CN100436459C - Recovery and purification method of hydrogen in exhaust gas of glyphosate acid production - Google Patents
Recovery and purification method of hydrogen in exhaust gas of glyphosate acid production Download PDFInfo
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- CN100436459C CN100436459C CNB2005100604534A CN200510060453A CN100436459C CN 100436459 C CN100436459 C CN 100436459C CN B2005100604534 A CNB2005100604534 A CN B2005100604534A CN 200510060453 A CN200510060453 A CN 200510060453A CN 100436459 C CN100436459 C CN 100436459C
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Abstract
The present invention discloses a method for recovering and purifying hydrogen gas of waste gas in the glyphosate production. The method has the following steps that (1) the waste gas in the production of glyphosate acid is washed once in a water scrubber, the primary washing pressure ranges from 0.2 to 1.2MPa, and the primary water washing temperature ranges from 10 to 60 DEG C; (2) the waste gas carries out acid washing in an acid liquor absorption tower, the acid washing pressure ranges from 0.2 to 1.2MPa, and the acid washing temperature ranges from 10 to 60 DEG C; (3) the waste gas is washed twice in the water scrubber, the secondary washing pressure ranges from 0.2 to 1.2MPa, and the secondary water washing temperature ranges from 10 to 60 DEG C; (4) the oxygen is removed in a reaction tower which is loaded with a palladium catalyst, the oxygen removal pressure ranges from 0.2 to 1.2MPa, the oxygen removal temperature ranges from 90 to 130 DEG C; (5) the waste gas is dried in a drying tower which is loaded with desiccants, and the dryness pressure ranges from 0.2 to 1.2Mpa; (6) the dry gas is led to a PSA pressure-swing adsorption device to be purified, and hydrogen gas with the content more than 99.8% is prepared. The present invention has the advantage that the hydrogen gas of the waste gas has high recovery rate and good quality in the production of glyphosate acid; the harmful impurities in the tail gas can be completely removed.
Description
Technical field
The present invention relates to the synthetic of glyphosphonic acid, relate in particular to the recovery method of purification of hydrogen in a kind of exhaust gas of glyphosate acid production.
Background technology
Glyphosate is a kind of weedicide of broad-spectrum high efficacy, and the chemical equation of IDA method synthesizing glyphosate acid is as follows:
By glyphosphonic acid synthetic the first step chemical equation (1) as can be known, diethanolamine and sodium hydroxide generate Iminodiacetic acid sodium salt salt and hydrogen tail gas under the effect of catalyzer.The generation of simultaneous part side reaction generates following impurity:
Glycine sodium salt (HNCH
2COONa), sodium oxalate (COONa)
2, also have unreacted diethanolamine [HN (CH completely
2CH
2OH)
2], these impurity with Iminodiacetic acid sodium salt salt, sodium hydroxide (NaOH), water etc. because the oxygen (O that also has trace that discharges with hydrogen is discharged in the effect of entrainment with hydrogen
2) and nitrogen (N
2).Resource, contaminate environment had again both been wasted in the discharging of inflammable gas hydrogen.Hydrogen tail gas composed as follows:
| Hydrogen | Glycine sodium salt | Sodium oxalate | Diethanolamine | Oxygen | Nitrogen | Sodium hydroxide | Water and other | Iminodiacetic acid sodium salt salt |
| 94.00％ | 0.05％ | 0.03％ | 0.15％ | 0.3％ | 1.92％ | 1.02％ | 2.18％ | 0.35％ |
Summary of the invention
The recovery method of purification that the purpose of this invention is to provide hydrogen in a kind of exhaust gas of glyphosate acid production.The step of method is as follows:
1) exhaust gas of glyphosate acid production is once washed through water wash column, once washing pressure is 0.2～1.2MPa, preferred 0.5～0.9Mpa, and one time washing temperature is 10～60 ℃, preferred 30～50 ℃;
2) through the pickling of acid solution absorption tower, pickling pressure is 0.2～1.2MPa, preferred 0.5～0.9Mpa, and pickling temperature is 10～60 ℃, preferred 30～50 ℃;
3) through the water wash column secondary water washing, secondary water washing pressure is 0.2～1.2MPa, preferred 0.5～0.9Mpa, and the secondary water washing temperature is 10～60 ℃, preferred 30～50 ℃;
4) through the reaction tower deoxygenation of interior dress palladium catalyst, deoxygenation pressure is 0.2～1.2MPa, preferred 0.5～0.9Mpa, and the deoxygenation temperature is 90～130 ℃, preferred 105～120 ℃;
5) drying tower through siccative is housed carries out drying, and drying pressure is 0.2～1.2MPa, preferred 0.5～0.9MPa;
6) dry gas is entered the PSA pressure-swing absorption apparatus and purify, acquisition content reaches the hydrogen more than 99.8%.
