CN102908958B - A kind of method by liquid-phase acetic acid and hydrogen mixed gas - Google Patents
A kind of method by liquid-phase acetic acid and hydrogen mixed gas Download PDFInfo
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- CN102908958B CN102908958B CN201210433499.6A CN201210433499A CN102908958B CN 102908958 B CN102908958 B CN 102908958B CN 201210433499 A CN201210433499 A CN 201210433499A CN 102908958 B CN102908958 B CN 102908958B
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Abstract
By a method for liquid-phase acetic acid and hydrogen mixed gas, be the gas mixing gasifying in evaporimeter by acetic acid and hydrogen, before mixing, hydrogen temperature is 100-300 DEG C, and acetic acid temperature is 30-160 DEG C, and acetic acid and Hydrogen Vapor Pressure are 1.0-20.0MPa.By controlling evaporimeter top mist temperature, the mist of the mol ratio obtaining H2/ acetic acid to be 1-250 pressure be 1.0-20.0MPa.Acetic acid can gasify by the present invention at the temperature lower than acetic acid boiling point under operating pressure, solves liquid-phase acetic acid High Temperature Corrosion, and can well control H2/ acetic acid mol ratio in mist.In addition, in the gas and vapor permeation gasification process of liquid-phase acetic acid and hydrogen, by the heating of external heat source Dichlorodiphenyl Acetate with the gasification latent heat providing acetic acid, the requirement of external supplying heat source can be reduced.
Description
Technical field
The present invention relates to chemical production field, be specifically related to a kind of method gasified by the gas and vapor permeation of liquid-phase acetic acid and hydrogen.
Technical background
Ethanol is a kind of important basic chemical industry raw material and organic solvent, or the free of contamination vehicle fuel of desirable high-octane rating and additive thereof.The industrial process of existing ethanol adopts fermentation method substantially, different according to raw material, can be divided into amylofermentation ethanol and cellulose ethanol.Alcohol fuel as clean energy resource development rapidly, but in China because cost of material and food problem restriction can not significantly be promoted, needs the new way of exploitation alcohol production badly.In recent years, along with the expansion of industrial acetic acid production capacity, acetic acid price continued to drop, and adopted acetic acid preparation of ethanol by hydrogenating technology to possess good economy, caused the attention of domestic and international scientific research institutions and large enterprise.
Acetic acid is the organic acid that a kind of corrosivity is very strong, liquid-phase acetic acid has corrosivity and can destroy catalyst and consersion unit under worst hot case, under worst hot case, the selection of acetic acid equipment is more difficult, and the acetic acid of current more than 120 DEG C then mainly adopts Hastelloy and zirconium material.And the acetic acid in gas phase has less corrosivity than the acetic acid in liquid phase, the needs to higher level material can be reduced, therefore reduce costs.
In recent years, acetic acid gas phase hydrogenation ethanol technology is extensively studied, and as USP 4,517,391 have reported Co-Cu-Mn-Mo sedimentation type catalyst, acetic acid gas phase hydrogenation can be converted into ethanol.USP 7,608,744 reports the catalyst based patent of mineral carbon load Co being applicable to acetic acid gas phase hydrogenation ethanol.USP 4,777, acetic acid also reacts by 303 in the gas phase.
Method by making gasification acetic acid hydrogenation produce ethanol of the Introduction To Cn Patent of application number 201180001961.9.In presence of hydrogen by acetic acid gasification thus the hydrogenation technique of producing and ethanol of making a living provides steam feed stream.Can by acetic acid in the temperature gasified lower than acetic acid boiling point under reactor operating pressure.Acetic acid described in this patent and hydrogen mixed gas method have the following disadvantages: first, accurately cannot control the mol ratio of H2/ acetic acid in mist.Secondly, hydrogen specific heat is little, and under high pressure hydrogen need be heated to very high-temperature guarantee acetic acid gasification, and external supplying heat source requires higher.
Summary of the invention
The object of this invention is to provide a kind of method by liquid-phase acetic acid and hydrogen mixed gas.
