CN102530857A - Method for producing hydrogen gas by using acetic acid tail gas - Google Patents
Method for producing hydrogen gas by using acetic acid tail gas Download PDFInfo
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- CN102530857A CN102530857A CN2010105923984A CN201010592398A CN102530857A CN 102530857 A CN102530857 A CN 102530857A CN 2010105923984 A CN2010105923984 A CN 2010105923984A CN 201010592398 A CN201010592398 A CN 201010592398A CN 102530857 A CN102530857 A CN 102530857A
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- tail gas
- hydrogen
- acid tail
- catalyst
- gas
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses a method for producing hydrogen gas by using acetic acid tail gas. The high-purity hydrogen gas is obtained by pretreatment, water vapor transformation reaction and hydrogen gas purification, with the acetic acid tail gas as a raw material. The pretreatment means that impurities such as methyl iodide, methyl alcohol and the like in the acetic acid tail gas are removed, or further the impurities such as methyl iodide, the methyl alcohol and the like are removed and then CO in the impurities is adsorbed by pressure varying adsorption; and the tail gas obtained by recovering the CO is used for a transformation reaction. The method disclosed by the invention has the advantages of facilitation for saving resources and protecting environment, low investment, high hydrogen capacity and low cost.
Description
Technical field
The present invention relates to the utilization of acetate acid tail gas and producing of hydrogen, be specifically related to a kind of method of utilizing acetate acid tail gas to produce hydrogen.
Background technology
It is present topmost Production Technology of Acetic Acid that acetic acid is produced in CO and carbonylation of methanol.In the process of producing acetic acid, also produced a large amount of acetate acid tail gas.Because the restriction of separation and recovery technology, majority is all done the emptying processing at present.Contain a large amount of CO in the acetate acid tail gas, CO is the basic raw material of acetic acid production, and the energy had both been wasted in a large amount of CO emptying, had increased the acetic acid production cost, had polluted environment again.Minority producer separates the CO in the purification tail gas with transformation absorption or membrane separating method, has saved the basic raw material of acetic acid production, and the tail gas after purifying still has the CO of high level, at present can only be as exhaust gas emission in atmosphere.
Summary of the invention
The conventional raw material of producing hydrogen on a large scale is Sweet natural gas, coal gas etc., and the cost of its hydrogen manufacturing is higher.The present invention aims to provide a kind of method of utilizing acetate acid tail gas to produce hydrogen, and cost is reduced greatly, not only helps saving national resources, and helps environmental protection.
To above-mentioned purpose; Technical conceive of the present invention is following: the tail gas with the acetic acid production process is raw material, and after pre-treatment, residual gas carries out transformationreation with water vapor under the effect of catalyzer; Product to transformationreation separates purification, the final high-purity hydrogens that obtain a large amount of cheapnesss.
The method of utilizing acetate acid tail gas to produce hydrogen of the present invention comprises:
(a), the impurity in the said acetate acid tail gas of removal;
(b), carry out the water vapour transformationreation;
(c), purifying hydrogen of hydrogen.
According to the present invention, CO concentration is 60%～85% in the said acetate acid tail gas.
According to the present invention, said impurity is methyl iodide, methyl alcohol, adopts washing, charcoal absorption to remove.
According to the present invention, after said step (a), also comprise the step of transformation absorption recovery CO, the tail gas behind the recovery CO is used for said step (b).
According to the present invention, said water vapour transformationreation is meant under the effect of transformation catalyst, said acetate acid tail gas and water vapor generation transformationreation, said transformationreation be middle change reaction, middle change string low become reaction or in low low reaction.
According to the present invention, said transformation catalyst is medium temperature shift catalyst or low temperature shift catalyst.Said medium temperature shift catalyst is Fe-Cr series catalyzer or cobalt molybdenum sulfur resistant catalyst; Said low temperature shift catalyst is copper base low change catalyzer or cobalt molybdenum sulfur resistant catalyst.
