, in prior art, adopt the mode of putting of speeding then to need supplementary fresh hydrogen tolerance to be 2m
3/ h, it is 0.75m that the present invention adopts the metacyclic mode of PSA recover hydrogen then only need supplement fresh hydrogen tolerance
3/ h, adopts this technique can save fresh hydrogen tolerance about 60% as calculated.
Similarly, produce ethanol by the method for prior art, need, by circulating hydrogen and acetic ester heating, to need to cool reaction product simultaneously.In this process, for the thermal load Q=3.5Kw of heating cycle hydrogen and acetic ester or cooling reaction product, required 3.4MPa(absolute pressure) superheated vapour (temperature is 430 DEG C) about 5kgh
-1or 137kgh
-1.With product gauge, needing quantity of steam to be about 2kg/kg product or recirculated water is about 40kg/kg product, is by 2.65kgh in embodiments of the invention here
-1the production capacity of feedstock amount (being equivalent to the pilot scale of annual output 20 tons of ethanol) calculate.But method of the present invention does not need the step of the heating and cooling in above-mentioned calculating, the quantity of steam therefore can saved and quantity of circulating water equal quantity of steam and the quantity of circulating water of the heating and cooling calculated above.
Claims (15)
1., by a method for acetic ester shortening continuous production ethanol, said method comprising the steps of:
I) fresh hydrogen (2) and circulating hydrogen (16) are mixed to get mix hydrogen (4) by with cooling after gas product (10) heat exchange carry out preheating after obtain the high-temperature hydrogen (5) that temperature is 170-240 DEG C;
Ii) be acetic ester (3) after the preheating of 190-250 DEG C by acetic ester (1) by obtaining temperature after carrying out preheating with high-temperature product gas (9) heat exchange;
Iii) by step I) high-temperature hydrogen (5) and the step I i that obtain) acetic ester (3) after the preheating that obtains mix after by pressure be 3-5MPa, temperature is that the middle pressure steam of 300-500 DEG C gasifies and is heated to 230-290 DEG C;
Iv) by described step I ii) to be isolated to temperature be the unstripped gas (8) of 230-290 DEG C and the acetic ester (7) that is not gasified totally for the material that obtains, hydrogenation reaction is carried out to described unstripped gas (8), obtains the high-temperature product gas (9) that temperature is 250-310 DEG C; Described high-temperature product gas (9) and acetic ester (1) heat exchange are obtained the gas product (10) after lowering the temperature, gas product (10) after cooling enters hydrogen preheater (21) and mixes hydrogen (4) heat exchange, obtains the gas product (11) that temperature is the cooling of 60-90 DEG C; The gas product (11) of described cooling is cooled again and obtains the product gas-liquid (12) that temperature is the gas-liquid two-phase of 30-40 DEG C; Gas-liquid separation is carried out to the product gas-liquid (12) of described gas-liquid two-phase and obtains head product (13) and circulation gas (14); Described circulation gas (14) is removed organic composition wherein through pressure-variable adsorption, obtain the parsing thing (17) of pressure-variable adsorption and the gas product (15) of pressure-variable adsorption, the gas product (15) of described pressure-variable adsorption obtains circulating hydrogen (16) and is used as fresh hydrogen (2) and retrieval system reaction after boosting; With
V) the parsing thing (17) of pressure-variable adsorption is separated together with head product (13), obtains alcohol product (18) and drop a hint (19).
2. method according to claim 1, wherein, described method also comprises the steps vi): by described step I v) in the acetic ester (7) be not gasified totally that obtains turn back to described step I ii) in mix with the acetic ester (3) after described preheating, high-temperature hydrogen (5) after by pressure be 3-5MPa, temperature is that the middle pressure steam of 300-500 DEG C gasifies and is heated to 230-290 DEG C.
3. method according to claim 1, wherein, described step I v) in the purity of circulating hydrogen (16) that obtains be more than 95 % by mole.
4. method according to claim 3, wherein, described step I v) in the purity of circulating hydrogen (16) that obtains more than 96 % by mole.
5. method according to claim 1, wherein, the temperature of described high-temperature hydrogen (5) is 170-235 DEG C.
6. method according to claim 5, wherein, the temperature of described high-temperature hydrogen (5) is 200-230 DEG C.
7. method according to claim 2, wherein, the temperature of described high-temperature hydrogen (5) is 170-235 DEG C.
8. method according to claim 7, wherein, the temperature of described high-temperature hydrogen (5) is 200-230 DEG C.
9. according to the method in any one of claims 1 to 3, wherein, described acetic ester (1) is selected from one or more in ritalin and vinyl acetic monomer.