For achieving the above object, a kind of method by liquid-phase acetic acid and hydrogen mixed gas provided by the invention, by gas mixing gasifying in evaporimeter of acetic acid and hydrogen, before mixing, the temperature of the gas of hydrogen is 100-300 DEG C, acetic acid temperature is 30-160 DEG C, the gas-operated pressure of acetic acid and hydrogen is 1.0-20.0MPa, and under this operating pressure, evaporimeter top mist temperature is lower than the acetic acid boiling temperature under operating pressure.Gained mixture pressure is 1.0-20.0MPa, and in mist, the mol ratio of H2/ acetic acid is 1-250.
Mixing gasifying principle of the present invention is: liquid-phase acetic acid enters evaporimeter from bottom, acetic acid is that continuous phase is distributed in evaporimeter, the gas of hydrogen passes through acetate layer in the mode of bubbling, with acetic acid contact process, under the effect of external heat source, by controlling evaporimeter top mist temperature, to realize the control for H2/ acetic acid mol ratio in mist.
Mixing gasifying condition of the present invention is: the gas temperature of hydrogen is 100-300
oc; Acetic acid temperature is 30-160
oc; The gas-operated pressure of acetic acid and hydrogen is 1.0-20.0MPa; Mixture pressure is 1.0-20.0MPa; In mist, the mol ratio of H2/ acetic acid is 1-250.
Hydrogen described in the gas of hydrogen used in the present invention can be hydrogen, also can be carbon monoxide, methane, acetylene, ethene, ethane, oxygen.Hydrogen content is greater than 0 at 0-100% in the gas of the hydrogen adopted.
Acetic acid used in the present invention can be acetic acid, also can be the carboxylic-acid substance such as formic acid, propionic acid, also can be the anhydrides such as acetic anhydride, propionic andydride material, also can be the aldehyde material such as acetaldehyde, propionic aldehyde.
In evaporimeter of the present invention, the gas of hydrogen is decentralized photo.
The gas of acetic acid used in the present invention and hydrogen derived from any suitable source, can comprise natural gas, oil, coal, living beings etc.Carbonylation of methanol, oxidation of acetaldehyde, ethylene, oxidative fermentation and anaerobic fermentation can be passed through and produce acetic acid.Can pass through electrolysis hydrogen, water-gas method hydrogen, by the synthesis gas of oil pyrolysis and natural gas hydrogen preparation gas.
The gas of hydrogen of the present invention can through pressure-swing absorber, film, packed tower or their combination to remove the impurity such as carbon monoxide and oxygen in hydrogen feed line.The gas of described hydrogen can be preheated by another stream of non-direct contact type heat exchanger, and external heat source also can be adopted to preheat.
Acetic acid of the present invention can be preheated by another stream of non-direct contact type heat exchanger, and external heat source also can be adopted to preheat.
External heat source of the present invention can be steam, conduction oil, fused salt, flue gas, and Electric heating also can be adopted to heat.
The material of evaporimeter of the present invention can be the corrosion-resistant metal materials such as stainless steel, dual phase steel, senior austenitic stainless steel, such as 304,316L, 2205,2507,904L, 254SMo etc., also can be the more high-grade resistant alloy such as nickel-base alloy, titanium alloy, zircaloy, such as G3, C276,625,800H, Ti2, ZR702 etc.The structure of evaporimeter of the present invention can be shell-and-tube, bushing type, coiled or jacket type.
Present invention obtains national high-tech research development plan (863 plan) to subsidize, compared with prior art, the invention has the advantages that: at the temperature lower than acetic acid boiling point under operating pressure, acetic acid is gasified, solve liquid-phase acetic acid High Temperature Corrosion, and H2/ acetic acid mol ratio in mist can well be controlled.In addition, compared with the Chinese patent of application number 201180001961.9, acetic acid gasifies by this patent in presence of hydrogen, hydrogen specific heat is little, under high pressure hydrogen need be heated to very high-temperature guarantee acetic acid gasification, and the external supplying heat source of this patent requires higher, and we are in the gas and vapor permeation gasification process of liquid-phase acetic acid and hydrogen, by the heating of external heat source Dichlorodiphenyl Acetate with the gasification latent heat providing acetic acid, the requirement of external supplying heat source can be reduced.