According to the present invention, said step (c) adopts transformation absorption silicol process purifying hydrogen of hydrogen.
The present invention makes acetate acid tail gas obtain rationally, utilize fully, for country has saved resource, is beneficial to environmental protection.And invest for a short time, the hydrogen manufacturing cost is low, the hydrogen producing amount is big, profitable, and efficient is high.
Description of drawings
Fig. 1 produces the process flow sheet of hydrogen for the present invention utilizes acetate acid tail gas.
Embodiment
In an embodiment of the present invention, used acetate acid tail gas is to produce in the acetic acid process with CO and carbonylation of methanol to produce.
CO and methyl alcohol are raw material, and through the synthetic acetic acid of carbonylation, equation is:
CH
3OH+CO→CH
3COOH
In the prior art, methanol carbonylation is divided into two kinds of high-pressure process and low-pressure processes according to synthesis pressure.High-pressure process is catalyzer with the cobalt-carbonyl, and iodine is promotor, and carbonylation reaction is acetic acid synthesized under 250 ℃ of temperature, pressure 63.74MPa condition, yield 88%-90%.Low-pressure process is catalyzer with the Trichlororhodium, and methyl iodide is a promotor, and carbonylation reaction is acetic acid synthesized under 150 ℃ of temperature, pressure 3MPa condition.CO concentration is 60%～85% in the acetate acid tail gas that produces in CO and the carbonylation of methanol production acetic acid process.
Because the impurity such as methyl iodide and methyl alcohol of trace are arranged in the acetate acid tail gas, remove the impurity such as methyl iodide and methyl alcohol in the tail gas with the method for low-temperature rectisol.
In the present invention, it is hts catalyst that middle temperature transformation uses iron, 280 ℃～320 ℃ of inlet temperatures, between the steam-to-gas ratio 0.7～1.2, becomes reaction in carrying out under the condition of pressure 1.2MP; It is low change catalyzer that low temperature shift is used copper, 180 ℃～220 ℃ of inlet temperatures, between the steam-to-gas ratio 0.5～0.8, hangs down under the condition of pressure 1.0MP to become and reacts, and reaction back gas detects each component gas content with vapor-phase chromatography.Separate purifying hydrogen of hydrogen, and detect the content of hydrogen through pressure absorption down, decompression desorb, three processes of boosting through the gas after the transformationreation with vapor-phase chromatography.
Below in conjunction with specific embodiment, the present invention is further specified.Should be understood that following examples only are used to the present invention is described but not are used to limit scope of the present invention.
In following examples, the acetate acid tail gas that is adopted is derived from 4 batches, and composition of acetate acid tail gas (Vol%) and tolerance are as shown in table 1.
The composition and the tolerance of table 1 embodiment acetate acid tail gas
Embodiment 1
In the present embodiment, the 1st, 2 batch of acetate acid tail gas obtains high-purity hydrogen through the removal of impurity, middle temperature transformation, low temperature shift and hydrogen purification.
With the 1st batch of component content is CO:69.34%, CO
2: 9.58%, H
2: 15.32%, N
2: 2.7%, CH
4: 3.06% removes methyl alcohol through washing earlier with the acetate acid tail gas of micro iodine methane, methyl alcohol; Remove methyl iodide through charcoal absorption again, the content that adopts ECD detector detection methyl iodide gets into shift-converter through the gas after the removal of impurity and carries out the middle temperature transformation reaction less than 50ppm; The B113-2 medium temperature shift catalyst that transformation catalyst adopts Liaohe River catalyst plant to produce; The middle inlet temperature that becomes is 280 ℃, steam-to-gas ratio 1.0, and reaction pressure is 1.2MP; Become outlet CO contents on dry basis 4.89% in the gas chromatographic detection, CO transformation efficiency 63.79%; The gas that therefrom becomes outlet adds suitable quantity of water steam makes steam-to-gas ratio reach 0.5;, heat exchange gets into low temperature shift reactor after making temperature reach 180 ℃; The B205 low temperature shift catalyst that transformation catalyst adopts Liaohe River catalyst plant to produce, the low temperature in that becomes is 180 ℃, steam-to-gas ratio 0.5; Conversion pressure 1.0MP; The low outlet CO contents on dry basis 1.80% that becomes of gas chromatographic detection, CO transformation efficiency 95.67% becomes gas that reactor drum comes out and is depressurized to 0.5Mpa, temperature≤40 ℃ and gets into the PSA-H that 5 adsorption towers are formed down from low
2System, in pressure swing adsorption system, arbitrary moment always has adsorber to be in adsorption step, feeds raw material by inlet end, obtains hydrogen at exit end.Every adsorber experiences successively at different time that absorption (A), pressure equalization are fallen (EiD), reversely put pressure (D), find time (V), pressure equalization liter (EiR), (FR) finally boosts.Product purity is that 99.99% hydrogen is through comparatively exporting under stable flow rate and the pressure behind the product gas surge tank.
The 2nd batch of acetate acid tail gas component content is CO:73.31%, CO
2: 6.62%, H
2: 14.49%, N
2: 2.27%, CH
4: 3.31% with micro iodine methane, methyl alcohol, treatment process is identical with the 1st batch of acetate acid tail gas, processing parameter is as shown in table 2.
Processing parameter in the table 2 embodiment technical process
Embodiment 2
In the present embodiment, the 3rd, 4 batch of acetate acid tail gas obtains high-purity hydrogen through the removal of impurity, transformation fractionation by adsorption CO, middle temperature transformation, low temperature shift and hydrogen purification.
With the 3rd batch of component content is CO:70.82%, CO
2: 9.45%, H
2: 14.20%, N
2: 2.59%, CH
4: 2.94% removes methyl alcohol through washing earlier with the acetate acid tail gas of micro iodine methane, methyl alcohol, removes methyl iodide through charcoal absorption again, adopts content that the ECD detector detects methyl iodide less than 50ppm; Get into the PSA-CO system through the gas after the removal of impurity, feed raw material, obtain CO at exit end by inlet end; The stripping gas feeding shift-converter of transformation absorption is carried out the middle temperature transformation reaction, the B113 medium temperature shift catalyst that transformation catalyst adopts Liaohe River catalyst plant to produce, middle change inlet temperature is 290 ℃; Steam-to-gas ratio 1.1; Reaction pressure is 1.2MP, becomes outlet CO contents on dry basis 5.03% in the gas chromatographic detection, CO transformation efficiency 64.94%; The gas that therefrom becomes outlet adds suitable quantity of water steam makes steam-to-gas ratio reach 0.7;, heat exchange gets into low temperature shift reactor after making temperature reach 190 ℃; The CB-5 low temperature shift catalyst that transformation catalyst adopts the river catalyst plant to produce, the low temperature in that becomes is 190 ℃, steam-to-gas ratio 0.7; Conversion pressure 1.0MP; The low outlet CO contents on dry basis 1.60% that becomes of gas chromatographic detection, CO transformation efficiency 96.20% becomes gas that reactor drum comes out and is depressurized to 0.5Mpa, temperature≤40 ℃ and gets into the PSA-H that 5 adsorption towers are formed down from low
2System, in pressure swing adsorption system, arbitrary moment always has adsorber to be in adsorption step, feeds raw material by inlet end, obtains hydrogen at exit end.Every adsorber experiences successively at different time that absorption (A), pressure equalization are fallen (EiD), reversely put pressure (D), find time (V), pressure equalization liter (EiR), (FR) finally boosts.Product purity 99.99% hydrogen is through comparatively exporting under stable flow rate and the pressure behind the product gas surge tank.
The 4th batch of acetate acid tail gas component content is CO:78.06%, CO2:5.89%, and H2:12.28%, N2:2.06%, CH4:1.71% and micro iodine methane, methyl alcohol, treatment process is identical with the 3rd batch of acetate acid tail gas, and processing parameter is as shown in table 2.
The total conversion rate of CO and transformation absorption back H2 purity and output after the table 3 embodiment transformationreation
The result that 4 batches of acetate acid tail gas among the embodiment 1 and 2 are produced hydrogen is as shown in table 3.Result by table 3 can know; The present invention is a main raw material with the tail gas of acetic acid production process, and after pre-treatment, residual gas carries out transformationreation with water vapor under the effect of catalyzer; Product to transformationreation carries out suitable separation, finally can obtain a large amount of high-purity hydrogens.Compared with prior art, the present invention has following advantage: acetate acid tail gas obtains rationally, utilizes fully, for country has saved resource; The present invention invests little, and the hydrogen producing amount is big, and is profitable, and efficient is high; The hydrogen manufacturing cost is low; Help environmental protection.
Claims (8)
1. a method of utilizing acetate acid tail gas to produce hydrogen is characterized in that, comprising:
(a), the impurity in the said acetate acid tail gas of removal;
(b), carry out the water vapour transformationreation;
(c), purifying hydrogen of hydrogen.
2. method according to claim 1 is characterized in that, CO concentration is 60%～85% in the said acetate acid tail gas.
3. method according to claim 1 is characterized in that, said impurity is methyl iodide, methyl alcohol, adopts washing, charcoal absorption to remove.
4. method according to claim 1 is characterized in that, behind said step a, also comprises the step of transformation absorption recovery CO, and the tail gas behind the recovery CO is used for said step b.
5. method according to claim 1; It is characterized in that; Said water vapour transformationreation is meant under the effect of transformation catalyst, said acetate acid tail gas and water vapor generation transformationreation, said transformationreation be middle change reaction, middle change string low become reaction or in low low reaction.
6. method according to claim 5 is characterized in that, said transformation catalyst is medium temperature shift catalyst or low temperature shift catalyst.
7. method according to claim 6 is characterized in that, said medium temperature shift catalyst is Fe-Cr series catalyzer or cobalt molybdenum sulfur resistant catalyst; Said low temperature shift catalyst is copper base low change catalyzer or cobalt molybdenum sulfur resistant catalyst.
8. method according to claim 1 is characterized in that, said step c adopts transformation absorption silicol process purifying hydrogen of hydrogen.
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| CN2010105923984A CN102530857A (en) | 2010-12-16 | 2010-12-16 | Method for producing hydrogen gas by using acetic acid tail gas |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9409846B2 (en) | 2013-03-15 | 2016-08-09 | Celanese International Corporation | Process for separating product gas using carbonylation processes |
| CN110346496A (en) * | 2019-07-29 | 2019-10-18 | 中国辐射防护研究院 | A kind of test method and a kind of method for testing activated carbon adsorption efficiency of iodomethane |
| CN115196590A (en) * | 2022-06-22 | 2022-10-18 | 上海富禧友好能源科技有限公司 | Process for co-producing hydrogen by capturing blast furnace gas carbon |
-
2010
- 2010-12-16 CN CN2010105923984A patent/CN102530857A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9409846B2 (en) | 2013-03-15 | 2016-08-09 | Celanese International Corporation | Process for separating product gas using carbonylation processes |
| CN110346496A (en) * | 2019-07-29 | 2019-10-18 | 中国辐射防护研究院 | A kind of test method and a kind of method for testing activated carbon adsorption efficiency of iodomethane |
| CN110346496B (en) * | 2019-07-29 | 2021-10-01 | 中国辐射防护研究院 | Method for testing methyl iodide and method for testing adsorption efficiency of activated carbon |
| CN115196590A (en) * | 2022-06-22 | 2022-10-18 | 上海富禧友好能源科技有限公司 | Process for co-producing hydrogen by capturing blast furnace gas carbon |
| CN115196590B (en) * | 2022-06-22 | 2024-02-09 | 上海富禧友好能源科技有限公司 | Process for co-production of hydrogen by capturing carbon in blast furnace gas |
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Application publication date: 20120704 |