10. method according to claim 9, wherein, described acetic ester (1) is vinyl acetic monomer.
11. methods according to any one of claim 1 to 8, wherein, the temperature of the acetic ester (3) after described preheating is 220-240 DEG C.
12. methods according to any one of claim 1 to 8, wherein, the temperature of described unstripped gas (8) is 250-270 DEG C.
13. 1 kinds for the equipment by acetic ester shortening continuous production ethanol, described equipment comprises:
Gas-liquid separator (23,26,31), for being separated with liquid phase gas phase;
Acetic ester preheater (20), hydrogen preheater (21), Heat Exchanger in Circulating Water System (25), for carrying out the exchange of heat;
The hydrogenator (24) be connected with described gas-liquid separator (23), for changing into high-temperature product gas (9) by unstripped gas (8);
The pressure-swing absorption apparatus (27) be connected with described gas-liquid separator (26), for removing the organic composition in circulation gas;
Be connected to the recycle compressor (28) between described pressure-swing absorption apparatus (27) and described hydrogen preheater (21), for the circulation gas boosting removing organic composition is obtained circulating hydrogen (16);
The gasifier (22) be connected with described acetic ester preheater (20), hydrogen preheater (21) and described gas-liquid separator (23) respectively, for gasifying to the acetic ester (3) after preheating, high-temperature hydrogen (5) and the acetic ester (7) that is not gasified totally;
Described acetic acid preheater (20) is for making acetic ester (1) and high-temperature product gas (9) heat exchange to obtain the acetic ester after preheating (3);
Described hydrogen preheater (21) is for making gas product (10) heat exchange after mixing hydrogen (4) and cooling to obtain the high-temperature hydrogen after preheating (5).
14. equipment according to claim 13, wherein, described equipment also comprises temperature-sensing valve (30), and the middle pressure steam amount controlling described gasifier (22) by described temperature-sensing valve (30) controls to enter the temperature of the unstripped gas (8) of described hydrogenator (24).
15. equipment according to claim 13 or 14, wherein, described gasifier (22) is also for making liquid phase fully contact and reduce gas phase drag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210510900.1A CN102942446B (en) | 2012-12-03 | 2012-12-03 | A kind of method reclaiming the acetic ester preparation of ethanol by hydrogenating of hydrogen recirculation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210510900.1A CN102942446B (en) | 2012-12-03 | 2012-12-03 | A kind of method reclaiming the acetic ester preparation of ethanol by hydrogenating of hydrogen recirculation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102942446A CN102942446A (en) | 2013-02-27 |
| CN102942446B true CN102942446B (en) | 2015-09-23 |
Family
ID=47725467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210510900.1A Active CN102942446B (en) | 2012-12-03 | 2012-12-03 | A kind of method reclaiming the acetic ester preparation of ethanol by hydrogenating of hydrogen recirculation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102942446B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588619B (en) * | 2013-11-20 | 2016-08-17 | 天津大学 | The production method of methyl acetate preparation of ethanol by hydrogenating and device |
| CN105439816B (en) * | 2014-08-27 | 2017-10-27 | 中国石油化工股份有限公司 | Acetic acid ester through hydrogenation produces the process of ethanol |
| CN105523880B (en) * | 2014-09-29 | 2018-01-26 | 大唐国际化工技术研究院有限公司 | A kind of method by acetate ethene |
| CN105585421B (en) * | 2014-10-24 | 2018-01-09 | 中国石油化工股份有限公司 | The method that ester high selectivity prepares alcohol |
| CN105523887B (en) * | 2014-10-24 | 2018-07-17 | 中国石油化工股份有限公司 | The highly selective method for preparing alcohol of ester |
| CN104860796B (en) * | 2015-05-04 | 2018-03-02 | 河南顺达化工科技有限公司 | A kind of technique with heat-exchange unit synthesizing alcohol |
| CN105669379B (en) * | 2016-04-08 | 2018-02-23 | 河南顺达化工科技有限公司 | A kind of technique of ethyl acetate preparation of ethanol through hydrogenation |
| CN106008155A (en) * | 2016-06-22 | 2016-10-12 | 江苏索普（集团）有限公司 | Integrated device and method for preparing ethanol from acetic acid and ethyl acetate through hydrogenation reaction |
| CN109422623A (en) * | 2017-08-20 | 2019-03-05 | 杭州林达化工技术工程有限公司 | A kind of energy-saving acetic acid adds the production technology and its device of hydrogen or ethyl acetate preparation of ethanol by hydrogenating |