Accompanying drawing explanation
Fig. 1 is evaporimeter schematic diagram.
Detailed description of the invention
The invention provides a kind of method by liquid-phase acetic acid and hydrogen mixed gas.
Below by specific embodiment, the present invention will be further described.
Embodiment 1
With reference to Fig. 1, this detailed description of the invention by the following technical solutions: temperature 160
othe acetic acid 1 of C, pressure 1MPa enters evaporimeter from bottom, and acetic acid is that continuous phase is distributed in evaporimeter; Temperature 230
othe gas 2 of the hydrogen of C, pressure 1MPa passes through acetate layer in the mode of bubbling, with acetic acid contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that H2/ acetic acid mol ratio is 15, the mist of pressure 1MPa.Under 1MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the acetic acid boiling temperature under this operating pressure.
In embodiment 2 to embodiment 7, each technological parameter data are in table 1, and other conditions are identical with embodiment 1.
Embodiment 8
Temperature 30
othe propionic aldehyde 1 of C, pressure 1MPa enters evaporimeter from bottom, and propionic aldehyde is that continuous phase is distributed in evaporimeter; Temperature 100
othe gas 2 of the hydrogen of C, pressure 1MPa passes through propionic aldehyde layer in the mode of bubbling, with propionic aldehyde contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that H2/ propionic aldehyde mol ratio is 1, the mist of pressure 1MPa.Under 1MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the propionic aldehyde boiling temperature under this operating pressure.
Embodiment 9
Temperature 160
othe propionic aldehyde 1 of C, pressure 20MPa enters evaporimeter from bottom, and propionic aldehyde is that continuous phase is distributed in evaporimeter; Temperature 300
othe gas 2 of the hydrogen of C, pressure 20MPa passes through propionic aldehyde layer in the mode of bubbling, with propionic aldehyde contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that H2/ propionic aldehyde mol ratio is 250, the mist of pressure 20MPa.Under 20MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the propionic aldehyde boiling temperature under this operating pressure.
Embodiment 10
Temperature 30
othe acetaldehyde 1 of C, pressure 1MPa enters evaporimeter from bottom, and acetaldehyde is that continuous phase is distributed in evaporimeter; Temperature 100
othe gas 2 of the hydrogen of C, pressure 1MPa passes through acetaldehyde layer in the mode of bubbling, with acetaldehyde contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that H2/ acetaldehyde mol ratio is 1, the mist of pressure 1MPa.Under 1MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the acetaldehyde boiling temperature under this operating pressure.
Embodiment 11
Temperature 160
othe acetaldehyde 1 of C, pressure 20MPa enters evaporimeter from bottom, and acetaldehyde is that continuous phase is distributed in evaporimeter; Temperature 300
othe gas 2 of the hydrogen of C, pressure 20MPa passes through acetaldehyde layer in the mode of bubbling, with acetaldehyde contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that H2/ acetaldehyde mol ratio is 250, the mist of pressure 20MPa.Under 20MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the acetaldehyde boiling temperature under this operating pressure.
Embodiment 12
Temperature 30
othe acetaldehyde 1 of C, pressure 1MPa enters evaporimeter from bottom, and acetaldehyde is that continuous phase is distributed in evaporimeter; Temperature 100
othe oxygenous gas 2 of C, pressure 1MPa passes through acetaldehyde layer in the mode of bubbling, with acetaldehyde contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that O2/ acetaldehyde mol ratio is 1, the mist of pressure 1MPa.Under 1MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the acetaldehyde boiling temperature under this operating pressure.
Embodiment 13
Temperature 160
othe acetaldehyde 1 of C, pressure 20MPa enters evaporimeter from bottom, and acetaldehyde is that continuous phase is distributed in evaporimeter; Temperature 300
othe oxygenous gas 2 of C, pressure 20MPa passes through acetaldehyde layer in the mode of bubbling, with acetaldehyde contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that O2/ acetaldehyde mol ratio is 250, the mist of pressure 20MPa.Under 20MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the acetaldehyde boiling temperature under this operating pressure.
Embodiment 14
Temperature 30
othe acetic acid 1 of C, pressure 1MPa enters evaporimeter from bottom, and acetic acid is that continuous phase is distributed in evaporimeter; Temperature 100
othe gas 2 containing ethene of C, pressure 1MPa passes through acetate layer in the mode of bubbling, with acetic acid contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that ethene/acetic acid mol ratio is 1, the mist of pressure 1MPa.Under 1MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the acetic acid boiling temperature under this operating pressure.
Embodiment 15
Temperature 160
othe acetic acid 1 of C, pressure 20MPa enters evaporimeter from bottom, and acetic acid is that continuous phase is distributed in evaporimeter; Temperature 300
othe gas 2 containing ethene of C, pressure 20MPa passes through acetate layer in the mode of bubbling, with acetic acid contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that ethene/acetic acid mol ratio is 250, the mist of pressure 20MPa.Under 20MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the acetic acid boiling temperature under this operating pressure.
Embodiment 16
Temperature 30
othe acetic acid 1 of C, pressure 1MPa enters evaporimeter from bottom, and acetic acid is that continuous phase is distributed in evaporimeter; Temperature 100
othe gas 2 containing acetylene of C, pressure 1MPa passes through acetate layer in the mode of bubbling, with acetic acid contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that acetylene/acetic acid mol ratio is 1, the mist of pressure 1MPa.Under 1MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the acetic acid boiling temperature under this operating pressure.
Embodiment 17
Temperature 160
othe acetic acid 1 of C, pressure 20MPa enters evaporimeter from bottom, and acetic acid is that continuous phase is distributed in evaporimeter; Temperature 300
othe gas 2 containing acetylene of C, pressure 20MPa passes through acetate layer in the mode of bubbling, with acetic acid contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that acetylene/acetic acid mol ratio is 250, the mist of pressure 20MPa.Under 20MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the acetic acid boiling temperature under this operating pressure.
Embodiment 18
Temperature 30
othe propionic acid 1 of C, pressure 1MPa enters evaporimeter from bottom, and propionic acid is that continuous phase is distributed in evaporimeter; Temperature 100
othe gas 2 of the hydrogen of C, pressure 1MPa passes through propionic acid layer in the mode of bubbling, with propionic acid contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that hydrogen/propionic acid mol ratio is 1, the mist of pressure 1MPa.Under 1MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the propionic acid boiling temperature under this operating pressure.
Embodiment 19
Temperature 160
othe propionic acid 1 of C, pressure 20MPa enters evaporimeter from bottom, and propionic acid is that continuous phase is distributed in evaporimeter; Temperature 300
othe gas 2 of the hydrogen of C, pressure 20MPa passes through propionic acid layer in the mode of bubbling, with propionic acid contact process, under the effect of external heat source, by controlling evaporimeter top mist 3 temperature, obtain that hydrogen/propionic acid mol ratio is 250, the mist of pressure 20MPa.Under 20MPa operating pressure, mist 3 temperature in evaporimeter top is lower than the propionic acid boiling temperature under this operating pressure.
Claims (4)
1., by a method for liquid-phase acetic acid and hydrogen mixed gas, it is characterized in that being that the acetic acid of 30-160 DEG C inputs evaporimeter from bottom by temperature, acetic acid is that continuous phase is distributed in evaporimeter; Temperature is that the gas of the hydrogen of 100-300 DEG C passes through acetate layer in the mode of bubbling, with acetic acid contact process, under the effect of external heat source, by controlling evaporimeter top mist temperature, the mist of the mol ratio obtaining H2/ acetic acid to be 1-250 pressure be 1.0-20.0MPa; Before mixing, the gas-operated pressure of acetic acid and hydrogen is 1.0-20.0MPa; Under this operating pressure, evaporimeter top mist temperature is lower than the acetic acid boiling temperature under operating pressure, and the gas of hydrogen is decentralized photo in evaporimeter.
2. the method by liquid-phase acetic acid and hydrogen mixed gas according to claim 1, wherein the hydrogen oxygen described in gas of hydrogen, ethylene gas, acetylene gas any one replace; Acetic acid adopts any one replacement of acetaldehyde, propionic aldehyde, propionic acid.
3. the method by liquid-phase acetic acid and hydrogen mixed gas according to claim 1, in the gas of wherein adopted hydrogen, hydrogen content is greater than 0 at 0-100%.
4. the method by liquid-phase acetic acid and hydrogen mixed gas according to claim 1, the material of wherein said evaporimeter is corrosion resisting alloy.
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| CN201210433499.6A CN102908958B (en) | 2012-11-02 | 2012-11-02 | A kind of method by liquid-phase acetic acid and hydrogen mixed gas |
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| CN201210433499.6A CN102908958B (en) | 2012-11-02 | 2012-11-02 | A kind of method by liquid-phase acetic acid and hydrogen mixed gas |
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| CN102908958B true CN102908958B (en) | 2015-10-28 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4517391A (en) * | 1982-06-04 | 1985-05-14 | Basf Aktiengesellschaft | Continuous preparation of ethanol |
| US4990655A (en) * | 1985-04-13 | 1991-02-05 | Bp Chemicals Limited | Alcohols production by hydrogenation of carboxylic acids |
| CN102421732A (en) * | 2010-02-02 | 2012-04-18 | 国际人造丝公司 | Process for vaporizing acetic acid for hydrogenation processes to produce ethanol |
-
2012
- 2012-11-02 CN CN201210433499.6A patent/CN102908958B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4517391A (en) * | 1982-06-04 | 1985-05-14 | Basf Aktiengesellschaft | Continuous preparation of ethanol |
| US4990655A (en) * | 1985-04-13 | 1991-02-05 | Bp Chemicals Limited | Alcohols production by hydrogenation of carboxylic acids |
| CN102421732A (en) * | 2010-02-02 | 2012-04-18 | 国际人造丝公司 | Process for vaporizing acetic acid for hydrogenation processes to produce ethanol |
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Inventor after: Song Qinhua Inventor after: Peng Jie Inventor after: Tang Li Inventor after: Yu Qingsheng Inventor after: Sun Rongyi Inventor after: Xia Wu Inventor after: Shao Shouyan Inventor after: Xiao Xiaoyu Inventor after: Ling Chen Inventor after: Wang Liushu Inventor after: Zhu Guisheng Inventor after: Yang Jun Inventor after: Zhu Huaisong Inventor before: Song Qinhua Inventor before: Peng Jie Inventor before: Tang Li Inventor before: Xia Wu Inventor before: Shao Shouyan Inventor before: Xiao Xiaoyu Inventor before: Ling Chen Inventor before: Wang Liushu Inventor before: Zhu Guisheng Inventor before: Yang Jun Inventor before: Zhu Huaisong |
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Free format text: CORRECT: INVENTOR; FROM: SONG QINHUA XIA WU SHAO SHOUYAN XIAO XIAOYU LING CHEN WANG LIUSHU ZHU GUISHENG YANG JUN ZHU HUAISONG PENG JIE TANG LI TO: SONG QINHUA XIA WU SHAO SHOUYAN XIAO XIAOYU LING CHEN WANG LIUSHU ZHU GUISHENG YANG JUN ZHU HUAISONG PENG JIE TANG LI YU QINGSHENG SUN RONGYI |
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Effective date of registration: 20200106 Address after: 212006 No. 88 Qiusuo Road, Jingkou District, Zhenjiang City, Jiangsu Province Co-patentee after: China Wuhuan Engineering Co., Ltd. Patentee after: Jiangsu Sopo Chemical Co.,Ltd. Address before: 212006 Long Gang, Dantu, Jiangsu, Zhenjiang Co-patentee before: China Wuhuan Engineering Co., Ltd. Patentee before: Jiangsu Soap (Group) Co., Ltd. |
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