Advantage of the present invention is that the hydrogen solvent recovery technology from vent gas of diethanolamine catalytic oxidative dehydrogenation process is simple, rate of recovery height, quality better and the detrimental impurity in the tail gas can be eliminated.Adopt this art breading hydrogen recovery rate to reach more than 90%, hydrogen content reaches more than 99.8%, the highlyest can reach 99.99%.
Embodiment
The hydrogen tail gas that produces in the diethanolamine catalytic oxidative dehydrogenation process is after condensation is collected, purify and to make the hydrogen of content 〉=99.8% through washing, pickling, secondary water washing, deoxygenation, drying, transformation absorption, the hydrogen source of this hydrogen and hydrogenated products synthetic as hydrogen peroxide, Isopropylamine, and make the raw material that hydrogen peroxide, Isopropylamine can be used as synthesizing glyphosate acid, glyphosate isopropyl amine salt.This invention can reach and overcome environmental pollution, reduces the purpose of resource consumption, is typical recycling economy.
The impurity of the hydrogen tail gas in the diethanolamine catalytic oxidative dehydrogenation process is more, shown in its table composed as follows:
| Hydrogen | Glycine sodium salt | Sodium oxalate | Diethanolamine | Oxygen | Nitrogen | Sodium hydroxide | Water and other | Iminodiacetic acid sodium salt salt |
| 94.00％ | 0.05％ | 0.03％ | 0.15％ | 0.3％ | 1.92％ | 1.02％ | 2.18％ | 0.35％ |
According to the inventive method, glycine sodium salt, sodium oxalate, diethanolamine, sodium hydroxide, Iminodiacetic acid sodium salt salt are water-soluble better, can wash with water earlier and remove major part, eliminate through pickling again, water flush away trace acid then, washing gas enters pressure swing adsorption system and removes the nitrogen purifying hydrogen of hydrogen by deoxygenation, drying.
Washing: hydrogen tail gas is washed through water wash column, removed NaOH, glycine sodium salt (HNCH in the tail gas
2COONa), sodium oxalate (COONa)
2, diethanolamine H N (CH
2CH
2OH)
2, water-soluble substances such as Iminodiacetic acid sodium salt salt.Water wash column can be used conventional towers such as packing tower, sieve-tray tower.
Pickling: preceding described gas by the acid solution absorption tower, is removed remaining alkaline matter.Acid solution comprises sulfuric acid, nitric acid etc., takes all factors into consideration the preferred vitriol oil, can in and alkaline matter, can dewater again.
Secondary water washing: after aforementioned gas is washed through water wash column, continue to remove water-soluble substances and trace acid.
Deoxygenation: the aforementioned gas that contains minor amounts of oxygen is through the reaction tower of interior dress palladium catalyst, water generation reaction and remove deoxidation.
Dry: the aforementioned carrier of oxygen that removes makes dry gas through the drying installation of siccative such as the molecular sieve or the vitriol oil is housed.Siccative is preferentially selected molecular sieve for use.
Transformation absorption (PSA device) purifying hydrogen of hydrogen, hydrogen content 〉=99.8%.
The method that is used for removing the tail gas impurity composition described in the invention can be carried out multiple combination.Do not do the limit explanation in the present invention, the combination of the processing scheme of being done on basis of the present invention also should be included within the present invention even be different from the described scheme of embodiment.
Embodiment 1
Draw a pipeline to two 6m from the dehydrogenation operation
3Band press surge tank (≤1.2MPa), this is canned spark arrester and safety valve.Band presses the gas of surge tank to wash with circulated sprinkling, and washing is to be to carry out in 300mm, the high packing tower for 4m, interior dress pottery rectangular saddle ring at 2 diameters, and once washing pressure is that 0.2MPa, a washing temperature are 10 ℃.
Gas after the washing carries out pickling, and pickling is to be to carry out in 300mm, the high packing tower for 4m, interior dress pottery rectangular saddle ring at diameter.Sulfuric acid circulated sprinkling in the tower is changed when content reaches 90%.Pickling pressure is that 0.2MPa, pickling temperature are 10 ℃.
It is 300mm, high for spraying washing in the packing tower of 4m that gas after the pickling enters two diameters.Secondary water washing pressure is that 0.2MPa, secondary water washing temperature are 10 ℃.
Gas is through the reaction tower of dress palladium catalyst in two diameter 300mm, the high 3m after the secondary water washing, and water generation reaction is removed the oxygen in the hydrogen by condensation, gas-water separation.Deoxygenation pressure is that 0.2MPa, deoxygenation temperature are 90 ℃.
Gas after the deoxygenation obtains dry gas through the drying installation that molecular sieve is housed, and drying pressure is 0.2Mpa.
Dried gas obtains 99.85% hydrogen through the PSA pressure-swing absorption apparatus.As the hydrogen source that is used to produce hydrogen peroxide, Isopropylamine or hydrogenating reduction product.Can also be as the fuel of boiler.
Embodiment 2
Draw a pipeline to two 6m from the dehydrogenation operation
3Band press surge tank (≤1.2MPa), this is canned spark arrester and safety valve.Band presses the gas of surge tank to wash with circulated sprinkling, and washing is to be to carry out in 300mm, the high packing tower for 4m, interior dress pottery rectangular saddle ring at 2 diameters, and once washing pressure is that 1.2MPa, a washing temperature are 60 ℃;
Once the gas after the washing carries out pickling, and pickling is to be to carry out in 300mm, the high packing tower for 4m, interior dress pottery rectangular saddle ring at diameter.Nitric acid circulated sprinkling in the tower is changed when content reaches 92%.Pickling pressure is that 1.2MPa, pickling temperature are 60 ℃;
It is 300mm, high for spraying washing in the packing tower of 4m that gas after the pickling enters two diameters.Secondary water washing pressure is that 1.2MPa, secondary water washing temperature are 60 ℃.
Gas is through the reaction tower of dress palladium catalyst in two diameter 300mm, the high 3m after the secondary water washing, and water generation reaction is removed the oxygen in the hydrogen by condensation, gas-water separation.Deoxygenation pressure is that 1.2MPa, deoxygenation temperature are 130 ℃.
Gas after the deoxygenation obtains dry gas through the drying installation that molecular sieve is housed, and drying pressure is 1.2Mpa;
Dried gas obtains 99.90% hydrogen through the PSA pressure-swing absorption apparatus.As the hydrogen source that is used to produce hydrogen peroxide, Isopropylamine or hydrogenating reduction product.Can also be as the fuel of boiler.
Embodiment 3
Draw a pipeline to two 6m from the dehydrogenation operation
3Band press surge tank (≤1.2MPa), this is canned spark arrester and safety valve.Band presses the gas of surge tank to wash with circulated sprinkling, and washing is to be to carry out in 300mm, the high packing tower for 4m, interior dress pottery rectangular saddle ring at 2 diameters, and once washing pressure is that 0.8MPa, a washing temperature are 35 ℃; Once the gas after the washing carries out pickling, and pickling is to be to carry out in 300mm, the high packing tower for 4m, interior dress pottery rectangular saddle ring at diameter.Sulfuric acid circulated sprinkling in the tower is changed when content reaches 90%.Pickling pressure is that 0.8MPa, pickling temperature are 35 ℃;
It is 300mm, high for spraying washing in the packing tower of 4m that gas after the pickling enters two diameters.Secondary water washing pressure is that 0.8MPa, secondary water washing temperature are 35 ℃.
Gas is through the reaction tower of dress palladium catalyst in two diameter 300mm, the high 3m after the secondary water washing, and water generation reaction is removed the oxygen in the hydrogen by condensation, gas-water separation.Deoxygenation pressure is that 0.8MPa, deoxygenation temperature are 115 ℃.
Gas after the deoxygenation obtains dry gas through the drying installation that molecular sieve is housed, and drying pressure is 0.8Mpa.
Dried gas obtains 99.95% hydrogen through the PSA pressure-swing absorption apparatus.As the hydrogen source that is used to produce hydrogen peroxide, Isopropylamine or hydrogenating reduction product.Can also be as the fuel of boiler.
Claims (5)
1. the recovery method of purification of hydrogen in the exhaust gas of glyphosate acid production is characterized in that the step of method is as follows:
1) exhaust gas of glyphosate acid production is once washed through water wash column, once washing pressure is that 0.2-1.2MPa, a washing temperature are 10-60 ℃;
2) through the pickling of acid solution absorption tower, pickling pressure is 0.2-1.2MPa, and pickling temperature is 10-60 ℃;
3) through the water wash column secondary water washing, secondary water washing pressure is 0.2-1.2MPa, and the secondary water washing temperature is 10-60 ℃;
4) through the reaction tower deoxygenation of interior dress palladium catalyst, deoxygenation pressure is 0.2-1.2MPa, and the deoxygenation temperature is 90-130 ℃;
5) drying tower through siccative is housed carries out drying, and drying pressure is 0.2-1.2Mpa;
6) dry gas is entered pressure-swing absorption apparatus and purify, acquisition content reaches the hydrogen more than 99.8%.
2. the recovery method of purification of hydrogen is characterized in that in a kind of exhaust gas of glyphosate acid production according to claim 1, and the step of method is as follows:
1) exhaust gas of glyphosate acid production is once washed through water wash column, once washing pressure is 0.5～0.9Mpa, and one time washing temperature is 30～50 ℃;
2) through the pickling of acid solution absorption tower, pickling pressure is 0.5～0.9Mpa, and pickling temperature is 30～50 ℃;
3) through the water wash column secondary water washing, secondary water washing pressure is 0.2～1.2MPa, and the secondary water washing temperature is 10～60 ℃;
4) through the reaction tower deoxygenation of interior dress palladium catalyst, deoxygenation pressure is 0.5～0.9Mpa, and the deoxygenation temperature is 105～120 ℃;
5) drying tower through siccative is housed carries out drying, and drying pressure is 0.5～0.9MPa;
6) dry gas is entered pressure-swing absorption apparatus and purify, acquisition content reaches the hydrogen more than 99.8%.
3. the recovery method of purification of hydrogen is characterized in that in a kind of exhaust gas of glyphosate acid production according to claim 1, and described acid solution is sulfuric acid or nitric acid.
4. the recovery method of purification of hydrogen is characterized in that in a kind of exhaust gas of glyphosate acid production according to claim 1, and described siccative is a molecular sieve.
5. the recovery method of purification of hydrogen is characterized in that in a kind of exhaust gas of glyphosate acid production according to claim 2, and described secondary water washing pressure is 0.5～0.9Mpa, and the secondary water washing temperature is 30～50 ℃.
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|---|---|---|---|
| CNB2005100604534A CN100436459C (en) | 2005-08-23 | 2005-08-23 | Recovery and purification method of hydrogen in exhaust gas of glyphosate acid production |
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|---|---|---|---|
| CNB2005100604534A CN100436459C (en) | 2005-08-23 | 2005-08-23 | Recovery and purification method of hydrogen in exhaust gas of glyphosate acid production |
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| CN100436459C true CN100436459C (en) | 2008-11-26 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102463032A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Treatment method of acid water head space gas |
| CN102020246B (en) * | 2010-12-23 | 2013-01-23 | 苏州市创新净化有限公司 | Hydrogen purified recovery system and process method |
| CN102206219B (en) * | 2011-01-14 | 2012-11-14 | 捷马化工股份有限公司 | Method for preparing urotropine by using glyphosate by-product ammonia gas and formaldehyde |
| CN110013759A (en) * | 2018-01-09 | 2019-07-16 | 中国石油化工股份有限公司 | Low-temperature catalytic oxidation handles the device and method of hydrogeneous periodic off-gases |
| CN112225176B (en) * | 2020-10-12 | 2023-05-09 | 艾氢技术(苏州)有限公司 | Solid hydrogen discharging and purifying system |
Citations (1)
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| CN1199921C (en) * | 2002-07-23 | 2005-05-04 | 浙江新安化工集团股份有限公司 | Technique for cleanly recovering byproduct methyl chloride of glyphosate acid |
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2005
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199921C (en) * | 2002-07-23 | 2005-05-04 | 浙江新安化工集团股份有限公司 | Technique for cleanly recovering byproduct methyl chloride of glyphosate acid |
Non-Patent Citations (4)
| Title |
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| 亚氨基二乙酸的合成研究. 曾小君等.农药，第41卷第6期. 2002 |
| 亚氨基二乙酸的合成研究. 曾小君等.农药，第41卷第6期. 2002 * |
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