| CN113461485B (en) * | 2021-06-18 | 2023-08-22 | 国家能源投资集团有限责任公司 | System, method and application for preparing crude ethanol by hydrogenation of hydrogenation raw material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202139179U (en) * | 2011-01-17 | 2012-02-08 | 山东华鲁恒升集团德化设计研究有限公司 | Device for producing ethylene glycol by dimethyloxalate with hydrogenation |
| CN102659513A (en) * | 2012-04-28 | 2012-09-12 | 上海戊正工程技术有限公司 | Process for producing alcohol and selectively co-producing 2-butanol by utilizing acetate and matching process system thereof |
| CN102718627A (en) * | 2012-06-25 | 2012-10-10 | 西安隽通电子设备有限公司 | Preparation method of ethanol by adding hydrogen to ethyl acetate |
| CN102766021A (en) * | 2012-07-24 | 2012-11-07 | 唐山市冀东溶剂有限公司 | Production system and production method for continuously producing ethanol by ethyl acetate through using hydrogenation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009532483A (en) * | 2006-04-05 | 2009-09-10 | ウッドランド バイオフュールズ インコーポレイテッド | Method for converting biomass to ethanol via synthesis gas |
| US8575404B2 (en) * | 2010-05-07 | 2013-11-05 | Celanese International Corporation | Process for recycling gas from acetic acid hydrogenation |
-
2012
- 2012-12-03 CN CN201210510900.1A patent/CN102942446B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202139179U (en) * | 2011-01-17 | 2012-02-08 | 山东华鲁恒升集团德化设计研究有限公司 | Device for producing ethylene glycol by dimethyloxalate with hydrogenation |
| CN102659513A (en) * | 2012-04-28 | 2012-09-12 | 上海戊正工程技术有限公司 | Process for producing alcohol and selectively co-producing 2-butanol by utilizing acetate and matching process system thereof |
| CN102718627A (en) * | 2012-06-25 | 2012-10-10 | 西安隽通电子设备有限公司 | Preparation method of ethanol by adding hydrogen to ethyl acetate |
| CN102766021A (en) * | 2012-07-24 | 2012-11-07 | 唐山市冀东溶剂有限公司 | Production system and production method for continuously producing ethanol by ethyl acetate through using hydrogenation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102942446A (en) | 2013-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102942446B (en) | A kind of method reclaiming the acetic ester preparation of ethanol by hydrogenating of hydrogen recirculation | |
| CN101255109B (en) | Technique for producing propenoic acid by dehydrating biomass lactic acid | |
| CN109503326B (en) | Process for indirectly producing ethanol by dimethyl ether | |
| CN103804142B (en) | A kind of system and method for hydrogenation of oxalate for preparing ethylene glycol | |
| CN102775274B (en) | System and method for preparing ethylene glycol through oxalate hydrogenation | |
| CN108997085B (en) | Method and system for recovering by-products in dimethyl oxalate synthesis process | |
| CN103467248B (en) | A kind of energy-saving ester through hydrogenation technique | |
| CN101830807B (en) | Synthesizing device and process for alkyl nitrite | |
| CN103451027B (en) | Esterification method for preparing biodiesel using waste oils and fats | |
| CN101735182B (en) | Process for continuously producing succinic anhydride through hydrogenation of maleic anhydride | |
| CN102675093A (en) | Process for synthesizing n-butyl acetate | |
| CN104250210A (en) | Method for production of acetic acid by methanol carbonylation | |
| CN102423539B (en) | Energy-saving technology of catalytic reaction distillation process and device thereof | |
| CN111943849B (en) | Efficient energy-saving ethyl lactate reactive distillation production method and device | |
| CN101798265B (en) | Novel method for preparing vinyl acetate from bioethanol | |
| CN102718627B (en) | Preparation method of ethanol by adding hydrogen to ethyl acetate | |
| CN104250209A (en) | Method for production of acetic acid by methanol carbonylation | |
| CN213050530U (en) | High-efficiency energy-saving ethyl lactate reaction rectification production device | |
| CN103540376B (en) | Synthetic gas methanation substitutes the method for Sweet natural gas | |
| CN109748791A (en) | Produce the power-economizing method of dimethyl adipate | |
| CN104262173A (en) | Method for synthesizing diglycolamine from diglycol by virtue of low-pressure process | |
| CN104086346B (en) | A kind of energy reclaiming method of oxygenatedchemicals propylene technique | |
| CN111253213B (en) | Technological method and system for preparing ethanol by acetate hydrogenation | |
| CN204939338U (en) | A kind of reactive system of coking crude benzene hydrogenation technique | |
| CN202376971U (en) | Tubular continuous esterification reaction device for synthesizing binary carboxylic ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |